`Ex. 1037 (Ray Attachment B)
`Reactive Surfaces Ltd. LLP v. Toyota Motor Corp.
`IPR2016-01914
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`Advances
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`EDI'IEL} BF
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`0923Ch03Frame Page 63 Monday, May 14, 2001 1:18 PM
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`3
`
`Composition
`of Latent Print Residue
`
`ROBERT S. RAMOTOWSKI
`
`Contents
`
`Introduction
`Skin Anatomy
`The Epidermis
`The Dermis
`Secretory Glands
`Eccrine Glands
`Inorganic Compounds
`Amino Acids
`Proteins
`Lipids
`Miscellaneous Constituents
`Sebaceous Glands
`Lipid Origin and Breakdown
`Chemical Composition of Sebum
`Fatty Acids
`Phospholipids
`Wax Esters
`Sterols
`Squalene
`Miscellaneous Organic Compounds
`Apocrine Glands
`Variation of Sebum Composition With Age of Donor
`Newborns
`Young Children
`Adolescents
`Post-Adolescence
`The Composition of Latent Print Residue
`United Kingdom Home Office
`Oak Ridge National Laboratory
`Pacific Northwest National Laboratory
`Savannah River Technical Center Research
`Forensic Science Service
`
`63
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`0923Ch03Frame Page 64 Monday, May 14, 2001 1:18 PM
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`64
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`DNA From Latent Prints
`DNA From Blood Prints and Stains
`DNA From Developed Latent Prints
`Miscellaneous Compounds and Contaminants
`Conclusions
`References
`
`Introduction
`
`The composition of human perspiration has been studied and reported
`extensively in the medical literature. The medical community has analyzed
`sweat for many purposes, including attempts to diagnose certain diseases,
`such as cystic fibrosis, and studies of skin conditions, such as acne. Even the
`perfume and cosmetics industry has an interest in determining the precise
`chemical nature of perspiration and how it might interact with their personal
`hygiene products. However, the information ascertained in these studies does
`not begin to address the issue that is most critical for forensic scientists.
`Knowing the precise contents of the various skin glands does not accurately
`represent the nature of what is actually secreted onto substrates from the
`fingers and palms. In operational scenarios, numerous contaminants are present
`in the fingerprint deposit, including material from other glands, cosmetics,
`perfumes, and food residues. In addition, the secreted material is almost imme-
`diately altered by oxidative and bacterial degradation mechanisms. These factors
`are particularly important since crime scene technicians seldom encounter latent
`print deposits immediately after they are deposited by a perpetrator. However,
`there is little information available that describes how a latent print deposit
`changes with time. Thus, a more thorough understanding of these transforma-
`tions would allow forensic scientists to develop specific reagents for visualizing
`compounds known to be stable for long periods of time.
`
`Skin Anatomy
`
`Skin serves several functions, including regulation of body temperature,
`water retention, protection, sensation, excretion, immunity, blood reservoir,
`and synthesis of vitamin D (except where noted, the information in this
`). The skin of an average adult exceeds
`section was obtained from Odland
`1
` in area; yet, in most places it is no more than 2 mm thick. While the
`2 m
`2
`average thickness of epidermal skin varies little over most of the body, the
`thickness on the palms and soles can be as much as 0.4 to 0.6 mm. The skin
`is usually divided into two distinct layers. The outer layer is a stratified
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`0923Ch03Frame Page 65 Monday, May 14, 2001 1:18 PM
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`65
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`epithelium called the epidermis, which has an average thickness of 75 to
`150 µm. The underlying layer of skin is called the dermis, a dense fibroelastic
`connective tissue that constitutes the primary mass of the skin. This portion
`of the skin contains most of the specialized excretory and secretory glands
`that produce sweat. Although the dermis constitutes between 90 to 95% of
`the mass of human skin, the epidermis accounts for the major proportion
`of the biochemical transformations that occur in the skin (although struc-
`tures that extend into the dermis, such as the various sweat glands and hair
`follicles, are also metabolically important).
`
`The Epidermis
`
` The innermost is
`The epidermis (Figure 3.1) consists of several cell layers.
`2
`known as the stratum germinativum (basal cell layer). It consists of one layer
`of columnar epithelial cells, which upon division push into the stratum
`spinosum. The stratum spinosum (prickle cell layer) consists of several layers
`that are held together by intercellular fibrils. The combined stratum spino-
`sum and stratum germinativum are often referred to as the Malpighian layer
`(named in honor of Marcello Malpighi, a 17th century Italian professor and
`fingerprint science pioneer who first used high magnification to detail the
`fine structure of ridges and pores).
