Hair

Morphology and Structure of

Human Hair

- Hair consists of dead cells which

are extruded from the base of the
follicle
- Hair consist of two parts;
the shaft, the root or follicle
 The hair is formed by cells of the
dermal papilla at the base of the
follicle.
 Follicles are formed during the growth
of the foetus, no new follicles are
formed post natally.
 The major function of hair is thermal
insulation.
On S.E. Microscope, the hair
shaft is seen to consist of three
regions.
 The cuticle – the outer region –
encircles the cortex, and is made of 5
to 15 overlapping layers. Externally is
seen as a series of uneven edges,
which can be forced outwards by
combing or friction. There are gaps
between these layers, permitting small
molecules to enter or leave the cortex.
 On S.E. Microscope, the hair
shaft is seen to consist of three
regions.
 The cortex – the middle region – which has
a fibrous appearance, long strands of fibers
run along the length of the hair,
interweaving so as to form a structure of
great strength and elasticity.
 The medulla – a central canal. The cells
are nucleated near the papilla, but the cell
contents are lost as they progress upwards.
Many hairs have no medulla.
Morphologically, there are
three types of hair:
 Vellus : are short, fine, soft, usually non
pigmented and unmedullated
 Terminal : are large, darkly pigmented and
often medullated
90% of the hairs on the chest, trunk,
shoulders, legs and arms of men are
terminal, only 45% on women.
 Intermediate : occur on the scalp, their
morphology falls between those of terminal
and vellus and they are medullated and
contain moderate amount of pigment.
Cyclic Activity of Hair

 Anagen phase: The hair grows at a

rate of about 1cm/ month, during
which the old hair is shed and new
growth begins.
Of 100,000 – 150,000 scalp hairs on
human adult, regardless of sex, 90%
are in the anagen phase
 Catagen phase: 5% resting phase
 Telogen Phase: 5%
Chemical Composition of
Human Hair
 Protein (keratin) 65-95%, depending
on its moisture content
- keratin is a biopolymer composed
of 25 different amino acids, 18 in
measurable amounts
 Lipids

 Pigment and trace elements.

The extreme strength and
insolubility of hair due to:
 Its large cystine content
 The filaments of the cortex are
composed of low sulphur proteins and
surrounding matrix is made up of high
sulphur proteins
 The cuticle cells do not contain any
low sulphur proteins.
The extreme strength and
insolubility of hair due to:
1- Amide links - CO – NH –
2- Very long polypeptide chains
3- Salt links R-NH3+ -OOCR
4- Disulpide bonds which bridges two
main chains and provides a strong
covalent link between them. R-S-S-R
5- Hydrogen bonding between the main
chains. NH ……..OC
Hair Loss
 Recently, elderly became interested
in lifestyle aim to provide better diet,
nutrition and drugs that not only
target long life but also better
quality of life.
Hair Loss

 Normally, around 90% of scalp follicles

are in anagen phase and 10% in
catagen and telogen phases. But many
factors can affect the cyclic activity of
hair. These factors shorten the anagen
phase, rendering terminal hair to fine
vellus hair. When anagen phase
shortens and telogen phase became
longer, considerable percentage of hair
fall out. With continuing fall of hair,
baldness becomes obvious.
Hair Loss

 Aging also affect the hair cycles

rendering terminal hair into vellus,
these changes may be explained by
decreased function of hair matrix cells
that produce hair, decreased blood
flow causing shortage in nutrients,
increased sensitivity of androgenic
hormones and excess secretions of
sebum that affect the healthy
environment of hair growth.
Hair Loss

 Other factors include malnutrition,

administration of certain drugs,
genetics, stress and tension may
affect the cyclic activity of hair.
 To treat hair loss, pharmaceuticals
and cosmetic firms developed new
products claimed to contain effective
ingredients to address the above
indirect causes of hair loss; include
nutrients, blood flow promoters,
Treatment of alopecia:
 Finastride and dutastride : synthetic
anti-androgen taken orally to treat
male pattern baldness, a form of
androgenic alopecia in men. It acts by
inhibiting 5-alpha reductase, the
enzyme that converts testosterone to
dihydrotestosterone (DHT).The U.S
Food and Drug Administration
approved finastride to treat male
pattern baldness.
Treatment of alopecia:
 Minoxidil : A topical agent used to
treat hair loss . Minoxidil acts as a
vasodilator that increases blood
supply to the follicle stimulating hair
growth.
 Herbal extracts have been used to
treat alopecia. For example, Linum
usitassimum (flax) seed extract has been
used to treat male pattern baldness by
inhibiting 5-alpha reductase, thus
reducing levels of DHT.
Treatment of alopecia:
 t-flavone from St John's wort
(Hypericum perforatum) is significantly
effective in treating male-pattern and
female pattern baldness. It promotes
hair growth and increases the
diameter of hair. t-flavone acts by
suppressing the activation cascade of
transforming growth factor- beta 2
(TGF-B2) , a catagen inducer
secreted from the dermal papilla .
Treatment of alopecia:
 6-(Benzylamino) purine; an adenine
derivative is also used to promotes hair
growth by converting the telogen phase
in to anagen , and by stimulating DNA
synthesis, allowing lengthening of hair
shaft . [5]
 Oral administration of soymetide-4, an
immunostimulating peptide derived from
soybean, is effective in treating alopecia.
[6]
Treatment of alopecia:

 The liposterolic extract of Saw

palmetto (Serenoa repens) and
hexane extract of Curcuma
aeruginosa are botanically derived
inhibitors of 5-alpha reductase , so
can be used to treat male pattern
baldness.
Saw palmetto (Serenoa
repens)
Fitoterpia, 2012 Jul;83(5):864-71. doi: 10.1016/j.fitote.2012.03.017. Epub 2012 Mar 21.
Anti-androgenic effect of sesquiterpenes isolated from the rhizomes of Curcuma aeruginosa
Roxb.
Suphrom N1, Pumthong G, Khorana N, Waranuch N, Limpeanchob N, Ingkaninan K.
Shampoos

1
2
 The primary function of shampoo is to clean hair
and scalp.
❖ THE TERM:
The word comes from the Hindi “to press”.
Originally used in English for “massaging”
It still describes part of process of a Turkish bath.

❖ The first shampoos contained soaps (Sodium,

potassium and ammonium salts of oleic and
coconut fatty acids), but these days they are based
on non-soap detergent (synthetic detergents have
replaced soaps as the primary surfactant in
shampoos because of their superior performance in
hard water).

3
❖ The first large-scale development of non-soap
detergent took place in Germany during the
First World War (because fats were in short
supply)

❖ The technology of complex shampoo emulsion

has also become more important as a result
of the development of effective two in one
shampoo, which clean and condition hair at
the same time.

4
 A WELL FORMULATED SHAMPOO

1. Should easily spread over the hair.

2. Produce a rich, creamy lather and stable
foam which easily rinsed out with water.
3. After drying, the hair should be left in
lustrous condition and easily manageable.
4. Surfactant level must be relatively high 10-
20%.
5. Viscosity at least 2000 cps
6. Must exhibit low skin and eye irritation.
5
 First shampoos (soaps) have several disadvantages

1. If they used with hard water or low pH,

they leave the hair with dull, tacky coating.
2. Soap solutions are alkaline, causing
roughening of scales of the cuticle, giving
rise to dullness and fly effect.
(Amine soap gives neutral solutions).
‫ ٭‬Nowadays, most shampoos are based on
synthetic detergent.

6
7
TYPES OF SURFACTANT (DETERGENTS)

Anionic

Cationic

Non-ionic

8
 Anionic
The alkyl and alkyl ether sulfate represent two most
widely used classes of surfactant for the formulation of
shampoos.

1. Alkyl sulphates
C12H25O.SO3 Na+ → SLS
C12H25O.SO3HN(CH2CH2OH)3 → TLS

They are usually mixture,C12 lauryl, C14 myristyl,

C16 cetyl, C18 stearyl.
Coconut oil contains 50% each of C12 and C14.
Lauryl produces the most lather and myristyl the richest
lather.

