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The Sun: The Good & the Bad

• 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
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
Source: Adapted from
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
Electromagnetic Spectrum
Check the UV Index Daily

UVA (Longwave Radiation)

• Range 320-400 nm

• Erythrogenic activity is weak, however

penetrates dermis
• Responsible for development of slow natural
• Most drug-induced photosensitivity rxn

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

UVC (Shortwave or Germicidal Radiation)

• Range 100-290 nm.

• Does not reach the surface of the earth.

• Is emitted from artificial ultraviolet

Skin Damage

• Very high energy

radiation (UVC) is
currently blocked by the
ozone layer
• High energy radiation
(UVB) does the most
immediate damage
• But lower energy
radiation (UVA) can
penetrate deeper into the
skin, leading to long term
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
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
• Measurement of erythema
What is UPF or SPF?

• UPF = Ultraviolet protection Factor

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 %

• 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

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


• 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.

• 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

• 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
• Mexoryl XL: drometrizole trisiloxane

• Tinosorb
Reflecting compounds

• Titanium dioxide
• Zinc oxide

• Microfine particles are now available

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
Organic Ingredients: The Basics

• Organic = Carbon Compounds Octyl methoxycinnamate

– H, O & N atoms often involved (C18H26O3)
• Structure an organic sunscreen
– 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
Sources: and original image
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

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
Why Do They Appear White?

• Traditional ZnO and TiO2

clusters are large
– (> 200nm)
• Large clusters scatter visible
– (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

Why Do They Appear White? II

Light eventually goes in one of two directions:

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

2. Forwards in the same general

direction it was moving (front
– Front-scattered light is
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
– Green/blue rays absorbed
– Only red/brown/yellow rays
Organic Sunscreen Molecules
are Too Small to Scatter Visible Light

200 nm TiO2 particle

Methoxycinnamate (<10 nm)
(Inorganic) (Organic)
Source: Images adapted from and
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

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

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

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
• 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.

PABA Esters (Padimate A, Padimate O,

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

• Similar application and adverse effect

• Less staining

Benzophenones (oxybenzone, dioxybenzone,

• Slightly less effective than PABA.
• Absorbs from 250-400 nm spectrum (ie, UVA &
• 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.

Cinnamates and Salicylates

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