`As these cells approach the skin surface, they begin to grow larger and
`form the next layer, the stratum granulosum (granular layer). Keratohyalin
`granules (the precursor of keratin, a fibrous, insoluble protein found in skin)
`are formed in this layer, which is approximately two to four cells thick. The
`nuclei are then either broken up or dissolved, resulting in the death of the
`epidermal cell and an increase in the number of cytoplasmic granules. The
`penultimate layer, the stratum lucidum (clear layer), is ill-defined and con-
`sists primarily of eleidin, which is presumed to be a transformation product
`of the keratohyalin present in the stratum granulosum. In the outermost
`layer, the stratum corneum (cornified layer), the eleidin is converted to ker-
`atin, which is the ultimate fate of the original epidermal cell. Keratin, which
`is continually sloughed off, must continuously be replaced by cells beneath
`it. It has been estimated that a typical individual will shed approximately 0.5
` The total cell cycle in the epidermis is
`to 1 g of dead skin cells per day.
`2
`estimated to take approximately 28 days. Figure 3.2 is a stained skin section
`showing all of the layers of the epidermis.
`
`The Dermis
`
`The dermis is a moderately dense fibroelastic connective tissue composed of
`collagen (a fibrous protein composed of primarily glycine, alanine, proline,
`and hydroxyproline), elastin fibers (a fibrous protein containing primarily
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`66
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`Figure 3.1
`The
`A schematic diagram showing the layers of the epidermis. (From
`Structure and Function of Skin, 3rd Edition
`, Montagna, W. and Parakkal, P.F.,
`Eds., Academic Press, 1974. With permission.)
`
`glycine, alanine, valine, and lysine), and an interfibrillar gel of glycosamin-
`proteoglycans, salts, and water. This layer contains up to five million secretory
` Collagen fibers
`glands, including eccrine, apocrine, and sebaceous glands.
`2
`form an irregular meshwork that is roughly parallel to the epidermal surface
`and provides skin tensile strength and resistance to mechanical stress. Elastin
`gives skin its elasticity and its ability to resume its natural shape after defor-
`mation. Fibrous mats of elastin are intermeshed with collagen to give skin
`its tension. This tension is greatest over body areas where the skin is thin and
`elastin is abundant (e.g., the scalp and face). Fibroblasts, which form elastin
`and collagen, and histiocytes, which form interferon for protection against
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`67
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`Figure 3.2
`A stained section of the epidermis from the palm showing all of the
`layers. Section A is the stratum corneum, section B is the stratum lucidum,
`section C is the stratum granulosum, and section D is the stratum malpighii.
`The structure evident in the stratum corneum is the duct of an eccrine sweat
`The Structure and Function of Skin, 3rd Edition
`gland. (From
`, Montagna, W. and
`Parakkal, P.F., Eds., Academic Press, 1974. With permission.)
`
`viral infections, are present in this layer. A system of blood, lymphatic, and
`nerve vessels is also present.
`The dermis is divided into two anatomical regions, the pars papillaris
`and the pars reticularis. The papillary dermis is the outermost portion of the
`dermal layer and contains smaller and more loosely distributed elastin and
`collagen fibrils than does the reticular dermis. The papillae are supplied by
`numerous capillaries, which ultimately supply nourishment to the epidermis
`via diffusion. The second region, the reticular dermis, lies beneath the pap-
`illary dermis and comprises the bulk of this layer. It is characterized by dense
`collagenous and elastic connective tissue. These collagen bundles are
`arranged predominately in interwoven strands that are parallel to the skin
`surface, although some tangentially oriented bundles are present.
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`68
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`Figure 3.3
`A schematic diagram of the three major secretory glands in relation
`The Structure and Function of Skin, 3rd
`to other cutaneous appendages. (From
`Edition
`, Montagna, W. and Parakkal, P.F., Eds., Academic Press, 1974. With
`permission.)
`
`Secretory Glands
`
`The three major glands (eccrine, apocrine, and sebaceous) responsible for
`the secretion of “sweat” are shown in Figure 3.3. The eccrine glands are
`usually found throughout the body, but the highest densities are found in
`the palms and soles. The sebaceous glands are typically localized to regions
`containing hair follicles, as well as the face and scalp. The apocrine glands
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`0923Ch03Frame Page 69 Monday, May 14, 2001 1:18 PM
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`69
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`are found primarily in the axillary regions (e.g., armpits and genital areas).
