Amazing Stem Cell Treatment for DiabetesIf recent research continues along its promising path, stem cells from women’s uteruses might turn out to be the "mother" of all treatments for type 1 diabetes -- eliminating the need for patients (men as well as women) to inject themselves with insulin! A group of scientists from Yale University School of Medicine in New Haven, Connecticut, has converted endometrial stem cells harvested from the base of adult female uteruses into cells that produce insulin. It’s possible that this will turn out to be a major breakthrough for the roughly three million Americans who have type 1 diabetes (meaning that their bodies don’t produce insulin). I contacted Hugh S. Taylor, MD, lead researcher of the study (published in the August 30, 2011 issue of Molecular Therapy) and a professor of obstetrics, gynecology and reproductive sciences at Yale to learn more about this intriguing new application for stem cells. While there are new technologies that are fairly easy to use to treat type 1 diabetes (like insulin pens and pumps), people who don’t naturally produce insulin still have to spend lots of time monitoring their blood sugar and need several injections of varying amounts a day. But even with these advances, insulin injection remains inexact and inefficient, said Dr. Taylor. "Glucose levels change so rapidly that no amount of monitoring allows diabetics to inject insulin at the precise times they need it," he explained. ABOUT THE RESEARCHDr. Taylor and his fellow researchers extracted the uterine stem cells from adult women and treated them with special nutrients and growth factors (indolactam and exendin) that earlier studies had shown would transform the cells into insulin producers. These new-and-improved cells were then injected into eight mice with type 1 diabetes, while six other mice with type 1 diabetes were injected with placebo cells. After five weeks, none of the mice that got the new insulin-producing cells developed diabetic problems -- their blood sugar didn’t rise any higher, and they started producing insulin. In contrast, blood sugar levels in all of the mice who received placebo cells continued to rise (above 220 mg/dL) and they also began to develop some of the common complications of diabetes that are so destructive, specifically cataracts and fatigue. While the mice with the insulin-producing cells were still considered diabetic, they were clearly in far better shape than their placebo-treated counterparts, and Dr. Taylor told me that he believes that injecting more such insulin-producing cells into them might even lower their blood sugar and make their diabetes actually go away. COMING SOON TO A DOCTOR NEAR YOU? Dr. Taylor seems quite optimistic that human beings will react well to this new therapy, too. He believes that we could see treatments based on this technique within three to four years but noted that this depends, of course, on the outcome of research that is currently underway. Thus far, no dangerous or harmful side effects have been identified. Though it is possible that people will need repeat stem cell injections (perhaps every few months or every few years), the stem cells are inexpensive to produce and the injections can be given directly into the skin in a process so simple that it can be done in a doctor’s office. This is a promising development to be watched. Source(s): Hugh S. Taylor, MD, chief of reproductive endocrinology and infertility, director, Yale Center for Reproductive Biology and professor of obstetrics, gynecology and reproductive sciences at the Yale University School of Medicine, New Haven, Connecticut.
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Wednesday, November 30, 2011
Sunday, November 27, 2011
Salt! Not So Bad After All?
Salt! Not So Bad After All?By matt Rating: Rate this listing
-->For years, we’ve been told that people who consume a lot of sodium (primarily in the form of dietary salt) are at increased risk for high blood pressure (hypertension).Now: The Journal of the American Medical Association recently published a European study that suggests the issue may be more complex than previously believed—a finding that may mean that many of us can safely use more salt.Recent finding: In an eight-year study, which followed more than 3,600 men and women ages 60 and younger (all of whom had normal blood pressure at the start of the research), researchers found that the one-third of study participants who had the highest sodium intake experienced only a slight rise in systolic (top number) blood pressure and no rise in diastolic (bottom number) blood pressure.Those in the highest intake group consumed an average of 6,000 mg of salt daily, which is more than twice the daily recommendation for adults in general. Even more surprising, the research found that the one-third of study participants with the lowest salt intake (an average of 2,500 mg daily) were 56% more likely to suffer a heart attack or stroke than the group consuming the most salt.Lower sodium levels reduce blood pressure but also increase resistance to insulin and sympathetic nervous system activity, including heart rate. If sodium levels fall too much, it can damage the cardiovascular system.What does this new research mean for people who are concerned about controlling their blood pressure…and avoiding heart attack and stroke?The results of the European study are controversial—some scientists point out that many of the people with low-sodium intake had pre-existing health problems that caused them to curtail their salt intake. The findings also call into question one of the most basic premises of good medicine—that a low-sodium diet helps prevent high blood pressure, which is itself a significant risk factor for heart attack and stroke.In fact, the CDC urges adults in general to not exceed 2,300 mg of sodium per day (about one teaspoon of salt). If you have hypertension or are among those at increased risk for it—such as adults ages 51 and older and African-Americans of any age—the CDC recommends no more than 1,500 mg per day.As a physician and researcher who has closely followed the scientific evidence on sodium consumption for the past 35 years, I believe this latest study simply confirms that the salt issue is not as straightforward as it might seem. In fact, there have been mixed results from about 15 major studies conducted over the past several years on the health effects of sodium consumption. Roughly one-third of those studies found no association between salt intake and mortality…one-third found that people who consumed more sodium (6,000 mg to 8,000 mg per day) were more likely to die and one-third found, like the new European study, that high salt intake does not increase one’s risk for death.Also recently, a review prepared by The Cochrane Collaboration of existing research involving 6,250 people found that cutting salt intake lowered blood pressure but had no effect on cardiovascular deaths. In fact, lower sodium increased risk for those with congestive heart failure.It’s important to remember that none of this research is definitive—all of the studies are observational, which means that researchers draw inferences about behaviors of people in the general population without creating a controlled environment. This type of research is limited in its ability to reveal a causal relationship between a biological factor—in this case, sodium intake—and a complex condition with many contributing factors, such as heart attack or stroke.Bottom line: Since there is currently no definitive evidence showing that reducing sodium saves lives or prevents heart attack and stroke among healthy adults—and a number of studies suggest that sodium restriction actually may be dangerous to at least some people’s health—there still are many unanswered questions.So, what should you do about salt? Important points to consider…1. Sodium intake is not the only factor that contributes to high blood pressure and related ailments. Over the past two decades, the percentage of American adults with high blood pressure has risen from one in four to about one in three—a trend that sodium-reduction advocates blame on our increased sodium intake from processed and fast foods.Problem with this theory: A recent analysis by Harvard nutritionist Walter Willett, MD, based on 24-hour urine samples (the best way to measure sodium consumption), found that US average sodium intake has remained quite steady over the past 50 years, at around 3,500 mg per day. This suggests that sodium is not the main reason for the higher incidence of hypertension and that other factors, such as rising rates of obesity and diabetes—both of which harm cardiovascular health in other ways—may be more to blame.2. Sodium has many important functions in the body. Most people are well aware of the research suggesting that reducing sodium intake lowers blood pressure—mainly by decreasing fluid retention, which in turn decreases blood volume.What is less well-known is that reducing sodium intake increases insulin resistance, triglycerides and sympathetic nervous system activity, all of which are harmful to the cardiovascular system. Reducing sodium also activates the renin angiotensin system, a network of hormones that controls blood pressure and fluid balance in the body. When this system is activated, it triggers the release of substances that cause the blood vessels to constrict and blood volume to increase—both of which promote increased blood pressure. This explains why blood pressure goes up in some people when they cut back on salt.3. People react to sodium differently. A significant percentage of people (including many with high blood pressure) are “salt-sensitive”—meaning that their blood pressure reacts more strongly than does the average person’s to increases in sodium. Others, however, are “salt-resistant” and need higher levels of sodium to maintain normal, healthy physiological functions.At present, we have no good way of determining which individuals are salt-sensitive or salt-resistant, though genetics, age, race and body mass all appear to play a role. People who are salt-sensitive tend to have relatively low levels of potassium in their diets, are over age 55, are obese, have hypertension or a family history of hypertension and/or are African-American.Research suggests that there is likely a range of healthy sodium intake that we instinctively aim for in our individual diets—and that if your sodium intake is either above or below this range, health problems, such as dehydration, high blood pressure and fluid retention, can occur. The health risks tend to occur when the kidneys are unable to excrete excess salt (for example, in people with kidney disease), so it accumulates in the blood, causing fluid buildup. This range will vary among individuals—it’s most likely about 2,000 mg to 4,000 mg a day for individuals who are not salt-sensitive—making it impossible to come up with a “one-size-fits-all” recommendation on sodium intake.Very important: There’s enough evidence to show that a low-sodium diet should be tried as part of any treatment plan for the one-third of Americans with hypertension (blood pressure of 140/90 mmHG and above) and the one-quarter of Americans with prehypertension (systolic pressure of 120 mmHG to 139 mmHG and/or diastolic pressure of 80 mmHG to 89 mmHG).But right now, there’s no good scientific evidence to suggest that people with normal blood pressure who are not at risk for hypertension should reduce sodium intake to a certain pre-determined number—this practice may do more harm than good. Ask your doctor what your target sodium levels should be based on your personal medical profile. Bottom Line/Health interviewed Michael Alderman, MD, distinguished emeritus professor of medicine and population health at Albert Einstein College of Medicine in New York City and editor of the American Journal of Hypertension. Dr. Alderman has authored more than 270 scientific papers, book chapters and textbooks describing his research on hypertension.
-->For years, we’ve been told that people who consume a lot of sodium (primarily in the form of dietary salt) are at increased risk for high blood pressure (hypertension).Now: The Journal of the American Medical Association recently published a European study that suggests the issue may be more complex than previously believed—a finding that may mean that many of us can safely use more salt.Recent finding: In an eight-year study, which followed more than 3,600 men and women ages 60 and younger (all of whom had normal blood pressure at the start of the research), researchers found that the one-third of study participants who had the highest sodium intake experienced only a slight rise in systolic (top number) blood pressure and no rise in diastolic (bottom number) blood pressure.Those in the highest intake group consumed an average of 6,000 mg of salt daily, which is more than twice the daily recommendation for adults in general. Even more surprising, the research found that the one-third of study participants with the lowest salt intake (an average of 2,500 mg daily) were 56% more likely to suffer a heart attack or stroke than the group consuming the most salt.Lower sodium levels reduce blood pressure but also increase resistance to insulin and sympathetic nervous system activity, including heart rate. If sodium levels fall too much, it can damage the cardiovascular system.What does this new research mean for people who are concerned about controlling their blood pressure…and avoiding heart attack and stroke?The results of the European study are controversial—some scientists point out that many of the people with low-sodium intake had pre-existing health problems that caused them to curtail their salt intake. The findings also call into question one of the most basic premises of good medicine—that a low-sodium diet helps prevent high blood pressure, which is itself a significant risk factor for heart attack and stroke.In fact, the CDC urges adults in general to not exceed 2,300 mg of sodium per day (about one teaspoon of salt). If you have hypertension or are among those at increased risk for it—such as adults ages 51 and older and African-Americans of any age—the CDC recommends no more than 1,500 mg per day.As a physician and researcher who has closely followed the scientific evidence on sodium consumption for the past 35 years, I believe this latest study simply confirms that the salt issue is not as straightforward as it might seem. In fact, there have been mixed results from about 15 major studies conducted over the past several years on the health effects of sodium consumption. Roughly one-third of those studies found no association between salt intake and mortality…one-third found that people who consumed more sodium (6,000 mg to 8,000 mg per day) were more likely to die and one-third found, like the new European study, that high salt intake does not increase one’s risk for death.Also recently, a review prepared by The Cochrane Collaboration of existing research involving 6,250 people found that cutting salt intake lowered blood pressure but had no effect on cardiovascular deaths. In fact, lower sodium increased risk for those with congestive heart failure.It’s important to remember that none of this research is definitive—all of the studies are observational, which means that researchers draw inferences about behaviors of people in the general population without creating a controlled environment. This type of research is limited in its ability to reveal a causal relationship between a biological factor—in this case, sodium intake—and a complex condition with many contributing factors, such as heart attack or stroke.Bottom line: Since there is currently no definitive evidence showing that reducing sodium saves lives or prevents heart attack and stroke among healthy adults—and a number of studies suggest that sodium restriction actually may be dangerous to at least some people’s health—there still are many unanswered questions.So, what should you do about salt? Important points to consider…1. Sodium intake is not the only factor that contributes to high blood pressure and related ailments. Over the past two decades, the percentage of American adults with high blood pressure has risen from one in four to about one in three—a trend that sodium-reduction advocates blame on our increased sodium intake from processed and fast foods.Problem with this theory: A recent analysis by Harvard nutritionist Walter Willett, MD, based on 24-hour urine samples (the best way to measure sodium consumption), found that US average sodium intake has remained quite steady over the past 50 years, at around 3,500 mg per day. This suggests that sodium is not the main reason for the higher incidence of hypertension and that other factors, such as rising rates of obesity and diabetes—both of which harm cardiovascular health in other ways—may be more to blame.2. Sodium has many important functions in the body. Most people are well aware of the research suggesting that reducing sodium intake lowers blood pressure—mainly by decreasing fluid retention, which in turn decreases blood volume.What is less well-known is that reducing sodium intake increases insulin resistance, triglycerides and sympathetic nervous system activity, all of which are harmful to the cardiovascular system. Reducing sodium also activates the renin angiotensin system, a network of hormones that controls blood pressure and fluid balance in the body. When this system is activated, it triggers the release of substances that cause the blood vessels to constrict and blood volume to increase—both of which promote increased blood pressure. This explains why blood pressure goes up in some people when they cut back on salt.3. People react to sodium differently. A significant percentage of people (including many with high blood pressure) are “salt-sensitive”—meaning that their blood pressure reacts more strongly than does the average person’s to increases in sodium. Others, however, are “salt-resistant” and need higher levels of sodium to maintain normal, healthy physiological functions.At present, we have no good way of determining which individuals are salt-sensitive or salt-resistant, though genetics, age, race and body mass all appear to play a role. People who are salt-sensitive tend to have relatively low levels of potassium in their diets, are over age 55, are obese, have hypertension or a family history of hypertension and/or are African-American.Research suggests that there is likely a range of healthy sodium intake that we instinctively aim for in our individual diets—and that if your sodium intake is either above or below this range, health problems, such as dehydration, high blood pressure and fluid retention, can occur. The health risks tend to occur when the kidneys are unable to excrete excess salt (for example, in people with kidney disease), so it accumulates in the blood, causing fluid buildup. This range will vary among individuals—it’s most likely about 2,000 mg to 4,000 mg a day for individuals who are not salt-sensitive—making it impossible to come up with a “one-size-fits-all” recommendation on sodium intake.Very important: There’s enough evidence to show that a low-sodium diet should be tried as part of any treatment plan for the one-third of Americans with hypertension (blood pressure of 140/90 mmHG and above) and the one-quarter of Americans with prehypertension (systolic pressure of 120 mmHG to 139 mmHG and/or diastolic pressure of 80 mmHG to 89 mmHG).But right now, there’s no good scientific evidence to suggest that people with normal blood pressure who are not at risk for hypertension should reduce sodium intake to a certain pre-determined number—this practice may do more harm than good. Ask your doctor what your target sodium levels should be based on your personal medical profile. Bottom Line/Health interviewed Michael Alderman, MD, distinguished emeritus professor of medicine and population health at Albert Einstein College of Medicine in New York City and editor of the American Journal of Hypertension. Dr. Alderman has authored more than 270 scientific papers, book chapters and textbooks describing his research on hypertension.
Saturday, November 26, 2011
Seniors who once lived in terror of losing their independence
This Woman IsBRAND NEW!
And remember—Alice is just one of thousands of Power Aging participants who
have experienced a similar surge in their mental and physical powers.
Seniors who once lived in terror of losing their independence are amazed at
how sharp they've become.
Imagine if someone you're worried about could make such a dramatic
turnaround!
The Power Aging study proves they can. Dr. Gary Null has uncovered the secret
of what really makes brains falter and fail. Very simply put...
Aging brains need ENERGY...
Huge amounts of it, all around the clock! You see, each time one brain cell
"talks" to another, an electrical impulse jumps between them. Just thinking
one little thought requires millions of these sparks...
