About Vitamin C (L-ascorbic acid)

Vitamin C (L-ascorbic acid) is one of the very few skin care ingredients that is supported by strong and reliable scientific research and evidence.

However, it is also one of the most difficult products to formulate with, because it is extremely unstable.

As soon as l-ascorbic acid is mixed with water it starts oxidizing. This makes the l-ascorbic acid ineffective and also dangerous, because oxidized L-ascorbic acid is a pro-oxidant which may increase the formation of free radicals.

So, the challenge has been to make stable L-ascorbic acid products, or to make l-ascorbic acid itself stable.

Currently there are three ways this has been done:

1. The Skinceuticals Vitamin C Plus Ferulic Acid + Vitamin E formulation: The Skinceuticals study and patent shows that Ferulic acid stabilizes L-ascorbic acid, and in a lab this is probably true. However, the reality is that by the time customers get their bottle of Skinceuticals C+E+Ferulic it has been sitting on the shelves for too long, and when they open their bottle the product has turned orange, which means the L-ascorbic has started oxidizing and has become pro-oxidant.

2. Anhydrous C: “Anyhydrous” means “without water,” and this is a great way to formulate with the unstable Vitamin C. Instead of dissolving the vitamin C powder in water, it is mixed and dispersed into a silicone gel. W hen the silicone is applied to the face it acts like a dermal patch. The l-ascorbic acid will slowly be dissolved by the natural moisture in the skin, and the L-ascorbic acid will then be absorbed into the skin.

3. Vitamin C derivatives: To improve the stability of vitamin C in skin care, scientists have been looking for alternative solutions. One of these has been to create Vitamin C derivatives. Usually these are made by combining ascorbic acid with other molecules. Examples of these are the water soluble Magnesium Ascorbyl Phosphate and the oil soluble Tetrahexyldecyl Ascorbate (which is also known as Ascorbyl Tetraisopalmitate)

Vitamin C derivatives

Magnesium Ascorbyl Phosphate (MAP)

Magnesium Ascorbyl Phosphate is a water-soluble vitamin C derivative. Magnesium Ascorbyl Phosphate is not acidic so it does not irritate the skin and it is more stable than vitamin C.

Studies have shown that Magnesium Ascorbyl Phosphate is JUST as effective at boosting skin collagen synthesis as L-ascorbic acid.

Magnesium Ascorbyl Phosphate has proven to be an effective skin lightener, reducing hyperpigemnetation in some test subject.

Finally, studies have shown that Magnesium Ascorbyl Phosphate protects against UVB induced skin damage, such as inflammation and free radical formation, both duuring and after exposure to sunlight.

Even Magnesium Ascorbyl Phosphate is a lot more stable than L-ascorbic acid, it still degrades slowly when exposed to light and air.

Tetrahexyldecyl Ascorbate ( Ascorbyl Tetraisopalmitate)

Tetrahexyldecyl Ascorbate is the latest development in Vitamin C derivatives.

Tetrahexyldecyl Ascorbate is oil soluble, just like your skin, which means that it easily penetrates into the skin. It is not acidic and it does not require a low pH to get it to penetrate the skin so it does not sting. It is also stable in air and water for up to 18 months, which means it will work as an anti-oxidant long after you start using it.

Studies have shown that Tetrahexyldecyl Ascorbate is an effective skin care product. It effectively suppresses UVB-induced skin pigmentation, possibly through its anti-oxidative activity.

Tetrahexyldecyl Ascorbate also prevented UVA induced oxidative stress, and it boosted collagen synthesis.

Magnesium Ascorbyl Phosphate (MAP) References

Kameyama K, Sakai C, Kondoh S, Yonemoto K, Nishiyama S, Tagawa M, Murata T, Ohnuma T, Quigley J, Dorsky A, Bucks D, Blanock K. Inhibitory effect of magnesium L-ascorbyl-2-phosphate (VC-PMG) on melanogenesis in vitro and in vivo.

Geesin JC, Gordon JS, Berg RA. Regulation of collagen synthesis in human dermal fibroblasts by the sodium and magnesium salts of ascorbyl-2-phosphate.