`However, in most instances, only the eccrine and sebaceous glands contribute
`significantly to the latent print deposit. Although the composition of sweat
` studies have shown that a considerable variety
`is approximately 99% water,
`3
`of chemical compounds are present. A recent study found approximately 346
`compounds (303 of which were positively identified) present in surface skin
`residues.
`4,5
`
`Eccrine Glands
`
`There are between two and four million eccrine sweat glands distributed
`throughout the human body surface (except where noted, the following
`information was obtained from Quinton
`). Each gland has been calculated
`6
`to have an estimated weight of 30 to 40 µg, for an aggregate weight of about
`100 g. In normal individuals, these glands are capable of secreting as much
`as 2 to 4 L of fluid per hour. The evaporation of this quantity of sweat requires
`approximately 18 kcal/min, which affords humans an ability to dissipate heat
`faster than any other animal. Sweat glands are most abundant on the soles
`) and least abundant on the back (64/cm
`).
` Gland for-
`of the feet (620/cm
`2
`2
`7
`mation begins around the third fetal month on the palms and soles and at
`about 5 months for the rest of the body. Typically, the glands have fully
`matured by the eighth fetal month. The eccrine gland is essentially a tubular
`shaped structure with a duct portion that coils in helical fashion down deep
`into the dermis layer. The function of the distal half of the sweat gland tubule
`is to reabsorb sodium, chloride, bicarbonate, glucose, and several other small
`solutes. Under normal conditions, this allows water to be evaporated from
`the skin surface without the loss of essential solutes.
`
`Inorganic Compounds
`Although eccrine sweat is usually in excess of 98% water, it also contains
`numerous organic and inorganic constituents. The presence of these solutes
`on the skin surface causes a reduction in sweat vapor pressure. These effects
` Excess secretion of certain chloride salts
`have been modeled and quantified.
`8
`has been reported to be a cause for increased rates of corrosion of metal
` This effect was particularly pronounced
`surfaces by particular individuals.
`9
`in patients suffering from hyperhidrosis, a condition which causes excess
`sweat production. The rate of eccrine sweating has been shown to depend
`on the amount of water ingested, but does not appear to exert an independent
` Sweat has
`effect on the relationship of sweat composition to sweat rate.
`10
`been reported to contain 0.5 to 8 m
`M
` total ammonia,
` which is 20 to 50
`11
`times higher than plasma levels. In addition, trace amounts of the following
`inorganic substances have also been detected in sweat: magnesium, iodide
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`0923Ch03Frame Page 70 Monday, May 14, 2001 1:18 PM
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`70
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`(5 to 12 µg/L), bromide (0.2 to 0.5 mg/L), fluoride (0.2 to 1.18 mg/L), phos-
`phate (10 to 17 mg/L), sulfate (7 to 190 mg/L), iron (1 to 70 mg/L),
` zinc,
`12
`copper, cobalt, lead, manganese, molybdenum, sulfur, tin, and mercury.
`13-15
`Interestingly, the eccrine gland is one of the target organs for cystic
`fibrosis. Historically, this condition has been diagnosed on the basis of ele-
`vated sodium chloride concentration in sweat. In general, the sweat sodium
`ion concentration appears to be isotonic to that of human plasma, although
`significant variations can be obtained depending on the method of collection
` One study found that
`(e.g., thermal vs. pharmacologically induced sweat).
`16
`the sodium concentration varied over a rather large range, from 34 to 266
`±
`mEq/L. Others reported the average concentration at 140
` 1.8 mEq/L
` and
`7
` The latter source reported that the chloride concentration is
`60 mEq/L.
`17
`generally lower than that of sodium, averaging around 46 mEq/L, and that
`the potassium level ranged from 5 to 59 mEq/L. In general, chloride levels
` Other studies have determined the potas-
`are isotonic with those in plasma.
`18
`sium levels to be between 4.9 to 8.3 mEq/L
` and 8.8 mEq/L.
` The amount
`16
`19
`of calcium in sweat was found to be about 3.4 mEq/L and the amount of
`magnesium was 1.2 mEq/L.