And, to produce all this energy, every cell in your body contains its own
built-in "power plant."
These are long, oval-shaped structures called mitochondria.
(Pronounced mite-oh-CON-dree-uh.)
They look a little like one-celled animals. They're constantly pulling in
fuel from your cellular fluids, and "burning" this fuel with oxygen. In fact,
these little guys use up 80% of the oxygen you breathe...
These mitochondria are the secret sourceof 95% of your
BRAINPOWER!
As long as they get the fuel they need, everything's fine. But as we age, our
mitochondria have trouble transporting and burning the fuel. RESULT? First you
feel a little fatigued. Then you start having "senior moments." As your
mitochondria continue to sputter and gasp, huge numbers of brain cells
die...
Senility sets in and it's time for the nursing home... OR IS
IT?
Dr. Gary Null says NO! He's perfected an astonishingly effective way
to get these starved mitochondria fueled up and humming again. Your FREE-Preview
copy of Bottom Line's POWER AGING reveals exactly how to do
it, with nutrients you can find at any health food store.
NOTE: Participants say their physical energy rockets as
well...
For good reason. Because your mitochondria also supply the energy
for your muscles, heart and lungs!
All the details are FREE in your FREE-Preview
volume, so why not send for it right now?
At Last, A Clinically Proven And Medically
DocumentedARTHRITIS CURE
Study proves
Dr. Gary Null's secret transforms nearly 90% of sufferers!
John F. says his joint pain got so horrible, "I underwent surgery to
fuse my wrist. My knees and neck were deteriorating, so I used
heavy medications." John had almost forgotten what it was like to live
without constant agony. Yet Dr. Gary Null's secrets made him...
"PAIN-FREE IN 4 WEEKS!"—John F., case
history #2,954
"I take no more medications," John continues, "and all swelling subsided. My
doctor commented that the condition of my knee joints is the best he has
observed. I am able to take long walks. I have reclaimed my life!"
Wonderful, yes? Yet I know you're probably thinking...
"Great for John, but what about ME?"
After all, one man's "miracle cure" may not work for others, right?
WRONG! Dr. Gary Null has clinically proven that John's turnaround
isn't unusual.
In fact, to test exactly how well his arthritis discoveries are working, he
enrolled a very special subgroup of people into his Power Aging study.
To get into this group, you needed a letter from your doctor
confirming that you'd been medically diagnosed with arthritis...SOME HAD
SUFFERED FOR OVER 25 YEARS!
Their pain wasn't imaginary. All of them really, truly, had chronic
arthritis—bad!
Yet after using Dr. Gary Null's natural arthritis cure, 87% of them were
substantially or completely improved. The pain went away. Inflammation
faded or vanished. Frozen limbs moved freely again!
And it didn't matter what type of arthritis they had.
Most were so utterly changed, their own personal
doctorsTOOK THEM OFF ALL ARTHRITIS MEDICATION...
If that's not a
cure, what is?
So do send for your FREE-Preview
copy of Bottom Line's POWER AGING right now. See the full
details of what these people did, starting on page 268. Try it yourself! And
then find out how thousands of people have found relief from nearly every other
pain, discomfort and disease of aging, including...
Paralyzing back pain, page 274."I had severe lower back
disc pain.I could not climb stairs and used crutches and a cane.
Eventually,I was paralyzed and confined to a wheelchair. Since
following Gary Null's [secrets], my body went from pain to joy. My backache
subsided. I easily climb 3 flights of stairs to my apartment. All past symptoms
are gone!" —Glenroy, age 65, case history #6,483
Bone spurs, page 170. "After one year, I no longer suffer
with the excruciating pain from heel spurs. The spurs are almost completely
cleared up." —Sharon, case history #8,398
Migraine, page 312. "I am migraine-free." —Jayne, case
history #4,665
Severe diabetes, page 171. "I used insulin and glucophage
for severe diabetes. [Now] I do not have to take diabetic medication!"
—Frantz, case history #1,556
Neuropathy and kidney disease, page 281. "I had neuropathy
in my hands and knees, and was diagnosed with kidney disease. Today, after
following Gary's directions, pain from neuropathy is no more. Tests determined
my kidney disease is reduced!" —Karina, case history #2,969
Allergies, page 271. "I am not allergic to dogs and cats
anymore." —Sam, case history #3,386
Hemorrhoids, page 284. "Hemorrhoids are completely gone."
—Maureen, case history #2,187
Gallstones, page 312. "No symptoms anymore!"—Bill,
case history #10,834
Now, I can fully understand if you're dubious, because these case histories
are astonishing...
But ask yourself: Could all these thousands of people in the 14-year
Power Aging study be lying? Could they all be imagining the results that have
been documented by blood tests and observed by their own family doctors? Could
all this hard evidence—that you can reverse the aging process—be a mass
hallucination?
No way! So isn't it time you found out for yourself why PBS
television stations, Larry King Live, Oprah and so many other
dyed-in-the-wool skeptics have been spotlighting the work of Dr. Gary Null?
Let me send you his ultimate book of Power Aging discoveries to preview
FREE...
"I no longer use eyeglasses during the day!"—Joseph I., age 63, case history #4,443
Days From Now, You Too Could Be Saying..."My
Physician Is AMAZED!"—Summer, case history
#10,657
Yes, of course it can happen for you, too! You've
heard Dr. Gary Null's breakthrough praised by some of TV's most responsible
broadcasters, and you've seen dozens of documented case histories in this
Special Report. You've learned how and why it's really happening. But why just
wonder at it all, when you could...
Wake up from your worst aging nightmares for FREE!
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No matter what, no purchase required! Generous? Yes, but this is
nothing compared to the gift of great health you'll be giving
yourself as soon as you open your FREE GIFTS...
And remember—Alice is just one of thousands of Power Aging participants who
have experienced a similar surge in their mental and physical powers.
Seniors who once lived in terror of losing their independence are amazed at
how sharp they've become.
Imagine if someone you're worried about could make such a dramatic
turnaround!
The Power Aging study proves they can. Dr. Gary Null has uncovered the secret
of what really makes brains falter and fail. Very simply put...
Aging brains need ENERGY...
Huge amounts of it, all around the clock! You see, each time one brain cell
"talks" to another, an electrical impulse jumps between them. Just thinking
one little thought requires millions of these sparks...
And, to produce all this energy, every cell in your body contains its own
built-in "power plant."
These are long, oval-shaped structures called mitochondria.
(Pronounced mite-oh-CON-dree-uh.)
They look a little like one-celled animals. They're constantly pulling in
fuel from your cellular fluids, and "burning" this fuel with oxygen. In fact,
these little guys use up 80% of the oxygen you breathe...
These mitochondria are the secret sourceof 95% of your
BRAINPOWER!
As long as they get the fuel they need, everything's fine. But as we age, our
mitochondria have trouble transporting and burning the fuel. RESULT? First you
feel a little fatigued. Then you start having "senior moments." As your
mitochondria continue to sputter and gasp, huge numbers of brain cells
die...
Senility sets in and it's time for the nursing home... OR IS
IT?
Dr. Gary Null says NO! He's perfected an astonishingly effective way
to get these starved mitochondria fueled up and humming again. Your FREE-Preview
copy of Bottom Line's POWER AGING reveals exactly how to do
it, with nutrients you can find at any health food store.
NOTE: Participants say their physical energy rockets as
well...
For good reason. Because your mitochondria also supply the energy
for your muscles, heart and lungs!
All the details are FREE in your FREE-Preview
volume, so why not send for it right now?
At Last, A Clinically Proven And Medically
DocumentedARTHRITIS CURE
Study proves
Dr. Gary Null's secret transforms nearly 90% of sufferers!
John F. says his joint pain got so horrible, "I underwent surgery to
fuse my wrist. My knees and neck were deteriorating, so I used
heavy medications." John had almost forgotten what it was like to live
without constant agony. Yet Dr. Gary Null's secrets made him...
"PAIN-FREE IN 4 WEEKS!"—John F., case
history #2,954
"I take no more medications," John continues, "and all swelling subsided. My
doctor commented that the condition of my knee joints is the best he has
observed. I am able to take long walks. I have reclaimed my life!"
Wonderful, yes? Yet I know you're probably thinking...
"Great for John, but what about ME?"
After all, one man's "miracle cure" may not work for others, right?
WRONG! Dr. Gary Null has clinically proven that John's turnaround
isn't unusual.
In fact, to test exactly how well his arthritis discoveries are working, he
enrolled a very special subgroup of people into his Power Aging study.
To get into this group, you needed a letter from your doctor
confirming that you'd been medically diagnosed with arthritis...SOME HAD
SUFFERED FOR OVER 25 YEARS!
Their pain wasn't imaginary. All of them really, truly, had chronic
arthritis—bad!
Yet after using Dr. Gary Null's natural arthritis cure, 87% of them were
substantially or completely improved. The pain went away. Inflammation
faded or vanished. Frozen limbs moved freely again!
And it didn't matter what type of arthritis they had.
Most were so utterly changed, their own personal
doctorsTOOK THEM OFF ALL ARTHRITIS MEDICATION...
If that's not a
cure, what is?
So do send for your FREE-Preview
copy of Bottom Line's POWER AGING right now. See the full
details of what these people did, starting on page 268. Try it yourself! And
then find out how thousands of people have found relief from nearly every other
pain, discomfort and disease of aging, including...
Paralyzing back pain, page 274."I had severe lower back
disc pain.I could not climb stairs and used crutches and a cane.
Eventually,I was paralyzed and confined to a wheelchair. Since
following Gary Null's [secrets], my body went from pain to joy. My backache
subsided. I easily climb 3 flights of stairs to my apartment. All past symptoms
are gone!" —Glenroy, age 65, case history #6,483
Bone spurs, page 170. "After one year, I no longer suffer
with the excruciating pain from heel spurs. The spurs are almost completely
cleared up." —Sharon, case history #8,398
Migraine, page 312. "I am migraine-free." —Jayne, case
history #4,665
Severe diabetes, page 171. "I used insulin and glucophage
for severe diabetes. [Now] I do not have to take diabetic medication!"
—Frantz, case history #1,556
Neuropathy and kidney disease, page 281. "I had neuropathy
in my hands and knees, and was diagnosed with kidney disease. Today, after
following Gary's directions, pain from neuropathy is no more. Tests determined
my kidney disease is reduced!" —Karina, case history #2,969
Allergies, page 271. "I am not allergic to dogs and cats
anymore." —Sam, case history #3,386
Hemorrhoids, page 284. "Hemorrhoids are completely gone."
—Maureen, case history #2,187
Gallstones, page 312. "No symptoms anymore!"—Bill,
case history #10,834
Now, I can fully understand if you're dubious, because these case histories
are astonishing...
But ask yourself: Could all these thousands of people in the 14-year
Power Aging study be lying? Could they all be imagining the results that have
been documented by blood tests and observed by their own family doctors? Could
all this hard evidence—that you can reverse the aging process—be a mass
hallucination?
No way! So isn't it time you found out for yourself why PBS
television stations, Larry King Live, Oprah and so many other
dyed-in-the-wool skeptics have been spotlighting the work of Dr. Gary Null?
Let me send you his ultimate book of Power Aging discoveries to preview
FREE...
"I no longer use eyeglasses during the day!"—Joseph I., age 63, case history #4,443
Days From Now, You Too Could Be Saying..."My
Physician Is AMAZED!"—Summer, case history
#10,657
Yes, of course it can happen for you, too! You've
heard Dr. Gary Null's breakthrough praised by some of TV's most responsible
broadcasters, and you've seen dozens of documented case histories in this
Special Report. You've learned how and why it's really happening. But why just
wonder at it all, when you could...
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Thursday, November 24, 2011
protect yourself from surgery, cancer, and worse
Heartburn: The Silent Killer?Find out how to stop a serious problem(one you may not know you have!) in 2 minutes,and protect yourself from surgery, cancer, and worseYou may not be familiar with the term "acid reflux"-but you could easily be among the 25 million Americans who experience this dangerous condition without even knowing it. Acid reflux is much more serious than "heart burn," but its symptoms are deceptively similar. That means it's too easy to ignore acid reflux as "no big deal." But ignoring acid reflux can cause serious and even deadly consequences. According to authors and doctors F. Balch, M.D. and Mark Stengler, N.D., if acid reflux persists it can even lead to life-threatening esophageal cancer. Most people don't know how easy it is to quickly stop acid reflux in its tracks-forever-with 3 common items from your grocery store. These items almost always bring relief within an hour or less.What is Acid Reflux? Acid reflux is technically known as gastroesophageal reflux disease, or GERD. It's caused by food, stomach acid, and other digestive juices backing up into the esophagus (the tube that connects our mouths to our stomachs). The acid causes the esophagus to become irritated and inflamed, and we may feel a burning sensation in the chest, sometimes radiating all the way to the neck and shoulders. It's the same root problem that causes heartburn. But when the symptoms occur twice a week or more, you've got a serious chronic condition. That's acid reflux. The number of cases has been growing nearly every year for the past two decades, probably as a result of an American diet loaded with processed foods and sugars. These foods are almost guaranteed to exacerbate acid reflux and disturb the bacterial balance in the stomach and intestinal tract.This disease causes a host of serious consequences, some deadly.Ignoring the Problem Can Lead to Cancer or the Need for Surgery When heartburn is just occasional, its effects are limited to just a few hours of discomfort. But with acid reflux happening more frequently, the body is under constant siege, especially the esophagus. Ignoring the problem leads to a variety of health complications, such as:==> Surgery to repair the damaged esophagus.==> Esophageal cancer, a very difficult cancer to treat. The MD Anderson Cancer Center estimates a 5-year survival rate of only 10-30%. In 2010, 16,640 new cases of esophageal cancer were diagnosed in the U.S. alone.Other serious and chronic problems caused by acid reflux include: Aspiration - acid enters the trachea, causing coughing or wheezing, and aggravating chronic lung disease and asthma (70% of asthmatics have acid reflux)Chronic cough - leading to persistent pain throughout the neck, lungs, and upper bodyLaryngopharyngeal reflux - acid damages the voice boxEsophagitis-inflammation of the lining of the esophagusEsophageal strictures or rings - narrowing of the esophagusBarrett's esophagus - abnormal developments of the esophageal liningLoss of tooth enamelReflux Drugs ... Ineffective and Loaded With Risks If you ask your doctor about your condition, you'll likely get a prescription for one of the drugs known as proton pump inhibitors (PPIs). The problem is, these drugs don't actually treat the disease-they just dull the symptoms. Over-the-counter drugs are no better. The cold, hard fact is that drug treatments, whether prescription or over-the-counter, cause a whole range of frightening side effects, from bone fractures to pneumonia! Federal regulators issued warnings recently about the serious risks of PPIs. The FDA reviewed 7 published studies on the drugs, 6 of which showed an increased risk of bone fractures. As a result, labels for these drugs now include strong warnings. A number of studies also show that these drugs promote bacterial growth that could increase your risk of infection, including infection from C. difficile, a bacterium that can cause diarrhea severe enough to require hospitalization. Surgery is yet another risky treatment. As the number of acid reflux sufferers soars, so does the number of related surgeries-especially for laryngopharyngeal reflux. Laryngopharyngeal reflux happens when the larynx (voice box) becomes irritated from stomach acid. It can result in permanent damage to the vocal cords. Unfortunately, surgeries for this condition are unsuccessful nearly 30% of the time, according to the University of Maryland Medical Center. That's nearly 1 in 3 failed surgeries! What's more, these procedures can stop working over time, or lead to more problems. As one patient reported, "I had a nissen fundoplication surgery... only to eventually have it taken down due to an increasing difficulty in swallowing, which was a result of a large buildup of scar tissue from the first surgery." This unlucky patient went through not one, but two surgeries, and yet still suffers from acid reflux!Simple Remedies that Work-Naturally and Safely No one should accept risky drugs or roll the dice with surgery when much better, safer, and-most importantly-effective alternatives are so easily available. Researchers in nutrition science and natural medicine have uncovered a variety of proven, simple, all-natural remedies for acid reflux. These remedies are proven again and again to quickly and permanently solve the real problems that cause acid reflux. The best news is that most of us already have the ingredients for these remedies in our homes right now. And if you don't have them on hand, these ingredients are incredibly simple and easy to find! Dr. Scott Sanders, a holistic doctor with more than a decade of dedicated experience in nutritional and alternative medicine, knows that most people need a variety of options for natural remedies. That's because people need to choose the combination of cures that best suits their lifestyle and preferences. Dr. Sanders recommends one comprehensive, easy-to-use kit that details all of the best and most effective natural solutions, including the 3 simple grocery store items that can bring relief in an hour. "People are different so there are a variety of ways to heal illnesses," says Sanders. "This kit takes this into account, giving you many options and providing the information you need to heal yourself and be independent of drugs and 'experts.' There is no hype or pushing a specific type of therapy." Over the last 7 years, this kit has helped more than 100,000 people stop their acid reflux overnight. Three common items from the grocery store, or even your own kitchen, are all you need to get started. No need of Rolaids, PPIs, or surgery. No side effects like pneumonia, bone disintegration, or life-long scar tissue. Just natural ingredients. The first step to recovery takes less than two minutes. Find out how to take that step by clicking here. Whatever you do, don't ignore acid reflux, not even for another week. Turn away from the threat of chronic illness and lifelong consequences and discover easy, natural solutions instead.If the links above are not working, just copy & paste the followingwebsite address onto your Internet browser:http://images.ultracart.com/aff/A1C7E20804C84A0131F32B389F051500/index.html?subid=nmmain_reflux_1124a4 Barton Publishing Inc | Post Office Box 50 | Brandon, SD 57005 © Copyright 2011 Barton Publishing Inc., All Rights Reserved.
