Creative Developments (Cosmetics) Limited

Skin Care 2000

 

Skin care by the application of cosmetics includes cleansing and toning, solar protection and anti-free radical activity; it includes moisturising, acne treatments, and the treatment of hyper-pigmentation, skin peels and other means of wrinkle reduction. The active ingredients may be natural oils and extracts or active principals isolated from plants or they may be minerals or synthetic chemicals. The form that these compositions can take varies from sprays to pastes and the packaging from aerosols and bottles to jars, tubes and sachets. Developments in skin care include improved carrier systems and time-release mechanisms, anti-inflammatory and protective ingredients, new active ingredients obtained from botanical sources, the use of microfine oxides for safe sun protection, of AHAs for skin rejuvenation and of advances in emulsifier and emollient systems.

 

This feature will review those materials that are claimed to slow the visible effects of ageing with particular reference to vitamins A and C and delivery systems that enhance their activity.

 

The prime purpose of skin care is to reduce the visible effects of aging. In her paper, A Global Approach to Skin Aging presented at the IFSCC Congress 1999 [REF 1], Isabelle Benoit described the modifications that occur in cutaneous tissue with time. Chronological changes are genetically programmed responses; extrinsic changes are connected to environmental aggression such as photo-aging and responses to heavy metals and other pollutants. These changes take place in both the dermis and epidermis. They alter the dermis architecture and skin mechanical properties of rigidity, elasticity and resilience and eventually lead to wrinkles. Extrinsic aging is primarily a response to oxidative damage to the skin triggered by an accumulation of reactive oxygen species as a result of photo damage following exposure to UV radiation and it may lead to carcinogenesis.

 

According to Benoit, given the multiplicity of mechanisms involved in cutaneous aging, a global and consistent approach to skin aging needs to be at both the extrinsic and intrinsic level. Active ingredients should support the antioxidant properties of the skin to protect the cells from oxidative stress and should also boost cell metabolism. Benoit described the development of a vegetable extract and methods that were used to prove its efficacy as an antioxidant and anti-inflammatory ingredient that also stimulated keratinocyte metabolism and which contributed towards the regeneration of the extra cellular matrix. The material is a natural plant extract rich in polyphenols, amino acids, peptides, sugars and trace elements. For further details contact Gattefosse, France.

 

The first commercial appearance of liposomes in a cosmetic product was ten years ago in “Capture” by Christian Dior. Since then they have appeared in many products with a variety of claims. A paper by Gabriel Blume [Ref 2] described the development of liposomes to act as a protective carrier system for active ingredients. If of a suitable structure, they improve skin penetration of the active to the target site and can protect the encapsulated material from premature oxidation. Those described by Blume are small-sized vesicules of 80-300nm with one to three bi-layers formed from phosphatidylcholine, obtained from soybean and with a high essential fatty acid content. The benefits of such a system were illustrated by an in-vitro experiment whereby ascorbic acid encapsulated in liposomes achieved four times the penetration of ascorbic acid in an emulsion. Liposomes may also be used to transport lipophilic actives and were used to apply a mixture of vitamins A, E and C to excised skin. Experimental results show that the mixture was an effective free-radical scavenger and protected DNA during UV-A exposure.  Similar liposomes can be used to transport AHAs with a resultant increase in skin moisture, improved smoothness and a reduction in wrinkles while another variation was used for the application of tyrosinase inhibitors in skin-whitening products.

 

The materials described by Blume are available from Rovi GmbH as Rovisomes. Natterman Phospholipid provide what is arguably the most comprehensive range of materials in liposome form supported by extensive literature and technical application data. There are many other sources of liposomes including LipoCeutical Complexes from Lipo Chemicals, and slow and fast-release systems from Collaborative Laboratories, which also supplies Catezomes, a non-phospholipid vesicle system with a cationic charge that makes them substantive to skin. They are used to deliver oil-soluble ingredients like UV absorbers and ceramides or water-soluble actives like panthenol. Lucas Meyer offers Pro-Lipo and Isocell microencapsulating systems; Lipotec supplies an extensive range of active ingredients in liposome form and provides a number in liposomes coated in a hydrophilic polymer that can be incorporated into emulsions, milks and gels.

