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INGREDIENTS: All about cosmetics, chemistry and fashion
Showing posts with label Ingredient of the Week. Show all posts



The Ingredient of the Week is ascorbic acid, also known as Vitamin C.

L-ascorbic acid (Vitamin C)
Vitamin C formulations are well-known in the world of cosmetics, and have been around for a while, but there have been some advances in their formulation. I thought now would be a good time to revisit this ingredient, and discuss its importance.

(For earlier discussions of Vitamin C, see here and here.)

Ascorbic acid occurs naturally in both plants and animals, but humans lack the ability to synthesize it so it must be obtained through our diet. Ascorbic acid is required for numerous biochemical pathways in the human body, including the biosynthesis of collagen, which is an important structural component of connective and epithelial tissue (which includes skin). A deficiency in Vitamin C gives rise to scurvy, a potentially fatal disease if not treated in time.

James Lind, a Scottish physician who carried out some of the first recorded
clinical experiments, showing that citrus fruits could be used to treat and prevent scurvy.
Ascorbic acid is also an antioxidant. Generally speaking, antioxidants are molecules which are readily oxidized and serve to protect other molecules from oxidation. Within the body's cells, ascorbic acid serves to keep the metal ions found in the catalytic centres of certain enzymes at the correct oxidation state, thus keeping the enzymes active as catalysts. It also serves to mop up free radicals and thus prevent them from attacking and damaging parts of the cell via oxidative reactions. (N.B. I have updated the Chemistry 101 page to discuss the terms I have used here; please refer to it to understand more about catalysts, oxidation state, reduction, oxidation and free radicals.)

Oxidation of ascorbic acid; last step carried out in the
presence of a metal ion, in this case silver (Ag+).
There have been numerous studies to show that topical application of Vitamin C is one of the best and easiest ways to boost skin radiance and to improve the appearance of wrinkles. The activity of Vitamin C is thought to work in a number of ways, including (1) to aid collagen production, thereby helping to maintain skin volume and firmness, and (2) to inhibit free radical damage and oxidative stress on skin tissue, due to environmental stressors such as U.V. radiation and pollution. However, there are serious obstacles to be overcome when trying to formulate Vitamin C into a working cosmetic formulation. Ascorbic acid is water soluble, but one of the main problems is that a water-based (aqueous) solution of ascorbic acid oxidizes readily upon contact with air, and becomes dehydroascorbic acid, which is biochemically inactive as an anti-oxidant. The oxidation of ascorbic acid is further accelerated by the presence of metal ions and light. It is for this reason that Vitamin C serums are almost always packaged in amber or opaque glass containers.

One way to preserve the activity of Vitamin C is to combine it with other antioxidants, the idea being that the presence of other antioxidants will compete for reaction with free radicals. An example of such an antioxidant is Vitamin E (also known as tocopherol).

alpha-Tocopherol (Vitamin E)
The other major problem of formulations of Vitamin C is how to get it to penetrate the skin to its site of activity, i.e. within the layers of the epidermis and the dermis where there are skin cells actively dividing. The stratum corneum, which is the outermost layer of the epidermis, is composed of mostly keratin and dead skin cells, and it is the main barrier to penetration of water-based solutions. If an aqueous solution of ascorbic acid is applied to the skin, much of it is oxidized at the outermost surface before it ever penetrates to the lower levels of the epidermis.

Cross section of epidermis
In order to get the ascorbic acid to penetrate to its site of activity where skin cells are actively dividing, and to do this before the ascorbic acid is oxidized, one has to use a relatively high concentration of ascorbic acid. The alternative is to use a derivative of ascorbic acid that is oil soluble, and can penetrate the outermost layers of skin more readily.

Cellex-C High Potency Serum (see below for ingredient list) is the original Vitamin C serum, introduced in 1994. It is a straightforward formulation of 10% ascorbic acid in water, along with acetyl tyrosine (an amino acid), zinc sulfate, sodium hyaluronate, and bioflavanoids derived from green tea (Camellia sinensis). It is free of any extraneous ingredients: it is fragrance- and colorant-free, as well as being free of preservatives.


Cellex-C High Potency Serum
(available in Toronto at The Anti-Aging Store) 
It is packaged in an amber glass bottle with a dropper, and it appears as a pale yellow solution that darkens over time, indicating the oxidation of ascorbic acid. The Cellex-C representative told me that I didn't have to keep it in the fridge, but I noticed that the solution darkened rapidly, becoming a dark yellow within a month after opening. I am currently on my second bottle and this one is kept in the fridge. About 5 drops is enough for one application; the serum should only be applied once a day, either morning or night. I have been applying it in the morning underneath SPF 30 sunscreen . As it is quite acidic, I felt a light stinging sensation when I first tried it, but this sensation went away after a few days of use. I was told to expect changes after about 4 weeks of regular use and this was the case. This serum is excellent for boosting skin "glow", but the other major effect is that it has really helped with refining skin texture and minimizing the appearance of pores.