‫٭‬alkyl sulphate clean the hair well, and leave it shiny, but
they tend to strip the hair, leaving it unmanageable.
9
2. Ether sulphates
C12H25 (OCH2CH2)n O.SO3Na +
Foaming potential decreases with the increase of
the number of (OCH2CH2) group, while mildness
and solubility increases. The optimum is 2-3.
They are generally more soluble than alkyl
sulphates.

3. Miscellaneous anionic surfactant

They are not widely used but incorporated with
primary ones as secondary surfactants, or used in
specialty product.
E.g. sulfosuccinates , linear alkylbenzene sulfonate .

10
Cationic

Cationic surfactant in shampoo formulations is

more limited than that of surfactant classes.
They are not as effective detergents due to their
ability to strongly bind to hair’s negatively charge
surface, and not efficiently removed during rinsing.
➢ Cetrimide is an example
CH3
|
C16H33 ― N+ ― CH3 Br–
|
CH3
11
 Notes

Shampoos containing only one of the previous

types of detergents tends to be harsh, and it’s
therefore necessary to add an auxiliary
detergent, usually weak detergents which:

1. Increase the viscosity of the shampoo.

2. Stabilize the foam.
3. Have conditioning effect on the hair.
4. Increase the solubility of the primary detergent.
 Non-ionic
For example, polyoxyehtylene lauryl ether
C12H25 (OCH2CH2)23

❖ THE MAIN THREE TYPES OF NON-IONIC

DETERGENTS:

1. Fatty alkanolamaides ( The ethanol amides)

They work as foam and viscosity enhancers. The main
component is the uncharged nonionic amide.
The major concern in formulating with alkanolamides is the
potential for free amine, particularly diethanolamine (DEA), to
form carcinogenic n-nitrosamines.
E.g. lauric diethanolamide
O
║ CH2CH2OH
C11H23C-N
CH2CH2OH
13
2. Amine oxide
Are prepared by the oxidation of tertiary amines with
hydrogen peroxide. They are best known for their ability
to enhance foam characteristic, and provide thick,
creamy, more stable lather at moderately acidic pH.
CH3
|
CH3 (CH2)11 ― N → O
|
CH3
e.g. Lauryldimethylamine oxide

➢ Nonionic surfactant are generally not used as primary

surfactants in shampoos due to inferior foaming
characteristics, which result from their large surface area per
molecule and the lack of charge on the surface films in
nonionic foams.
The advantage of the use of nonionic is their ability to reduce
eye irritation and sting.

14
Ampholytes (Amphotrics)
- They have very low irritation potential and are almost completely non-
stinging to the eyes.

- Can be formulated in many types of shampoos.

- Should avoid low pH when formulating because the amphotric become
positively charged since this can result in increased irritation.

CH3
| _
C12H25 ― N + ― CH 2COO N- lauryl betaine
|
CH3
 Other Additives

Many additives associated with shampoos are added to

provide various additional benefits to the product;
some are critical and others are optional.

1. Viscosity modifiers
- Auxiliary detergents and conditioning polymers can provide a
thickening effect to a shampoo.
- Salts increase viscosity of detergent solutions, NaCl 1-2%,
Ammonium chloride at pH well below 7 to avoid liberation of
ammonia, salting out mechanism (bell-shaped curve).
- Cellulose derivatives (0.5-1.5%)

2. Weak organic acids

A shampoo having the same pH as hair would do the least
damage.

‫ ٭‬Hair pH = 5-6 , S. Detergent pH = 6-8

An addition of citric acid will decrease pH to optimum pH 5.5

16
3. Opacifiers
The opacifying agent are usually stearates (stearic acid,
magnesium stearate, ethylene glycol monostearate), are used
in less than 1% concentration to give creamy appearance.

4. Antioxidants/ Sequestrants / UV Absorber

➢ Antioxidants are included in shampoo formulation to avoid
oxidation of unsaturated components, such as vegetable oil.
➢ Sequestering agent is included in shampoo to prevent
discoloration and to improve the performance of the anti
microbial agents by forming soluble complex with metal ions.
➢ Shampoo in clear packaging should contain a UV absorber,
e.g. benzophenone-4, to protect against color fading and other
reasons upon prolonged exposure to light.
5. Preservatives
Are essential component of a shampoo formulation to protect
against microbial growth.
E.g. parabens.
17
 Effect of shampoo on hair

Shampoos are also involved in damage of hair, either directly;

through removal of structural components of the hair fibers,
of indirectly; through removal of protective deposits on the
hair.

1. Direct damage:
Studies indicated that the nonkeratinious regions of the hair,
which include the endocuticle, or inner portion of the cuticle,
and the cell membrane complex are susceptible to damage by
surfactant molecules.
Exposure to shampoos can have deleterious effect on hair
structure over time.

2. Indirect damage:
It is a result of fiber abrasion occurring when hairs are
rubbed against each other during cleaning. More important is
the removal of sebum from the fiber surface during
shampooing (sebum act as natural lubricant for hair).
18
 Shampoo benefits

Shampoo formulations are classified into four

basic functions:
Cleaning, mild (or baby), conditioning, and
antidandruff.

‫ ٭‬Mild or baby shampoos is required to allow only

minimal eye, scalp, and skin irritant.
They often contain mild surfactant systems,
such as nonionics and amphotrics.

19
Examples of shampoo’s formulas
Cleansing shampoo
Ingredient %
Ammonium lauryl ether 15
sulfate
Cocamide DEA 2
Cocamidopropyl betain 2
Fragrance 0.7
Preservative 0.5
Citric acid 0.1
Ammonium chloride 0.2
Color 0.001
Water q.s
20
 Baby shampoo
Ingredient %
PEG-80 sorbitan 12
laurate
Sodium trideceth 5
sulfate
Sodium 5
lauroamphoacetate
PEG-120 methyl 2
glucose dioleate
Cocamidopropyl 1
hydroxysultaine
Fragrance 0.7
Preservative 0.5
Color 0.01
Water q.s

21
Conditioners

22
Does hair need conditioner?
Conditioners are formulated to impart conditioning to
hair, for example; improve combing, softness, and
manageability, in addition to the usual cleaning
benefits.

Physical damaging effect:

♦ Wind, weather, ultraviolet radiation, brushing and
combing.

Chemical damaging effects:

1. Shampoos which remove natural lipids
2. Dyeing require preliminary bleaching
3. Bleaching with alkaline hydrogen peroxide
Drastic treatment which cause severe weakening of
the hair fibers and loss of elasticity
4. Permanent waving
Where peroxide and thioglycollate attack the
disulphide and peptide bonds of keratin.

23
➢ Conditioning term is difficult to define

The process of conditioning involves at

least four functions:
1. Rendering the hair manageable, easy to comb and
set.
2. Preserve its natural appearance and luster.
3. Exerting a softening effect.
4. Giving “BODY” to the hair.

24
 Conditioners ingredients

Emollients

Compounds containing positively

charged nitrogen

Acids

Proteins

25
Emollients

Oil adheres to hair fibers → body + luster +

lubrication
Excessive greasiness can be overcome by applying
the lipid in the form of diluted O/W emulsion and
by using high melting point lipids, such as
cetostearyl alcohol.

➢ Vegetable oil, lanolin and its soluble derivatives

(POE or quaternaries), synthetic esters, sebum
substitutes, Octyl stearates and Squalene

➢ Silicones have high refractive indices, and are

therefore good luster producing compounds.

26
 Compounds containing positively charged nitrogen

Keratin contains more acid groups than basic groups,

and therefore tend to attract positively charged
molecules and ions.

1. Cationic compounds (quaternary ammonium

compounds), a typical example → cetrimide
2. Amidoamides (tertiary amines).a typical example →
stearamidopropyl dimethylamine lactate
3. Alkanolamide, example → Coconut diethanolamides
4. Ampholytes, example → N- alkylbetaines as anti
irritant.
5. Polyvinylpyrolidone (PVP).

