Nano Sunscreen

The Wave of the Future?

Modified slightly from the NanoSense web materials

Copyright 2005 SRI International

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Nano Products
Number of products using nanomaterials is
growing very rapidly
Doubling every year?
Clothing, food and beverages, sporting goods,
coatings, cosmetics, personal care
Sunscreens: many use nanomaterials
Some labeled as containing nanoparticles
Some not labeled
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http://www.masspolicy.org/p
df/workshop/rejeski.pdf
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Why Use Sunscreen?

Too much unprotected sun exposure
leads to:

Premature skin aging (e.g. wrinkles)

Sunburns

Skin cancer

Sources: http://www.oasishospital.org/previousnews.html; http://wohba.com/archive/2005_03_01_archive.html

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Skin Cancer Rates are Rising Fast

Probability of Skin cancer:
getting skin cancer: Is ~50% of all cancer
1930 : 1 in 5,000 cases
2004 : 1 in 65 Has > 1 million cases
2050 : 1 in 10 diagnosed each year
Causes 1 person to die
every hour

Causes of the increase:

Decrease ozone protection
Increased time in the sun
Increased use of tanning beds
Sources: http://www.msnbc.msn.com/id/8379291/site/newsweek/ ;
http://www.skincarephysicians.com/skincancernet/whatis.html; http://www.msu.edu/~aslocum/sun/skincancer.htm
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What are sun rays?

The sun emits several kinds of electromagnetic
radiation: Visible (Vis), Infrared (IR) and Ultra
Violet (UV)

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
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The Full Electromagnetic Spectrum

Visible, Infrared and UV radiation are only part of
the full spectrum of electromagnetic radiation

Source: http://www.mhhe.com/physsci/astronomy/arny/instructor/graphics/ch03/0305.html
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The Suns Radiation Spectrum

Most of the suns radiation is UV, Vis & 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
.

waves, and radio waves

Source: Adapted from http://www.ucar.edu/learn/imgcat.htm

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What is Radiation?
Light radiation is often thought
of as a wave with a wavelength
(l) and frequency (f) related by
this equation:

Since c (the speed of light) is constant, the

wavelength and frequency are inversely related

This means that light with a short wavelength will

have a high frequency and visa versa
Source: http://www.pueblo.gsa.gov/cic_text/health/sun_uv/sun-uv-you.htm
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Two Ways to Think about Radiation Energy

1. Energy Comes in Packets (Photons)

The size of an energy packet (E) is determined by
the frequency of the radiation (f)

Radiation with a higher E Ef

frequency has more
energy in each packet
The amount of energy in
a packet determines how
it interacts with our skin
f
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Two Ways to Think about Radiation Energy

2. Total Energy
This relates not only to how much energy is in each
packet but also to the total number of packets arriving
at a given location (such as our skin)
Total Energy depends on many
factors including the intensity of
sunlight
The UV Index rates the total intensity
of UV light for many locations in the
US daily:
http://www.epa.gov/sunwise/uvindex.html

Source: http://www.epa.gov/sunwise/uvwhat.html
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Skin Damage
The kind of skin damage is determined by the
size of the energy packet ( E = h x f)
The UV spectrum is broken into three parts:
Very High Energy (UVC)
High Energy (UVB)
Low Energy (UVA)
As far as we know,
visible and IR
radiation dont harm High Energy Low Energy

the skin

Source: http://www.arpansa.gov.au/is_sunys.htm
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Skin Damage II
Very high energy
radiation (UVC) is
currently blocked by the
ozone layer (ozone hole
issue)
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
Source: N.A. Shaath. The Chemistry of Sunscreens. In: Lowe NJ, Shaath NA,damage
Pathak MA, editors. Sunscreens, development,
evaluation, and regulatory aspects. New York: Marcel Dekker; 1997. p. 263-283.
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Sun Radiation Summary

Radiation Characteristic Energy per % of Effects on Visible
Type Wavelength (l) Photon Total Radiation Human Skin to
Reaching Earth Human
Eye?
UVC ~200-290 nm Increasing ~0% DNA Damage No
(Short-wave UV) Energy
High Energy (<1% of all UV)