Tuesday, November 22, 2011
clinical cancer prevention and codirector of clinical cancer genetics
Are Women Getting Breast Cancer Younger?If you’re a woman and carry a mutation in your BRCA1 or BRCA2 gene, you probably already know that you’re more likely to develop breast or ovarian cancer than women who don’t carry such a genetic mutation. But what you probably didn’t know is that if you have either one of those mutations and your mom or aunt had breast or ovarian cancer, then there’s a good chance that you could be diagnosed with cancer nearly eight years earlier than your mom or aunt was, according to a recent study from The University of Texas MD Anderson Cancer Center in Houston. This research adds to the small but growing body of reports about this trend. I called the lead study author, Banu K. Arun, MD, associate professor of breast medical oncology and clinical cancer prevention and codirector of the Clinical Cancer Genetics program at the university, to talk about the results and what they might mean for my readers.Dr. Arun and her colleagues analyzed 132 women with breast cancer who tested positive for either a BRCA1 or BRCA2 mutation between 2003 and 2009 -- these women served as the "younger" generation in the study. (Dr. Arun decided to look at only women in the younger generation who had breast cancer, not ovarian cancer, because she works in the breast department at the university.) Of these women with both breast cancer and a BRCA mutation, 106 had aunts or mothers who had had either breast or ovarian cancer, so their aunts and mothers made up the "older" generation in the study. By analyzing the ages of cancer diagnosis among the families in both generations, Dr. Arun and her team found that the median age of the cancer diagnosis was 7.9 years earlier for women in the younger generation. WHY THE SHIFT?This type of news is disappointing, especially now, when we think we have made great strides in preventing cancer -- or at least in delaying it. I asked Dr. Arun to tell me what is going on. Several relatively recent trends may have helped lead to earlier BRCA-related cancer diagnoses in younger women, said Dr. Arun, including…An increase in BRCA mutation awareness, plus an increase in the availability of genetic tests (both of which may have led to an increase in genetic testing).Improvements in imaging techniques (which has likely led to getting more accurate diagnoses). More environmental influences, such as taking estrogen replacement hormone therapy or exposure to estrogen-like substances in the environment (which some studies have associated with an increased risk for breast cancer). Another reason that BRCA-related cancer diagnoses are happening earlier in some women’s lives, she said, may have something to do with what epidemiologists call anticipation. It’s an unfortunate phenomenon in some inherited diseases in which DNA instability causes an illness to strike at a younger age and/or with increased severity in subsequent generations. (This happens with Huntington’s disease, for example.) In other words, these findings are not necessarily dire. They could mean that women are developing the disease at younger ages or that they’re simply discovering it sooner -- or both. Since all of those reasons listed above probably play a role, said Dr. Arun, the study’s findings are likely due to a mixture of factors. One limitation of the study is that the researchers assumed that the older generation’s breast or ovarian cancer was caused by a BRCA1 or BRCA2 mutation -- but there was no way to know for sure (because in some cases, the aunts and moms had already passed away and, in other cases, they never took genetic tests). So the younger generation’s cancer may have been hereditary or those women may have been the first generation in their families with the mutation. KNOW YOUR RISKFor women who have a BRCA mutation and are therefore at high risk for both breast and ovarian cancer, the question is: How soon and how frequently should you get screened? How soon to start. The American Cancer Society (ACS) recommends that high-risk women begin getting screened for both types of cancer at age 30, but they caution that it’s a good idea to discuss the best age with your doctor -- because if your mom or aunt got either disease at a young age, you may want to start getting screened earlier.How often to go. The ACS recommends that high-risk women get yearly breast screenings that should include a magnetic resonance imaging (MRI) scan, a mammogram and a clinical breast exam (where a doctor examines your breasts). A pelvic exam done by your doctor during your annual gynecological exam is usually the best way to get screened for ovarian cancer -- your doctor might also want to give you a CA-125 blood test, which checks for the level of a certain protein found on the surface of ovarian cancer cells. In spite of the questions this study raises, it is clear on one point -- those at high risk for breast cancer must be aggressive in their screening and do all that they can to reduce environmental and lifestyle risk factors for the disease.Source(s): Banu K. Arun, MD, professor of breast medical oncology and clinical cancer prevention and codirector of clinical cancer genetics, The University of Texas MD Anderson Cancer Center, Houston.
Monday, November 21, 2011
Truth telling should be done with grace and kindness
TELL THE (RESPECTFUL) TRUTH Being honest doesn’t have to be painful -- for you or the people in your life. The problem is that few people understand how to do it well. Truth telling should be done with grace and kindness, in a way that’s respectful of the person you are talking to, Zander said. She noted that the goal should be to learn how to tell -- and receive -- the truth in a way that is emotionally safe for you and those with whom you interact. Here are the three steps:Identify the areas in your life where you’re telling lies. For example, maybe you told your son last night that you "don’t mind" when he doesn’t help do the dishes after dinner -- when deep down it drives you nuts. But don’t beat yourself up about what you’ve been doing, because you’re on the way to fixing it. Pay close attention to what goes on in your head and what comes out of your mouth. Then evaluate how well they match up. You will probably be surprised to find that they often don’t! Think about it -- do you ever tell yourself that you’re sticking to your diet because you had a salad for dinner? But in reality, you canceled out the nutritious benefits of those greens with loads of high-fat dressing -- and then washed it all down with three glasses of wine?Focus on learning to tell the truth in all areas. And remember -- exaggerating is a form of lying. For instance, if your sister or friend asks you how much you paid for your shoes and you find yourself giving her the retail price -- even though you got the pair off a sale rack -- then train yourself not to inflate how expensive your wardrobe is to try to impress others. There’s nothing wrong with saying, "I got a great deal!" When you’re telling the truth to someone, do it carefully so you don’t hurt their feelings. For example, try saying: "When you say _(fill in the blank)_, it makes me upset, because _(fill in the blank)_. And I don’t want to be upset with you, because I care about you." Keep in mind that not all lies are malicious -- sometimes we tell a lie to avoid sounding mean. For example, telling a subordinate at work what we think he or she wants to hear (even if we don’t mean it) -- like "Good memo!" -- when instead honesty would actually help the employee improve. You could say: "Sending out a memo with typos in it makes it seem like you’re not as smart as I know you are." And lying to your partner about how great last night was may make pillow talk less awkward in the morning, but it won’t enhance your relationship. Next time, try to open up in a loving way by saying what would really please you. Not only will it bring the two of you closer, but what might it do for your love life! THE TRANSFORMATION OF TRUTH "To be a truthful person, you have to accept how much you lie -- we all do it," said Zander. But once you face your lies and start to transform yourself into a truthful person, then you won’t waste any energy covering your lies. Plus, your confidence will swell and life will become richer and more exciting. "Once you understand how to be truthful, your vitality will return and you will feel so much better," she said. "You will be on your way to becoming who you really are." Source(s): Lauren Zander, cofounder and chairman, The Handel Group, New York City. www.HandelGroup.com.
Friday, November 18, 2011
Olive Oil! Lose weight . . . Lower cholesterol and blood pressure . . .
Discover
The Amazing Powers of Olive Oil! Lose weight . . .
Lower cholesterol and blood pressure . . .Prevent heart disease and cancer .
. . and much, much more.
In Italy olive oil
always has been an integral part of the culture. But Italians also have long
known of its health benefits and healing properties. Whether the problem is a
case of sunburn, persistent earaches, or dry hair, Italians traditionally have
turned to olive oil.
Now, new research highlighting the healing qualities of extra virgin olive
oil not only confirms these uses but also reveals even more beneficial effects
from its use.
Whether a malady is heart disease, diabetes, digestion, or age-related
deterioration, olive oil has been shown to be beneficial in its prevention and
treatment.
In this book, The Healing Powers of Olive Oil, author Cal
Orey has consulted top doctors, nutritionists, olive oil producers, and chefs,
bringing together all you'll ever need to know about the healing powers of this
liquid gold and showing you how to start improving your health right away!
Lower your risk of heart disease and cancer
Enhance your immune system
Prevent cancer
Stave off diabetes
Fight fat
Help turn back the clock on aging
Add years to your life
Fight infections
Soothe inflammation
Ward off arthritis
Stop pain
Deter memory loss
Help beat osteoporosis
Yours FREE — a $14 Value, You Just Can't
Miss . . . Go Here Now.
Discover 30 Amazing FolkRemedies You Can Use Every Day
One tablespoon of olive oil has the power to wipe out the cholesterol-raising
effects of two eggs. You can take years off your biological age by changing your
diet and lifestyle — and olive oil can play a vital role.
Olive oil also is considered one of the most popular folk remedies. Orey
reveals more than 30 amazing folk remedies where olive oil plays a key role,
including:
Beating bladder infections
Helping heal skin burns naturally
Curing coughs
Easing constipation
Curing dandruff
Relieving diaper rash
And much, much more . . . Discover all 30 amazing folk remedies in
The Healing Powers of Olive Oil today!
PLUS You Get More Than 50 Delicious RecipesThat Make
Olive Oil Part of a Long, Healthy Life!
Olive oil has been praised by leading health experts as one of Mother
Nature's most healthful fats. And now, olive oil is making news worldwide and is
here to stay in homes, restaurants, and even fast-food chains!
People from all walks of life, including some olive oil pioneers and
contemporary medical experts, believe olive oil helps fight body fat, keeps
blood pressure down, and combats heart disease. It's also known to help relieve
colds and maintain healthy skin.
Jean Carper, a leading authority on health and nutrition, points out that new
Italian research finds olive oil contains antioxidants similar to those found in
tea and red wine that fight heart disease, including LDL cholesterol's ability
to clog arteries.
This book will show you how using olive oil is one of the best things you can
do for yourself — and your health! One of the best things is that you DON'T have
to swallow a tablespoon a day. Orey has included more than 50 recipes to help
heal your body, mind and spirit.
Olive oil is like "virtual youth in a bottle." Start living a more healthy
life today! Go Here Now.
Special
Bonus:Get Dr. Crandall's Heart
Health Report — FREE!
With your free copy of The Healing Powers of Olive Oil, you
also get an INCREDIBLE BONUS: a FREE three-month trial subscription to
Dr. Crandall's Heart Health Report!
Each month in Dr. Crandall's Heart Health Report, you'll get
incredibly vital health information, topics include:
Lowering your risk for heart attack
How to keep your blood pressure in check
Simple steps to reverse heart disease
Easy ways to lower cholesterol
How to get off prescription heart drugs
Heart disease prevention strategies
Successful angina treatments
Plus much, much more!
Dr. Chauncey W. Crandall, M.D., F.A.C.C., is chief of the Cardiac Transplant
Program at the world-renowned Palm Beach Cardiovascular Clinic in Palm Beach
Gardens, Fla., where he practices interventional, vascular, and transplant
cardiology.
He makes frequent guest appearances as a heart expert on national television
and radio programs. He also lectures regularly, both nationally and
internationally, about preventive cardiology, cardiology healthcare of the
elderly, healing, interventional cardiology, and heart transplants.
Dr. Crandall received his post-graduate training at Yale University School of
Medicine, where he also completed three years of research in the Cardiovascular
Surgery Division.
Not Your Typical
Doctor
Dr. Crandall is not your
typical heart doctor. He's been on both sides of the examination table — as a
heart doctor and as a heart patient.
With no family history of heart disease, and without warning, at age 48 Dr.
Crandall had a massive heart attack. To save his life, doctors performed
emergency surgery and placed two stents in his heart.
And that's when his life changed. He realized from this episode that if he
wanted to continue to make a significant contribution to this world, he had to
take better care of his own health, and particularly his heart.
At that moment, Dr. Crandall began his own fight with heart disease — a fight
he won.
Not Just Any
Newsletter
Like many of you, Dr. Crandall knows the stresses of fighting heart disease.
He also knows the secrets to reversing it. And the enormous relief of living a
life without this debilitating disease.
Dr. Crandall's Heart Health Report is loaded cover to cover
with the strategies he used to heal his own heart and the hearts of countless
patients.
No matter whether you've just been diagnosed with heart disease, have been
battling it for years, or just want to prevent it, you'll discover every issue
of Dr. Crandall's Heart Health Report to be an outstanding
source of real-world strategies to help you live symptom free, drug free, and
stress free.
And Remember: It Costs You Nothing.
Get our special free gift, just pay shipping, PLUS protect yourself and your
family today with a FREE, three-month trial subscription to Dr.
Crandall's Heart Health Report. Take advantage of this special offer
and get your free copy of The Healing Powers of Olive Oil.
The Amazing Powers of Olive Oil! Lose weight . . .
Lower cholesterol and blood pressure . . .Prevent heart disease and cancer .
. . and much, much more.
In Italy olive oil
always has been an integral part of the culture. But Italians also have long
known of its health benefits and healing properties. Whether the problem is a
case of sunburn, persistent earaches, or dry hair, Italians traditionally have
turned to olive oil.
Now, new research highlighting the healing qualities of extra virgin olive
oil not only confirms these uses but also reveals even more beneficial effects
from its use.
Whether a malady is heart disease, diabetes, digestion, or age-related
deterioration, olive oil has been shown to be beneficial in its prevention and
treatment.
In this book, The Healing Powers of Olive Oil, author Cal
Orey has consulted top doctors, nutritionists, olive oil producers, and chefs,
bringing together all you'll ever need to know about the healing powers of this
liquid gold and showing you how to start improving your health right away!
Lower your risk of heart disease and cancer
Enhance your immune system
Prevent cancer
Stave off diabetes
Fight fat
Help turn back the clock on aging
Add years to your life
Fight infections
Soothe inflammation
Ward off arthritis
Stop pain
Deter memory loss
Help beat osteoporosis
Yours FREE — a $14 Value, You Just Can't
Miss . . . Go Here Now.
Discover 30 Amazing FolkRemedies You Can Use Every Day
One tablespoon of olive oil has the power to wipe out the cholesterol-raising
effects of two eggs. You can take years off your biological age by changing your
diet and lifestyle — and olive oil can play a vital role.
Olive oil also is considered one of the most popular folk remedies. Orey
reveals more than 30 amazing folk remedies where olive oil plays a key role,
including:
Beating bladder infections
Helping heal skin burns naturally
Curing coughs
Easing constipation
Curing dandruff
Relieving diaper rash
And much, much more . . . Discover all 30 amazing folk remedies in
The Healing Powers of Olive Oil today!
PLUS You Get More Than 50 Delicious RecipesThat Make
Olive Oil Part of a Long, Healthy Life!