27
 Acids

The conditioning effects of weak acids have been

known since ancient times (lemon juice, vinegar)

1.They dissolve calcium and magnesium deposits.

2.Neutralize excess alkali after bleaching or
permanent waving.
3.Precipitate the soluble keratin products resulted
from the rupture of peptide bonds by the action of
peroxide or thiglycollate.

➢ A suitable lipid mixture is emulsified with cationic

surfactant → O/W and a small quantity of weak
organic acid and protein can be added.

28
 Proteins

Proteins are actually mixture of:

1. Proteins
2. polypeptides
3. peptide
4. amino acids

We can prepare them by hydrolyzing protein

usually with enzyme → Collagen, Milk, Oats,
Wheat, Soya.

29
 Protection of hair treated by protein

Cosmetic process without protein with protein

Bleaching Cuticle removed Cuticle intact

Waving Extensive damage Swelling, but no

damage

Its recommended that protein hydrolsates are used

before, with or after the chemical process.

30
Absorption of protein fragments has
been demonstrated in several ways:

1.Treatment with – methionine was found

to retain radioactivity after rinsing.
2.Stronger color and ninhydrin, transverse
section stained more deeply
3.Hydroxyprolin of collagen ( analysis)

Undamaged Moderately Bleached

Absorbed bleached waved

0.08% 0.2% 3.0%

31
 Example of conditioner formula

Ingredient concentration %

Primary surfactant 12-20

Dehydrogenated tallow Phthalic 4-7

acid amide

Dimethicone 0.5-3

Cocamide DEA 1-5

Miscellaneous q.s

32
 Hair Dyes
Hair dyes fall naturally in three
classes:
1- Temporary
2- Permanent
3- Semi-permanent
4/19/2021 1
 Temporary Dyes
• Which last, at the most, until the next
shampoo
• These take the form of a modified setting
lotion.
• A suitable dye or mixture of dyes is added
to a solution of a film former, on drying a
colored transparent envelope is left around
each hair fiber.

4/19/2021 2
 Permanent dyes
• They are also called oxidation or para
dyes.
• They are uncolored molecules which are
small enough to pass between the pores
of the cuticle into the cortex.
• Once inside they polymerize to form large
colored molecules which are too big to
leave the hair by the same route as they
entered
4/19/2021 3
The basis of permanent dyes is:
• p-phenylenediamine

Or its derivatives, e.g.

• p-toluenediamine

4/19/2021 4
4/19/2021 5
 Permanent dyes
• These molecules are small enough to enter the
cortex when applied in alkaline solution, which
swells the hair and provides easier access.
• The dye mixture, dissolved in ammonia solution
is mixed with hydrogen peroxide immediately
before application.
• The diamines penetrate the hair, where they are
oxidized to form quinone, which polymerizes
(Eq. 1)

4/19/2021 6
4/19/2021 7
 Permanent dyes
• The polymer is a long
chain of alternating
double and single bonds,
and is therefore dark
brown to black in color.

• The color of the polymer

is varied by complexing
other compounds with it.
• Thus catechol (III) gives
gray color,
• 2-nitro-1,4-
phenylenediamine (IV),
brownish red, and so on.
4/19/2021 8
4/19/2021 9
 Semi-permanent dyes
• They vary in efficiency from a very
good temporary to a poor permanent.
• They have moderate resistance to
shampooing.
• Hydrogen peroxide is not used in their
devlopment.

4/19/2021 10
 Semi-permanent dyes are
classified as follows:
1- Fiber reactive dyes
These become fixed to the hair through
chemical groups on the dye molecule,
which interact with keratin.
- Basic dyes : have positive charge on the
active part of the molecule. Methylene
blue is an example, they are substantive to
hair and, unfortunately to the scalp.

4/19/2021 11
Fiber reactive dyes
• Basic dyes have the disadvantage that they are
not fast to light.

- Acid dyes : have negative charge which usually

comes from a sulphonic acid group as with
orange G (VI), but some time carboxy group is
involved.
4/19/2021 12
Fiber reactive dyes
• Acid dyes are fast to light, but are not substantive to hair
as they are negatively charged.
• To over come this difficulty, they use the color rinses
which are powder mixtures consisting of 1 to 10% of acid
dye mixture with an organic acid, such as citric or tartaric
or sulphamic acids.
The acid protonates keratin in accordance with Equ. (1)
and (2), with the result that the hair becomes positively
charged and the acid dye becomes substantive to the
hair.
COO- + H+ COOH
NH2 + H+ NH3+

4/19/2021 13
Acid dyes
• A more recent trend is
to synthesize dyes
which contain at least
one quaternary
ammonium group.
- Basic brown 16 (VII)
is an example. It
gives a mahogany
color and does not
fade.
4/19/2021 14
2- Oxidation dyes
These are so called because the dye molecules are similar
to those used in permanent oxidation dyes

a- Nitro dyes - are small, colored

molecules which pentrate the cuticle
and remain in the cortex. Because
they are small molecules, they are
gradually leached out with
subsequent shampooings
- Examples are
2- nitro-1,4-phenylenediamine (red)
and 4- nitro-1,2-phenylenediamine
(yellow)
4/19/2021 15
2- Oxidation dyes
b- Dyes developed by atmospheric
oxidation
- are colorless molecules which
develop a color on contact with
the atmosphere.

Example – 2,4,6- Triaminophenol.

It is applied as 3% solution at pH
8 and the color develops in about
15 minutes.
4/19/2021 16
3- Solvent assisted dyes
• In the textile industry, dyes are applied to
wool from a hot nearly boiling dye bath.
• This is obviously too hot for human hair.
• Temperature is also a problem in textile
industry, because wool shrinks at high
temperatures.
• This has been overcome by adding an
organic solvent to the dye aqueous
solution.
4/19/2021 17
3- Solvent assisted dyes
• The solvent must be only sparingly soluble in
water, and good solvent for the dye, but not as
good as the hair. The aqueous phase then acts
as a reservoir from which the dye is transferred
continuously to the fiber.
• Benzyl alcohol (soluble 1 in 400 in water) is the
most popular solvent.
• An electrolyte, e.g. sodium sulphate or formic
acid are added to reduce solubility of acid dye.

4/19/2021 18
4- Disperse dyes
• Are water insoluble dyes which are applied to
the hair as an aqueous suspension.
• The dyes are hydrophobic, and as such are
substantive to keratin
5- Metallic dyes
The most commonly used materials for this
method are lead acetate. A suspension of
precipitated sulfur in lead acetate solution,
applied daily, will slowly deposit a mixture of lead
sulfide and lead oxide on the cuticle, so that the
hair slowly darkens.

4/19/2021 19
6- Vegetable dyes
• Henna (lawsonia inermis)
• Walnut (Juglas regia)
• Commomile
• Hibiscus
• Senna (Neutral henna)

4/19/2021 20
 A quantitative study of the effect of pH on the dyeing
process with juglone
B. I. AMRO, Faculty of Pharmacy, University of Jordan
Visiting Associate Prof., Faculty of Pharmacy, Amman University

• Bleached wool felts have been dyed with juglone, the

principal coloring agent of walnut.
• A dissolution technique that could evaluate uptake and
substantivity was adopted. The mass of juglone removed
from the wool was assessed from the reflectance
readings related to changes in L.a.b. values of dyed felts
which were recorded before and after extraction.
• A theory linking dyeing performance to
electrolytic dissociation of juglone and keratin
protonation was developed from the results.

4/19/2021 21
• The UV spectra of juglone solutions go through an isosbestic point
of 265 nm, suggesting that the ionized and the unionized species
are involved in pH-dependent equilibrium (Eq. 1).

