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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 prodection.
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 prodection. 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.⁴
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 tyrosinse 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:
• 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
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
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
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:
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