Olive oil has been praised by leading health experts as one of Mother
Nature's most healthful fats. And now, olive oil is making news worldwide and is
here to stay in homes, restaurants, and even fast-food chains!
People from all walks of life, including some olive oil pioneers and
contemporary medical experts, believe olive oil helps fight body fat, keeps
blood pressure down, and combats heart disease. It's also known to help relieve
colds and maintain healthy skin.
Jean Carper, a leading authority on health and nutrition, points out that new
Italian research finds olive oil contains antioxidants similar to those found in
tea and red wine that fight heart disease, including LDL cholesterol's ability
to clog arteries.
This book will show you how using olive oil is one of the best things you can
do for yourself — and your health! One of the best things is that you DON'T have
to swallow a tablespoon a day. Orey has included more than 50 recipes to help
heal your body, mind and spirit.
Olive oil is like "virtual youth in a bottle." Start living a more healthy
life today! Go Here Now.
Special
Bonus:Get Dr. Crandall's Heart
Health Report — FREE!
With your free copy of The Healing Powers of Olive Oil, you
also get an INCREDIBLE BONUS: a FREE three-month trial subscription to
Dr. Crandall's Heart Health Report!
Each month in Dr. Crandall's Heart Health Report, you'll get
incredibly vital health information, topics include:
Lowering your risk for heart attack
How to keep your blood pressure in check
Simple steps to reverse heart disease
Easy ways to lower cholesterol
How to get off prescription heart drugs
Heart disease prevention strategies
Successful angina treatments
Plus much, much more!
Dr. Chauncey W. Crandall, M.D., F.A.C.C., is chief of the Cardiac Transplant
Program at the world-renowned Palm Beach Cardiovascular Clinic in Palm Beach
Gardens, Fla., where he practices interventional, vascular, and transplant
cardiology.
He makes frequent guest appearances as a heart expert on national television
and radio programs. He also lectures regularly, both nationally and
internationally, about preventive cardiology, cardiology healthcare of the
elderly, healing, interventional cardiology, and heart transplants.
Dr. Crandall received his post-graduate training at Yale University School of
Medicine, where he also completed three years of research in the Cardiovascular
Surgery Division.
Not Your Typical
Doctor
Dr. Crandall is not your
typical heart doctor. He's been on both sides of the examination table — as a
heart doctor and as a heart patient.
With no family history of heart disease, and without warning, at age 48 Dr.
Crandall had a massive heart attack. To save his life, doctors performed
emergency surgery and placed two stents in his heart.
And that's when his life changed. He realized from this episode that if he
wanted to continue to make a significant contribution to this world, he had to
take better care of his own health, and particularly his heart.
At that moment, Dr. Crandall began his own fight with heart disease — a fight
he won.
Not Just Any
Newsletter
Like many of you, Dr. Crandall knows the stresses of fighting heart disease.
He also knows the secrets to reversing it. And the enormous relief of living a
life without this debilitating disease.
Dr. Crandall's Heart Health Report is loaded cover to cover
with the strategies he used to heal his own heart and the hearts of countless
patients.
No matter whether you've just been diagnosed with heart disease, have been
battling it for years, or just want to prevent it, you'll discover every issue
of Dr. Crandall's Heart Health Report to be an outstanding
source of real-world strategies to help you live symptom free, drug free, and
stress free.
And Remember: It Costs You Nothing.
Get our special free gift, just pay shipping, PLUS protect yourself and your
family today with a FREE, three-month trial subscription to Dr.
Crandall's Heart Health Report. Take advantage of this special offer
and get your free copy of The Healing Powers of Olive Oil.
science reveals that being of service to others brings numerous health benefits.
Helping Others Helps the HelperBy matt Rating: Rate this listing
-->It feels good to be a Good Samaritan, of course. But there’s more to the story—because science reveals that being of service to others brings numerous health benefits. Maria E. Pagano, PhD, an associate professor of psychiatry at Case Western Reserve University School of Medicine in Cleveland, has investigated the helper therapy principle (HTP), which is based on the concept that when people help others, they are also helping themselves—particularly when the helper and the recipient of that help share a common malady. Alcoholism Treatment Quarterly published her recent review article on the topic. Among the evidence cited were studies showing that...People with chronic pain who counseled other pain patients reported a significant decrease in their own symptoms of pain and depression.Multiple sclerosis (MS) patients who were trained to have monthly 15-minute supportive phone conversations with other MS sufferers showed improvement in self-confidence and self-esteem as well as reduced depression.Alcoholics who helped other alcoholics were almost twice as likely to stay sober in the year following treatment...had lowered levels of depression in the three months after they started helping other alcoholics...and had significantly improved self-image. Dr. Pagano explained, “Helping others with a desire to live sober transforms the helper’s dark past and pain to greater good and enables him or her to be uniquely helpful to a fellow sufferer.”While service to fellow sufferers is a cornerstone of 12-step programs of recovery, such as Alcoholics Anonymous, Dr. Pagano noted that it is not necessary to share a common health problem in order to benefit from doing good. For instance, helping others in general has been linked with longer life, less depression, higher self-esteem and greater life satisfaction.Bottom line: For a “helper’s high” and a significant health boost, lend a helping hand to someone in need. Maria E. Pagano, PhD, is a psychologist and an associate professor of psychiatry at Case Western Reserve University School of Medicine in Cleveland. She also is a recipient of a career development award funded by the National Institute on Alcohol Abuse and Alcoholism. www.HelpingOthersLiveSober.o
-->It feels good to be a Good Samaritan, of course. But there’s more to the story—because science reveals that being of service to others brings numerous health benefits. Maria E. Pagano, PhD, an associate professor of psychiatry at Case Western Reserve University School of Medicine in Cleveland, has investigated the helper therapy principle (HTP), which is based on the concept that when people help others, they are also helping themselves—particularly when the helper and the recipient of that help share a common malady. Alcoholism Treatment Quarterly published her recent review article on the topic. Among the evidence cited were studies showing that...People with chronic pain who counseled other pain patients reported a significant decrease in their own symptoms of pain and depression.Multiple sclerosis (MS) patients who were trained to have monthly 15-minute supportive phone conversations with other MS sufferers showed improvement in self-confidence and self-esteem as well as reduced depression.Alcoholics who helped other alcoholics were almost twice as likely to stay sober in the year following treatment...had lowered levels of depression in the three months after they started helping other alcoholics...and had significantly improved self-image. Dr. Pagano explained, “Helping others with a desire to live sober transforms the helper’s dark past and pain to greater good and enables him or her to be uniquely helpful to a fellow sufferer.”While service to fellow sufferers is a cornerstone of 12-step programs of recovery, such as Alcoholics Anonymous, Dr. Pagano noted that it is not necessary to share a common health problem in order to benefit from doing good. For instance, helping others in general has been linked with longer life, less depression, higher self-esteem and greater life satisfaction.Bottom line: For a “helper’s high” and a significant health boost, lend a helping hand to someone in need. Maria E. Pagano, PhD, is a psychologist and an associate professor of psychiatry at Case Western Reserve University School of Medicine in Cleveland. She also is a recipient of a career development award funded by the National Institute on Alcohol Abuse and Alcoholism. www.HelpingOthersLiveSober.o
Tuesday, November 15, 2011
A new study shows that a curcumin derivative may help treat chemo-resistant head and neck cancer.
If you’ve ever cooked or ordered Indian food, then you’re probably familiar with the spice turmeric. For years, turmeric’s active ingredient -- curcumin -- has been shown to have amazing health benefits. Now, researchers have found yet another one to add to the list: A new study shows that a curcumin derivative may help treat chemo-resistant head and neck cancer. Lead study author Thomas E. Carey, PhD, codirector of the Head and Neck Oncology Program at University of Michigan Comprehensive Cancer Center in Ann Arbor, had heard from colleagues that a curcumin compound made inroads in treating prostate cancer, so he and his colleagues composed their own study, which was published in the May 2011 edition of Archives of Otolaryngology -- Head and Neck Surgery. I called Dr. Carey because I was curious to know just how much this wonder spice could do -- and how, exactly, it works its magic in our bodies. THE CHEMO CONUNDRUM For unknown reasons, some patients with head and neck cancer do not respond well to chemotherapy -- their tumor cells become resistant to cisplatin, a platinum-based, highly toxic drug that is the typical first-line treatment for this type of cancer. As patients become resistant, doctors must increase the dosage of cisplatin, which increases the likelihood of serious and even debilitating side effects such as severe kidney impairment, painful urination, hearing loss, loss of balance, ringing in the ears, swelling in the feet or ankles, unusual tiredness and seizures. "It’s really hellish," said Dr. Carey.So he and his coauthors analyzed cells in vitro in a lab -- they tested tumor cell lines derived from head and neck cancer patients for naturally occurring chemo-resistance. Once they found chemo-resistant cancer cells, they split them into two groups and then tested a different treatment on each. In one group of cells, they tested a new chemo combination of cisplatin and a curcumin-based compound called FLLL 32, while the control group of cells was given the traditional chemo treatment of cisplatin alone. When analyzing the results from the group that got the combo chemo drug, researchers found that they were able to use four times less of the highly toxic cisplatin while still killing tumor cells just as effectively as a higher dose of cisplatin alone. How? The curcumin compound lowered the level of a protein called STAT3 that leads to chemo resistance. "In head and neck cancer, we don’t really understand why some tumors have high levels of the STAT3 protein and others don’t," said Dr. Carey. "But if we can create a drug out of this curcumin compound, we could use it along with cisplatin to make the chemotherapy more effective without adding toxicity or to make it equally effective and less toxic."WHAT THE FUTURE HOLDS Before he can celebrate too much, however, Dr. Carey has a lot of work ahead. For all its promise, the curcumin compound is not yet ready for human trials, because right now it’s poorly absorbed by the body. The team of chemists on the curcumin project are working to make the treatment soluble and more bioavailable. Then the next step will be to replicate the experiment "in vivo" by placing human cancer cells into mice with inactive immune systems and trying to achieve the same result with treatment involving curcumin. Past studies, according to Dr. Carey, have shown that eating a diet rich in curcumin (a diet rich in the turmeric spice) is associated with a lower risk of developing certain cancers. In other words, there’s a chance that curcumin may not just be useful as a treatment for head and neck cancer but also as a form of prevention, though that hasn’t yet been studied. What about taking curcumin supplements? Dr. Carey said to talk to your doctor first. "We don’t know if supplements would have similar effects," he said. But you may want to cook or order turmeric-rich foods, like Indian dishes. If nothing else, it’ll make your taste buds happy.Source(s): Thomas E. Carey, PhD, researcher, professor of otorhinolaryngology and pharmacology, University of Michigan Medical School, and codirector of the head and neck oncology program, University of Michigan Comprehensive Cancer Center, Ann Arbor.Be well, Carole Jackson Bottom Line's Daily Health NewsYou received this free E-letter because you have requested it. You are on the mailing list as enayetallah@msn.com. Or... a friend forwarded it to you. Click here to easily subscribe.You can easily unsubscribe by clicking here.To change your e-mail address click here.To update your e-mail preferences click here.Important: Help your friends live more healthfully -- forward this E-letter to them.Better: Send it to many friends and your whole family.This is a free e-mail service of BottomLineSecrets.com and Boardroom Inc.Need to contact us? Boardroom Inc. 281 Tresser Boulevard Stamford, CT 06901-3246 ATTN: Web TeamPrivacy Policy: BottomLinePublications.com Web Site Privacy PolicyRequired Disclaimer: The information provided herein should not be construed as a health-care diagnosis, treatment regimen or any other prescribed health-care advice or instruction. The information is provided with the understanding that the publisher is not engaged in the practice of medicine or any other health-care profession and does not enter into a health-care practitioner/patient relationship with its readers. The publisher does not advise or recommend to its readers treatment or action with regard to matters relating to their health or well-being other than to suggest that readers consult appropriate health-care professionals in such matters. No action should be taken based solely on the content of this publication. The information and opinions provided herein are believed to be accurate and sound at the time of publication, based on the best judgment available to the authors. However, readers who rely on information in this publication to replace the advice of health-care professionals, or who fail to consult with health-care professionals, assume all risks of such conduct. The publisher is not responsible for errors or omissions.Bottom Line's Daily Health News is a registered trademark of Boardroom, Inc.Copyright (c) 2011 by Boardroom Inc. 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Monday, November 14, 2011
Rediscovery of Lost विटामिन Stuns Medical World
Rediscovery of Lost Vitamin Stuns Medical WorldNew research has finally revealed the true identity of a “lost vitamin,” that has the power to prevent and treat bone loss, heart disease, cancer and Alzheimer’s.This lost vitamin kept our ancestors disease free for thousands of years, but until recently was unknown to researchers and scientists.The power of this vitamin to reverse deadly, chronic diseases makes it one of the important breakthroughs of our time. Doctors are already saying this could be the next world-wide phenomenon, much like vitamin D was 10 years ago.Today, you’ll discover the 75-year old mystery that lead up to the re-discovery of this lost vitamin and how you can use it right away to help you and your family overcome the threat of chronic disease“X-Factor” May Be Missing Link to a Disease-Free LifeThe story starts back in 1930s, when a doctor from Ohio left his practice in search of the real cause of the degeneration and disease he saw in his patients.Traveling around the world and living with Native cultures, he discovered their diet contained an unknown nutrient he called the “X-Factor.” And when the natives stayed true to their native diets, the presence of the X-Factor kept them disease free for life.About the Author Jason Kennedy is a widely-read health writer, researcher and editor with nearly a decade of experience writing books, articles and newsletters for the leading anti-aging doctors in the United States. Training under some of the most respected medical doctors, healers and innovators in the alternative health field, Jason has unrestricted access to the latest cures and medical breakthroughs that heal without drugs and surgery. But when they started eating a Western diet that was missing this “X-Factor,” they started to fall victim to heart disease, bone loss and cancer… just like we do.Turns out this X-Factor was “hiding” in the organ meat and butter fat our ancestors thrived on, but we don’t eat anymore.Now there’s a simple, easy way to get this lost nutrient back into our diet WITHOUT having to eat organ meat or hunt for our food.The power of the X-Factor is off the charts: Scrubs your arteries clear of the dangerous plaque that clog your blood vessels and lead to heart attack.Strengthens your bones and slashes your risk of osteoporosis.Kills specific kinds of cancer cells without harming the healthy cells around them.Protects your brain from senility, dementia and Alzheimer’s.Reduces inflammation and fight arthritis.Normalizes your blood sugar and protect against diabetes.“Activates” the critical vitamins A and D, making them stronger and more effective.Doctors Agree: X-Factor May Be More Powerful than Vitamin DThe research is impressive and well documented, but it’s been largely overlooked and quietly pushed into the background by the big drug companies who are afraid of igniting another “vitamin D miracle,” like we had a few years ago.As you’ll see, many doctors believe this could be even more powerful than vitamin D.And I STRONGLY believe this is something you should know about.I’m skeptical of the word “breakthrough” but this story so compelling I consider it a “must read.” It’s the closest thing to real hope I’ve seen in a long time.Click here to read on and discover the lost vitamin…© Copyright 2011 Discovery Health Publishing, Inc. All Rights Reserved. Disclaimer: The entire contents of this website are based upon research conducted by the author, unless otherwise noted. The publisher and the author present this information for educational purposes only. The information and material provided on this site are for educational purposes only and any recommendations are not intended to replace the advice of your physician. You are encouraged to seek advice from a competent medical professional regarding the applicability of any recommendations with regard to your symptoms or condition. It is important that you do not reduce, change or discontinue any medication or treatment without consulting your physician first. The personal stories shared on this website are personal to the users and will not be typical of the results you will have if you follow the advice provided on this website. The information and recommendations provided on this website have not been evaluated by the Food and Drug Administration and are provided for educational purposes only.About Us - Privacy Policy - Become an AffiliateDiscovery Health Publishing 11924 W. Forest Hill Blvd. 22-315 Wellington, FL 33414
Sunday, November 13, 2011
Hydrogen Evolution from Water under Visible Light
J. Am. Chem. SOC. 1981, 103,2923-2921 2923
Ultrafine and Specific Catalysts Affording Efficient
Hydrogen Evolution from Water under Visible Light
Illumination
Pierre- Alain Brugger, Pierre Cuendet, and Michael Gratzel*
Contribution from the Institut de Chimie Physique, Ecole Polytechnique Fgdgrale de Lausanne,
IO1 5 Lausanne. Switzerland. Received March 12, 1980
Abstract: Platinum particles of 32-A diameter were produced in aqueous solution by citrate reduction of hexachloroplatinate.