O
O

+ H+

-O O
OH O

4/19/2021 22
 Table I - L.a.b. Values of Wool Felts after Dyeing with
Juglone at Various pH Values

pH
3 4 5 6 7 9
L
Before dissolution 48.96±0.34 48.05±0.44 47.22±0.26 47.73±0.76 52.24±0.69 54.74±0.90
After dissolution 47.89±0.63 47.93±0.96 46.76±0.96 47.06±0.54 53.26±0.29 56.76±0.55
a
Before dissolution 14.29±0.36 14.17±0.49 14.44±0.36 14.16±0.51 12.74±0.33 8.69±0.11
After dissolution 14.46±0.23 14.43±0.42 14.33±0.51 13.18±0.23 13.08±0.72 8.24±0.10
b
Before dissolution 31.95±0.42 31.70±0.22 31.97±1.01 31.38±0.71 27.90±0.46 23.94±0.12
After dissolution 30.94±0.43 30.90±0.62 31.10±0.12 31.53±0.43 30.77±0.40 26.37±0.46
a/b
Before dissolution 0.45 0.45 0.45 0.45 0.46 0.36
After dissolution 0.47 0.47 0.46 0.42 0.42 0.31
Δa 0.17 0.25 -0.11 -0.98 0.34 -0.45
Δb -1.01 -0.80 -0.87 0.14 2.87 2.42

4/19/2021 23
 Table II - Distribution of Charged Species in Keratin
and Juglone at Various pH Values

pH
________________________________________
3 4 5 6 7 9
Percentage of total charged
Species in keratin
Positively charged 99.95 99.5 95.0 50.0 5.0 0.05
Negatively charged 0.05 0.5 5.0 50.0 95.0 99.95
Percentage of total
Juglone molecules
Anion 18.0 68.75 95.72 99.55 99.95 100.0
Undissociated 82.0 31.25 4.28 0.45 0.05 0.0

Relative probability
of interaction 100 100 95 50 5 0
_____________________________________________________________________

4/19/2021 24
Hair Styling Products
- Laquers, Sprays
- Gels, mousse

1
Lacquers, Sprays

 Quick – drying preparations which are

sprayed onto the dry hair.

 They vary from Normal to Hard to

extra hard holding.

 Are presented either as puffer spray

or more commonly as an aerosol.

2
Setting lotions, Gels, &
mousse
- These are applied to wet hair. The
hair is then molded to the required
style and dried.

- Styling preparations consists of a film

former, usually a synthetic polymer
dissolved in a suitable volatile solvent,
which evaporates leaving the polymer
in the form of a thin sheath.
3
The properties of the film
1- It must have good holding ability
2- It should be flexible, so that the hair can be
combed easily without the film flaking.
3- The preparation should dry rapidly, without
becoming tacky. (especially with lacquers
and sprays).
4- The film must be clear, otherwise the hair will
lack sheen.
5- It should also be resistant to changes in
atmospheric conditions; a humid climate
render the film tacky, and an arid climate
produce a brittle or an opaque film.
6- The polymer should be easily washed out.
4
Solvents
1- Water is not a good solvent for lacquers, it dries too
slowly. It also presents formulation difficulties with
aerosols.
Setting lotion and gels contain water.
2- Ethanol – An excellent solvent. It almost odorless, and
evaporates easily. Its main disadvantages are cost and
legal restrictions.
3- Denatured ethanol – 39 parts of ethanol mixed with 1
part of isopropanol.( cheap)
4- Isopropanol – is a good solvent, cheap, volatile,
completely miscible with water, and not legally
controlled. It has a characteristic unpleasant odor,
which is difficult to mask.

5
Film formers

1- Shellac – The oldest film former, but it is still

used in cheap hair sprays.
- It is a resinous substance prepared from a
secretion which encrusts the bodies of a
scale insect, Laccifer lacca.
- Shellac occurs in many grades, the best are
light in color, bright and transparent, and in
the form of scales.
- It has tenacious holding power.
- Applied as a solution in ethanol, isoprapanol

6
Film formers

Shellac disadvantages:
- Variable composition associated with all
natural products.
- Its yellow color makes it unsuitable for very
fair hair.
- Its Insoluble in water and detergent
solutions, so that it is difficult to remove
from the hair.
- The film produced is brittle.

7
Film formers
2- Polyvinylpyrolidone (PVP)
- Is a polymer which is soluble in water,
ethanol, and most propellants.
- Substantive to hair (positive nitrogen)
- It gives the hair a pleasant soft feel,
due to the moisture content of the film.
- It is easily removed by shampooing

8
 Film formers
2- Polyvinylpyrolidone (PVP)
 The major disadvantage
of PVP (I) is that it is very
susceptible to
atmospheric conditions,
becoming dry and brittle,
flaking off in arid climates,
and becoming sticky in
high humidity.

9
 Film formers
3- PVP/ Polyvinyl Acetate
(PVP/VA)
 These consist of polymeric chains
in which PVP and VA (II) are
joined together in a random
fashion.
 It combines the substantivity and
water solubility of PVP and VA’s
resistance to atmospheric
conditions.
 PVP/ VA 60/40 for normal use
 PVP/ VA 70/30 for hard hold
situations

10
 Film formers
4- Polystyrene/ Sodium
Sulphonate
 It is readily soluble in water,
and is stable over a wide
range of pH, but insoluble in
ethanol and isopropanol.

 It is claimed to form a hard

tough and clear film.

11
Additives

 Plasticizers – 10% of the film former are

added to increase the flexibility of the film.
- Examples are phthalate diesters, castor oil,
isopropylmyristate and polyethylene glycol.
 Luster giving additives – when the hair is
dry it lacks luster, and the effect is
potentiated by the transparent film. Lanolin,
castor oil and silicon oil are used for this
purpose.

12
Additives
 Dispersants - In badly formulated preparations,
individual droplets can remain static on the hair, dry,
and form “hotspots”. Sometimes two hairs become
stuck together by a hotspot.
- This can be overcome by adding a dispersant
(Surfactants).
 Antistatic agents - Polymer films, like other plastics,
tend to accumulate static electricity, which in turn
attracts dust. Cationic surfactants and diethanolamides
are used as antistatics.
 Perfumes -They may have a plasticizing effect on the
film, rendering it too soft, or sticky. (perfume selection)

13
Waving and relaxing preparation
 Waving and relaxing preparation

• From the time when early Egyptian curled

their hair by means of wet mud, and
through the Romans up to present day, the
desire of all women has been to possess
an attractive & beautiful coiffure.
• Curly or wavy hair is more attractive than
straight hair & at the same time provides
more opportunities for rearrangement in a
suitable fashionable styles.
Basically these processes involve breaking the
bonds holding the polypeptides chains of keratin
together, and restoring them in a manner which
imparts the desired shape to the hair

Hydrogen bonds Water

Salt Link Strong acids , strong alkali

Disulphide Bonds Reducing agents

 Waving

The first P. Waves :

Electric heaters + alkaline solution, based on ammonia and / or borax
to break salt and peptide,
later sodium sulphite was added disulphide bond

Disadvantages:
1- rebuilding by atmospheric oxidation
2- High pH 3- long Processing time

Major breakthrough came with :

Thioglycollic acid, capable of reducing disulphide bonds at
moderate pH and reasonable processing times.
 Reactions involved

polypeptide – S – S – polypeptide 2 Polypeptide – SH

pH values between 9-9.5 recommended by using ammonium

Hydroxide Bad small (Rotten eggs).

Sodium Hydroxide
Ammonia (Upper pH 10) , Monoethanlamine Not volatile
 Neutralizing or rebuilding by Oxidation :

this involve :
1- Oxidation of excess thioglycolate and the hydro sulfide groups on
the hair
2- Reduction of the pH
3- Drying

Can be achieved by:

1- atmospheric oxygen
2- more effective with hair dryer
3- most commonly used, hydrogen peroxide lotion.
Low pH Waving Lotions
1- increasing concentration 2- temperature or 3- Swelling agent

1) 19 % solution of ammo. thioglycolate buffered at PH 7 perms

in less than 10 minutes.
2) Ammoium thiogl. at pH = 6 + swelling agent (urea) to
accelerate the process
3) Glyceryl monothioglycollate, with heating cap.
CH2O . CO. CH2 -SH
I
CHOH
I
CH2OH
Low PH Waves Hazard

Low pH increase lipid solubility

Increase percutaneous absorption and toxicity.