Austria R, Semenzato A, Bettero A., Stability of vitamin C derivatives in solution and topical formulations.

Kobayashi S, Takehana M, Kanke M, Itoh S, Ogata E. Postadministration protective effect of magnesium-L-ascorbyl-phosphate on the development of UVB-induced cutaneous damage in mice.

Kobayashi S, Takehana M, Itoh S, Ogata E. Protective effect of magnesium-L-ascorbyl-2 phosphate against skin damage induced by UVB irradiation.

Tetrahexyldecyl Ascorbate ( Ascorbyl Tetraisopalmitate References

Xiao L, Kaneyasu K, Saitoh Y, Terashima Y, Kowata Y, Miwa N. Cytoprotective effects of the lipoidic-liquiform pro-vitamin C tetra-isopalmitoyl-ascorbate (VC-IP) against ultraviolet-A ray-induced injuries in human skin cells together with collagen retention, MMP inhibition and p53 gene repression.

Ochiai Y, Kaburagi S, Obayashi K, Ujiie N, Hashimoto S, Okano Y, Masaki H, Ichihashi M, Sakurai H. A new lipophilic pro-vitamin C, tetra-isopalmitoyl ascorbic acid (VC-IP), prevents UV-induced skin pigmentation through its anti-oxidative properties.

Fitzpatrick RE, Rostan EF. Double-blind, half-face study comparing topical vitamin C and vehicle for rejuvenation of photodamage.

Without a doubt the most popular skin care products are those which use Vitamin C, also known as L-ascorbic acid.

In this post I will write about Cellex C and Skinceuticals C E Ferulic, two popular anti aging skin care products that use Vitamin C as their main active ingredients.

I will also discuss the problems with using Vitamin C in anti ageing skin care products and some other the alternatives that are available in the form of Vitamin C derivatives.

In the next post I will be giving some examples on how we can make our own DIY Cellex C and DIY Skinceuticals C E Ferulic products.

Vitamin C and anti-aging skin care

Vitamin C is one of the most popular ingredients in anti aging skin care products. Vitamin C can benefit the skin in two ways. First it can increase collagen production, and second as an antioxidant it can reduce and prevent skin damage caused by free radicals.

Vitamin C is also one of the most studied active ingredients in anti aging skin care. These studies examined the various ways in which Vitamin C increases collagen synthesis, and the way in which vitamin C prevents free radical damage, as well as UVB damage.

For more details about these studies, please look at this list of abstracts.

Cellex C

Commercial skin care products with vitamin C started with Cellex C. Developed by Lorraine Meisner , who is a cell biologist at UW-Madison, Cellex-C was quite revolutionary. There is an interesting article about her here.

From a DIY skin care point of view Cellex C is not very practical.  The three main ingredients are: L-ascorbic acid, the mineral zinc and the amino acid tyrosin.

Tyrosin has poor solubility in water and alcohol, and requires the use of some very professional (and dangerous) solvents.

Also, L-ascorbic acid is unstable, and this is what the main problem is.

Unstable L-ascorbic Acid

It is well known that L ascorbic acid is unstable.  It reacts with water and air, and will easily oxidize. Oxidized Vitamin C is not good for the skin, instead of an antioxidant, it becomes a pro-oxidant. This means that it will increase the formation of free radicals, instead of doing what it is supped to do and decrease free radicals in the skin.

Vitamin C derivatives

Many efforts have been made to use Vitamin C in skin care products. Most of these efforts have involved developing Vitamin C derivatives. For example, products such as: Ascorbyl palmitate, Magnesium ascorbyl phosphate, and Ascorbyl Tetraisopalmitate (also known as Tetrahexyldecyl Ascorbate).

Magnesium ascorbyl phosphate and Ascorbyl Tetraisopalmitate / Tetrahexyldecyl Ascorbate, have shown to increase collagen production, and they are good stable alternatives to L-ascorbic acid. However, it would be nice if we could still use the real deal.

Stable L-ascorbic acid in skin care products

Two other solutions have been developed. One is the L-ascorbic acid in silicone. I blogged about this recently, and you can read all about it here.