A variety of synthetic polymers were tested with respect to their protective action and activity to catalyze hydrogen evolution
from reduced methylviologen (MV’) and water according to 2MVt + 2H20 3 2MV2+ + 20H- + H2. MV+ is produced
in a light-induced redox reaction of methylviologen with Ru(bpy)?’. Carbowax-20M-protected Pt particles were found to
give outstanding stability and achieve high hydrogen generation rates even at concentrations as low as 1.4-mg Pt/L. An even
higher activity is obtained when the microparticles are protected by the cationic polysoap PVP-CI6. In a photoredox system
containing Ru(bpy)32+ or zinc tetrakis(N-methylpyridy1)porphyrin as a sensitizer and N-tetradecyl-N’-methyl-4,4’-bipyridine
as an electron relay, the latter catalyst can intercept the thermal back reaction by specific interaction with the reduced relay.
The access of the oxidized sensitizer to the PVP-CI6 protected microparticles is impaired by electrostatic and hydrophobic
forces.
Introduction
Previously, a number of homogeneous or microheterogeneous
solution systems were reported which under illumination with
visible light produce hydrogen from water.’ The essential ingredients
of such a system are a sensitizer (S), an electron relay
(R), and a catalyst. Excitation of the sensitizer induces electron
transfer
S + R (1) - S+ + R- hu
which is followed by a catalytic step
catalyst R- + H20 - 1/2H2 + R + OHleading
to H2 generation. The back conversion of S+ into S may
be achieved by sacrificing a donor added to the solution through
irreversible oxidation:
D + S++ D++ S
Alternatively, the recycling of the sensitizer can be coupled to
water oxidation
(4)
via catalysis by noble metal oxides such as PtOz, Ir02,2 and RuO2.,
For the successful operation of such a cyclic water decomposition
system, it is mandatory that both catalysts operate selectively
and at a high rate.”
(3)
catalyst
S+ + 1/2H20 - S + 1/40+2 H +
(1) (a) B. V. Koryakin, T. S. Dzhabiev, and A. E. Shilov, Dokl. Akad.
Nauk. SSSR, 238,620 (1977); (b) J. M. Lehn and J. P. Sauvage, Noun J.
Chim., 1, 441 (1977); (c) K. Kalyanasundaram, J. Kiwi, and M. Gratzel,
Helu. Chim. Acra, 61, 2720 (1978); (d) A. Moradpour, E. Amouyal, P.
Keller, and H. Kagan, Nouu. J. Chim., 2,547 (1978); (e) B. 0. Durham, W.
J. Dressick, and T. J. Meyer, J . Chem. SOC.C, hem. Commun., 381 (1979);
(f) P. J. Delaive, B. P. Sullivan, T. J. Meyer, and D. G. Whitten, J. Am. Chem.
Soc., 101, 4007 (1979); (8) A. I. Krasna, Photochem. Photobiol., 29, 267
(1979); (h) T. Kawai, K. Tanimura, and T. Sakada, Chem. Lett., 137 (1979);
(i) M. Kirsch, J. M. Lehn, and J. P. Sauvage, Helu. Chim. Acta, 62, 1345
(1979); 6) K. Kalyanasundaram and M. Gratzel, J. Chem. SOC., Chem.
Commun., 1138 (1979); (k) A. I. Krasna, Photochem. Photobiol., 31, 75
(1980); (1) G. M. Brown, S. F. Chan, C. Creutz, H. A. Schwarz, and N.
Sutin, J. Am. Chem. Soc., 101, 7638 (1979); (m) G. M. Brown, B. S.
Brunschwig, C. Creutz, J. F. Endicott, and N. Sutin, ibid., 101, 7638 (1979).
(2) J. Kiwi and M. Gritzel, Angew. Chem., Int. Ed. Engl., 17,860 (1978).
(3) (a) J. Kiwi and M. Gritzel, Angew. Chem., Int. Ed. Engl., 17, 860
(1978); (b) Chimia, 33,289 (1979); (c) M. Graitzel in “Dahlem Conferences
1978 on Light-Induced Charge Separation”, H. Gerischer and J. J. Katz, Eds.,
Verlag Chemie, Weinheim, Germany, 1979, p 299; (d) J. Kiwi and M.
Gritzel, Angew. Chem., 91,659 (1979); (e) J. M. Lehn, J. P. Sauvage, and
R. Ziessel, Nouu. J. Chim., 3,423 (1979); (f) K. Kalyanasundaram and M.
GrBtzel, Angew. Chem., Inr. Ed. Engl., 18, 701 (1979).
0002-7863/8l/lS03-2923$01.25/0
Recently, we investigated light-induced hydrogen evolution from
a photochemical system in which Ru(bpy)?’ was used as a
sensitizer, methylviologen (MV2t) as an electron relay and a
centrifuged Pt sol stabilized by a polymeric material as a catalyst!
These studies established a trend to higher activity as the radius
of the Pt particles decreased. The results obtained encouraged
us to search for Pt aggregates having minimal size and low polydispersity.
We report here on the preparation, stabilization, and
performance of such a sol in the photoinduced H2 generation from
water. Furthermore, pathways are exploited to achieve specificity
of the Pt microelectrodes with respect to their intervention in the
water reduction process.
Experimental Section
Preparation and Characterization of the Catalysts. The colloidal
platinum was obtained via reduction of hexachloroplatinate solutions by
sodium citrate. The reduction procedure was similar to the one described
by Turkevich et aL5 A solution of 255 mL of H20 containing 15 mg
of Pt (in the form of H,PtCl,) was brought to boiling temperature; 30
mL of sodium citrate (1% weight aqueous solution) were added and the
mixture refluxed for 4 h. Thereafter the solution was cooled in an ice
bath. For excess citrate and electrolyte removal, the solution was stirred
with an Amberlite-MB-1 exchange resin in its Ht and OH- form until
the conductivity of the solution was smaller than 5 pS/cm. After filtration
the protective agent was added and allowed to equilibrate with
the Pt sol for at least 1 h. A schematic summary of this preparation
mode is given in Figure 1. The platinum content of the solution was
determined by atomic absorption spectroscopy using a Pye Unicam-SP
191 spectrophotometer. The size of the platinum particles was determined
by transmission electron microscopy (TEM). Samples were prepared
by spraying the colloidal solutions in small droplets (I-10-pm
diameter) with a nebulizer on Formvar membranes coated with carbon.
Observations were made with the Hitachi HU-12 electron microscope of
the Centre de Microscopie Electronique de I’Universitt de Lausanne.
Apparatus: Continuous photolysis experiments were carried out with
an XBO 450-W xenon lamp. Experimental details are given below. The
volume of the irradiated solution was always 35 mL. Prior to photolysis,
the samples were flushed with highly purified argon for removal of oxygen.
A ferrioxalate chemical dosimeter was employed to measure the
photon flux. Hydrogen was analyzed by gas chromatography, using a
Carbosieve 5-8, column at 35 “C and a Gow-Mac thermal conductivity
detector with a detection limit of 1 nmol. Laser photolysis experiments
(4) (a) J. Kiwi and M. Grltzel, Nature (London) 281, 657 (1979); (b)
J. Kiwi and M. Gratzel, J. Am. Chem. Soc., 101, 7214 (1979).
(5) (a) J. Turkevich, J. Chem. Phys., 13, 235 (1945); (b) J. Turkevich,
P. C. Stevenson, and J. Hillier, Discuss. Faraday Soc., 11, 55 (1951); (c) J.
Turkevich and G. Kim., Science, (Washington, D.C.) 169, 873 (1970); (d)
J. Turkevich, K. Aika, L. L. Ban, I. Okura, and S. Namba, J. Res. Insf. Carol.,
Hokkaido Uniu., 24,54 (1976); (e) J. Turkevich, Proceedings of a Symposium
on Electrocatalysis of Fuel Cell Reactions, Brookhaven, NY, p 123.
0 198 1 American Chemical Society
LYL4 J. Am. Lnem. JUC., 101. ivJ. 1"". 1 1 , 1.101
:heme for the preparation of ultrafine Pt :le$.
Figure 2. Fraction of R precipitated after difTerent times as a function
of the Carbowax 20 M-platinum ratio: NaCl = 1% (wt/v). Pt = 45
mg/L.
were performed with a J. K. frequency doubled nwdymium laser. The
Qswitched pulse had a duration of 20 ns. Details of the fast kinetic
detection method haw ken reported elsewhere?
Materink Hexachlomplatinic acid hexahydrate (Merck, pa.). sadium
citrate (Fluka, PA.). Ru(bpy),CI, (Strem), and methylnologen (BDH)
wen used as supplied. The synthesis of N-tctradayl-N'-methylviologen
has ken prNiOUS!y described.' The polymer protective agent Carbowax-
20M was supplied by Union Carbide. The poly(ethylene glycols)
(M, 5oM). 10000, 20oM)) were generous gifts from Dr. Tadros. IC1
Corporation. The cationic polysoap was synthesized by Dr. Humphrey-
Baker in our laboratory according to the following procedure: 0.5
g of poly(4-vinylpyridine) (M,68 700). supplied by Ciba-Geigy Cop. was
dissolved together with 0.16 g of bromohenadecane in 25 mL of dimethylformamide.
The solution was heated at 50 "C for 1 h and the
solvent rapidly evaporated under vacuum. The solid residue was taken
up in a mixture of IO-mL methanal and 4 0 " diethyl ether. After
decanting it was refluxed for 2 h in ether, filtered. and dried. NMR
analysis shows that approximately 50% of the pyridine groups are quaternized
by hcxadecyl chains.
Results and Discussion
Effect of Polymers on the Stability of the Pt Sol Against
Flocculation by Salts. In these experiments the Pt sol prepared
according to the procedure given above was added to an aqueous
solution of NaCl and the concentration of platinum measured as
a function of time. The platinum content of the solution was
determined either by atomic absorption spectroscopy or more
simply from optical absorbance measurements. (This sol shows
a characteristic absorption rising steadily toward the UV?
Precipitation diminishes the intensity of the band without changing
its shape. Hence, at a given value, the absorbance of the solution
is proportional to the R concentration.) Amongst a variety of
polymers tested as protective agents for the ultrafine particles,
(6) G. Rothcnkgm, P. P. Infclta. and M. Gritzel. 1. Phys. Chcm., 83,
(7) M.-P. F'ileni, A. M. Braun, and M. Gratzcl, Photochem. Photobiol..
(8) The UV-sbsorplion spcctrum of the sol has been published prcViously.
1871 (1979).
31,423 (19x0).
cf. ref 5d.
Brugger. Cuender, and Gratzel
Fipre3. Eleclron micrographs from different Pt sols. (a. lap) Unprotected
platinum, magnification 3400OOX, Pi = 0.4 mg/L in the original
solution. (b, middle) Carbowax/Pt, magnification 18OOOOX. Pi = 4
mg/L in the original solution, R = 2.5. (c. bottom) Carbowai/Pt.
magnification 300000X, Pt = 40 mg/L in the original solution, R = 2.5.
Carbowax-20M9 and PVP-C16 were found to be particularly effective.
Figure 2 illustrates the flocculation behavior in 1% NaCl
solution as a function of polymer concentration. In the case of
Carbowax-2OM stability is achieved when the mass ratio of
polymer to platinum is at least 1. A somewhat higher value, Le.,
R = 2 is required for efficient protection by PVP-Ct6.
In view of the excellent stabilization achieved with Carbcwax-
20M, it is interesting to note that simple poly(ethylene glycols)
(M, 10000 or 20000) are very poor protective agents. A subtle
difference in the structure of these compounds brings about this
opposing behavior. Carbowax-20M is a block copolymer containing
two poly(ethylene glycol) chains (each, M, 6000) linked
by a short hydrophobic epoxide chain.I0 The presence of the latter
is crucial in that it is anchored in the Pt surface, the remaining
chain segments forming loops that protrude into the aqueous
bulk."J2 These loops afford the repulsive forces required to
(9) Carbawar-20M was first noted by Horisberger to be the best stabilizer
of colloidal gold used as a marker for electron mienscopy (M. Horiskrgcr,
Bid. Cell. 36, 253 (1979).
(10) "Carbowax Polyethylene Glycols". Union Carbide Corporation
Chemicals and Plastics. New York, 1978.
(11) (a) E. Vincent, Ado. ColIoidInter/occSei.,4, 193 (1974): (b)Th.
F. Tadros, review to be published in Colloids Sur/. and references cited in
thee reviews.
Hydrogen Evolution from Water
prevent aggregation of colliding particles. The poor protective
effect exhibited by the simple poly(ethy1ene glycols) reflects weak
adsorption on the Pt particles.
Structure and Constitution of the Pt/Polymer Particles. The
extraordinary stability and activity (see below) of the Pt/Carbowax
catalyst prompted us to perform more detailed investigations on
the nature of the colloidal aggregates present in such a solution.
Electron microscopy was selected as the most suitable method
relative to other alternatives such as light scattering. This technique
was previously applied by Turkevich et al. to characterize
a variety of colloidal metal dispersions? Results are given in Figure
3 which shows electron micrographs of three different sols: (a)
was taken in the absence of protective agent. It reveals the
presence of spherical monodisperse particles having a diameter
of 30-35 A. When Carbowax is present as a protective agent the
dilute solution (4 mg of Pt/L) gives a similar result. Particle
diameters are between 30 and 35 A. At high concentrations (40
mg of Pt/L, Figure 3c), the formation of clusters becomes apparent.
A fraction of the Pt particles form loosely connected
assemblies extending over regions of several hundred nanometers.
From these data, it may be inferred that the unprotected as
well as the protected Pt sol in dilute aqueous solution consists of
uniformly sized particles having a diameter of 30-35 A. This
finding is in agreement with the results obtained by Turkevich
et alSs who obtained 32-A Pt aggregates with a mean deviation
of 12% in particle size.
Catalysis of Photoinduced H2 Production from Water. (a)
Sacrificial Systems. In these experiments the 32-A Pt particles
were tested for their activity in Hz-generating photolytic systems.
The aqueous solution contained R ~ ( b p y ) , ~(+4 X M) as
sensitizer and methylviologen (MV2+) as an electron relay.
Kinetics and mechanism of the processes occurring under illumination
have been investigated earlier.1d,4,13 The excited state
of the ruthenium complex transfers an electron to MV2+
*Ru(bpy)t+ + MV2+ - MV+ + Ru(bpy),,+ (5)
which in the presence of Pt catalyst is reoxidized by water under
hydrogen generation:
(6)
We shall first describe experiments in which R~ ( b p y ) , ~i+s reconverted
to the 2+ oxidation state by ethylenediaminetetraacetic
acid (EDTA) ( M). The latter is used as a sacrificial donor
which undergoes irreversible oxidation. The aim of these studies
was to establish optimum conditions for Hz production. The
procedure is now described in detail for the Pt/Carbowax catalyst.
Irradiations were carried out in the cell device consisting of an
Osram XBO 450-W lamp in conjunction with a cutoff filter (400
nm) and a 15-cm water cell to absorb the infrared radiation. The
solution (35 mL) is contained in a cylindrical cell (path length
15 mm) which is equipped with side arms for deoxygenation prior
to illumination and for volumetric determination of hydrogen.
Both the H2 burette and the cell are imbedded in a water jacket
which was thermostated at 25 OC. The light beam after traversing
the cell impinges on a monochromator connected to a photodiode
(Hamamatsu R 314), allowing for the measurement of optical
density changes in the solution during illumination.
We first examined, for a fixed Carbowax/Pt ratio (R = 2.7),
the effect of catalyst concentration on the hydrogen evolution rate.