 

Lipoid GmbH produces Ultraspheres, which are finely dispersed nano-emulsions with lecithin as the only emulsifier and with a lipophilic active enclosed within a phospholipid monolayer. This can form the internal oil phase of an o/w emulsion, without the addition of further emulsifiers. The vesicle form ensures enhanced penetration of the lipophilic ingredient into the upper layers of the skin. Excess lecithin passes into the water phase and spontaneously forms liposomes, which themselves can encapsulate water-soluble actives. Kryosomes from Lipoid are described as “dry liposomes” They are formed by freeze-drying liposome dispersions in the presence of a polysaccharide cryoprotectant that maintains the liposome structure as a porous sponge. This enables highly active materials to be produced without the need for preservatives and which may be readily hydrated to provide a liposome dispersion. 

 

LIBIOL provides a number of active ingredients in liposome form including vitamin A, various enzymes and ceramides.   Ultrasomes from AGI Dermatics contain the enzyme UV-endonuclease prepared from milk by biotechnology and supplied in liposome form for sun-repair products. The same company supplies Photosomes, which are liposomes containing an enzyme obtained from plankton, and Oxysomes, magnesium ascorbyl phosphate encapsulated within a liposome membrane that contains vitamin E. Enzymes are finding increasing application in skin care but Laminarghane from SECMA, France, is said to control sebum production, follicular inflammation and hyperkeratinisation by inhibiting the activity of 5-α reductase in oily skin disorders.

 

A paper by Diana Smith [Ref 3] given at the IFSCC Congress described the use of polyester technology for optimising actives. Their effect is the opposite of liposome delivery systems. Whereas the latter assist penetration of the epidermis, polyesters mitigate skin penetration and this is of advantage where a protective barrier is required as with organic sun filters. According to Smith it was found possible to design the polyester structure in order to optimise the effect achieved with various active ingredients. This was used for the delivery of AHAs, which because they were retained in the upper layer of the stratum corneum, they gave the maximum effect where it was most required. It was possible to reduce the concentration required while maintaining product efficacy, which resulted in reduced stinging potential and less irritation. Dihydroxyacetone was also used with a polyester delivery system and its activity was enhanced by the increased contact time with the skin surface. The polyesters described are available through Innolex Chemical Co., USA.

 

The many different retinoids and their use in dermatology were described by Christos Zouboulis [Ref 4] at the Cosmetic Science Conference 2000. The term retinoid includes both naturally occurring molecules and synthetic compounds showing biological activities, which are characteristic of vitamin A. They affect cell growth and differentiation, sebum production and collagen synthesis and possess anti-inflammatory properties. They are used to treat sebum disorders, acne and psoriasis, photodamage, hyperpigmentary disorders and skin cancers.  Zouboulis described the many different forms of retinoid available and the factors affecting their activity. Because of adverse effects caused by retinoic acid less toxic compounds were investigated and it was found that biological activity could be maintained with a reduction in toxicity by altering the molecular structure. Zouboulis investigated the mechanism of retinoid biological activity, their effect on receptor proteins and the complex interactions between them and hormonal signal transduction molecules.

