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CO S M ET I C S
R A D I C A L S K I N STAT U S FAC TO R ( R S F )
T. Herrling* •, K. Jung•
The Radical Skin Status Factor RSF –
An Universal Indicator for the Classification
of Skin Changes
Part III – Physical and Chemical Influences
Introduction
The physical treatment of skin with environmental noxa can influence the skin’s
radical status. Among these treatments,
the whole spectrum of electromagnetic
radiation from ionizing radiations up to
radio waves have to be considered.
A second class of influence can be initiated by ultrasound, resulting in mechanical traction, pressure or hit.
The skin consistence determines its physical properties influenced by the hydrophilic muscle and hydrophobic fat
tissues. This ratio of muscle to fat influences the number of generated free radicals/ROS (reactive oxygen species).
Additionally, chemical hazards can influence the radical status especially in the
upper layer (stratum corneum) of the
skin. The water/salt(enzymes)/fat content determines the skin’s answer to external chemical influences. Acids, leaches, salts and gases determine the chemical effect of external treated influences.
The aim of the present work is the description of the influence of various
physical and chemical treatments of the
skin on the Radical Status. The water
content of the skin layers is one of the
most important driving parameters that
modulates the activity of external noxa
and treatments.
Physical Influences
Water content in skin
Skin is a large water reservoir that actively participates in the regulation of
the fluid balance in the organism. Water
enters the skin via capillaries by ultrafil22
tration caused by the difference between the hydrostatic blood pressure
and the pressure in the interstitium.
There is a continuous passive diffusion of
water across the different skin layers
outwards leading to thermal loss by
evaporation of the insensible transepidermal water loss (TEWL) from the skin
surface.
The rate of TEWL is regulated mainly by
the skin barrier in the stratum corneum,
by the humidity, velocity and temperature of ambient air (concerning winter
xerosis of the skin) and by clothing, which
adjusts the »mini-climate« on the skin
surface. TEWL varies depending on the
skin region.
The structure and chemical composition
of the lamellar skin barrier in the intercellular space of corneal cell layers are
quite well known, as well as the mechanism of its repair after injuries. Ceramides, cholesterol, and free fatty acids
form the major lipid components between water layers. (1) Adverse environmental exposures (chemical or physical)
Abstract
P
hysical and chemical effects caused by environmental conditions
have an influence on the radical status of skin. UV and IR radiation
from the sun, mechanical distortions from tractions and ultrasound
can have detrimental effects. Daily contact with several chemicals like
soaps or cleanser and hair shampoos can change the radical status.
Electromagnetic radiation from the sun with wavelength λ < 400 nm performs the main part of environmental radical influences. No other influence has such a high significance. Radical generation correlates with the
energy of the photon. The visual and infrared part of the solar spectrum
has only a minor part for radical generation.
In contrast to radical prevention by various antioxidant formulations the
enrichment of moisture alone has a radical promoting effect in the skin.
The Radical Status Factor RSF measures the skin answer to a defined provoked oxidative stress and quantifies all influences (products and treatments) directed against them.
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R A D I C A L S K I N STAT U S FAC TO R ( R S F )
may cause disturbance in barrier function, increase TEWL and cause clinical
symptoms: irritation, desquamation, loss
of corneal elasticity, and eventually, surface cracks. Repeated irritations may initiate an inflammatory cycle and lead to
eczema.
For the health and normal function of
the skin, the grade of the humidity in the
corneal layer is of major importance. The
water content of the normal skin (Fig. 1)
decreases from about 70% in the dermis
towards the outmost layer of stratum
corneum being 30% by weight in the
lower and only 15% in the upper corneal
layers of a healthy skin, both considerably less hydrated than the viable epidermis (2 ). The superficial layers of stratum corneum are less hygroscopic and
less capable of holding water than its
deeper portions (3). Water content of
stratum corneum depends on both the
degradation products of the keratin and
on the components of sweat and sebum
(so called natural moisturizing factor) as
well as on the intercellular lipids, the essential components of the lamellar skin
barrier (4).
Electromagnetic Radiation
The electromagnetic radiation is characterized by its dualism, the wave nature
and the particle nature.
The impact of electromagnetic waves on
skin is caused by both the wave length
and the appropriate quantum energy.
These two physical parameters of solar
radiation are decisively concerning their
effect on skin
The wavelength λ is responsible for the
penetration depth of the electromagnetic radiation into the skin/water (Fig. 2)
and the photon energy (Fig. 3) determines their effect on the molecular structure of the target.
Fig. 1 Water content of skin layers in healthy skin
(SC=stratum corneum, GR=str. granulosum, SP=str. spinosum, B=str. basale.) (2)
sorption occurs preferentially at certain
characteristic wavelengths, while the
balance of the spectrum is transmitted
with minimal effects .
Particle Nature
• Photon Energy (ε): ε = h f
• Energy carried as energy quant
(photon)
Wave Nature
• Energy carried in fields
• Relationship between wavelength (λ)
and frequency (f): c = λ f
During the transmission of electromagnetic radiation through a medium containing water molecules, portions of the
electromagnetic spectrum are absorbed
by the water molecules. This water ab24
Fig. 2 Liquid water absorption spectrum across a wide wavelength range
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CO S M ET I C S
R A D I C A L S K I N STAT U S FAC TO R ( R S F )
The Electromagnetic Spectrum
Fig. 3 The Wavelength and the corresponding quantum energy (photon)
The wavelength λ (Fig. 2) is responsible
for the penetration depth of the electromagnetic radiation into the skin and
the energy(photon) (Fig. 3) determines
their effect on the molecular structure
of the target.
The quantum energy ranges over 18 decimal powers from 10-11 eV for Radio waves
to 107 eV for Gamma rays.