Results are presented in Figure 4. The hydrogen output under
photostationary conditions rises steeply with Pt concentration up
to 1.4 mg of Pt/L from where on further augmentation is relatively
s10w.I~ At the break point, the rate is already astonishingly high
in view of the very small Pt concentration (-7 X lod M) present
MV+ + HzO - MV2+ + 1/2Hz + OHJ.
Am. Chem. SOC., Vol. 103, No. 11, 1981 2925
(12) W. Heller and W. Tanaka, Phys. Rev., 82,301 (1951); W. Heller and
T. C. Pugh, J. Chem. Phys., 22, 1778 (1954); W. Heller and T. C. Pugh, J.
Polynt. Sci., 97, 203 (1960).
(13) C. R. Bock, J. J. Meyer, and D. G. Whitten, J. Am. Chem. Soc., 96,
4710 (1974).
(14) At higher Pt levels the H, evolution rate decreases again. This effect
is caused by absorption of light by the Pt particles. The extinction coefficient
of the Pt solution is 2.3 X lo3 M-' cm-' at 450 nm.
Figure 4. Effect of Pt Carbowax concentration on the H2 generation rate
(R = 2.7), Ru(bpy),j* = 4 X M, MV2+ = 2 X lo-) M, EDTA =
M, potassium hydrogen phthalate buffer 5 X M, pH 4.5.
0,
IN 2
L
0
QJ
LL
% O
An
T>- A
R, [mg Carbowax 20-MImg Pt]
Figure 5. Effect of mass ratio of Carbowax 20 M-platinum on (a) the
rate of H2 generation and (b) the photostationary concentration of MV'
measured 30 s after beginning of photolysis. Pt = 6 mg/L, other conditions
as in Figure 4.
in solution. In fact, this figure can even be further improved, since
at the Ru(bpy)?+ concentration employed only a fraction of the
incident light-the maximum percentage is 86 for X = 452 nm-is
absorbed by the solution. This condition was selected intentionally
for our kinetic studies in order to avoid inhomogeneities due to
complete light absorption over a small path length. Given these
facts, the hydrogen evolution obtained with 1.4 mg of Pt/
Carbowax per L becomes comparable with that observed4 for
Pt/PVA at ca. 100 mg of Pt/L.
Secondly, it was attempted to check the effect of Carbowax
concentration on the rate of light-induced H2 evolution. Figure
5 shows that upon increasing the mass ratio of polymer to platinum
(R)f rom 0 to 2, the hydrogen output augments by a factor of
more than 4. At the same time the MV+ level present under
photostationary conditions decreases. This effect is particularly
pronounced between R values of 1 and 2 where the MV' concentration
diminishes abruptly by a factor of 8. At R values above
2, one notes a decrease of the hydrogen output concomitant with
a rise of the MV+ level present in the photostationary state.
Apparently, at very high Carbowax concentrations, the coating
of the Pt surface by the polymer blocks the access of the electron
relay to the active sites. At R values below 1 the Pt sol is unstable
as was shown above. Larger aggregates are formed which leads
to a decreased activity under these conditions.
A final noteworthy point concerns the surprisingly stable o p
eration of this catalytic system. Thus under optimum conditions
(R = 2, Pt = 1-10 mg/L), the Hz evolution rate establishes itself
at 7-8 mL/h in the presence of M EDTA. Hz formation
continues at this rate until more than 90% of the EDTA is consumed,
yielding one Hz per EDTA molecule. At this time the
turnover numbers for the sensitizer and electron relay are 200 and
4, respectively. Interested in the performance of the Carbowax
system at longer times, we photolyzed a solution containing lo-'
instead of M EDTA over a longer period. After an induction
time of several minutes, H2 is generated here at 9 mL/h. This
can be sustained for several hours without any noticeable degradation
of the sensitizer, turnover numbers being in excess of
1000. The process of hydrogen generation slows down once the
2926 J. Am. Chem. Soc., Val. 103, No. I / . 1981
solution pH raises due to exhaustion of the buffer. Higher pH
conditions are detrimental" for both the sensitizer and the electron
relay.I6
Apart from Carbowax-20M. we tested a series of other polymen
with respect to their Hz generating activity. Only polymers that
prevent effectively aggregation of the 32-A Pt particles were found
to be satisfactory. Amongst those one notices still a surprisingly
large difference in catalytic activity. Thus, the protective agents
PVP-C,,, Carbowax-ZOM, and PVA M, 60000 all give stable sols
at a polymer/Pt ratio of ca. 2. However, the PVP-C,, protected
catalyst is 4 times more active than PVA and 1.5 as active as
Carbowax/Pt. Evidently, these agents differ in their degree of
interaction with active sites while maintaining the same size and
shape of the Pt aggregates.
(b) Development of Ultrafine and Selective Catalysts for Cyclic
Water Decomposition Systems. In the preceding chapters, the
salient features of catalytic H, generation with ultrafine platinum
particles were explored. The results obtained serve now as a basis
for the development of catalysts which, apart from their high
activity, are operating selectively on one redox species. Only such
mediators are suitable for cyclic water decomposition systems.
The problem which has to be solved in this case is lo make the
Pt particle selectively interact with the reduced electron relay
(MV+). Contact of the cathodically tuned particle with the
oxidized donor [Ru(bpy),'+] has to be avoided, since this could
lead to short circuiting of the back reaction: reduction of Ru-
(bpy),'+ would occur instead of hydrogen production. Such a
photocatalytic system performs the transformation
"20
R- t S* (7)
The cycle of light-induced water decomposition can then be closed
either by addition of Ru02 catalyst3f or by coupling to an oxygen-
producing half-cell."
In the search for such a system, we based our strategy on the
use of the methylviologen derivative
n. S + R
m 3 * W - , r H 2 A - c P 3
2c1-
C,,MV2*
as an electron relay. Due to its strongly hydrophilic nature, this
surfactant shows little tendency to form micellesI8 or interact with
amphiphilic agents. By contrast, the monoreduced form (C,,MV+)
exhibits pronounced hydrophobicity and hence is prone to solubilization
by surfactant assemblies. This effect has been exploited
to achieve charge separation in the photoinduced redox reaction
between Ru(bpy)?+ and C,,MV2+. The CI4MV+ produced is
rapidly entrapped into a cationic micelle to which Ru(bpy)F,
for reasons of electrostatic repulsion, has no access.'8 Hence, a
drastic retardation of the back reaction is observed.
A similar principle was applied in the development of a platinum
catalyst that achieves both charge separation and hydrogen formation.
In this case, it is desirable to employ the cationic plysoap
PVP-C16 as the protective agent. As shown above by the flocculation
studies, the latter is an excellent stabilizing agent for the
Brugger. Cuender. and Grurzel
(IS) M. Gohn and N. Gctaff, Z. Nofurlorsch. A 34.. I135 (1979).
(16) MV" can be reduced by H2 to MV+ in the presence of Pi/Carbowar
catalyst. In nentral aqueous solution the latter was found lo decay aver a
pcricd of 2 h. probably due to catalytic hydrogenation (W. F. Sasse. private
communieation). The rateof this pr-s decreased drasticly an lowering the
oH. Interstinz. C,.MV+ men under neutral conditions a.v. w n t o be resistant
io hydrogenat& '.
(17) M. Neumann-Spallart. K. Kdyanasundaram, C. Gritzcl. and M.
GrHlzel, Hclu. Chim. Am. 63, I I I I (1980).
(18) P.-A. Bruggerand M. Gratzel. J. Am. Chem.Soe.. 102,2462 (1980).
P.-A. Bruggcr. P. P. Infelta, A. M. Braun, and M. Gratzcl. ibid., 103. 320
(1981).
Laser puke
Figure 6. Oscilloscope traces obtained from a deaerated solution of
Ru(bpy)p (10- M). C,,MV2+2CI- (5 X IO4 M), PVP-C,, (40 mg/L),
and colloidal Pt (20 mg/L). Upper trace. transient absorbance at 602
nm; lower tract, transient absorbance at 470 nm.
LIGHT INDUCED ELECTRON TRANSFER
COUPLED TO HYDROGEN EVOLUTION
OVERALL REACTION
S + H,O S' + ;H, + OH
& CIIT1ONIC POLISOIIP
C,.M"" C " , . W N ~ICII,',: C",
* C I ~
Figure 7. Scheme for the specific intervention of PVP-C,,-protected PI
microspheres in the photoredox process.
32-A particles. Mass ratios of surfactant platinum of 2.0 are
sufficient to produce stable sols. However, the Pt particles protected
by PVP-C,, are different from the Carbowax catalyst in
that they are positively charged and their surface has amphiphilic
properties.
Photolysis experiments were carried out with solutions containing
IO-] M CI,MV", IO4 M Ru(bpy),'+, IO4 M of colloidal
Pt, and 40 mg of PVP-C,,. The excited state of Ru(bpy),'+
reduces Cl,MV2+ with a specific rate of 8 X IO8 M-' s? . The
back reaction
C,,MV+ + Ru(bpy),'+ - C14MVz+ + Ru(bpy),'+ (8)
has a rate constant of 2 X IO9 M-' s ~ u' n der the conditions
employed. We shall now investigate the fate of ClIMV+ and
Ru(bpy)? in solutions containing PVP-C,,-protected platinum
particles. Laser photolysis results are presented in Figure 6. The
temporal behavior of the two transient species was monitored by
following the absorbance of the solution at 602 and 470 nm,
respectively. The initial rise of the signal at 602 nm is due to the
Hydrogen Evolution from Water
formation of C14MV+a fter laser excitation of R~ ( b p y ) , ~+T.h e
absorption decays sharply N 30 ps) back to the zero level,
indicating rapid consumption of CI4MV+. The formation of
R ~ ( b p y ) , ~is+ a pparent from the bleaching at 470 nm. There is
a fractional recovery of the negative signal to a plateau constituting
4030% of the initial value from where on no further changes are
noted. This indicates that a major part of R ~ ( b p y ) , ~f+or med
in the photoredox reaction is preserved and does not undergo back
reaction with CI4MV+.
The rapid disappearance of C14MV+ may be interpreted by a
mechanism involving first scavenging by the Pt particles through
hydrophobic interaction with the protective agent (Figure 7).
Charge transfer and water reduction occur simultaneously on the
Pt surface. The formation of hydrogen is readily seen in continuous
photolysis. Selectivity is achieved by making use of
electrostatic and hydrophobic interaction: Ru(bpy),,+ has no
access to the surface of the Pt aggregates. Hence, neither the
reduced relay nor the particle itself can interact with Ru(bpy)d+
which explains its astonishingly long lifetime in such a system.
Figure 6 demonstrates that the electron transfer from the reduced
viologen to the Pt particles is fast enough at lo4 M Pt to
intercept efficiently the back reaction. Under typical conditions
employed in our laser experiments, the latter proceeds with a first
half-lifetime of ca. 65 ps (initial concentration of Ru(bpy)d+ and
CI4MV+ E 4 X 10" M, k8 = 2 X lo9 M-' s-'). In Figure 7, the
first half-lifetime of the C14MV+ decay is 35 ps. From the difference
in the decay times obtained in the absence and presence
of catalyst one calculates a pseudo-first-order rate constant for
the electron transfer from CI4MV+ to the Pt particles of N lo4
s-l. This corresponds to a second-order rate constant of ca. lo8
M-' s-l if the analytical Pt concentration is used as a reference.
However, on the basis of particle concentration (the aggregation
number of Pt is 1200), the specific rate is 10" M-' s-l. This shows
that the reaction with the colloidal particles occurs at a very high
rate essentially controlled by the diffusion of the reactants. Similar
rates have been obtained for the discharge of ketyl radicals on
ultrafine Pt particles in a water/alcohol mixture.19
Selective intervention of the Pt microelectrodes is not restricted
to the case where Ru(bpy)32+ serves as a sensitizer. A similar
effect can be achieved, for example, also with zinc tetrakis(Nmethylpyridy1)
porphyrin (ZnTMPyp+) as the photoactive donor.
Electron transfer from the porphyrin triplet to C14MV2+ produces
CI4MV+ and ZnTMPyP5+.I8 In the presence of 32-A Pt particles
(lo4 M Pt) protected by PvP-c16, the CI4MV+ dissappears within
200 ps effecting HzO reduction. By contrast, ZnTMPyP5+, which
is readily identified by its characteristic absorption between 600
and 750 nm, is stable over many milliseconds. This is due to
repulsion of the porphyrin cation from the surface of the Pt
particles by electrostatic and hydrophobic interactions. The case
of ZnTMPyP4+ is particularly interesting as the photoredox reaction
occurs here with a solvent cage escape yield of practically
100% compared to 30% for the Ru(bpy):+/viologen couple.l* The
choice of the protective agent is crucial in order to obtain Pt
microelectrodes capable of operating specifically. Thus, selectivity
is lost when PvP-cl6 is replaced by Carbowax-20M. If the latter
J. Am. Chem. SOC., Vol. 103, No. 11, 1981 2927
catalyst is employed in a system which does not contain a sacrificial
agent, there is no hydrogen formation. Instead, it was noted from
laser photolysis experiments that the rate of the back reaction
between oxidized sensitizer and reduced relay was increased
significantly in the presence of this catalyst: both the rate of decay
of the viologen radical as well as the bleaching recovery of Ru-
(bpy),*+ are enhanced. Apparently, in the case of Carbowax
protection, the Pt particles simply short circuit the back electron
transfer from reduced viologen to R~(bpy),~+.
These data are corroborated by results obtained from continuous
photolysis experiments. Carbowax-20M-protected Pt catalyst
when coupled to Ru02 fails to split water under illumination of
a cyclic system containing Ru(bpy),*+ as a sensitizer and methylviologen
as an electron relay. By contrast, if the Pt microspheres
are protected by PvP-cl6 and C14MV2+ is used as relay,
simultaneous H2 and O2 production are observed. The lack of
specificity of the Carbowax-20M-protected particles is attributed
to the strongly hydrophylic nature of this protective polymer,
providing facile access of the Ru(bpy)?+ cation to the platinum
surface. Uncharged hydrophylic polymers are thus unsuitable
for Pt protection in cyclic water decomposition systems.20
Conclusion
An important fact emerging from the present study concerns
the activity of colloidal redox catalyst operating in H2-producing
systems. The trends established earlier4 relating high activity to
small particle size are unambiguously confirmed. This finding
corroborates a fundamental principle of electrocatalysis: a small
particle size is advantageous, both from the viewpoint of mass
transport of the electroactive species and from the viewpoint of
surface area per gram of catalyst employed. Further optimization
is possible by employing a particle size below 30 A. A separate
paper2' will deal with the synthesis and catalytic action in the
photolytic water cleavage of such ultrafine Pt aggregates.
High activity is only one prerequisite to be satisfied if such
catalysts are to be used in cyclic water decomposition systems.
Equally important but more difficult to obtain is the specificity
of intervention in the water reduction step. The present study
for the first time establishes pathways to achieve selective performance
of the Pt microspheres. The development of such
catalysts is of primordial importance to improve the performance
of cyclic water decomposition systems.
Acknowledgment. We are grateful for support of this work by
the Swiss National Foundation (2.168.0.78), Ciba-Geigy AG,
Basel, Switzerland, and Engelhard Industries, Metro Park, NJ.
We also thank Drs. J. Kiwi, M. Horisberger, and A. Gautier for
stimulating discussions and B. Demarchi and B. Muller for their
assistance in the experimental work. Furthermore, the generous
gift of the polymer samples by Dr. Th. F. Tadros of IC1 Ltd.,
England, is greatly appreciated.
(19) C. K. Grltzel and M. Grltzel, J. Am. Chem. Soc., 101,7741 (1979).
(20) The use of protective polymers can be avoided by employing mineral
supports which yield excellent activity and also selectivity. Thus, water
decomposition using a bifunctional Pt/RuO, redox catalyst and Ru(bpy)?+
as a sensitizer has recently been achieved; e.g., E. Borgarello et al., Angew.
Chem., 92, 663 (1980).