Additives

Cold wave lotions are extremely reactive , additives should be tested

on mixing and after storage.
1) their effect on the pH of the solution
2) their effect on the reducing power.
3) the effect of pH and thioglycollate on the additives.
4) the combined effects on the hair, scalp.
 Wetting agents

The ensure contact and to facilities penetrations of the hair shaft.

Cationic can be used, but non-ionics (Polysorbate-80) are preferred.

Opacifiers
To give richness and mildness latex suspensions, or emulsions
The effect of waving lotions on the hair
Stress elongation
Normally the hair breaks at 60% elongation.

The stress / strain at the first inflection will never returns to normal.
1- some of the peptide links broken
2- hydrosulphide not finding them sufficiently near.

Relaxing

- Thioglycollate usually to mild.

- Sodium Hydroxide is the most common. In which the C-S bond of

cystein rather than S-S which is attacked.
Sunscreens
 Sunscreens
Sunscreens were first developed for soldiers in World War II to
absorb “sunburn causing rays”. The red veterinary petrolatum which
is working as a physical blocker of ultraviolet radiation. (but it is red
and sticky substance).
Exposure to sun light leads to erythema (reddening) which leads to
Formation of tan (protective reaction of human body).increase
melanin production.
The sun emits constant flow of energy in the form of
electromagnetic radiation.
The lower energy radiation takes the form of electric & radio
waves with wavelengths up to 105 m .
Middle -the optical range = UV (100-400) nm Photo-chemical
effect.
- Visible light (400-800)nm (light effect)
- (800-1000)nm is near IR (detected as heat).
Highest energy; its represented by (gamma and cosmic rays).¹
The classification of UV radiation according to
physiological effects :
1- UV A range, 320 - 400 nm: . Vitamin D production Which effects
direct tanning of the skin without erythema ( sunburn). it causes
wrinkles and accelerates aging of the skin.
2-UV B range, 280 - 320 nm: UVB are erythemogenic radiations,
produce sun burn irritating reactions and stimulate the formation of
melanin which leads to the development of tan.UVB causes
cataracts, immune system damage, and skin carcinomas.
3-UV C range, 100 - 280 nm:(germicidal UV) , absorbed by the ozone
layer and does not reach the earth.¹
The sun’s light is strongest when it is highest in the sky (normally from
10 AM to 4 PM). UV rays are strongest during the summer. ¹
UVA radiation is stronger in the early morning and late afternoon
when the sun's rays reach the Earth at an angle².
UVB radiation is stronger between late morning and early afternoon
when the sun's rays are directed straight down at the Earth.³
Tanning:
Exposure to sun light leads to erythema (reddening) which leads to
Formation of tan (protective reaction of human body).increase
melanin production. ¹
Melanin is synthesized in the melanocytes found in the epidermal
basal layer, within the melanocytes melanin is bound to protein
matrix to form melanosomes. The melanocytes transfer their
melanosomes to surrounding keratinocytes and migrate upward
through the epidermis.
Direct effect of UV radiation
In UV-induced melanogenesis
1-UVR activate Nitric oxide (NO) syanthase and 2-the resulting NO
produced by melanocytes and keratinocytes activates the
melanocytic-soluble adenylate cyclase. 3-This leads to higher
concentraions in cyclic guanosine monophosphate (cGMP)
4-which in turn stimulate melanogenesis (increase pyrimidine dimers)
via the enhancement of tyrosinase expression and activity.⁴
 UV-A radiation creates oxidative stress, which in turn oxidises
existing melanin and leads to rapid darkening of the melanin. it does
not lead to greatly increased production of melanin.⁵
UV-B radiation increases production of melanin
(melanogenesis), which is the body's reaction to direct photodamage
(formation of pyrimidine dimers) from UV radiation.⁶
There are three types of Tanning:
1. Immediate tanning: (300 – 660) nm. Involves the immediate
darkening of unoxidized melanin granules. It reach maximum after
one hour and begins to fade 2—3 hrs after exposure. UV-A
2. Delayed tanning:(295-320 )nm. Involves the oxidation of melanin
granules present in the basal cell layer of the epidermis and their
migration towards the surface of the skin. Starts one hour after the
exposure and fades rapidly after 100-200 hr following the
exposure.
3. True tanning:(295-320 )nm. Starts two days after exposure, it
reaches its maximum about (2-3) weeks later. UV-B¹
 Adverse effects of sunlight:
-Short term effect Sunburn:
Temporary damage of the epidermis.
-Symptoms:
slight erythema, painful burns, Blistering followed by peeling, fever,
nausea and pruritus.
-A first-degree sunburn reddens the skin.
-A second-degree sunburn causes reddening of the skin with
some water blisters¹⁰.
-Sunburn of skin is a direct result of:
1-Denaturing of its protein constituents.
2-Histamine like substances released by the damaged cells are
responsible for the dilation of blood vessels and erythema and
swelling (edema).
3-Photochemical degradation products which trigger a series of free-
radical reactions leading to the formation of the biologically active
substances Produce symptoms described.¹
 -Chronic Exposure:

Mainly affect (sailors, farmers, and construction workers)

This long term effect can cause:

1-The development of skin cancer.

2-Degenerative changes in the connective tissue of the corium,

(premature aging of the skin).
-loss of natural elasticity.
-appearance of’ wrinkles.
-thickening of the skin.
all resulting from the loss of the skin’s water- binding capacity.(TEWL)

3-Increased tendency to form skin blemishes.

4-Berlock dermatitis ( irregular discoloration), bergamot and other

citrus oils followed by exposure to sunlight (perfume).¹
 -Beneficial Effects Of Sun light:
1-Psychologically & physiologically in general sense of fitness,
peace of mind & general well being.¹
- Sunlight stimulates the production of Serotonin, a neurotransmitter in the
brain that regulates mood. Moderately high serotonin levels result in more
positive moods and calm yet focused mental outlook.
-Sunshine decreases the symptoms of depression by releasing endorphins.
Endorphins are the body's natural anti-depressants and are very beneficial
in cases of seasonal depression.⁷
2-It stimulates blood circulation.¹ Sunshine enhances blood circulation
by dilating blood vessels in the skin. This brings more nutrients and oxygen
to cells when capillaries are open resulting in a better health.⁷

3-Increases the formation of hemoglobin.¹Sunlight greatly increases

the body's consumption of oxygen. Through added numbers of red cells
and increase in their hemoglobin, the oxygen carrying power of the blood
is increased.⁷

4-Promote reduction in Blood Pressure.¹It makes the heart healthier by

lowering the resting pulse rate and decreasing blood pressure⁷.
5-Prevention &treatment of Rickets.¹ Sunlight stimulates the body
to create vitamin D. A single sun exposure to the face, neck, arms
and legs for 10-15 minutes can produce anywhere from 1000
international units (IU) to 3000 IU of vitamin D depending on your
skin type, which is all that is required by your body in a day. This
vitamin promotes the absorption of calcium in the gut and transfers
calcium across the cell membranes, which provides strength to the
bones. Vitamin D can offer protection from some cancers (such as
lung, prostate, colon and skin cancer), osteoporosis, rickets and
diabetes. It also helps to lower blood cholesterol levels thus helping
to fight heart disease.⁷

6-Treatment of Psoriasis.¹The mechanism of action probably

involves activation of psoralen by UVA light which inhibits the
abnormally rapid production of the cells in psoriatic skin. There are
multiple mechanisms of action associated with PUVA, including
effects on the skin immune system (reduces the number of dendritic
cells).⁸

7-Formation of the body’s natural protective mechanism against

sun burn by thickening the skin & producing Melanin.¹
 -Protection of the skin by radiation-screening agents

Anytime light interacts with some material, 3 things can happen.