 

The use of retinoic acid in dermatology has promoted the use of retinol and retinyl esters in cosmetics for skin care. Retinol is the alcohol form and although substantially less effective than the acid it is significantly more effective than the esters. It should be used at from 0.01% – 0.10% w/w in products for topical application. At higher concentrations it is likely to induce irritation because of its ability to penetrate into the skin. The material is sensitive to pH, temperature, heavy metals and oxygen, which make formulation with it difficult. Coletica, France, claims to have overcome these problems by micro-encapsulation of retinol in a combination of acacia and alginate polysaccharides. Termed Cylaspheres, they have a strong affinity for the skin surface, binding to the corneocytes in the stratum corneum and they greatly reduce the depth of penetration of the retinol. The retinol content is released over time with a consequent improvement in its efficacy at the site where it is most needed and there is a significant reduction of adverse local and systemic side effects. Retinol Cylaspheres contain 1% retinol and are incorporated into emulsions at a level between 1% and 10%w/w. They must be added at ambient temperature and the finished product packed in an airtight container.

 

Retinoids and vitamin C are both used in skin whitening compounds. This is a major growth area for cosmetic skin care because pigment disorders are one of the most visible signs of ageing. Also, with the use of hydroquinone being discontinued in most countries of the world the industry is looking for new materials. Vitamin C has much potential as a cosmetic ingredient for topical application as both an antioxidant and in skin whitening compounds but it is notoriously unstable. Including it in the inner water-phase of a w/o/w emulsion is one method of protecting it from oxidation. Using a derivative such as ascorbyl glucosamine simplifies handling but there is a great increase in cost and it is less effective.

 

A presentation by Arun Puri [Ref 5] at the cosmetic science conference described a method of entrapping active agents in a methyl methacrylate/glycol dimethacrylate cross-polymer and then encapsulating this in gelatine. The actives described in the paper were retinol and ascorbic acid. The cross-polymer is a patented method developed by Advanced Polymer Systems as Microsponge controlled release system and the gelatine capsules protect the actives from light and oxygen, greatly improving stability.

 

An alternative method was described by G.Fabrizi [Ref 6] whereby two derivatives of ascorbic acid were packaged in an air-free pump. The materials were the water-soluble magnesium L-ascorbyl-2-phosphate (VC-PMG) and the lipo-soluble dellihexyldecanoyl-L-ascorbic acid (VC-IP). Both undergo hydrolysis by skin enzymes to release ascorbic acid. According to the authors, because of the differences in their penetrative powers the water-soluble form penetrated more deeply while the liposoluble form stayed at the cutaneous level and was hydrolysed more slowly. Further work using VC-IP described by S Ukaji [Ref 7] showed it to reduce melanogenesis and to enhance collagen synthesis. A different approach to improving the stability of ascorbic acid is suggested by Grant Industries, which has incorporated it in a gel of cyclomethicone and polysilicone-11.

 

Skin care cosmetics consist of more than an active ingredient in a liposome. The most popular carrier form remains an emulsion and improving the application characteristics of this is one method of enhancing product efficacy. Silsoft 034 from CK Witco is caprylyl methicone that is described as a modified trisiloxane lipophobe with surface-active properties. It is said to lower surface tension of the oil-phase and to promote its spreading properties, providing a uniform film that is ideal for the application of oil-soluble ingredients. Silicone compounds have long been an active area of cosmetic ingredient development. New introductions include the vinylpyrrolidone/polycarbamyl polyglycol esters from Phoenix Chemicals sold in the form of hydrogels. They are said to complex with a wide range of organic molecules including antimicrobial compounds and UV absorbers and to dry on the skin as a water-resistant film, making them ideal for sun protection products.

 

1.                  Benoit, I., A global approach to skin aging; IFSCC Congress South Africa 1999.

2.                  Blume, G., Liposomal carriers; how to make an active efficient. ibid

3.                  Smith, D., Delivering the goods – Polyester technology for optimising actives. Ibid

4.                  Zouboulis, C., Retinoids: is there a new approach? Cosmetic Science Conference 2000, Barcelona

5.                  Puri, A., Unique way to stabilise retinol and vitamin C in cosmetics using softgel technology. Ibid

6.                  Fabrizi, G. et al, New perspectives on vitamin C. ibid

7.                  Ukaji, S. et al, A new Vitamin C based compound for whitening and anti aging. ibid