(21) E. Borgarello, J. Kiwi, E. Pelizzetti, M. Visa, and M. Grltzel, " w e
(London), 289, 158 (1981
Ultrafine and Specific Catalysts Affording Efficient
Hydrogen Evolution from Water under Visible Light
Illumination
Pierre- Alain Brugger, Pierre Cuendet, and Michael Gratzel*
Contribution from the Institut de Chimie Physique, Ecole Polytechnique Fgdgrale de Lausanne,
IO1 5 Lausanne. Switzerland. Received March 12, 1980
Abstract: Platinum particles of 32-A diameter were produced in aqueous solution by citrate reduction of hexachloroplatinate.
A variety of synthetic polymers were tested with respect to their protective action and activity to catalyze hydrogen evolution
from reduced methylviologen (MV’) and water according to 2MVt + 2H20 3 2MV2+ + 20H- + H2. MV+ is produced
in a light-induced redox reaction of methylviologen with Ru(bpy)?’. Carbowax-20M-protected Pt particles were found to
give outstanding stability and achieve high hydrogen generation rates even at concentrations as low as 1.4-mg Pt/L. An even
higher activity is obtained when the microparticles are protected by the cationic polysoap PVP-CI6. In a photoredox system
containing Ru(bpy)32+ or zinc tetrakis(N-methylpyridy1)porphyrin as a sensitizer and N-tetradecyl-N’-methyl-4,4’-bipyridine
as an electron relay, the latter catalyst can intercept the thermal back reaction by specific interaction with the reduced relay.
The access of the oxidized sensitizer to the PVP-CI6 protected microparticles is impaired by electrostatic and hydrophobic
forces.
Introduction
Previously, a number of homogeneous or microheterogeneous
solution systems were reported which under illumination with
visible light produce hydrogen from water.’ The essential ingredients
of such a system are a sensitizer (S), an electron relay
(R), and a catalyst. Excitation of the sensitizer induces electron
transfer
S + R (1) - S+ + R- hu
which is followed by a catalytic step
catalyst R- + H20 - 1/2H2 + R + OHleading
to H2 generation. The back conversion of S+ into S may
be achieved by sacrificing a donor added to the solution through
irreversible oxidation:
D + S++ D++ S
Alternatively, the recycling of the sensitizer can be coupled to
water oxidation
(4)
via catalysis by noble metal oxides such as PtOz, Ir02,2 and RuO2.,
For the successful operation of such a cyclic water decomposition
system, it is mandatory that both catalysts operate selectively
and at a high rate.”
(3)
catalyst
S+ + 1/2H20 - S + 1/40+2 H +
(1) (a) B. V. Koryakin, T. S. Dzhabiev, and A. E. Shilov, Dokl. Akad.
Nauk. SSSR, 238,620 (1977); (b) J. M. Lehn and J. P. Sauvage, Noun J.
Chim., 1, 441 (1977); (c) K. Kalyanasundaram, J. Kiwi, and M. Gratzel,
Helu. Chim. Acra, 61, 2720 (1978); (d) A. Moradpour, E. Amouyal, P.
Keller, and H. Kagan, Nouu. J. Chim., 2,547 (1978); (e) B. 0. Durham, W.
J. Dressick, and T. J. Meyer, J . Chem. SOC.C, hem. Commun., 381 (1979);
(f) P. J. Delaive, B. P. Sullivan, T. J. Meyer, and D. G. Whitten, J. Am. Chem.
Soc., 101, 4007 (1979); (8) A. I. Krasna, Photochem. Photobiol., 29, 267
(1979); (h) T. Kawai, K. Tanimura, and T. Sakada, Chem. Lett., 137 (1979);
(i) M. Kirsch, J. M. Lehn, and J. P. Sauvage, Helu. Chim. Acta, 62, 1345
(1979); 6) K. Kalyanasundaram and M. Gratzel, J. Chem. SOC., Chem.
Commun., 1138 (1979); (k) A. I. Krasna, Photochem. Photobiol., 31, 75
(1980); (1) G. M. Brown, S. F. Chan, C. Creutz, H. A. Schwarz, and N.
Sutin, J. Am. Chem. Soc., 101, 7638 (1979); (m) G. M. Brown, B. S.
Brunschwig, C. Creutz, J. F. Endicott, and N. Sutin, ibid., 101, 7638 (1979).
(2) J. Kiwi and M. Gritzel, Angew. Chem., Int. Ed. Engl., 17,860 (1978).
(3) (a) J. Kiwi and M. Gritzel, Angew. Chem., Int. Ed. Engl., 17, 860
(1978); (b) Chimia, 33,289 (1979); (c) M. Graitzel in “Dahlem Conferences
1978 on Light-Induced Charge Separation”, H. Gerischer and J. J. Katz, Eds.,
Verlag Chemie, Weinheim, Germany, 1979, p 299; (d) J. Kiwi and M.
Gritzel, Angew. Chem., 91,659 (1979); (e) J. M. Lehn, J. P. Sauvage, and
R. Ziessel, Nouu. J. Chim., 3,423 (1979); (f) K. Kalyanasundaram and M.
GrBtzel, Angew. Chem., Inr. Ed. Engl., 18, 701 (1979).
0002-7863/8l/lS03-2923$01.25/0
Recently, we investigated light-induced hydrogen evolution from
a photochemical system in which Ru(bpy)?’ was used as a
sensitizer, methylviologen (MV2t) as an electron relay and a
centrifuged Pt sol stabilized by a polymeric material as a catalyst!
These studies established a trend to higher activity as the radius
of the Pt particles decreased. The results obtained encouraged
us to search for Pt aggregates having minimal size and low polydispersity.
We report here on the preparation, stabilization, and
performance of such a sol in the photoinduced H2 generation from
water. Furthermore, pathways are exploited to achieve specificity
of the Pt microelectrodes with respect to their intervention in the
water reduction process.
Experimental Section
Preparation and Characterization of the Catalysts. The colloidal
platinum was obtained via reduction of hexachloroplatinate solutions by
sodium citrate. The reduction procedure was similar to the one described
by Turkevich et aL5 A solution of 255 mL of H20 containing 15 mg
of Pt (in the form of H,PtCl,) was brought to boiling temperature; 30
mL of sodium citrate (1% weight aqueous solution) were added and the
mixture refluxed for 4 h. Thereafter the solution was cooled in an ice
bath. For excess citrate and electrolyte removal, the solution was stirred
with an Amberlite-MB-1 exchange resin in its Ht and OH- form until
the conductivity of the solution was smaller than 5 pS/cm. After filtration
the protective agent was added and allowed to equilibrate with
the Pt sol for at least 1 h. A schematic summary of this preparation
mode is given in Figure 1. The platinum content of the solution was
determined by atomic absorption spectroscopy using a Pye Unicam-SP
191 spectrophotometer. The size of the platinum particles was determined
by transmission electron microscopy (TEM). Samples were prepared
by spraying the colloidal solutions in small droplets (I-10-pm
diameter) with a nebulizer on Formvar membranes coated with carbon.
Observations were made with the Hitachi HU-12 electron microscope of
the Centre de Microscopie Electronique de I’Universitt de Lausanne.
Apparatus: Continuous photolysis experiments were carried out with
an XBO 450-W xenon lamp. Experimental details are given below. The
volume of the irradiated solution was always 35 mL. Prior to photolysis,
the samples were flushed with highly purified argon for removal of oxygen.
A ferrioxalate chemical dosimeter was employed to measure the
photon flux. Hydrogen was analyzed by gas chromatography, using a
Carbosieve 5-8, column at 35 “C and a Gow-Mac thermal conductivity
detector with a detection limit of 1 nmol. Laser photolysis experiments
(4) (a) J. Kiwi and M. Grltzel, Nature (London) 281, 657 (1979); (b)
J. Kiwi and M. Gratzel, J. Am. Chem. Soc., 101, 7214 (1979).
(5) (a) J. Turkevich, J. Chem. Phys., 13, 235 (1945); (b) J. Turkevich,
P. C. Stevenson, and J. Hillier, Discuss. Faraday Soc., 11, 55 (1951); (c) J.
Turkevich and G. Kim., Science, (Washington, D.C.) 169, 873 (1970); (d)
J. Turkevich, K. Aika, L. L. Ban, I. Okura, and S. Namba, J. Res. Insf. Carol.,
Hokkaido Uniu., 24,54 (1976); (e) J. Turkevich, Proceedings of a Symposium
on Electrocatalysis of Fuel Cell Reactions, Brookhaven, NY, p 123.
0 198 1 American Chemical Society
LYL4 J. Am. Lnem. JUC., 101. ivJ. 1"". 1 1 , 1.101
:heme for the preparation of ultrafine Pt :le$.
Figure 2. Fraction of R precipitated after difTerent times as a function
of the Carbowax 20 M-platinum ratio: NaCl = 1% (wt/v). Pt = 45
mg/L.
were performed with a J. K. frequency doubled nwdymium laser. The
Qswitched pulse had a duration of 20 ns. Details of the fast kinetic
detection method haw ken reported elsewhere?
Materink Hexachlomplatinic acid hexahydrate (Merck, pa.). sadium
citrate (Fluka, PA.). Ru(bpy),CI, (Strem), and methylnologen (BDH)
wen used as supplied. The synthesis of N-tctradayl-N'-methylviologen
has ken prNiOUS!y described.' The polymer protective agent Carbowax-
20M was supplied by Union Carbide. The poly(ethylene glycols)
(M, 5oM). 10000, 20oM)) were generous gifts from Dr. Tadros. IC1
Corporation. The cationic polysoap was synthesized by Dr. Humphrey-
Baker in our laboratory according to the following procedure: 0.5
g of poly(4-vinylpyridine) (M,68 700). supplied by Ciba-Geigy Cop. was
dissolved together with 0.16 g of bromohenadecane in 25 mL of dimethylformamide.
The solution was heated at 50 "C for 1 h and the
solvent rapidly evaporated under vacuum. The solid residue was taken
up in a mixture of IO-mL methanal and 4 0 " diethyl ether. After
decanting it was refluxed for 2 h in ether, filtered. and dried. NMR
analysis shows that approximately 50% of the pyridine groups are quaternized
by hcxadecyl chains.
Results and Discussion
Effect of Polymers on the Stability of the Pt Sol Against
Flocculation by Salts. In these experiments the Pt sol prepared
according to the procedure given above was added to an aqueous
solution of NaCl and the concentration of platinum measured as
a function of time. The platinum content of the solution was
determined either by atomic absorption spectroscopy or more
simply from optical absorbance measurements. (This sol shows
a characteristic absorption rising steadily toward the UV?
Precipitation diminishes the intensity of the band without changing
its shape. Hence, at a given value, the absorbance of the solution
is proportional to the R concentration.) Amongst a variety of
polymers tested as protective agents for the ultrafine particles,
(6) G. Rothcnkgm, P. P. Infclta. and M. Gritzel. 1. Phys. Chcm., 83,
(7) M.-P. F'ileni, A. M. Braun, and M. Gratzcl, Photochem. Photobiol..
(8) The UV-sbsorplion spcctrum of the sol has been published prcViously.
1871 (1979).
31,423 (19x0).
cf. ref 5d.
Brugger. Cuender, and Gratzel
Fipre3. Eleclron micrographs from different Pt sols. (a. lap) Unprotected
platinum, magnification 3400OOX, Pi = 0.4 mg/L in the original
solution. (b, middle) Carbowax/Pt, magnification 18OOOOX. Pi = 4
mg/L in the original solution, R = 2.5. (c. bottom) Carbowai/Pt.
magnification 300000X, Pt = 40 mg/L in the original solution, R = 2.5.
Carbowax-20M9 and PVP-C16 were found to be particularly effective.
Figure 2 illustrates the flocculation behavior in 1% NaCl
solution as a function of polymer concentration. In the case of
Carbowax-2OM stability is achieved when the mass ratio of
polymer to platinum is at least 1. A somewhat higher value, Le.,
R = 2 is required for efficient protection by PVP-Ct6.
In view of the excellent stabilization achieved with Carbcwax-
20M, it is interesting to note that simple poly(ethylene glycols)
(M, 10000 or 20000) are very poor protective agents. A subtle
difference in the structure of these compounds brings about this
opposing behavior. Carbowax-20M is a block copolymer containing
two poly(ethylene glycol) chains (each, M, 6000) linked
by a short hydrophobic epoxide chain.I0 The presence of the latter
is crucial in that it is anchored in the Pt surface, the remaining
chain segments forming loops that protrude into the aqueous
bulk."J2 These loops afford the repulsive forces required to
(9) Carbawar-20M was first noted by Horisberger to be the best stabilizer
of colloidal gold used as a marker for electron mienscopy (M. Horiskrgcr,
Bid. Cell. 36, 253 (1979).
(10) "Carbowax Polyethylene Glycols". Union Carbide Corporation
Chemicals and Plastics. New York, 1978.
(11) (a) E. Vincent, Ado. ColIoidInter/occSei.,4, 193 (1974): (b)Th.
F. Tadros, review to be published in Colloids Sur/. and references cited in
thee reviews.
Hydrogen Evolution from Water
prevent aggregation of colliding particles. The poor protective
effect exhibited by the simple poly(ethy1ene glycols) reflects weak
adsorption on the Pt particles.
Structure and Constitution of the Pt/Polymer Particles. The
extraordinary stability and activity (see below) of the Pt/Carbowax
catalyst prompted us to perform more detailed investigations on
the nature of the colloidal aggregates present in such a solution.
Electron microscopy was selected as the most suitable method
relative to other alternatives such as light scattering. This technique
was previously applied by Turkevich et al. to characterize
a variety of colloidal metal dispersions? Results are given in Figure
3 which shows electron micrographs of three different sols: (a)
was taken in the absence of protective agent. It reveals the
presence of spherical monodisperse particles having a diameter
of 30-35 A. When Carbowax is present as a protective agent the
dilute solution (4 mg of Pt/L) gives a similar result. Particle
diameters are between 30 and 35 A. At high concentrations (40
mg of Pt/L, Figure 3c), the formation of clusters becomes apparent.
A fraction of the Pt particles form loosely connected
assemblies extending over regions of several hundred nanometers.
From these data, it may be inferred that the unprotected as
well as the protected Pt sol in dilute aqueous solution consists of
uniformly sized particles having a diameter of 30-35 A. This
finding is in agreement with the results obtained by Turkevich
et alSs who obtained 32-A Pt aggregates with a mean deviation
of 12% in particle size.
Catalysis of Photoinduced H2 Production from Water. (a)
Sacrificial Systems. In these experiments the 32-A Pt particles
were tested for their activity in Hz-generating photolytic systems.
The aqueous solution contained R ~ ( b p y ) , ~(+4 X M) as
sensitizer and methylviologen (MV2+) as an electron relay.
Kinetics and mechanism of the processes occurring under illumination
have been investigated earlier.1d,4,13 The excited state
of the ruthenium complex transfers an electron to MV2+
*Ru(bpy)t+ + MV2+ - MV+ + Ru(bpy),,+ (5)
which in the presence of Pt catalyst is reoxidized by water under
hydrogen generation:
(6)
We shall first describe experiments in which R~ ( b p y ) , ~i+s reconverted
to the 2+ oxidation state by ethylenediaminetetraacetic
acid (EDTA) ( M). The latter is used as a sacrificial donor
which undergoes irreversible oxidation. The aim of these studies
was to establish optimum conditions for Hz production. The
procedure is now described in detail for the Pt/Carbowax catalyst.
Irradiations were carried out in the cell device consisting of an
Osram XBO 450-W lamp in conjunction with a cutoff filter (400
nm) and a 15-cm water cell to absorb the infrared radiation. The
solution (35 mL) is contained in a cylindrical cell (path length
15 mm) which is equipped with side arms for deoxygenation prior
to illumination and for volumetric determination of hydrogen.
Both the H2 burette and the cell are imbedded in a water jacket
which was thermostated at 25 OC. The light beam after traversing
the cell impinges on a monochromator connected to a photodiode
(Hamamatsu R 314), allowing for the measurement of optical
density changes in the solution during illumination.
We first examined, for a fixed Carbowax/Pt ratio (R = 2.7),
the effect of catalyst concentration on the hydrogen evolution rate.