`-CO
` buffer system appears to play a critical role in maintain-
`The HCO
`2
`ing sweat pH. The pH of sweat isolated from human secretory coils (in the
`dermis) is approximately 7.2, while the pH of sweat secreted from the gland
`can vary from as low as 5.0 (at a low sweat rate) up to 6.5 to 7.0 (at a high
`sweat rate). This indicates that the duct itself acidifies the sweat, presumably
` in exchange for a Na
` ion.
`by reabsorbing bicarbonate and/or secreting H
`+
`+
`20
`At low sweat rates, this mechanism can conserve bicarbonate (and other
`solutes) efficiently and thus maintain a slightly acidic sweat pH. At higher
`sweat rates, the mechanism is overwhelmed and cannot reabsorb solutes
`effectively. This results in secreted sweat containing higher amounts of bicar-
`bonate and thus it has a higher pH. The typical bicarbonate concentration
`has been reported to be between 15 to 20 m
`M
`.
`
`3–
`
`Amino Acids
`Of critical importance to latent print visualization with ninhydrin is the
`concentration of amino acids and proteins. The total amount of amino acids
` The
`present in a print has been reported to be between 0.3 to 2.59 mg/L.
`14
`β
`-naphtha-
`first amino acid found in eccrine sweat was serine, isolated as
`linesulfoserine by using a microbiological method, and was reported by
`Embden and Tachau in 1910. A study of samples of pharmacologically
`induced sweat (using pilocarpine hydrochloride) collected after a hygienic
` Amino acid amounts in sweat have been
`bath yielded 22 amino acids.
`21
`reported to be several times higher than corresponding values in plasma.
`22
`One study found the most abundant amino acids to be serine and alanine,
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`0923Ch03Frame Page 71 Monday, May 14, 2001 1:18 PM
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`71
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`Table 3.1 A Summary of the Relative Abundance
`(Serine Ratio) of Amino Acids in Fingerprint Deposits
`
`Hamilton
`
`28
`
`Hadorn et al.
`27
`
`Oro and Skewes
`29
`
`Serine
`Glycine
`Ornithine
`(Ornithine, lysine)
`Alanine
`Aspartic acid
`Threonine
`Histidine
`Valine
`Leucine
`Isoleucine
`Glutamic acid
`Lysine
`Phenylalanine
`Tyrosine
`
`100
`67
`32
`42
`27
`22
`17
`17
`12
`10
`8
`8
`10
`7
`6
`
`100
`54
`45
`47
`35
`11
`9
`13
`10
`7
`6
`12
`5
`5
`3
`
`100
`59
`45
`45
`28
`22
`18
`14
`9
`10
`8
`5
`—
`5
`5
`
`15.44 and 14.63 mg%, respectively. Another study of both active and inactive
`participants found that in both cases, serine, glycine, and alanine were the
` A similar trend was also reported by several
`most abundant amino acids.
`23
`others.
`24-26
`Quantitatively, amino acid concentrations can vary as much as 2 to 20
`times depending on collection methods (e.g., thermally induced sweat vs.
`exercise-induced sweat) and by sample location on the body. A study com-
`paring sweat samples obtained from the back and hands of subjects found
` The samples from the backs of subjects showed
`some significant differences.
`27
`higher amounts of amino acids involved in the urea cycle. These and other
`differences appeared to be independent of plasma and urine amino acid
`levels, suggesting that amino acids do not appear in sweat as a result of
`
`filtration from the blood plasma. Table 3.1
`summarizes the relative amino
`acid abundance values from several different studies. One study reported a
`series of ninhydrin positive substances, in addition to amino acids, in human
`
` Some of these substances include o
`-phosphoserine, methion-
`eccrine sweat.
`30
`α
`α
`-amino-isobutyric acid, glucosamine,
`-amino-
`n
`-valeric
`ine sulfoxide,
`β
`γ
`acid, cystathionine,
`-amino-isobutyric acid, ethanolamine,
`-amino-
`butyric acid, and carnosine.
`
`Proteins
`The total protein content in sweat has been determined to range between 15
`to 25 mg/dL. One study using two-dimensional electrophoresis and ultra-
`sensitive silver staining found over 400 polypeptide components.
` Some
`31
`specific examples determined by sodium dodecyl sulfate polyacrylamide gel
`
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`0923Ch03Frame Page 72 Monday, May 14, 2001 1:18 PM
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`72
`
`α
`-glycoprotein,
`electrophoresis (SDS-PAGE) include albumin, Zn-
`2
`α
`lysozyme, and the
`-acid glycoprotein orosomucoid.