Dr. Lisa Kellett is a well-known dermatologist based in Toronto. Along with a cosmetic dermatology practice, she also has her own skin care line. Thanks to Helen Vong, editor-in-chief of TheSkiny.com, I got the chance to review Dr. Kellett's Topical Vitamin C Ferulic Serum (see below for ingredient list).

Kellett Topical Vitamin C Ferulic Serum
(available in Toronto at DLK on Avenue;
also available online HERE)
Unlike the Cellex-C serum which is water-based, the Kellett serum is based primarily on liquid silicone, cyclomethicone. Liquid silicones can be used as a carrier for hydrophobic (oil-soluble) compounds.

The form of Vitamin C found in the Kellett serum is tetrahexyldecyl ascorbate, which is an oil-soluble derivative of ascorbic acid. As tetrahexyldecyl ascorbate is oil-soluble, it can penetrate the skin much more readily than ascorbic acid. According to the formulators of this serum, tetrahexyldecyl ascorbate penetrates the skin three times higher than ascorbic acid, when both are applied at the same concentration. The Kellett serum contains additional antioxidants, Vitamin E (tocopherol), green tea extract, and ethylhexyl ferulate (an oil-soluble form of ferulic acid, a plant-derived antioxidant). The combination of antioxidants acts to stabilize each other and thus increase their overall effectiveness, as well as increase the shelf-life and stability of the formulation.

Finally, the Kellett serum contains tridecyl salicylate, an oil-soluble derivative of salicylic acid, a chemical exfoliant which serves to further refine skin texture. It is free of fragrance, colorants, and preservatives.

The Kellett serum is comparable to SkinCeuticals C+E Ferulic Skin Serum (see earlier review here). Although the Kellett serum comes with instructions to apply every other night, I decided to follow the same regimen as with the SkinCeuticals serum, i.e. applying in the morning, followed by SPF 30 sunscreen over top, before heading out for the day, the idea being to use the antioxidants in the serum to protect skin against oxidative damage from environmental exposure during the course of the day. However, due to the presence of the salicylate, those with sensitive skin should stick with applying the serum at night, and be sure to wear sunscreen during the day.

Because this is a silicone solution, it is appears as a very thin, oily liquid that absorbs quickly with a very fast dry-down, so you have to spread very quickly before it absorbs. When I first started using this, I used about 5 drops, but found that after about a week of this regimen, I started to break out and I was getting a lot of plugged pores. From long experience, I know that silicone-based formulations don't work well on my oilier, stress-prone skin type, and so I was not surprised that I had this initial reaction to the Kellett serum. (Besides the breakouts, too much of it makes my skin feel uncomfortable and slightly itchy.) I cut back to 2-3 drops per application, working quickly to apply a very thin film, and that has worked out better for me - no breakouts and far fewer plugged pores. If you have a similar issue with silicone-based formulations, I think the key to this one is to apply very sparingly.

The Kellett serum definitely helps to boost radiance and to refine skin texture. Unlike the Cellex-C serum, the Kellett serum is colourless. More importantly, it does not appear to change colour over time, and it does not need to be refrigerated. The Kellett serum has almost no odour at all, a big plus compared to the SkinCeuticals serum, which had a strong, unpleasant odour of amines, similar to uncooked hotdogs. This serum is recommended for its ease of use, and its anti-ageing and skin-protective effects.

*In this review: Cellex-C High Potency Serum was purchased by me; Kellett Topical Vitamin C Ferulic Serum courtesy of TheSkiny.Com and DLK on Avenue. Thank you to Helen Vong, editor-in-chief of TheSkiny.Com for the opportunity to review the Kellett serum. This review is cross-posted to TheSkiny.Com, an e-magazine dedicated to the latest in beauty and dermatology - please check it out here!



***
Ingredients

Cellex-C High Potency Serum: water, ascorbic acid, acetyl tyrosine, zinc sulfate, sodium hyaluronate, bioflavanoids (from Camellia sinensis).

Kellett Topical Vitamin C Ferulic Serum: cyclomethicone, tetrahexyldecyl ascorbate, tridecyl salicylate, dimethiconol, hexyldecanol, bisabolol, cetyl cetyl hydroxyproline palmitate, stearic acid, rapeseed sterols, tocopherol, ethylhexyl ferulate, Camellia oleifera (green tea) extract.