The other solution was offered by Pinnel and others in their paper “Ferulic Acid Stabilizes a Solution of Vitamins C and E and Doubles its Photoprotection of Skin”.

L-ascorbic acid with Ferulic acid

The Pinnell paper proposes that:

“Ferulic acid is a potent ubiquitous plant antioxidant. Its incorporation into a topical solution of 15% L-ascorbic acid and 1% tocopherol improved chemical stability of the vitamins (C+E) and doubled photoprotection to solar-simulated irradiation of skin from 4-fold to approximately 8-fold as measured by both erythema and sunburn cell formation. Inhibition of apoptosis was associated with reduced induction of caspase-3 and caspase-7. This antioxidant formulation efficiently reduced thymine dimer formation. This combination of pure natural low molecular weight antioxidants provides meaningful synergistic protection against oxidative stress in skin and should be useful for protection against photoaging and skin cancer.”

This study (and the patent) led to the Skinceuticals C E + Ferulic product. The Skinceuticals skin care product is certainly very popular and many people swear by it.

However, is it really stable?

This sentence “Ferulic acid is a potent ubiquitous plant antioxidant. Its incorporation into a topical solution of 15% L-ascorbic acid and 1% tocopherol improved chemical stability of the vitamins (C+E)” would suggest it is.

However, some forum members have commented that their product is colored orange, and an orange product with L-ascorbic acid means that the asacorbic acid has oxidized.

Did the Pinnell study also look at for how long Ferulic acid can stabilize a solution of Vitamin C and Vitamin E?

I don’t know, and it really does not matter, because this product is something that we can DIY ourselves.

The advantage of making your own version of Skinceuticals C+E+Ferulic is that it can be made fresh every week, so it will never oxidize.

In my next post I will discuss various DIY recipes for the SkinCeuticals product.  In the meantime there are already some recipes available on our website:  ce ferulic 1 and ce ferulic 2

Active ingredients for DIY Skinceuticals CE + Ferulic

http://www.bulkactives.com/ascorbicacid.htm

http://www.bulkactives.com/ferulicacidnatural.htm

http://www.bulkactives.com/dpanthenol.htm

http://www.bulkactives.com/nah.htm

Recent posts on various DIY skin care forums have discussed the issue of the penetration of L-ascorbic acid suspended in a silicone base into the skin.

More precisely, a few posters have started promoting the idea that L-ascorbic acid cannot penetrate into the skin, because silicone forms a barrier on the skin.

I would like to address this issue in more detail.

Background: Stable L-ascorbic acid products for skin care

The DIY skin care community has long struggled with the formulation of a stable L-ascorbic acid skin care product. In fact, professional skin care companies and formulators have also struggled with the same problem.

Some attempts have been made by professionals to develop a stable vitamin C skin care product.  The best example of this is the Skinceuticals C+E+Ferulic product.  This is based on the 2006 study “Ferulic acid stabilizes a solution of vitamins C and E and doubles its photoprotection of skin” by Pinnel and others.

This study claimed that

“Ferulic acid is a potent ubiquitous plant antioxidant. Its incorporation into a topical solution of 15% L-ascorbic acid and 1% tocopherol improved chemical stability of the vitamins (C+E) and doubled photoprotection to solar-simulated irradiation of skin from 4-fold to approximately 8-fold as measured by both erythema and sunburn cell formation.” http://www.nature.com/jid/journal/v125/n4/full/5603565a.html

However, consumers have found that skinceuticals C E ferulic product is often orange tinted.  This color usually indicates that the L ascorbic acid has oxidized, thus making it pro-oxidant.  So, even though Ferulic acid may stabilize l ascorbic acid in the lab, in practicality there appear to be some serious issues that have not been addressed.

DIY skin care formulators are able to work around this.  By making a CE Ferulic product at home, it is possible to have a fresh supply every week, thus reducing (but not eliminating) the amount of vitamin C oxidization.

Solution: The Fitzpatrick study

Another study of interest is the 2002 “Double-blind, half-face study comparing topical vitamin C and vehicle for rejuvenation of photodamage” by Fitzpatrick.

Even though this study predates the CE+Ferulic study, it did not start getting discussed on the DIY skin care forums until quite recently.