UVB ~290-320 nm ~.35% Sunburn No

(Mid-range UV) Medium Energy DNA Damage
(5% of all UV) Skin Cancer

UVA ~320-400 nm ~6.5% Tanning No

(Long-wave UV) Skin Aging
Low Energy (95 % of all UV) DNA Damage
Skin Cancer
Vis ~400-700 nm ~43 % None Yes
Lower Energy Currently
Known
IR ~700-120,000 nm ~49% Heat Sensation No
Increasing Lowest Energy (high l IR)
Wavelength
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With all of this possible damage,

it pays to wear sunscreen, but
which one should you use?

Source: http://www.niehs.nih.gov/oc/factsheets/genes/home.htm
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Which Sunscreen Should You Use???

New and Improved

Now with Nano-Z

Broadband Protection
Safe for Children
SPF 50
Goes on Clear
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The Challenge: 3 Essential Questions

1. What are the most important factors to consider

in choosing a sunscreen?

2. How do you know if a sunscreen has nano

ingredients?

3. How do nano sunscreen ingredients differ

from other ingredients currently used in
sunscreens?
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A Brief History of Sunscreens:

The Beginning
First developed for soldiers
in WWII (1940s) to block
sunburn causing rays
These were called UVB rays
WWII soldier in the sun

Shorter wavelengths Longer wavelengths

(more energy) called UVC (less energy) called UVA
Sources: http://www.bbc.co.uk/wiltshire/content/articles/2005/05/05/peoples_war_feature.shtml
http://www.arpansa.gov.au/is_sunys.htm
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A Brief History of Sunscreens:

The SPF Rating
Sunscreens first developed to prevent sunburn
Ingredients were good UVB blockers
SPF (Sunscreen
Protection Factor)
Number
Measures the strength of
UVB protection only
Higher SPF # = more
protection from UVB
Doesnt tell you anything
about protection from UVA
Sources: http://www.shop.beautysurg.com/ProductImages/skincare/14521.jpg and
http://www.shop.beautysurg.com/ProductImages/skincare/14520.jpg
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A Brief History of Sunscreens:

The UVA Problem
UVA rays have no
immediate visible effects
but cause serious long
term damage
Cancer
Skin aging
Sunscreen makers
working to find UVA
blockers
No official rating of UVA Twenty different skin cancer lesions

protection yet

Source: http://www.cs.wright.edu/~agoshtas/fig8.jpg
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How do you know if your

sunscreen is a good UVA blocker?
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Know Your Sunscreen:

Look at the Ingredients
UV blocking agents suspended in a lotion
Colloidal suspension
Lotion has inactive
ingredients
Dont block UV light
UV blocking agents are
active ingredients
Usually have more than
one kind present
Two kinds of active ingredients
Organic ingredients and inorganic ingredients
Source: Original Image
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Organic Ingredients: The Basics

Organic = Carbon Atoms

Octyl methoxycinnamate (C18H26O3)
an organic sunscreen ingredient
Hydrogen, oxygen & nitrogen
atoms are also often involved
Structure
Covalent bonds
Exist as individual molecules
Size
Molecular formula determines
size
Typical a few to several dozen
(<10 nm)
Sources: http://www.3dchem.com/molecules.asp?ID=135# and original image
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Organic Ingredients: UV Absorption

1. Electrons capture
the energy from UV
rays
2. They jump to
higher energy
levels hf=2.48 eV 3hf=2.48 eV
3. The energy is
released as infrared
rays which are
harmless (each ray
is low in energy)

Source: Adapted from http://www.3dchem.com/molecules.asp?ID=135#and http://members.aol.com/WSRNet/tut/absorbu.htm

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Organic Ingredients: Absorption Range

Organic molecules only absorb UV rays whose
energy matches difference between electron
energy levels
Different kinds of molecules have different peaks and
ranges of absorption
Using more than one kind of ingredient (molecule)
gives broader protection

One Ingredient Two Ingredients Three Ingredients

Source: Graphs adapted from http://www.aims.gov.au/pages/research/projects/sunscreens/pages/sunscreens02.html
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Organic Ingredients:
Absorption Range cont.
Most organic ingredients that are currently used
were selected because they are good UVB
absorbers
The FDA has approved 15 organic ingredients
Sunscreen makers are trying to develop organic
ingredients that are good UVA blockers
Avobenzone (also known as Parasol 1789) is a new
FDA approved UVA blocker

Source: http://jchemed.chem.wisc.edu/JCEWWW/Features/MonthlyMolecules/2004/Oct/JCE2004p1491fig4.gif
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How are inorganic sunscreen

ingredients different from organic
ones?