This week's Ingredient is phenoxyethanol.


2-phenoxy-1-ethanol

As mentioned in last week's review of parabens, it is becoming more and more popular to market products as being "paraben-free". In such products, phenoxyethanol is commonly used as a replacement for parabens in the formulation. Seeing as its popularity as a preservative is only bound to rise in the face of all the negative press regarding parabens, it is worth taking a closer look at phenoxyethanol.


Phenoxyethanol acts as a bactericide, by inhibiting synthesis of nucleic acids in bacteria, as well as acting on bacterial cell walls by causing them to become more permeable to potassium ions (see Gilbert et al., Microbios. 1977;19(75):17-26; Microbios. 1977;19(76):125-41.). It is effective against both gram-negative and gram-positive bacteria as well as yeast. It is also used as an antiseptic, tissue preservative, and organic solvent. It is naturally occurring in certain green teas.


Phenoxyethanol is present in concentrations of up to 5% in a skin care formulation, typically in concentrations of around 1%; in Europe, it is allowable in concentrations up to 1% with the provision that it may be included in higher concentrations if it is to be used for other purposes besides a preservative (see J. Am. Col. Toxicol. v. 9, no. 2, 1990; link)


The main selling point of phenoxyethanol is that is does not have the weak estrogen-mimicking activity of the parabens. From the formulator's point of view, although it is slightly more expensive than parabens, it has similar formulation characteristics to the parabens, making it a fairly straightforward replacement (I should mention here, the cost of raw ingredients for creating skin care products is a major factor when deciding what ingredients to include in a formulation).


It is accepted as a safe cosmetic preservative by government regulatory agencies in the U.S., Europe and Japan. However, it has not been entirely free of controversy. Like many other organic solvents, phenoxyethanol is known to be a depressant of the central nervous system and an irritant that may cause vomiting and diarrhea, if exposed at high enough concentrations. In 2008, the FDA published a warning against Mommy's Bliss Nipple Cream for use by nursing mothers, as it contained both phenoxyethanol and chlorphenesin, another preservative known to have harmful effects on the central nervous system (link: original FDA report). 


Many children's toiletry products that are marketed as paraben-free contain phenoxyethanol as the preservative. An example is the Treehouse body lotion I reviewed earlier (see here).


Treehouse Unscented Body Lotion by Nature Clean
(see review here)


When deciding what skin care products to buy for yourself or your family, one has to balance risk versus benefit. As with the parabens, the precautionary principle applies. In the case of children's products like a nipple cream or a lip balm, something that is obviously going to be ingested by a young child, then it is definitely not worth the risk of exposure. (As mentioned in my review of the Treehouse lotion here, one has to be particularly vigilant about what chemicals children are exposed to.) However, for most other products that are going to be applied topically to either skin or hair, then the presence of phenoxyethanol is probably not a significant concern since the amount of phenoxyethanol absorbed through the skin is likely far too low to trigger the symptoms noted above. 


As always, I continue to look for safe alternatives and will report as I find them. I have an extensive review coming soon on a series of products that does not contain either parabens or phenoxyethanol - please stay tuned!

This week's featured Ingredients are food-grade preservatives sometimes used in cosmetics and beauty products: benzoic acid, sorbic acid, levulinic acid, and their related salts.

Soya sauce contains sodium benzoate.


These preservatives are growing in popularity, particularly in the green/eco segment of the beauty market, mainly due to the negative press surrounding parabens, and to a lesser extent, phenoxyethanol (see earlier reviews of parabens here and phenoxyethanol here), and the belief that food-grade preservatives are safer to use. Let's take a closer look at them!

Benzoic acid has a long history, having been discovered back in the sixteenth century. It is the chief component of benzoin gum, a resin derived from several species of trees in the genus Styrax. It is also found in many other plants, particularly plants with berry fruit (e.g. cranberries, bilberries). Its antimicrobial effect was first noticed in 1875, and it has been used as a food preservative since then.

Harvesting resin from a Styrax benzoin tree;
the dried resin is sold as benzoin gum.

Benzoic acid
Salts of benzoic acid, e.g. sodium benzoate and potassium benzoate, are preferred as preservatives, as they are water soluble; they are commonly used in processed foods and drinks. In a water-based solution, the salt dissociates into the metal ion (sodium or potassium) and benzoate ion. Benzoic acid and benzoate are effective as preservatives at acidic pH levels.