` An agarose gel iso-
`32
`1
`tachophoresis analysis of thermally induced sweat detected transferrin, fast-
`γ
`α
`β
` It
`migrating
`-globulins,
`- and
`-lipoproteins, and several glycoproteins.
`33
`has been determined by size fractionation HPLC that the bulk of the peptides
`in sweat are in the low end of the molecular weight range. Secretion of higher
`molecular weight proteins (i.e., in excess of 10,000 Da) has been reported to
`increase as the rate of sweating increases.
`
`Lipids
`The lipid content of secretions from the eccrine gland has also been investi-
` Contamination of samples by lipids of sebaceous and epidermal
`gated.
`34
`origin is a major consideration in these analyses. In this particular study, thin
`layer chromatography was used to separate the lipid fraction collected from
`both “clean” and “scraped” sweat samples. Results indicated that the
`“scraped” samples contained a significant amount of lipids that were consis-
`tent with those found in the stratum corneum. In contrast, the “clean” sam-
` contained only
`ples collected using the method described by Boysen et al.
`35
`one significant lipid band, which corresponded to the cholesterol/fatty acid
`standard. In the samples collected, fatty acid concentrations ranged from less
`than 0.01 to 0.1 µg/mL and sterol concentrations ranged from less than 0.01
`to 0.12 µg/mL. These results would indicate that “scraped” samples were
`contaminated by lipids from the epidermis, while “clean” samples gave a more
`realistic characterization of eccrine lipids.
`
`Miscellaneous Constituents
`Lactate and urea have been reported at significant levels in perspiration. The
`M
` at low sweat rates
`amounts of these compounds can vary from 30 to 40 m
` Other miscellaneous components
`to as low as 10 to 15 m
`M
` at higher rates.
`13
` glucose (0.2 to 0.5 mg/dL),
`of eccrine sweat include creatine, creatinine,
`36
`M
`), cAMP, phenobarbitone, and immunoglobulins.
`pyruvate (0.2 to 1.6 m
`37
`Numerous enzymes have also been detected in dissected sweat glands, includ-
`ing alkaline phosphatase, acid phosphatase, Na/K ATPase, phosphatidic acid
`phosphatase, monoamine oxidase, acetyl cholinesterase, and lactic, malic,
`glucose-6-phosphate, isocitric, and succinic dehydrogenases.
` Sulfonamides, antipyrine,
`Drugs have also been found in eccrine sweat.
`38
`and aminopyrine were found to exhibit sweat concentrations that were
`directly proportional to plasma levels. Simple diffusion, aided by the relatively
`low ionization of the drugs studied within the physiological pH range, was
`assumed to be the mechanism by which these drugs entered the sweat glands.
`Another study found that L-dimethylamphetamine as well as its metabolite
` After taking 25 mg
`L-methamphetamine were found to be excreted in sweat.
`39
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`73
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`Table 3.2 A Summary of the Composition of Eccrine Sweat
`
`Inorganic (trace)
`Magnesium
`Zinc
`Copper
`Cobalt
`Lead
`Manganese
`Molybdenum
`Tin
`Mercury
`
`Organic (lipids)
`Fatty acids
`Sterols
`
`0.01–0.1 µg/mL
`0.01–0.12 µg/mL
`
`34–266 mEq/L
`4.9–8.8 mEq/L
`3.4 mEq/L
`1–70 mg/L
`0.52–7 mg/mL
`0.2–1.18 mg/L
`0.2–0.5 mg/L
`5–12 µg/L
`15–20 m
`M
`10–17 mg/L
`7–190 mg/L
`M
`0.5–8 m
`
`0.3–2.59 mg/L
`15–25 mg/dL
`0.2–0.5 mg/dL
`
`30–40 mM
`10–15 m
`M
`0.2–1.6 m
`M
`
`Inorganic (major)
`Sodium
`Potassium
`Calcium
`Iron
`Chloride
`Fluoride
`Bromide
`Iodide
`Bicarbonate
`Phosphate
`Sulfate
`Ammonia
`
`Organic (general)
`Amino acids
`Proteins
`Glucose
`Lactate
`Urea
`Pyruvate
`Creatine
`Creatinine
`Glycogen
`Uric acid
`Vitamins
`
`Miscellaneous
`Enzymes
`Immunoglobulins
`
`Note:
`
`Some compounds and species were only listed as present in sweat in the literature. No
`concentrations were specified for these components.