The light can be transmitted, it can be reflected, or it can be
absorbed
If we say that light is “blocked” it means that it is either absorbed or
reflected by the material

In principle two groups of substances offer themselves as

alternatives. One is opaque to radiation and largely reflects the
radiation, whilst the other group absorbs the harmful rays but is
transparent to the remainder of the radiation.¹
 -

Skin type & recommendations for the choice of sunscreens:

Individuals can be classified into 6 skin types:
I-Always burns easily; never tans (sensitive).SPF 30-50
II-Always burns easily; tans minimally (sensitive).SPF30-50
III-Burns moderately ;tan gradually, light brown (normal).SPF15-30
IV-Burns minimally; tans well, moderate brown (normal).SPF10-15
V- Barely burns; trans profusely, dark brown (insensitive).SPF5-10
VI- Never burns ;deeply pigmented (insensitive).Sunscreens None
indicated
 SPF
SPF = (UV energy required to produce minimal erythemal dose on protected skin)
(UV energy required to produce minimal erythemal dose on unprotected skin)

• Similarly,

• SPF= MED(PS)
MED(US)
MED is defined as the minimum quantity of radiant energy of specific wave
length or range of wavelength which produce the first unambiguous Redding of
human skin 24hr after exposure.
 The Sun Protection Factor(SPF):
• SPF Number (Sunburn Protection Factor) measures
the strength of UVB protection only. Higher SPF
number reflects more protection from UVB, but it
doesn’t correspond to UVA protection.(5-50)
• The FDA has just proposed a 4-star UVA rating,
previously adopted by Boots, to be included on
sunscreen labels.¹
• Highest ★★★★ High ★★★☆ Med★★☆☆
Low★☆☆☆
 -Sunscreen Agents

Sunscreen agents can be classified into organic & inorganic

sunscreens.
Organic Sunscreen:
Organic ingredients involve carbon and hydrogen atoms. Hydrogen,
oxygen & nitrogen atoms are also often involved. They exist as
individual molecules.

Molecules capture energy from the sun’s UV rays . Electrons capture

the energy from UV rays. They jump to higher energy levels. The
energy give the molecule thermal motion (vibrations and rotations),
the energy is released and re-emitted as harmless long wave infra-red
rays¹.
Each organic ingredients has a specific absorption range. Organic
molecules only absorb UV rays whose energy matches difference
between electron energy levels.
Using more than one kind of sunscreen ingredients gives broader
protection as they have different peaks and ranges of absorption.
Most organic ingredients that are currently used were selected
because they are good UVB absorbers.¹
 -UV A Sunscreens:

1. Benzpheneones (3,4,8):
Benzophenone-3 absorption peak is (320)nm used as UVA up to
10%, it may combined with UVB to give broad spectrum protection.
2. Anthrnilates:
Menthylanthrnilates it is usually used as UVA, the absorption peak
at (336)nm & can be used up to 5%.
3. Avobenzone (also known as Parasol 1789) is not intrinsically
photostable and requires photostabilizers to prevent significant
degradation in light.
4. Ecamsule (Mexoryl SX) is a new sunscreen ingredient designed to
absorb UVA rays. Ecamsule (trade name Mexoryl SX, INCI
terephthalylidene dicamphor sulfonic acid) is an organic compound. It
is a benzylidene camphor derivative, many of which are known for
their excellent photostability. (meaning it doesn't degrade
significantly when exposed to light).¹
Although there are a few different UV absorbers with the trade name
Mexoryl, only two of them are widely used where approved. Mexoryl
SX (water soluble) and Mexoryl XL (INCI Drometrizole trisiloxane, oil
soluble). Together they show a synergistic effect in protection.The
patents are held by L'Oréal. Sunscreens containing ecamsule are
exclusive to L'Oréal and its brands.¹
 -UV B Sunscreens

1. P-Amino Benzoic Acid (PABA) derivatives:

The most commonly used is Padimate Octyl Dimethyl PABA,
the allowable level is 8% & the absorption peak is (311)nm.

2. Cinnamate derivatives:
e.g.: 2-ethylhexyl-P-methoxycinnamate (Octyl Methoxy
Cinnamate), the allowable level is 10% & the absorption peak is
(311)nm.
Estrogenic effects were noted in laboratory animals at
concentrations close to those experienced by sunscreen users .
However, a more recent study concluded that octyl
methoxycinnamate and other sun screening agents do not
penetrate the outer skin in sufficient concentration to cause any
significant toxicity to the underlying human keratinocytes.¹
3-Salicylate derivatives :
Such Octyl salicylate & the allowable level is 5%. Homosalate
(Homo methyl salicylate), absorption max. 306nm, 10-15%
4. Octocrylene (Cyno diphenyl acrylic acid, ethylhexyl ester):
Its allowable level up to 10% & has absorption max. 303nm. The
extended conjugation of the acrylate portion of the molecule absorbs
UVB and short-wave UVA (ultraviolet) rays with wavelengths from
280 to 320 nm, protecting the skin from direct DNA damage. The
ethylhexanol portion is a fatty alcohol, adding emollient and oil-like
(water resistant) properties.
5- Phenylbenzimidazole , 290-340
6- Octyl triazone [Uvinul] 290-330
Inorganic (physical) sunscreens:
1.Zinc oxide:
2.Titanium dioxide:
- These either reflect light depending on the wavelength of the light
& the particle dimensions of the physical sunscreen or absorb UV
light.
Small particle size (nano size) leads to decrease in skin whitening as
more of the longer wavelength light transmitted until little or no
reflection occurs.
Inorganic sunscreen ingredients are different from organic ones.
This affect the way they absorb UV light.
The ionic attraction molecules forms clusters.
Size varies with number of ions in cluster. Typically ~10 nm – 300
nm.
Inorganic ingredients come in different cluster or “particle” size.
Different number of ions can cluster together
Inorganic sunscreens appear white on our skin. Many people don’t
like how this looks, so they don’t use sunscreen with inorganic
ingredients or apply too little to get full protection.¹
Traditional ZnO and TiO2 products appears white because:
1. Their clusters are large (> 200nm). Large clusters can scatter light in many
different directions
2.When reflected visible light of all colors reaches our eyes, the sunscreen
appears white. Organic sunscreen molecules are too small to scatter visible light
Nanosized inorganic clusters would not scatter visible light as they are smaller
(100 nm or less) than that of traditional.
Nanoparticle sunscreen ingredients are small inorganic clusters that:
1-Provide good UV protection by absorbing most UVB and UVA light.
2-Appear clear on our skin because they are too small to scatter visible light.¹