Fitzpatrick’s method was as follows:

“Ten patients having facial photodamage were recruited for a double-blind pilot study of a newly formulated vitamin C complex having 10% ascorbic acid, a water soluble acid, and 7% tetrahexyldecyl ascorbate, a lipid soluble analog.

Both of these are combined in an anhydrous polysilicone gel base, which acts as a ‘dermal patch,’ releasing the water soluble acid slowly and the lipid soluble analog rapidly. The active vitamin C complex was applied to one side of the face and the inactive placebo base was applied to the opposite side of the face once a day.” http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=pubmed&cmd=Retrieve&dopt=AbstractPlus&list_uids=11896774&query_hl=7&itool=pubmed_ExternalLink

Now, this is where a very few posters start having some issues.  The base used is an anhydrous silicone gel, and the doubt seems to be in the fact that a very few posters believe that silicone forms a barrier and therefore hinders the absorption of active ingredients.

However, let’s look at the next part of Fitzpatrick’s study:

“Biopsies showed increased Grenz zone collagen, as well as increased staining for mRNA for type I collagen. This formulation of vitamin C results in clinically visible and statistically significant improvement in wrinkling when used topically for 12 weeks. This clinical improvement correlates with biopsy evidence of new collagen formation.”

Now, if silicone prevents the absorption of active ingredients, than there would not have been an increase collagen.

So, this should put to rest the claims that using silicone as a base prevents the absorption of active ingredients.

Flawed study

There is one troubling aspect about the Fitzpatrick study.  The study did not test the use of each key ingredient separately.

The two key ingredients in the anhydrous C product are L-ascorbic acid (which is water soluble), and Ascorbyl Tetraisopalmitate (also known as Tetrahexyldecyl Ascorbate ) which is oil soluble.

So, even though the study shows that the combination the two active ingredients in a silicone base led to an increase of collagen, we do not know if this was caused by the Tetrahexyldecyl Ascorbate, the Vitamin C, or the combination of the two.

This brings us back full circle to the original problem! We do not know which active is responsible for the increase in collagen. So it is possible to claim that the L-ascorbic acid is in fact not absorbed by the skin, and that the increase of collagen is cause by the Tetrahexyldecyl Ascorbate.

The blame for this confusion can be put purely with Fitzpatrick. It seems a simple matter to have tested the activity of both l-ascorbic and Tetrahexyldecyl Ascorbate in anhydrous silicone, separately. However, he chose not to do this.

So, we remain with his original statement.

“Both of these are combined in an anhydrous polysilicone gel base, which acts as a ‘dermal patch,’ releasing the water soluble acid slowly and the lipid soluble analog rapidly.”

To me the dermal patch idea makes sense, and I personally put more trust in this than the doubt caused by a very few (but very ‘vocal’) posters on skin care forums.

In the end the choice is yours.

I will continue to use the anhydrous C product as my number one weapon in anti aging skin care.  Why? Because no matter which active did the job, somehow this product has improved my skin and that is ultimately what I want.

http://www.bulkactives.com/siliconegel.htm

http://www.bulkactives.com/ascorbicacid.htm

http://www.bulkactives.com/ascorbyltetraisopalmitate.htm

In the last two articles we have covered the types of UV damage, and looked at the current range of common ingredients. With that out of the way, it is time to cover botanical sun care.

The simple truth is that, with the issues surrounding some of the chemical UV protection ingredients, you may not always want to lather up. When it comes to those days that you will spend hours out in the sun, the benefits outweigh the risks, and you should protect yourself from the suns damage.

For the days that you won’t be in the sun for long periods of time, though, it is better to use botanical products. Many botanical ingredients provide anti-oxidant protection, have anti-inflammatory properties, and have been shown to be able to repair the suns effects.

The advantage to using botanical sun products is that you aren’t covering your body in harmful chemicals. For the times that you are using the chemical products, a good botanical antioxidant can also provide protection against the damaging effects of the sunscreen itself.

Botanical Sun Care Ingredients

Studies are currently being done into botanical ingredients that provide UV protection. Some of the ingredients that I have listed do provide mild UVB protection, but they aren’t adequate for long term exposure. What you really want when you start to make a sun care product, from botanicals, are ingredients that provide antioxidant protection, and ingredients that help to repair the suns damage.

