Melanin number

In addition to their well known role in protein structure, amino acids also act as precursors to a number of other important biological molecules. For example, the synthesis of haem (see also Section 5.3.1), which occurs in, among other tissues, the liver begins with glycine and succinyl-CoA. The amino acid tyrosine which maybe produced in the liver from metabolism of phenylalanine is the precursor of thyroid hormones, melanin, adrenaline (epinephrine), noradrenaline (norepinephrine) and dopamine. The biosynthesis of some of these signalling molecules is described in Section 4.4. 

With tyrosinase, on the contrary, a two-electron oxidation occurs, as no EPR signal was detected in the catechol oxidation at pH 5.3 Melanins are polymerization products of tyrosine, whereby tyrosinase catalyses the first steps the formation of dopa (3,4-dihydroxyphenylalanine) and of dopaquinone, leading to an indolequi-none polymer The peroxidase mechanism for the conversion of tyrosine into dopa in melanogenesis was not substantiated In natural and synthetic melanins free radicals of a semiquinone type were detected by EPR 4-10 x 10 spins g of a hydrated suspension (the material was modified on drying and the number of free spins increased). The fairly symmetrical EPR signal had a g-value of 2.004 and a line-width of 4-10 G The melanins seem to be natural radical scavengers. 

The dendrites of a melanocyte contact about 36 keratinocytes and are able to transfer melanosomes to these adjacent cells. The numbers and sizes of the melanosomes as well as melanin structure determine differences in skin color.131 Similar cells in amphibians, the melanophores, also contain light receptors p Their melanosomes are not transferred to other cells but may be either clustered near the center of the cell or dispersed. The location can be changed quickly by transport of the melanosomes along a network of microtubules allowing the animals to change in response to changes in light color.0)... 

The principal pigment of human skin, hair, and eyes is melanin, which is synthesized in specialized cells, the melanocytes. They lie between the epidermis (outer layer) and the dermis (inner layer) as shown in Box 8-F. Melanocytes originate from embryonic nervous tissue and migrate into the skin by the third month of fetal life. They retain the highly branched morphology of neurons. Persons of different races all have the same numbers of melanocytes but the numbers and sizes of the pigmented melanosomes (Box 8-F) vary as does the content and chemical composition of the melanin.a d Melanosomes not only are found in the dendrites of the melanocytes but are transferred from them into adjacent epithelial cells.6 1... 

Nevi (moles) are clusters of melanocytes that start to appear in the third year of life. They gradually increase in numbers but disappear in old age. Freckles appear beginning at about age six in genetically susceptible individuals. They are regions in which a higher concentration of melanin is formed.3... 

Hair dyes are of two types permanent and semipermanent. Permanent dyeing is achieved with a synthetic dye, applied with hydrogen peroxide that first bleaches the natural pigment melanin. Semipermanent dyes are generally made with vegetable extracts, such as henna, that coat rather than penetrate the hair shaft. There are a number of questions about the safety of synthetic hair dyes, since some of the products they contain cause cancer. 

The substance melanin is found in the germinative layer, where it is formed by cells called melanocytes. The number of melanocytes is fairly constant and differences in skin colour are due to the amount of melanin produced. Exposure to sunlight promotes the synthesis of increased amounts of melanin. The function of melanin is to protect the skin from the harmful effects of some of the sun s rays. 

Note Numbers are in units of ng cocaine/10 mg hair. The hair was exposed to 2.5 pg/mL of cocaine containing tracer for 1 h, rinsed two times with distilled water, and dried. After centrifugation, all the digested hair in the supernatant could not be separated from the melanin pellet. Therefore, some residual amount of the drug remained associated with the melaiun pellet. This amount is estimated to be between 2 to 10% of the total. Thus, the amount of cocaine actually associated with the melanin fraction is even less than that cited above. 

Blond hair contains elliptical and oval melanosomes. The granules in melanosomes are small, few in number, and likely represent eumelanin, although pheomelanin also may be present in blond hair. T22,24 Ortonne and Prota suggested that blond hair results from a quantitative decrease in the synthesis of melanin in comparison to black and brown hair. The main features which distinguish brown hair from blond hair are the presence of more melanosomes and a higher concentration of melanin in brown hair. - Melanosomes present in the shaft of blond hair also appear to be more susceptible to degradation than melanosomes in black hair. Cesarini reported that melanosomes may not be present in the shaft of blond hair, possibly due to digestion of melanosomes by lysosomes. 

Besides these enzyme substrates, a number of biological molecules are likely to give rise to fairly stable and hence observable free radicals. The more important of these are the quinonoid molecules, particularly vitamin Q quinone (ubiquinone), vitamin E quinone, vitamins K, Ks and vitamin E quinone, the flavins and flavoproteins and the important neurochemicals dopa, dopamine, and closely related phenolic and quinonoid molecules. In many of these cases, the generation of free radicals from these molecules should occur in vivo, but as yet only a few radicals such as the ascorbyl radical and the bacteriochlorophyll radical have been directly identified in intact systems. Free radicals from melanins (polymers from dopaquinone) have been demonstrated both in vivo and in vitro, but these radicals are so stable that it has not yet been possible to identify a biological role for the radicals per se. 

AHA peels help rid the superficial layers of the epidermis of an excess of melanin, and AHA creams applied daily increase keratinocyte turnover, with the melanin produced being diluted in the increased number of keratinocytes. Combined used of effective sun protection reduces melanocyte production and improves the results. 

The understanding of melanin structure has been attempted via analytical and biosynthetic approaches. The analytical one originally explored by Nicolaus (3,7,310) has led to the development of a number of useful methods for characterizing natural and synthetic melanins in terms of elemental composition, functional groups, and structural features of the pigment backbone. These methods helped in the elucidation of the partial polymeric structure of the eumelanin sepiomelanin (3) seen below. 

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