Nanosized Large
ZnO ZnO
particles particles

~ 100nm ~ 200nm Traditional

 -Natural alternatives to chemical sunscreens:
Black tea:
The study published in the International Journal of Cosmetic Science, reports
that erythema appeared after 4 h and reached a peak at 24 h on control site,
whereas no erythema was observed in any of the six subjects on black tea gel
applied sites. it was concluded that black tea gel protected the skin from a
broad range UV (200–400 nm) radiation and can be safely applied on large skin
surfaces.
Green tea:(Camellia sinensis)
The polyphenols present in green tea are known as
epicatechin. The major epicatechins found are epicatechin,
epicatechin-3-gallate, epigallocatechin and epigallocatechin-3-gallate (EGCG).
These epicatechin are antioxidant in nature and have been shown to function
as anti-inflammatory and anti-carcinogenic agents in various biological models
in vitro and vivo.¹
Chronic exposure of human skin to solar UV radiation is the primary cause of
cutaneous malignancy.
The two main photo-protective effects of Green Tea are: anti-inflammatory
effects and anti-carcinogenic effects.¹
1-Topical application of green tea polyphenols (GTP) or EGCG to the
backs of human before UV irradiation result in less erythema
development, decreased myeloperoxidase activity and infiltration of
leukocytes as compared to UV alone (without GTP or EGCG) exposed
skin sites.
2-EGCG was also found to inhibit UVB-induced production of
prostaglandin metabolites, which play a critical role in inflammatory
disorders and in proliferative skin disease.
3-Topical application of GTP inhibited photo-carcinogenic and lower
tumor burden as compared to non-GTP-fed control animals.
Green tea, specifically EGCG, has the ability to block UVB-induced
leukocyte infiltration in mouse as well as in human skin, and thus
may be able to inhibit UVB-induced production of ROS (reactive
oxygen species ) by these infiltrating leukocytes .
Although ROS help the host to destroy invading microorganism,
excessive and uncontrolled production can also damage host tissues
and predispose to various diseases. Thus, the application of EGCG
may prove helpful in decreasing the harmful effects caused by UVB
exposure through decreased ROS production by acting at different
active sites of the ROS generating cascade.¹
EGCG treatment of mouse skin before UV exposure results in:
1. Decrease number of hydrogen peroxide producing and inducible
nitric oxide synthase expressing cells, and reduction in the
production of hydrogen peroxide and nitric oxide.
2. Inhibition of UV-induced epidermal lipid peroxidation, which
may protect human skin from solar UV light-induced basal cell and
squamous cell carcinogenesis and photoaging.
3. Protection of anti-oxidant enzymes in human skin.
4. Decrease the formation of cyclobutane pyrimidine induced in
DNA by UV radiation. These cyclobutane pyrimidine dimers are
critical in initiating the process of UV-induced mutagenesis and
carcinogenesis.
It’s reported that a number of tumors appear to produce IL-10.
The immunosuppressive effects of IL-10 might be one possible
mechanism by which these tumors escape immunologic control. It
was found that application of EGCG before UV exposure reduced
the UV-induced production of IL-10 and UV-induced
immunosuppression in the skin and draining lymph nodes, and
increase the production of IL-12 in draining lymph nodes.¹
 - -Artificial Suntan preparation :

1-Artificial suntan preparation stains(walnut juice, henna).

2-Dihydroxy acetone(DHA):
- colorless lotion produce gradual tanning within 6 hours of
application.
- Investigation showed that :
The DHA reacts with free amino groups, in particular with the free
amino group in Arginine forming aldehyde-amino products which
condense & polymerize to form dark-colored melanoidins.

3-Photosensitizing Compounds:
Photosensitizing psoralen reacts on exposure to ultraviolet light to
increase the melanin in the skin. Some psoralen-type
photosensitizers are used to enhance skin pigmentation or tanning in
the treatment of skin diseases, such as vitiligo.¹
 -Sunscreen Formulation
Formulation of Water-proof sunscreen products involves the
following recommendations:
1- Use water- insoluble sunscreens.
2-Use high- oil phases.
3- Use water- resistance resins and film-formers. Silicon oil is extremely
resistance to water penetration & easily spread with thin continuous
water repellent film formed such dimethicone350, cyclomethicone .
More recently other film formers have gained favor as water proofing
agents (alkylated polyvinylprolidones are closely related to that found in
film former in hair spray).
4-Use minimal levels of hydrophilic emulsifiers.
5- Use water in oil emulsions.
6- Make an oil in water emulsion invert to water in oil emulsion as it is
rubbed into the skin. A new patent applied by Croda International
A composition contains at least one sunscreen and a protein-PVP
copolymer. The sunscreen may be organic and/or inorganic, particularly
titanium dioxide. The protein-PVP copolymer improves the effectiveness
of the sunscreen, resulting in increased SPF values of the composition.¹
-Sun protection factor study
Emulsion rheology is an important factor influencing the effectiveness
of sun protection products based on physical sunscreens . An
independent study was conducted to evaluate the waterproof sun
protection factor (SPF) of a Crodafos CES (It is a phosphate-based
conditioning and emulsifying system whose phospholipid-like
character creates an ingredient that is naturally substantive to skin as
it is chemically similar to the skin’s lipid bilayer¹³) emulsion compared
to a nonionic emulsion. Results show that Crodafos CES provides
greater oil deposition and improved resistance to wash-off, producing
sunscreen preparations with higher static SPFs and more persistent
waterproof SPFs.¹
Regarding the side-effects of many organic sunscreens, efforts
towards developing safer products. In recent study, titanium dioxide
(TiO2) was incorporated into solid lipid nanoparticle (SLN)
formulations using both classical and novel preparation methods. the
use of crystalline lipid particles as active carriers for physical
sunscreens offers the possibility of creating more effective and safer
sunscreen formulations and gives an opportunity to reduce UV filter
content depending on their crystalline structure with no influence on
their high UV-protection level.¹
Formulation of Mild sunscreen products involves the
following recommendations:

- Minimize emulsifier levels. (Some emulsifying agents can

interfere with chemical sunscreen activity, especially when
higher SPFs are used)
- Minimize the use of soap systems. (Alkaline)
- Minimize the use of preservatives. (Toxicity)
- Minimize the use of fragrances. (Irritation(
- Maximize the use of long-chain esters and other mild
ingredients.(Emollients)
- Minimize the use of high levels of sunscreen actives.(Higher
concentrations of chemical sunscreens potentially irritating)
The sunscreen market is governed by hot trends
concerning the following:
Product claims:
- High-SPF
-PABA-free -
PABA damages cell DNA, thus-
increasing the risk of skin cancer¹⁵. -
-Sensitive skin-
-Non-comedongenic
(oil-free ,won't clog pores)-
- Broad-spectrum
- Water proof

Product forms :
- Sticks, Gels, Pumps and Wipes.¹
Segmentation:
- Infant and toddlers
- Multi-purpose product.
- Skin care, hair care, make-up and foundation.
- Sports enthusiasts.
- Year-round use.
The sunscreen market future prospects involve the following
-Search for new UV-A activities.
- Encapsulated sunscreens. In Sol-Gel Technologies, the
microencapsulation approach loads UV filters into silica shells ,It
may help to lower the incidence of contact allergies¹².
- Micro-sponges. Microsponge delivery systems are uniform,
spherical polymer particles. Long lasting product efficacy, with
improved protection against sunburns and sun related injuries
even at elevated concentration and with reduced irritancy and
sensitization¹⁶.
-Market segmentation:-
a) Melanoma patients :Many cancer patients have sun
sensitive skin due to chemotherapy or radiation
treatments . Some sunscreens provide broad spectrum
UV-A and UV-B coverage .
b) Senior citizens: Seniors only need to apply
sunscreen once a day . They should use a broad
spectrum sunscreen that blocks both UVA and UVB
rays.¹⁷
c) Adolescents .“Time-to-reapply“ sensors.¹
References:
1-Bassam Amro , Sunscreens, University of Joran,Amman , Jordan ,2011(1-27).
2-Parisi AV, Kimlin MG, Wong JC, Wilson M, Personal exposure distribution of solar erythemal ultraviolet radiation in
tree shade over summer,Centre for Astronomy and Atmospheric Research, University of Southern Queensland,
Toowoomba, Australia. 2000;45(2):349-56.
3- Richard L. McKenzie,Lars Olof Björn,Alkiviadis Bais,Mohammad Ilyasd, Changes in biologically active ultraviolet
radiation reaching the Earth’s surface, National Institute of Water and Atmospheric Research, NIWA Lauder, PB 50061
Omakau,(2003, 2, 6)
4-BassamAmro, skinlightining,University of Joran,Amman , Jordan ,2011(1,8).
5- Miyamura Y,The deceptive nature of UVA tanning versus the modest protective effects of UVB tanning on human
skin, Res. 2011 Feb;24(1):136-47.
6- Nita Agar; Antony R. Young (2005). "Review: Melanogenesis: a photoprotective response to DNA
damage?". Mutation Research/Fundamental and Molecular Mechanisms of Mutagenesis 571(1-2).
7- M. Nathaniel Mead, Benefits of Sunlight: A Bright Spot for Human Health,2008 April; 116(4): A160–A167.
8- Menter A, Griffiths CE (July 2007). "Current and future management of psoriasis". Lancet 370 (9583): 272–84..
9-headcovers.com/685/elta-sunblock-spf-32-3.0-oz.
10- emedicinal.com/diseases/sunburn.php
11-healingcancernaturally.com/healingwithlight6.html.
12- Divya R. Sambandan, BA,and Desiree Ratner, MD ,Sunscreens: An overview and update , New York, ( J Am
Acad Dermatol 2011;64:748-58.),page 7
13-croda.com/home.aspx?d=content&s=157&r=401&p=2810
14- dermalinstitute.com/us/news/?p=1266
15-livestrong.com/article/134435-what-is-paba-sunscreen/
16-Viral Shaha ,Hitesh Jain , Jethva Krishna,Pramit Patel,Microsponge drug delivery: A Review, Viral Shaha et al. | Int.
J. Res. Pharm. Sci. Vol-1, Issue-2, 212-218, 2010 P(212,216)
17-slideshare.net/akstout18/sun-safety-1698273
Skin lightening