With that let’s look at some botanical ingredients that work well for sun care. The idea that some ingredients are better than others does hold true here, and I have tried to indicate the best ingredients for the job.

Botanical Antioxidants and Sun Care Ingredients

Conclusion – Protect Yourself

With the last three article we have covered UV damage, and how to protect yourself. You should now have a good knowledge of ingredients that can be harmful, and those that work for you. With this last article you also have a good guide to ingredients to use in your botanical sun care products.  When it comes to sun protection and to DIY skin care, choosing the right ingredients for the job is important to ensuring your skin’s health!

It is fairly common knowledge that the sun has damaging effects on the skin. Anyone who has spent anytime soaking up the sun’s rays can likely tell you all about sunburns, and anyone who has ever read a newspaper or watched the evening news will likely be able to tell you that the sun is responsible for many types of skin cancer. What most of us aren’t aware of, however, are the different types of UV light and the effects that they can have on our skin.

In this article we will look at the different types of UV radiation, and how they affect us. In a world where skin cancer is now the leading cause of cancer-related deaths, understanding the sun is more important than ever.

UVA, UVB, and UVC Rays

To begin our look at the sun’s damaging rays let’s first begin with a look at the different types of UV radiation. When we generalize, without getting extremely scientific, there are three basic types of UV radiation. They can be divided into categories according to wavelength:

• UVC: 100-290nm
• UVB: 290-320nm
• UVA: 320-400nm

The two types of UV rays that have damaging effects on the skin are UVB, and UVA rays. The other type, UVC, is absorbed by the atmosphere and has no damaging effects.

UVB Rays

The most well known type of UV ray is UVB. These rays vary throughout the day, and are at their highest from 10am to 2pm. The summer months tend to be the worst for UVB damage, accounting for 70% of most people’s exposure.

UVB rays are responsible for tanning, sunburns, and in general cause the most immediately visible damage.UVB is generally considered to be the most potent and damaging type of UV light. It directly affects the epidermis (upper layer of skin), and causes damage quickly.

This is what most sunscreens protect against. In fact, that Sun Protection Factor (SPF), which is listed on your commercially bought sunscreen, directly correlates to UVB protection.

UVA Rays

The other type of UV light that causes harm is UVA. There are actually two types of UVA rays: shortwave UVA (also known as UVA II), and long-wave UVA (UVA I). The second type (UVA I) is the one that is most damaging to the skin.

Until recently UVA light was thought to have little effect on the skin. Recent studies have altered that perception.

UVA light is different than UVB in that it has some unique qualities. Firstly, it isn’t more prevalent at any time of the day. Whenever the sun is up, UVA light remains constant. It is also different in that it cannot be filtered by common glass. Window glass and automobile glass cannot stop UVA rays from passing through.

UVA has the ability to penetrate deep within the skin to affect the dermis. Its effects are more long term, and exposure to UVA light can build with time. Most sunscreens do not protect against UVA light, and until recently actually, none of them did.

Understanding the Effects of UVA and UVB Exposure

With a basic understanding of UV light, let’s begin to discuss how sunlight really affects the skin. Exposure to the sun has both short and long term effects, and understanding those dangers is the first step in being able to protect yourself.

Short-term Effects of UV Exposure

UVB light is responsible for most of the shorter term effects of sun damage. These include: sunburn, discoloration, tanning (yes a tan is damage to), and skin hyperplasia, as well as other short term effects. Too much exposure to UVB light leads to a thickening of the outer layer of skin. This is the body’s natural defense but can also cause more damage, since it also causes the epidermis to absorb and scatter more of the UVB light.

The most damaging effects of UVB light come with sunburn. Acute sunburn can lead to even more damage. The most danger occurs when the skin peels.

Peeling occurs when the body kills its cells as a last ditch effort to repair the outer layer of skin, this process is called Apoptosis. The problem is that when this occurs, under certain conditions that come with UV exposure, the body is unable to properly kill the cell. This can lead to a damaged cell that divides and turns into a tumor, and even becomes cancerous.