Results are presented in Figure 4. The hydrogen output under
photostationary conditions rises steeply with Pt concentration up
to 1.4 mg of Pt/L from where on further augmentation is relatively
s10w.I~ At the break point, the rate is already astonishingly high
in view of the very small Pt concentration (-7 X lod M) present
MV+ + HzO - MV2+ + 1/2Hz + OHJ.
Am. Chem. SOC., Vol. 103, No. 11, 1981 2925
(12) W. Heller and W. Tanaka, Phys. Rev., 82,301 (1951); W. Heller and
T. C. Pugh, J. Chem. Phys., 22, 1778 (1954); W. Heller and T. C. Pugh, J.
Polynt. Sci., 97, 203 (1960).
(13) C. R. Bock, J. J. Meyer, and D. G. Whitten, J. Am. Chem. Soc., 96,
4710 (1974).
(14) At higher Pt levels the H, evolution rate decreases again. This effect
is caused by absorption of light by the Pt particles. The extinction coefficient
of the Pt solution is 2.3 X lo3 M-' cm-' at 450 nm.
Figure 4. Effect of Pt Carbowax concentration on the H2 generation rate
(R = 2.7), Ru(bpy),j* = 4 X M, MV2+ = 2 X lo-) M, EDTA =
M, potassium hydrogen phthalate buffer 5 X M, pH 4.5.
0,
IN 2
L
0
QJ
LL
% O
An
T>- A
R, [mg Carbowax 20-MImg Pt]
Figure 5. Effect of mass ratio of Carbowax 20 M-platinum on (a) the
rate of H2 generation and (b) the photostationary concentration of MV'
measured 30 s after beginning of photolysis. Pt = 6 mg/L, other conditions
as in Figure 4.
in solution. In fact, this figure can even be further improved, since
at the Ru(bpy)?+ concentration employed only a fraction of the
incident light-the maximum percentage is 86 for X = 452 nm-is
absorbed by the solution. This condition was selected intentionally
for our kinetic studies in order to avoid inhomogeneities due to
complete light absorption over a small path length. Given these
facts, the hydrogen evolution obtained with 1.4 mg of Pt/
Carbowax per L becomes comparable with that observed4 for
Pt/PVA at ca. 100 mg of Pt/L.
Secondly, it was attempted to check the effect of Carbowax
concentration on the rate of light-induced H2 evolution. Figure
5 shows that upon increasing the mass ratio of polymer to platinum
(R)f rom 0 to 2, the hydrogen output augments by a factor of
more than 4. At the same time the MV+ level present under
photostationary conditions decreases. This effect is particularly
pronounced between R values of 1 and 2 where the MV' concentration
diminishes abruptly by a factor of 8. At R values above
2, one notes a decrease of the hydrogen output concomitant with
a rise of the MV+ level present in the photostationary state.
Apparently, at very high Carbowax concentrations, the coating
of the Pt surface by the polymer blocks the access of the electron
relay to the active sites. At R values below 1 the Pt sol is unstable
as was shown above. Larger aggregates are formed which leads
to a decreased activity under these conditions.
A final noteworthy point concerns the surprisingly stable o p
eration of this catalytic system. Thus under optimum conditions
(R = 2, Pt = 1-10 mg/L), the Hz evolution rate establishes itself
at 7-8 mL/h in the presence of M EDTA. Hz formation
continues at this rate until more than 90% of the EDTA is consumed,
yielding one Hz per EDTA molecule. At this time the
turnover numbers for the sensitizer and electron relay are 200 and
4, respectively. Interested in the performance of the Carbowax
system at longer times, we photolyzed a solution containing lo-'
instead of M EDTA over a longer period. After an induction
time of several minutes, H2 is generated here at 9 mL/h. This
can be sustained for several hours without any noticeable degradation
of the sensitizer, turnover numbers being in excess of
1000. The process of hydrogen generation slows down once the
2926 J. Am. Chem. Soc., Val. 103, No. I / . 1981
solution pH raises due to exhaustion of the buffer. Higher pH
conditions are detrimental" for both the sensitizer and the electron
relay.I6
Apart from Carbowax-20M. we tested a series of other polymen
with respect to their Hz generating activity. Only polymers that
prevent effectively aggregation of the 32-A Pt particles were found
to be satisfactory. Amongst those one notices still a surprisingly
large difference in catalytic activity. Thus, the protective agents
PVP-C,,, Carbowax-ZOM, and PVA M, 60000 all give stable sols
at a polymer/Pt ratio of ca. 2. However, the PVP-C,, protected
catalyst is 4 times more active than PVA and 1.5 as active as
Carbowax/Pt. Evidently, these agents differ in their degree of
interaction with active sites while maintaining the same size and
shape of the Pt aggregates.
(b) Development of Ultrafine and Selective Catalysts for Cyclic
Water Decomposition Systems. In the preceding chapters, the
salient features of catalytic H, generation with ultrafine platinum
particles were explored. The results obtained serve now as a basis
for the development of catalysts which, apart from their high
activity, are operating selectively on one redox species. Only such
mediators are suitable for cyclic water decomposition systems.
The problem which has to be solved in this case is lo make the
Pt particle selectively interact with the reduced electron relay
(MV+). Contact of the cathodically tuned particle with the
oxidized donor [Ru(bpy),'+] has to be avoided, since this could
lead to short circuiting of the back reaction: reduction of Ru-
(bpy),'+ would occur instead of hydrogen production. Such a
photocatalytic system performs the transformation
"20
R- t S* (7)
The cycle of light-induced water decomposition can then be closed
either by addition of Ru02 catalyst3f or by coupling to an oxygen-
producing half-cell."
In the search for such a system, we based our strategy on the
use of the methylviologen derivative
n. S + R
m 3 * W - , r H 2 A - c P 3
2c1-
C,,MV2*
as an electron relay. Due to its strongly hydrophilic nature, this
surfactant shows little tendency to form micellesI8 or interact with
amphiphilic agents. By contrast, the monoreduced form (C,,MV+)
exhibits pronounced hydrophobicity and hence is prone to solubilization
by surfactant assemblies. This effect has been exploited
to achieve charge separation in the photoinduced redox reaction
between Ru(bpy)?+ and C,,MV2+. The CI4MV+ produced is
rapidly entrapped into a cationic micelle to which Ru(bpy)F,
for reasons of electrostatic repulsion, has no access.'8 Hence, a
drastic retardation of the back reaction is observed.
A similar principle was applied in the development of a platinum
catalyst that achieves both charge separation and hydrogen formation.
In this case, it is desirable to employ the cationic plysoap
PVP-C16 as the protective agent. As shown above by the flocculation
studies, the latter is an excellent stabilizing agent for the
Brugger. Cuender. and Grurzel
(IS) M. Gohn and N. Gctaff, Z. Nofurlorsch. A 34.. I135 (1979).
(16) MV" can be reduced by H2 to MV+ in the presence of Pi/Carbowar
catalyst. In nentral aqueous solution the latter was found lo decay aver a
pcricd of 2 h. probably due to catalytic hydrogenation (W. F. Sasse. private
communieation). The rateof this pr-s decreased drasticly an lowering the
oH. Interstinz. C,.MV+ men under neutral conditions a.v. w n t o be resistant
io hydrogenat& '.
(17) M. Neumann-Spallart. K. Kdyanasundaram, C. Gritzcl. and M.
GrHlzel, Hclu. Chim. Am. 63, I I I I (1980).
(18) P.-A. Bruggerand M. Gratzel. J. Am. Chem.Soe.. 102,2462 (1980).
P.-A. Bruggcr. P. P. Infelta, A. M. Braun, and M. Gratzcl. ibid., 103. 320
(1981).
Laser puke
Figure 6. Oscilloscope traces obtained from a deaerated solution of
Ru(bpy)p (10- M). C,,MV2+2CI- (5 X IO4 M), PVP-C,, (40 mg/L),
and colloidal Pt (20 mg/L). Upper trace. transient absorbance at 602
nm; lower tract, transient absorbance at 470 nm.
LIGHT INDUCED ELECTRON TRANSFER
COUPLED TO HYDROGEN EVOLUTION
OVERALL REACTION
S + H,O S' + ;H, + OH
& CIIT1ONIC POLISOIIP
C,.M"" C " , . W N ~ICII,',: C",
* C I ~
Figure 7. Scheme for the specific intervention of PVP-C,,-protected PI
microspheres in the photoredox process.
32-A particles. Mass ratios of surfactant platinum of 2.0 are
sufficient to produce stable sols. However, the Pt particles protected
by PVP-C,, are different from the Carbowax catalyst in
that they are positively charged and their surface has amphiphilic
properties.
Photolysis experiments were carried out with solutions containing
IO-] M CI,MV", IO4 M Ru(bpy),'+, IO4 M of colloidal
Pt, and 40 mg of PVP-C,,. The excited state of Ru(bpy),'+
reduces Cl,MV2+ with a specific rate of 8 X IO8 M-' s? . The
back reaction
C,,MV+ + Ru(bpy),'+ - C14MVz+ + Ru(bpy),'+ (8)
has a rate constant of 2 X IO9 M-' s ~ u' n der the conditions
employed. We shall now investigate the fate of ClIMV+ and
Ru(bpy)? in solutions containing PVP-C,,-protected platinum
particles. Laser photolysis results are presented in Figure 6. The
temporal behavior of the two transient species was monitored by
following the absorbance of the solution at 602 and 470 nm,
respectively. The initial rise of the signal at 602 nm is due to the
Hydrogen Evolution from Water
formation of C14MV+a fter laser excitation of R~ ( b p y ) , ~+T.h e
absorption decays sharply N 30 ps) back to the zero level,
indicating rapid consumption of CI4MV+. The formation of
R ~ ( b p y ) , ~is+ a pparent from the bleaching at 470 nm. There is
a fractional recovery of the negative signal to a plateau constituting
4030% of the initial value from where on no further changes are
noted. This indicates that a major part of R ~ ( b p y ) , ~f+or med
in the photoredox reaction is preserved and does not undergo back
reaction with CI4MV+.
The rapid disappearance of C14MV+ may be interpreted by a
mechanism involving first scavenging by the Pt particles through
hydrophobic interaction with the protective agent (Figure 7).
Charge transfer and water reduction occur simultaneously on the
Pt surface. The formation of hydrogen is readily seen in continuous
photolysis. Selectivity is achieved by making use of
electrostatic and hydrophobic interaction: Ru(bpy),,+ has no
access to the surface of the Pt aggregates. Hence, neither the
reduced relay nor the particle itself can interact with Ru(bpy)d+
which explains its astonishingly long lifetime in such a system.
Figure 6 demonstrates that the electron transfer from the reduced
viologen to the Pt particles is fast enough at lo4 M Pt to
intercept efficiently the back reaction. Under typical conditions
employed in our laser experiments, the latter proceeds with a first
half-lifetime of ca. 65 ps (initial concentration of Ru(bpy)d+ and
CI4MV+ E 4 X 10" M, k8 = 2 X lo9 M-' s-'). In Figure 7, the
first half-lifetime of the C14MV+ decay is 35 ps. From the difference
in the decay times obtained in the absence and presence
of catalyst one calculates a pseudo-first-order rate constant for
the electron transfer from CI4MV+ to the Pt particles of N lo4
s-l. This corresponds to a second-order rate constant of ca. lo8
M-' s-l if the analytical Pt concentration is used as a reference.
However, on the basis of particle concentration (the aggregation
number of Pt is 1200), the specific rate is 10" M-' s-l. This shows
that the reaction with the colloidal particles occurs at a very high
rate essentially controlled by the diffusion of the reactants. Similar
rates have been obtained for the discharge of ketyl radicals on
ultrafine Pt particles in a water/alcohol mixture.19
Selective intervention of the Pt microelectrodes is not restricted
to the case where Ru(bpy)32+ serves as a sensitizer. A similar
effect can be achieved, for example, also with zinc tetrakis(Nmethylpyridy1)
porphyrin (ZnTMPyp+) as the photoactive donor.
Electron transfer from the porphyrin triplet to C14MV2+ produces
CI4MV+ and ZnTMPyP5+.I8 In the presence of 32-A Pt particles
(lo4 M Pt) protected by PvP-c16, the CI4MV+ dissappears within
200 ps effecting HzO reduction. By contrast, ZnTMPyP5+, which
is readily identified by its characteristic absorption between 600
and 750 nm, is stable over many milliseconds. This is due to
repulsion of the porphyrin cation from the surface of the Pt
particles by electrostatic and hydrophobic interactions. The case
of ZnTMPyP4+ is particularly interesting as the photoredox reaction
occurs here with a solvent cage escape yield of practically
100% compared to 30% for the Ru(bpy):+/viologen couple.l* The
choice of the protective agent is crucial in order to obtain Pt
microelectrodes capable of operating specifically. Thus, selectivity
is lost when PvP-cl6 is replaced by Carbowax-20M. If the latter
J. Am. Chem. SOC., Vol. 103, No. 11, 1981 2927
catalyst is employed in a system which does not contain a sacrificial
agent, there is no hydrogen formation. Instead, it was noted from
laser photolysis experiments that the rate of the back reaction
between oxidized sensitizer and reduced relay was increased
significantly in the presence of this catalyst: both the rate of decay
of the viologen radical as well as the bleaching recovery of Ru-
(bpy),*+ are enhanced. Apparently, in the case of Carbowax
protection, the Pt particles simply short circuit the back electron
transfer from reduced viologen to R~(bpy),~+.
These data are corroborated by results obtained from continuous
photolysis experiments. Carbowax-20M-protected Pt catalyst
when coupled to Ru02 fails to split water under illumination of
a cyclic system containing Ru(bpy),*+ as a sensitizer and methylviologen
as an electron relay. By contrast, if the Pt microspheres
are protected by PvP-cl6 and C14MV2+ is used as relay,
simultaneous H2 and O2 production are observed. The lack of
specificity of the Carbowax-20M-protected particles is attributed
to the strongly hydrophylic nature of this protective polymer,
providing facile access of the Ru(bpy)?+ cation to the platinum
surface. Uncharged hydrophylic polymers are thus unsuitable
for Pt protection in cyclic water decomposition systems.20
Conclusion
An important fact emerging from the present study concerns
the activity of colloidal redox catalyst operating in H2-producing
systems. The trends established earlier4 relating high activity to
small particle size are unambiguously confirmed. This finding
corroborates a fundamental principle of electrocatalysis: a small
particle size is advantageous, both from the viewpoint of mass
transport of the electroactive species and from the viewpoint of
surface area per gram of catalyst employed. Further optimization
is possible by employing a particle size below 30 A. A separate
paper2' will deal with the synthesis and catalytic action in the
photolytic water cleavage of such ultrafine Pt aggregates.
High activity is only one prerequisite to be satisfied if such
catalysts are to be used in cyclic water decomposition systems.
Equally important but more difficult to obtain is the specificity
of intervention in the water reduction step. The present study
for the first time establishes pathways to achieve selective performance
of the Pt microspheres. The development of such
catalysts is of primordial importance to improve the performance
of cyclic water decomposition systems.
Acknowledgment. We are grateful for support of this work by
the Swiss National Foundation (2.168.0.78), Ciba-Geigy AG,
Basel, Switzerland, and Engelhard Industries, Metro Park, NJ.
We also thank Drs. J. Kiwi, M. Horisberger, and A. Gautier for
stimulating discussions and B. Demarchi and B. Muller for their
assistance in the experimental work. Furthermore, the generous
gift of the polymer samples by Dr. Th. F. Tadros of IC1 Ltd.,
England, is greatly appreciated.
(19) C. K. Grltzel and M. Grltzel, J. Am. Chem. Soc., 101,7741 (1979).
(20) The use of protective polymers can be avoided by employing mineral
supports which yield excellent activity and also selectivity. Thus, water
decomposition using a bifunctional Pt/RuO, redox catalyst and Ru(bpy)?+
as a sensitizer has recently been achieved; e.g., E. Borgarello et al., Angew.
Chem., 92, 663 (1980).
(21) E. Borgarello, J. Kiwi, E. Pelizzetti, M. Visa, and M. Grltzel, " w e
(London), 289, 158 (1981
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