There was some controversy in the 1990s when trace amounts of benzene were discovered in some soft drinks that had been stored for long periods of time. This is because under certain conditions, benzoic acid or benzoate ion can decarboxylate (i.e. lose its carboxylic acid group) to form carbon dioxide (CO2) and benzene, which is a known carcinogen. Two possible mechanisms for this decarboxylation reaction are shown below (Britt, P. F.,  et al. (1999, August). "Mechanistic investigations into the decarboxylation of aromatic carboxylic acids." In Conference: National American Chemical Society Meeting, New Orleans, Los Angeles.).
Proposed reaction mechanisms for decarboxylation of benzoic acid under acidic conditions,
such as commonly found in food and drinks. Benzene is the simple 6-member aromatic ring shown as the final compound in each reaction pathway (1) and (2).
(Source) 

In addition to the above mechanism, the decarboxylation of benzoic acid in water solution can also be catalyzed by the presence of ascorbic acid (Vitamin C) and a transition metal such as copper (II) and iron (III) (Gardner, L. K., et al. (1993) "Benzene production from decarboxylation of benzoic acid in the presence of ascorbic acid and a transition-metal catalyst." Journal of Agricultural and Food Chemistry 41(5): 693-695; source). Benzoic acid itself is believed to be relatively non-toxic. Benzene formation is believed to only be a concern if the preparation is stored for long periods of time and at appropriate reaction conditions that would allow it to form.

Like benzoic acid, sorbic acid was also first discovered as a component of a plant. In this case, sorbic acid was discovered in the berries of the rowan tree, Sorbus aucuparia, in 1859. The antimicrobial effect of sorbic acid was discovered in the late 1930s. Salts of sorbic acid are the preferred form, as they are water soluble. Potassium sorbate is a commonly used salt of sorbic acid.
Berries of the rowan tree;
sorbic acid is naturally occurring in these berries. 

Sorbic acid

Levulinic acid is yet another compound first derived from a plant, and later discovered to have an antimicrobial effect. Levulinic acid was first isolated from corn. As with benzoic acid and sorbic acid, you will see the salts of levulinic acid more commonly used in cosmetic formulations.
Corn (Zea mays).
Commercially available levulinic acid continues to be sourced from corn as it is so abundant.

Levulinic acid
Compared to parabens and phenoxyethanol, the food-grade preservatives including benzoic acid, sorbic acid and levulinic acid, are not as effective at inhibiting microbial growth. Typically you will see these preservatives in processed foods that have a limited shelf life or else they have special storage considerations, such as refrigeration or packaging with an air-tight seal. When used in cosmetics, the shelf life of the formulation is somewhat shorter compared to comparable formulations containing parabens or phenoxyethanol. Also, their antimicrobial activity is limited to formulations that are acidic (pH < 7), which limits the type of formulation they may be used in. In order to boost their efficacy, different food-grade preservatives are often combined to inhibit a broader range of microbes.

The Diane Lai body lotions contain sodium benzoate and potassium sorbate, but note that these lotions are also packaged in an air-excluding pump, which helps to protect the formulation.
Diane Lai Rejuvenate and Soothe lotions, along with the lip balms;
link to review here.
One of the original green/eco brands, Neal's Yard Remedies products incorporate levulinic acid or sodium levulinate, the sodium salt of levulinic acid.
Neal's Yard Remedies Baby Bath & Shampoo
contains levulinic acid.
(reviewed earlier here)
By now, I hope you will have seen a theme here: all of the preservatives I have reviewed thus far, including parabens and phenoxyethanol, are naturally occurring in various plants. All of these compounds serve the same purpose in plants as they do in cosmetic formulations: to protect from microbial growth, particularly fungal growth. For this reason, antimicrobial agents are often found in flowers and fruits, which are particularly prone to microbial attack, as they are loaded with sugars and nutrients. From an evolutionary standpoint, it makes sense for plants to protect these parts from microbes, as it is important for the plant to preserve the freshness of its flowers for pollinators and its fruits for passing birds and animals to consume (and then carry its seeds to other locations). It just so happens that parabens are very weakly estrogenic, while phenoxyethanol has negative side effects if consumed in high enough quantities: this again underlines the fact that just because something is natural does not mean it is automatically good for you! The food-grade preservatives appear to carry the least amount of risk but they are also not as effective as preservatives in cosmetic formulations. As stated before, it's up to the consumer to decide how much risk they are willing to take on when deciding on a beauty product.

***

On a personal note: apologies for my absence last week. Things got really crazy over the past two weeks and I am just catching my breath now. Doing my best to get back on track now! I am still working on my major review of a new brand, which I hope to complete soon.

In other news, Google Reader was retired on July 1. If you were using Google Reader and you don't have a Blogger account, you can continue to follow via Feedly as well as Bloglovin, Facebook and Twitter (for these last three, please click the appropriate media follow button over to the right). 

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