Some of the other short term effects of exposure to both UVB and UVA light include:

1. A reduction in  collagen production
2. An increase in free radicals which prevent normal cell function
3. Damage to enzymes  that repair DNA
4. Negative effects on your immune system as a whole.
5. Free Radical Production that causes damage to the cells, and also causes serious long term effects.

Long Term Effects of UV Exposure

The long term effects are where things begin to get even scarier. Both UVA and UVB light have long term effects.

One thing that should be noted is that exposure to UVA light builds over time. Unlike UVB exposure where the epidermis is damaged and the body then repairs it, UVA exposure adds upon itself. In other words – 5 minutes today, 1 hour in the sun tomorrow, 3 hours on the beach last Friday, and tomorrows trip to the zoo – all combine and add to the damage that has already been done.

This leads to a few common long term problems. These include free radical damage, photo-aging, and photocarcinogenisis.

Free Radical Production: One of the long term effects of UV exposure is free radical production. Free radicals are chemical particles that have at least one malfunctioning or missing electron. In the skin the most common free radicals are oxygen molecules. These tiny particles have the ability to chip away at a cell, causing it damage. After a cell is damaged the free radicals can further damage DNA and RNA that actually make the cell. Free radicals contribute to both photo-aging, and photocarcinogenesis.

Photo-Aging: UVA light is the type of ray mostly responsible for photo-aging. UVB exposure can add to this by repeatedly damaging the skin, but most UVB light is absorbed by the epidermal layer. UVA gets right under the epidermis.

Photocarcinogenesis: Both UVA and UVB light can cause skin cancer. UVB light does so by causing damage, and promoting free radicals that can alter DNA. Recent studies are beginning to show that UVA light is capable of directly altering DNA through the production of free radicals as well, which can lead to malignant tumors and even cancer.

The simple truth is that a basic understanding of UV light and the damage it can cause is the first step in protecting yourself from the negative effects of the sun.

References

Negishi, K; Higashi, S; Nakamura, T; Otsuka, C; Watanbe , M; Negishi, T. (2007) Oxidative DNA Damage Induced by 364-nm UVA Laser in Yeast Cells. Originally published by the Japanese Environmental Mutagen Society. Accessed online July 16^th 2008 from http://www.jstage.jst.go.jp/article/jemsge/28/2/74/_pdf

Brannon, Heather MD. (March 23, 2008). Effects of Sun on the Skin: Cellular Skin Changes Caused by UV Radiation. Article hosted on about.com. Accessed July 16^th, 2008 from http://dermatology.about.com/cs/beauty/a/suneffect.htm

Hugget, J. (June 28, 2005) Less Than Full Protection: Most Sunscreens Do Only Half the Job, Blocking Unsafe UVB Rays But Not Skin-Damaging UVA. Can We Get Better Cover. Washington Post. Accessed July 16^th 2008 from http://www.washingtonpost.com/wp-dyn/content/article/2005/06/27/AR2005062701099.html

Eldich, R Dr. and Various other Authors (2004) Photoprotection by Sunscreens with Topical Antioxidants and Systemic Antioxidants to Reduce Sun Exposure.  Journal of Long-Term Effects of Medical Implants. Begal House Inc. Accessed July 16^th 2008 from http://www.pacificcenterplasticsurgery.com/articles/Photoprotection-by-Sunscreens.pdf

Reinheckel, Thomas,  Bohne, Marisela,  Halangk, Walter,  Augustin, Wolfgang,  Gollnick, Harald. Evaluation of UVA-mediated oxidative damage to proteins and lipids in extracorporeal photoimmunotherapy. A Study hosted on findarticles.com Accessed July 16^th 2008 from http://findarticles.com/p/articles/mi_qa3931/is_199905/ai_n8838478

Columbia-Presbyterian Medical Center, no author listed. Two Cancer Studies: Tomatoes, Green Tea, and Cancer. Originally published in the P&S Journal: Fall 1997, Vol.17, No.3 Research Reports. Accessed July 16^th 2008 from http://cpmcnet.columbia.edu/news/journal/journal-o/archives/jour_v17n03_0009.html