Enzymes in Cosmetic Formulations

Florence Barrett-Hill

Enzymes are effective cellular catalysts responsible for controlling thousands of reactions in the cell. Discovered in 1833, it was not until 1926 that it was established that enzymes were special, active proteins.

Diastase the first to be extracted (from malt) was eventually shown to be amylase, an enzyme that converts starch to sugar.

The next enzymes discovered, also in the late 19th century, were isolated from the stomach and identified as pepsin and trypsin. These are proteases, which are enzymes that digest protein by breaking down peptide bonds.

Normal binding of substrate

Enzymes are highly specific and complex protein catalysts that increase the rate at which reactions occur.
At the temperature and pH usually present in the cells, most chemical reactions would not proceed fast enough to maintain cell viability without enzymes.

Enzymes are specific for the type of reaction they catalyse, and they may be specific for the type of substrate they use: therefore, there are no by-products and no side effects.

Enzymes work by a shape recognition method, the substrate must form a complex with the enzyme. When the enzyme locks onto the substrate a reaction (energy) will occur. When this happens, the substrate then binds with the enzymes reactive site.

Action of enzyme inhibitors

Medical science has shown that it is possible to synthesize powerful inhibitors that closely resemble the transition state and bind to the enzyme. Most commonly, inhibition occurs when one molecule interferes with the binding of the substrate to the enzyme.
Interest in the use of inhibitors in cosmetics has increased, and much of it has been directed toward those with and anti-tyrosinase activity for whitening of the skin, those who exhibit anti-elastase activity, which prevents elastin from cross-linking and results in the skin losing its flexibility.
These cosmetic inhibitors work by non-competitively binding to the enzyme, altering its structure, so that it either does not work as well, or it does not work at all.

Coenzymes and Cofactors
Some enzymes consist only of proteins and contain no other chemical groups. Other enzymes, the globular conjugated proteins require an additional chemical component, known as a cofactor.

Either the cofactor can be inorganic or a complex organic molecule called a coenzyme. Many of the coenzymes are derivatives of vitamins, other enzymes depend on specific cofactor minerals.
Many coenzymes are the water-soluble B vitamins, such as calcium pantothenate, niacin and pyridoxine hydrochloride. Cofactors include the following metals: zinc, iron, magnesium, copper, and others.

Enzyme Categories

Class 1: the oxidoreductases, datayze oxidation and reduction reactions:       

Dehydrogenases Oxygenases Peroxidases
Oxidases Hydroxylases Reductases

Class 2: the transferases, transfer chemical groups from one molecule to another or within a single molecule      

Amino-transferase Glucosyl-transferase Acyl-transferase
Phosphoryl-tranferase Methyl-transferase Kinases

Class 3: the hydrolases, use water to cleave a single molecule into two molecules    

Esterases Phospholipases Glycosidases
Amidases Peptidases Ribonuclease

Class 4: the lyases, split molecules using a non-hydrolytic process, leaving double bonds. They can also split molecules by adding groups to double bonds.     

Decarboxylases Hydratases Synthases
Aldolases Dehydratases

Class 5: the isomerases, change isometric structures by intramolecular rearrangements.  

Racemases cic-Isomereases Intramolecular
Epimerases trans-Isomerases transferases

Class 6: the ligases, create a chemical bond to join two molecules using energy from ATP.
In particular, the synthetases from C-O, C-S, C-N, and C-C bonds.

Enzymes in cosmetic formulations and clinic treatments
The use of coenzymes and cofactors in cosmetics may represent a safe way to promote the efficient functions of the enzymes in the skin to help maintain the healthy appearance of the skin.

The coenzymes and cofactors are stable, low in molecular weight and should penetrate through the stratum corneum to help activate the enzymes present. They are relatively easy to formulate into cosmetics and most important, these materials offer a good degree of safety when topically applied.

Coenzyme derivatives

 Vitamin  Coenzyme  Groups
 Thiamine Vit B1  Thyamine pyrophosphate  Aldehyde
 Riboflavin Vit B2  Flavine adenine dinucleotide/mononucleotide  Hydrogen
 Nicotinate (niacin)  Nicotinamide adenine dinucleotide  Hydrode Ions
 Pyridoxine Vit B6  Pyridoxal phosphate  Amino groups
 Panthothenate  Coenzyme A  Acyl groups
 Biotin  Covalently bonded to carboxylases  Carbon dioxide
 Folate  Tetrahydrofolate  One C groups
 Cobalamin  Cobamide coenzyme B12  Hydrogen/alkyl

The use of many enzymes themselves in cosmetic formulations if fraught with difficulty as high molecular weight entities require a specific shape to function effectively. This is difficult to maintain when adding to a cosmetic formulation.

The cosmetic industry however, has for some time now been using the proteolytic (dissolves protein) enzymes, such as papain, bromelaine and others for resurfacing and skin smoothing. These substances have proven to be a very useful tool for the skin treatment therapist in treating many the skin conditions related to skin aging, acne, congestion and pigmentation.

Free radicalEnzymes as anti-free radicals
One area where the topical application of enzymes has been shown to have significant benefits is in skin protection.

Some materials with excellent cosmetic stability exist. They are enzymes with the ability to capture free radicals, preventing damage to the skin caused by environmental pollution, bacteria, smoke, sunlight and other harmful factor. Here the enzyme can work successfully on the surface of the skin.

There is no need for them to penetrate down to the living cells (although it might be helpful). Perhaps one of the most ubiquitous protective enzymes is superoxide dismutase. (SOD) This is found in almost all-living organisms and works to protect the cell from free radical oxygen attack in the aqueous environment.

Superoxide Dismutase (SOD) and Catalase:
SOD in combination with catalase is responsible for protecting the proteins from aging due to oxidation. SOD works by dismutation, a process by which a dangerous highly reactive oxygen free radical is converted to a less reactive form.
It is important to aerobic cells that the oxygen molecule be completely reduced to two water molecules by accepting four electrons.
If oxygen is only partially reduced by accepting one electron, the product is the superoxide radical.

Superoxide radicals are extremely toxic to cells because they attack unsaturated fatty acid components of membrane lipids, thus damaging membrane structure, causing cell injury.

There are possible benefits for using enzymes in cosmetics; they may help to slow the visible signs of aging and the damaging effects of the environment on the epidermis.
Research scientists will continue exploring the possibilities until the mystery, benefits and use of all enzymes that may be used in cosmetics is known. Maybe that key to the fountain of youth is just around the corner.

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