`
`of the L-dimethylamphetamine, the maximum concentration in sweat was
`found to be approximately 2 to 4 µg/mL, within a few hours after ingestion.
`Unlike the urine concentration, L-dimethylamphetamine levels in sweat were
`found to be independent of pH. Ethanol has also been detected. Several
`relatively rapid, noninvasive methods have been proposed to examine the
` The
`ethanol (as well as other volatile organics) present in perspiration.
`40
`composition of eccrine sweat is summarized in Table 3.2.
`
`Sebaceous Glands
`
`The second major class of secretory glands, sebaceous glands, are located
`throughout the body, except for the palms and dorsum of the feet (except
`where noted, the information in this section was obtained from Strauss
`
`
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`0923Ch03Frame Page 74 Monday, May 14, 2001 1:18 PM
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`74
`Table 3.3 Anatomical Variation in the Amount and Composition of Human
`Sebum Collected After 12 hr of Accumulation (in Weight Percent)
`
`Site
`
`Forehead
`Cheek
`Chest
`Back
`Arm
`Side
`Leg
`
`Total lipid
`(µg/cm2)
`
`288
`144
`122
`84
`76
`57
`57
`
`CH CE
`
`TG
`
`DG
`
`FA
`
`1.1
`1.1
`1.3
`2.2
`4.8
`4.3
`6.3
`
`2.7
`3.4
`2.6
`2.0
`4.3
`4.5
`6.0
`
`29.6
`39.4
`29.7
`35.9
`34.3
`47.1
`44.6
`
`3.5
`2.7
`5.4
`4.5
`2.4
`1.9
`1.5
`
`27.2
`15.4
`24.9
`17.4
`18.4
`7.6
`10.2
`
`WE
`
`25.9
`26.9
`25.7
`27.4
`27.7
`24.9
`23.1
`
`SQ
`
`TG+DG+FA
`
`10.1
`11.2
`10.3
`10.6
`8.1
`9.6
`8.1
`
`60.3
`57.5
`60.0
`57.8
`55.1
`56.6
`56.3
`
`Note: CH = cholesterol; CE = cholesterol esters; TG = triglycerides; DG = diglycerides; FA = free fatty
`acids; WE = wax esters; SQ = squalene; and TG + DG + FA = total glycerides plus free fatty acids.
`Source: Greene, R. S., Downing, D. T., Pochi, P. E., and Strauss, J. S., Anatomical variation in the
`amount and composition of human skin surface lipid. J. Invest. Dermatol., 54(3), 246, 1970.
`With permission.
`
`). Gland density is greatest around the face and scalp, where as many
`et al.
`41
`as 400 to 800 glands per cubic centimeter may be found. The sebaceous
`glands are generally associated with hair follicles and open inside the hair
`shaft canals. Unlike eccrine secretions, which empty directly onto the skin
`surface, the sebum produced by sebaceous glands first travels into the folli-
`cular canal and then onto the skin surface. The lipid is produced by a holo-
`crine mechanism, whereby lipid-laden cells disintegrate and empty their
` These glands
`contents through the sebaceous duct onto the skin surface.
`42
`develop during fetal life between weeks 13 and 15 and have achieved a nearly
` The glands are fully developed and functioning
`full size by the time of birth.
`43
`before birth, probably due to stimulation by maternal hormones. At birth,
`with the termination of the source of these hormones, the glands soon
`become mostly inactive. Table 3.3 summarizes sebum production and com-
`position for various anatomical regions.
`44
`Sebaceous gland activity appears to be controlled by a somewhat complex
`process. It appears that mid-brain dopamine stimulates the anterior and
`intermediate lobes of the pituitary gland to release various hormones via
` In turn, these glands
`certain glands (e.g., thyroid, adrenals, and gonads).
`45
`secrete additional hormones that stimulate sebum production. Several
` Testosterone
`androgens have been found to stimulate sebum production.
`46
`is an especially potent stimulator of sebum production in humans. It has
`been reported that sebum production levels in castrated males are consider-
`ably lower than in intact men.
` The administration of testosterone to cas-
`47
`trated males has been reported to result in a significant increase in sebaceous
` However, administration of testosterone to the normal adult
`gland activity.
