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Sunscreens

The Sun: The Good & the Bad

BENEFITS: HARMS:
• Heat • Suntan
• Light • Sunburn
• Photosynthesis • Premature aging
• Outdoor environment • Freckles
for physical activity • Liver spots
• Production of • Wrinkles
vitamin D • Loss of elasticity
• Happy and positive • Cataracts
• Suppression of
feelings
immune system
• Actinic keratosis
• Skin cancer
The Sun’s radiation spectrum

Most of the sun’s radiation is Ultraviolet (UV),


Visible & Infrared (IR) :
• ~ 43% is in the
visible range
• ~ 49% is in the near
infrared range
• ~ 7% is in the
. ultraviolet range
• < 1% is x-rays,
gamma rays, radio
waves
Source: Adapted from http://www.ucar.edu/learn/imgcat.htm
Some types of electromagnetic radiation

• The sun emits several kinds of electromagnetic


radiation: Visible (Vis), Infrared (IR) and Ultra Violet
(UV). Note the split into UVA, UVB, UVC

High Energy Low Energy


• Each kind is distinguished by a characteristic
wavelength, frequency and energy
• Higher energy radiation can damage our skin
Source: http://www.arpansa.gov.au/is_sunys.htm
Electromagnetic Spectrum
Check the UV Index Daily
ULTRAVIOLET RADIATION
SPECTRUM

UVA (Longwave Radiation)


• Range 320-400 nm

• Erythrogenic activity is weak, however


penetrates dermis
• Responsible for development of slow natural
tan
• Most drug-induced photosensitivity rxn
occurs
ULTRAVIOLET RADIATION
SPECTRUM

UVB (Middlewave Radiation)


• Range 290-320 nm

• Erythrogenic activity is the highest

• Produces new pigment formation, sunburn,


Vit D synthesis
• Responsible for inducing skin cancer
ULTRAVIOLET RADIATION
SPECTRUM

UVC (Shortwave or Germicidal Radiation)


• Range 100-290 nm.

• Does not reach the surface of the earth.

• Is emitted from artificial ultraviolet


sources.
Skin Damage

• Very high energy


radiation (UVC) is
currently blocked by the
ozone layer
• High energy radiation
(UVB) does the most
immediate damage
(sunburns)
• But lower energy
radiation (UVA) can
penetrate deeper into the
skin, leading to long term
damage
Source: N.A. Shaath. The Chemistry of Sunscreens. In: Lowe NJ, Shaath NA, Pathak MA, editors. Sunscreens, development, evaluation, and
regulatory aspects. New York: Marcel Dekker; 1997. p. 263-283.
What is an SPF?

• Sun Protection Factor


• Typically range from 2 to 60
• Rating is calculated by comparing the amount of
time needed to produce a sunburn on protected
skin to the amount of time needed to cause a
sunburn on the unprotected skin.
Measuring protection

SPF = MED with sunscreen


MED without sunscreen
A measure of protection against erythema
Primarily a measure of UVB protection
MED is the Minimal Erythemal Dose and is
defined as the threshold dose that may produce
sunburn.
MMD on the other hand is the Minimal
Melanogenic Dose and is equal to the lowest dose
required to develop a visible suntan.
SPF determination

• Defined radiation source (solar simulator, natural sunlight)


• Defined skin types of volunteers
• Specified amount of sunscreen (2ml/cm2) / uniformity of
application
• Measurement of erythema
What is UPF or SPF?

• UPF = Ultraviolet protection Factor


or
SPF= Sun protection Factor

• The higher the UPF the more UV


that’s blocked

• SPF is a measure of UVB protection,


not a measure of UVA protection.
Does SPF 30 have twice as much
protection as SPF 15?

• No! The SPF protection does not increase


proportionately with the designated SPF number.
• In higher SPFs such as SPF 30, 97% of rays are
absorbed; however, an SPF of 15 indicates 93%
absorption, and an SPF of 2 indicates 50 %
absorption.
SUNSCREENS

• Factors which influence effectiveness of SPFs


– Difference in skin types.

– Thickness of the applied sunscreen.

– Time of day.