How might this affect the way

they absorb UV light?
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Inorganic Ingredients: The Basics

Atoms Involved
Detail of the ions in
Zinc or Titanium one cluster

Oxygen
Structure
Ionic attraction
Cluster of ions
Formula unit doesnt dictate
size
Size
Varies with # of ions in cluster
~10 nm 300 nm Group of TiO2 particles

Source: http://www.microspheres-nanospheres.com/Images/Titania/TIO2%20P7.jpg and image adapted from

http://www.cse.clrc.ac.uk/msi/projects/ropa.shtml
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Inorganic Ingredients: Cluster Size

Inorganic ingredients come in different cluster
sizes (sometimes called particles)
Different number of ions can cluster together
Must be a multiple of the formula unit
ZnO always has equal numbers of Zn and O atoms
TiO2 always has twice as many O as Ti atoms

~100 nm TiO2 particle ~200 nm TiO2 particle

Source: Images adapted from http://www.cse.clrc.ac.uk/msi/projects/ropa.shtml

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Inorganic Ingredients: UV Absorption

Inorganics have a
different absorption
mechanism than
organics
Absorb consistently
through whole UV
range up to ~380nm
How is the
absorption pattern
different than for
organics?

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

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If inorganic sunscreen
ingredients block UVA light, why
doesnt everybody use them?

Source: http://www.loc.gov/rr/scitech/mysteries/images/sunscreen2.jpg
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Appearance Matters
Traditional inorganic
sunscreens have appear
white on our skin

Many people dont like

how this looks, so they
dont 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
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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 dont organic sunscreen

ingredients scatter visible light?

Source: Adapted from http://www.loc.gov/rr/scitech/mysteries/images/sunscreen2.jpg

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Organic Sunscreen Molecules

are Too Small to Scatter Light

~200 nm TiO2 particle Methoxycinnamate

(Inorganic) (Organic)

(Note that these images are not drawn to scale)

Source: Images adapted from http://www.cse.clrc.ac.uk/msi/projects/ropa.shtml and http://www.3dchem.com/molecules.asp?ID=135#
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Waves and obstacles

Waves go around small obstacles
Waves scatter all around from obstacles of sizes
comparable to a wavelength
Water wave (ripple tank) simulation:
http://www.falstad.com/ripple/
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What could we do to inorganic

clusters to prevent them from
scattering visible light?

Source: Adapted from http://www.loc.gov/rr/scitech/mysteries/images/sunscreen2.jpg

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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
wont scatter visible light

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

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Nano-Sunscreen Appears Clear

Nanosized Large ZnO

ZnO particles particles

Source: http://www.science.org.au/sats2003/images/barber-slide3.jpg
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Lets Look at Some Real Data

Three sunscreens were tested for scattering

with different wavelengths of light
One contains nanosized inorganic ingredients
One contains traditional inorganic ingredients
One contains organic ingredients

Can you answer these three questions:

1. Which one is which and how do you know?
2. Will each one appear white or clear on your skin?
3. What size (approximately) are the clusters in each
sunscreen?
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Light Scattering by Three Sunscreens

Sunscreen 1 Sunscreen 2 Sunscreen 3
100

90
Percent of Light Scattered

80

70

60

50

40

30

20

10

0
300 310 320 330 340 350 360 370 380 390 400 410 420 430 440 450 460 470 480 490 500

Wavelength of Light
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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
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Essential Questions: Time for Answers

1. What are the most important factors to consider

in choosing a sunscreen?

2. How do you know if a sunscreen has nano

ingredients?

3. How do nano sunscreen ingredients differ

from other ingredients currently used in
sunscreens?