`48
`male does not lead to an increase in sebum production. This would indicate
`
`
`
`0923Ch03Frame Page 75 Monday, May 14, 2001 1:18 PM
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`75
`
`Table 3.4 The Approximate Composition of Sebum
`and Surface Epidermal Lipids
`
`Constituent
`
`Sebum
`(wt%)
`
`Surface epidermal lipid
`(wt%)
`
`Glyceride/free fatty acids
`Wax esters
`Squalene
`Cholesterol esters
`Cholesterol
`
`57.5
`26.0
`12.0
`3.0
`1.5
`
`65
`—
`—
`15
`20
`
`Source: Downing, D. T. and Strauss, J. S., Synthesis and composition
`of surface lipids of human skin, J. Invest. Dermatol., 62, 231,
`1974. With permission.
`
`that maximum stimulation of the sebaceous glands is accomplished by
`endogenous testosterone. Other studies have found slight increases in skin sur-
`face lipids after administering testosterone.49 Testosterone given to children also
`produced a significant increase in sebum production.50 Metabolism and elim-
`ination of these compounds in human skin samples has been reported.51 It
`appears that excretion of C19- and C18-steroids through the skin may exceed
`their urinary elimination.
`
`Lipid Origin and Breakdown
`Radioactive labeling studies have illuminated the formation and origin of
`lipids.52 Autoradiograms from one study showed that radioactivity (from
`incubating samples of subcutaneous fat from scalp biopsies with [14C] ace-
`tate) found in total lipid extracts was confined to squalene, wax esters, tri-
`glycerides, and phospholipids. It is significant to note that cholesterol,
`cholesterol esters, and free fatty acids did not contain any significant amount
`of radioactivity. That would imply that these compounds are of epidermal
`origin rather than being produced in the sebaceous gland. The differences
`in lipid classes between lipids of sebaceous and epidermal origin are listed
`in Table 3.4. Another study proposed that sebaceous lipids are derived from
`two different sources, the body’s circulation (exogenous lipid) and from de
`novo synthesis (endogenous lipids).53 They assumed that the composition of
`both of these sources remained constant, but that their relative contribution
`to sebum was variable. Examples of possible exogenous lipids would include
`linoleate (an essential fatty acid), cholesterol, cholesterol esters, and triglyc-
`erides. However, the fact that circulating cholesterol esters and triglycerides
`have different fatty acid compositions than their sebaceous counterparts
`makes it unlikely that they are incorporated directly into sebum. Examples
`of endogenous lipids that are not available from blood include ∆6 fatty acids,
`squalene, and wax esters.
`
`
`
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`76
`
`Various oxidative and bacteriological changes occur after sebum is
`excreted. Lipolysis by enzymes derived from the epidermis or bacteria present
`in skin surface debris from human skin has a tendency to break down tri-
`glycerides and methyl esters.54 That particular study reported that, in ether,
`triolein and tristearin were converted primarily to free fatty acids and 1,2-di-
`glycerides and only trace amounts of 1,3-diglycerides and monoglycerides.
`This evidence leads to the conclusion that the majority of free fatty acids
`present in sweat originate from the hydrolysis of sebum triglycerides. Evi-
`dence of varying degrees of bacterial lipolysis has been offered for Coryne-
`bacterium acnes,55,56 staphylococci,57 Pityrosporum ovale,58 Pityrosporum
`acnes, Pityrosporum granulosum,59 Micrococcaceae, and propionibacteria.60
`Several studies have shown that treatment of skin with antibiotic compounds
`(e.g., clindamycin) reduced bacterial populations and led to a concurrent
`decrease in free fatty acids.61-63 However, one study found that treatment with
`neomycin failed to affect the C. acnes population.64 It is likely that certain
`bacteria, such as C. acnes, are present within the hair follicles and would be
`inaccessible to topical antibiotics.
`
`Chemical Composition of Sebum
`There is a considerable variety of organic compounds present in sebum.
`Several factors can influence a particular individual’s sebum profile, including
`diet and genetics. It is possible that each person may have a unique scent
`signature, as demonstrated by the ability of certain breeds of dogs to track
`humans over wide areas. In addition, in animals, certain lipids may function
`as a means of communication. One study determined that in certain species,
`short-chained aliphatic acids were found to act as pheromones.65 These com-
`pounds also allow animals to recognize members of their own social group.
`It is possible that a similar situation was once present in humans; however,
`modern hygiene practices may have diminished our ability to recognize the
`signals. In fact, in humans, sweat has to be broken down bacterially before
`it acquires a detectable, characteristic odor. A summary of sebum composi-
`tion by lipid class