– Altitude: each 1,000 ft increase adds 4% to the


intensity of erythema producing UV radiation; thus
intensity is about 20% greater in Pocatello than at
sea level.
– Environment: snow/white surfaces reflect 70-
90%, and when directly overhead water reflects
nearly 100% of UVR.
– Vehicle: determines skin penetration of
sunscreen.
SUNSCREENS

Category Skin Type SPF


I Always burns, never tans 15 >
II Burns easily 15
III Burns moderately, (avg caucasian) 10-15
IV Burns minimally, tans well (olive skin”) 6-10
V Rarely burns, tans profusely (brown skin) 4-6
VI Never burns (black skin) none
CHOOSING SPF RATING

HIGH SPF SUNSCREENS


• Can achieve higher SPF by combining two
or more agents.
• SPF 30 (3%) vs 15 (6%) of radiation
penetrating skin.
sunscreen and a sunblock

• What is the difference between a


sunscreen and a sunblock?
• Sunscreens absorb UV rays; Sunblocks deflect
UV rays.
SUNSCREEN CLASSIFICATIONS

• Physical
– Opaque formulations containing:
• titanium dioxide
• talc, kaolin
• zinc oxide
• ferric chloride
• icthyol, red petrolatum
– Mechanism: scatters or reflects UV radiation
due to large particle size
SUNSCREEN CLASSIFICATIONS

• Chemical
– Formulations containing one or more:
• PABA, PABA esters
• benzophenones
• cinnamates
• salicylates
• digalloyl trioleate
• anthranilates
– Mechanism: absorbs UV radiation
Suntans & Sunburns

• A suntan tells you that your skin is trying to protect


itself from damaging UV rays.

• Suntans may give some protection from sunburn, but


the skin gets damage while getting the tan, including
aging from UVA rays.

• Cumulative sun exposure (including tanning) can lead


to skin cancer.

• Sunburns increase risk for developing melanoma.


Type of sunscreen
Absorbing compounds

• Octyl methoxycinnamate
• Octocrylene
• Ethylhexyl methoxycinnamate
• Octyl dimethyl PABA

• Parsol 1789/ avobenzone


• Benzophenone 3/ oxybenzone
• Mexoryl SX: terepthalylidene dicamphor sulfonic
acid
• Mexoryl XL: drometrizole trisiloxane

• Tinosorb
Reflecting compounds

• Titanium dioxide
• Zinc oxide

• Microfine particles are now available


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Sunscreen Ingredients Overview

Organic Ingredients Inorganic Ingredients


Atoms Carbon, Hydrogen, Zinc, Titanium, Oxygen
Involved Oxygen, Nitrogen
Structure Individual molecule Clusters of various size
(not drawn to scale)

UV Blocking Absorb specific bands Absorb all UV with


of UV light l < critical value
Appearance Clear Large clusters = White
Small clusters = Clear
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Organic Ingredients: The Basics

• Organic = Carbon Compounds Octyl methoxycinnamate


– H, O & N atoms often involved (C18H26O3)
• Structure an organic sunscreen
ingredient
– Covalent bonds
– Exist as individual molecules
• Size
– Molecular formula determines
size (states the number and
type of atoms in the molecule)
– Typically a molecule measures
a few to several dozen Å (<10
nm)
Sources: http://www.3dchem.com/molecules.asp?ID=135# and original image
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Organic Ingredients: UV Blocking

Organic Sunscreen Ingredients can absorb UV rays

1. Molecules capture
energy from the
sun’s UV rays
2. The energy give the
molecule thermal
motion (vibrations
and rotations)
3. The energy is re-
emitted as
harmless long
wave IR
Source: Adapted from http://www.3dchem.com/molecules.asp?ID=135#and http://members.aol.com/WSRNet/tut/absorbu.htm
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How are inorganic sunscreen


ingredients different from organic ones?

How might this affect the way they


absorb UV light?
Why not use inorganics?

• Appearance Matters
• Traditional inorganic
sunscreens have appear
white on our skin
• Many people don’t like
how this looks, so they
don’t use sunscreen with
inorganic ingredients
• Of the people who do use
them, most apply too little
to get full protection
Source: http://www.4girls.gov/body/sunscreen.jpg
Why Do They Appear White?