Dr. Bassam Amro

Color of the skin?
◼ The dermis and epidermal cells gives
yellowish white background according to
skin thickness.
◼ Superficial blood vessels gives red or blue
tone. It varies according to state of nearness
and dilation.
◼ Pigments carotene.
◼ Melanin responsible of racial color
differences.
 Color of the skin?

◼ Melanin is synthesized in the

melanocytes found in the epidermal
basal layer, within the melanocytes
melanin is bound to protein matrix
to form melanosomes.
The melanocytes transfer their m.somes
to surrounding keratinocytes and migrate
upward through the epidermis.
Figure1 Schematic drawing of an epidermal melanin unit showing a melanocyte and the group
of keratinocytes with which it maintains functional contacts. I, endoplasmatic reticulum
where tyrosinase is synthesized; II, premelanosome stage I; III, fully melanized
melanosome; IV, passage of melanin granules from the melanocyte to keratinocytes; V,
liberation of melanosomes free in the cytoplasm of keratinocytes. B.M., basal membranes;
M, mitochondria; MS, melanosome; N, nucleus; E, endoplasmic reticulum; M.G., melanin
granules.
Melanin, the skin pigment
◼ Visible pigmentation in mammals results from the
synthesis and distribution of melanin in the skin, hair
bulbs, and eyes.
◼ Melanin plays a crucial role in:

- the absorption of free radicals generated within the

cytoplasm.
- shielding the houst from various types of ionizing
radiations, including UV radiations.
Thus melanin protects the skin against sunburn, actinic
damage and cancer.
- can act as a thermoregulator by absorbing different
forms of energy and dissipate them as heat.
 Melanins types :
◼ Eumelanins;
which are brown or black.
◼ Phaemelanins;
Which are red or yellow. Interestingly, it
has the capacity to produce free radicals
in response to UV radiation, inflicting cell
injury, contributing to intensify UV induced
skin damage, rather than to protect the
skin.
Melanin biosynthesis
◼ The essential enzyme in the melanin
biosynthetic pathway is tyrosinase.
◼ However, recent studies have shown that
mammalian melanogenesis is not regulated
solely by tyrosinase at the enzymatic level,
and additional melanogenic factors have been
identified, which can modulate pigmentation
in either a positive or negative way.
Tyrosinase, the enzyme
behind the tan
◼ Tyrosinase is a multifunctional, glycosylated,
copper containing oxidase.
◼ Tyrosinase is synthesized by melanosomal
ribosomes found on the rough endoplastic
reticulum.
◼ After synthesis, it is glcosylated.
◼ It is subsequently delivered to melanosomes
via coated vesicles in an inactive form. To
date it remains unclear how tyrosinase is
initially activated.
Tyrosinase, the enzyme
behind the tan
Tyrosinase is the rate-limiting, essential
enzyme. As such it catalyes three different
reactions in the biosynthetic pathway of
melanin :
1-The hydroxlation of tyrosine to 3,4-
dihydroxyphenylalanine (Dopa)
2-The oxidation of DOPA to DOPA-quinone
3-The oxidation of 5,6-dihydroxyindole (DHI) to
indole quinone.
The rate-limiting steps are 1 and 2. The quantity of
melanin synthesized is thus proportional to the
amount of tyrosinase activity present in the cell.
 Albinism
◼ Albinism in humans (from the
Latin albus, "white"; also called
achromia, achromasia, or
achromatosis) is a congenital
disorder characterized by the
complete or partial absence of
pigment in the skin, hair and
eyes due to absence or defect
of tyrosinase
 Phenylketonuria (PKU),
◼ Phenylketonuria (PKU), inborn error
of amino acid metabolism, results
when a deficiency of the enzyme
phenylalanine hydroxylase (PAH)
impairs the body’s ability to
metabolize the essential amino acid
phenylalanine. This leads to
accumulation of phenylalanine in
body fluids.
◼ Many patients are fair-haired, fair
skinned and blue eyed due to the
disruption in melanin synthesis.
Additional melanogenic factors
◼ There is now evidence that dopachrome can
be converted to either 5,6-dihydroxyindole or
the carboxy derivative 5,6-dihydroxyindole
carboxylic acid (DHICA).This step appears to
be catalyzed either by metal ions or by a
recently discovered enzyme, dopachrome
tautomerase (occurs in melanosomes).
◼ Also peroxidases can utilize DHI as a
substrate and thus may play a potential role
in melanogenesis.
Regulation of Melanogensis
Is controlled at many different levels:
◼ Genetic level : Melanocytes are initially derived from
the neural crest and migrate throughout the embryo
during development. These migration patterns are
under strict gentic control and can lead to some
interesting patterns when the final melanocyte
distribution in the skin is not uniform, as in zebras
and giraffes.
◼ Cellular level by melanocytes synthesizing melanin
within melanosomes; in varying sizes, numbers, and
densities.
◼ Subcellular level where the synthesis and expression
of various melanogenic enzymes and inhibitors play a
critical role.
These migration patterns are under strict gentic control
and can lead to some interesting patterns when the
final melanocyte distribution in the skin is not uniform.
Regulation of Melanogensis
◼ Skin pigmentation depends upon the organization and
functioning of epidermal melanin unit and several separate but
related events :

- Melanoblast migration from the neural crest.

- Melanoblast differentiation into melanocytes.
- The rate of synthesis and melanization of melanosomes.
- The size of melanosomes.
- Synthesis of melanin.
- The efficacy of melanosome transfer into keratinocytes.
- The rate of melanosome degradation within the keratinocytes.
- The rate of synthesis, inhibition and decay of tyrosinase.
- Activity of tyrosinase in melanosomes.
 Differences in racial pigmentation

◼ Skin color is a function of the size, number and

distribution of melanosomes, and not of density of
melanocytes. In fact, the number of melanocytes is
the same in all races.
However, melanocytes of darkly pigmented skin
have thicker, longer, branched dendrites.
◼ Melanocytes derived from black skin have up to ten
times more tyrosinase activity and produce up to ten
times more melanin than do melanocytes from white
skin.
The number of tyrosinase molecules present in
white skin melanocytes is equal to the one found in
black skin.
 Differences in racial
pigmentation

◼ In black skin, melanin persists within the

horny layer and leaves the skin in the end by
natural desquamation, whereas in white skin
the pigment is degraded in the granular
layer, probably via specific enzymatic
process.
That means stratum corneum of white skin
does not contain any melanin.
The control of melanin production

◼ Direct effect of UV radiation

◼ Melanocyte stimulatory

hormone (MSH) secreted from

pituitary gland
◼ Oestrogens exert local effect

during pregnancy.
Mechanisms of depigmentation
◼ Selectively destroy the melanocytes
◼ Inhibit the formation of melanosomes
◼ Inhibit the biosynthesis of tyrosinase
◼ Inhibit the formation of melanin
◼ Interfere with the transfer of
melanosomes
◼ Have a chemical effect on melanin