• Traditional ZnO and TiO2


clusters are large
– (> 200nm)
• Large clusters scatter visible
light
– (400-700 nm)
– Maximum scattering occurs for
wavelengths twice as large as
the clusters
• The scattered light is reflected
to our eyes, appearing white

Source: Original image


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Why Do They Appear White? II

Light eventually goes in one of two directions:


1. Back the way it came (back
scattering)
– Back-scattered light is
reflected

2. Forwards in the same general


direction it was moving (front
scattering)
– Front-scattered light is
transmitted
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Why Do They Appear White? III

• When reflected visible light


of all colors reaches our eyes,
the sunscreen appears white

• This is very different from


what happens when sunlight
is reflected off our skin
directly
– Green/blue rays absorbed
– Only red/brown/yellow rays
reflected
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Organic Sunscreen Molecules
are Too Small to Scatter Visible Light

200 nm TiO2 particle


Methoxycinnamate (<10 nm)
(Inorganic) (Organic)
Source: Images adapted from http://www.cse.clrc.ac.uk/msi/projects/ropa.shtml and http://www.3dchem.com/molecules.asp?ID=135#
Nanosized Inorganic Clusters

• Maximum scattering occurs for wavelengths


twice as large as the clusters
– Make the clusters smaller (100 nm or less) and they
won’t scatter visible light

Source: Graph adapted from http://www.aims.gov.au/pages/research/projects/sunscreens/pages/sunscreens02.html


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Nanosized Inorganic Clusters

• Maximum scattering occurs for wavelengths twice as


large as the clusters
– Make the clusters smaller (100 nm or less) and they
won’t scatter visible light

Source: Graph adapted from http://www.aims.gov.au/pages/research/projects/sunscreens/pages/sunscreens02.html


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In Summary I

Organic Inorganic Inorganic


Ingredients Ingredients Ingredients
(Nano) (Large)
Structure Individual Cluster ~100 nm Cluster > 200
molecule in diameter nm in diameter
Interaction Absorb Absorb all UV < Absorb all UV <
w/ UV light specific l of critical l critical l
UV light
Absorption Parts of UVA Broad spectrum, Broad spectrum,
Range or UVB both UVA and both UVA and
spectrum UVB UVB
Interaction None None Scattering
w/Vis light
Appearance Clear Clear White
In Summary…

• Nanoparticle sunscreen ingredients are


small inorganic clusters that:
– Provide good UV protection by absorbing
both UVB and UVA light
– Appear clear on our skin because they are
too small to scatter visible light

Source: http://www.smalltimes.com/images/st_advancednanotech_inside_.jpg
SUNCREEN AGENTS
PABA (Para-aminobenzoic acid)
• Very effective in the UVB range (200-320 nm).
• Most effective in conc of 5% in 70% ethanol.
• Maximum benefit when applied 60 min prior to
exposure (to ensure penetration and binding to stratum
corneum).
• Does NOT prevent drug/chemical-induced
photosensitivity rxn.
• Contact dermatitis can develop.
• May produce transient drying/stinging from alcohol
content (may be alleviated by adding 10-20% glycerol).
• May stain clothing.
SUNCREEN AGENTS

PABA Esters (Padimate A, Padimate O,


Glyceryl PABA)
• Also very effective in UVB range (280-
320)
• Most effective in conc. 2.5-8% in 65%
alcohol
• May penetrate less effectively than PABA

• Similar application and adverse effect

• Less staining
SUNCREEN AGENTS

Benzophenones (oxybenzone, dioxybenzone,


sulisobensone)
• Slightly less effective than PABA.
• Absorbs from 250-400 nm spectrum (ie, UVA &
UVB).
• Combined with PABA or PABA ester improves
penetration and is superior to either agent used alone
(200-400 nm wavelength coverage).
• Beneficial in preventing photosensitivity rxns.
• Contact dermatitis is rare.
SUNCREEN AGENTS

Cinnamates and Salicylates


• Minimally effective, absorb UVB
spectrum.
• Generally used in combination with one of
the above.
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