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R A D I C A L S K I N STAT U S FAC TO R ( R S F )
According to the theory concerning
atoms, electrons move in orbits around
the nucleus. If an electron absorbs energy, it is promoted to a higher energy orbit (Fig. 4). This situation is very unstable, so that after a very small period of
time (much less than a second), it falls
back to its previous orbit or it forms a
semistable free radical. During the fall it
emits a photon. The energy of a photon
depends on radiation frequency; there
are photons of all energies from highenergy gamma- and X-rays, through visible light, to low-energy infrared and radio waves. All photons travel at the speed
of light. Photons do not have electric
charge or rest mass and one unit of spin;
they are field particles that are thought
to be the carriers of the electromagnetic field.
The wavelength of light λ (in meters), is
related to the frequency v (in Hz) and
to the speed of light c, by the equation:
λ = c/v
where c is the speed of light with a constant value of 300 million meters per
second, is the frequency of the light in
hertz (Hz) , and is the wavelength of the
light in meters. From this relationship it
is clear that the wavelength of light is inversely proportional to the frequency. An
increase in frequency produces a proportional decrease in the wavelength of
light with a corresponding increase in
the energy of the photons that make up
the light. Upon entering a new medium
(such as glass or water), the speed and
wavelength of light is reduced, although
the frequency remains unaltered.
The relationship between the energy of
a photon and it's frequency is dictated
by equation:
E = hv = hc/λ
where E is the energy in kilo Joules per
mole, h is Planck's constant with a value
of 6.626 x 10-34 Joule-seconds per particle, and the other variables were defined
above. From this equation, it is clear that
the energy of a photon is directly proportional to its frequency and inversely
proportional to its wavelength. Thus as
frequency increases (with a corresponding decrease in wavelength), the photon
energy increases and vice versa.
26
Fig. 4 An electron absorbs energy and is promoted to a higher Energy orbit
These two physical parameters of solar
radiation are decisively concerning their
effect on skin. The wavelength λ (Fig. 2)
is responsible for the penetration depth
of the electromagnetic radiation into the
skin and the energy of photons (Table 1)
determines their effect on the molecular structure of the target.
The relevant part of the sun radiation
reaching the earth and influencing the
human skin and hair expands from infrared to UV enclosing wavelength from
1000 nm (IR) to 280 nm (UVB). The most
painful effects are generated by UVB and
UVA. Corresponding to their penetration
depth UVB and UVA radiation generate
primary free radicals followed by secondary daughter radicals like Lipid radicals.
The near ultraviolet (UVB – UVA) from
280 nm to 400 nm is absorbed very
strongly in the surface layer of the skin
Spectrum
UV
C
B
A
IR
by electron transitions. As we go to higher energies (UVC - UVB) from 100 nm to
280 nm the ionization energies for many
molecules are reached and the more
dangerous photo ionization processes
take place. Sunburn is primarily an effect
of near UV. Ionisation produces the direct risk of skin cancer.
The quantum energy of infrared photons
is in the range 0.001 to 1.6 eV which is
in the range of energies separating the
quantum states of molecular vibrations.
The result of infrared absorption is heating of the tissue since it increases the
molecular vibration activity.
Free Radical Formation by Ultrasound
Ultrasounds are mechanical vibrations
with frequencies above the human limit
of audibility. The use of ultrasounds in
order to obtain images for medical diag-
Wave length λ
Energy ε
100 nm - 280 nm
280 nm - 320 nm
320 nm - 400 nm
760 nm - 1 mm
12.3 - 9.8 eV
9.8 - 9.2 eV
9.2 - 8.1 eV
1.6 - 10-3 eV
Table 1 Spectrum of UV and IR radiation and its photon energ
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CO S M ET I C S
R A D I C A L S K I N STAT U S FAC TO R ( R S F )
nostic purposes, typically employs frequencies ranging from 2 MHz to about
12 MHz (5, 6). Ultrasound does not use
ionizing radiation.
In contrast to ionizing radiation, which
can damage biological materials by dislodging electrons from atoms and molecules, ultrasounds do not cause ionisation. They usually interact with human
tissue primarily by generating heat, but
also non-thermal effects which are ascribed to cavitation (i.e. micro-bubble)
(7). The process of cavitation includes ultrasounds mechanical effects which lead
to hydrodynamic breaks of hydrogen
bonds and oscillation of hydrogen ions,
and chemical effects produced by the
occurrence of free radicals (8) in intercarionic space in the process of cavitation (Fig. 5). The very high temperatures
Fig. 5 At high acoustic pressure, ultrasound is capable of causing rapid bubble
which grow and collapse among them (a) and cells (b). This mechanism results in
the production of sufficient energy to disrupt chemical bonds and produce reactive free radicals, that may interfere with DNA
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CO S M ET I C S
R A D I C A L S K I N STAT U S FAC TO R ( R S F )
and pressures induced by acoustic cavitation in collapsing gas bubbles in aqueous solutions exposed to ultrasound lead
to the thermal dissociation of water vapor into H atoms and OH radicals. Theoretically, these free radicals may interfere
with DNA, causing chromosomal damage.
Chemical Skin Irritants
Skin is a valuable tissue – but chemical
irritants can harm it. Different chemicals
can irritate the skin. Some chemicals remove fat and oils from the skin. When
this occurs, the skin becomes cracked
and dry. Irritants can also cause severe
burns. Or irritants can cause oils and
waxes to plug hair follicles and sweat
ducts. This can cause dermatitis and acne. Chemical irritants can cause the generation of free radicals and can work as
a catalyzer for UV generated free radicals (9, 10).
Types of irritant are shown in Table 2.
Application Examples
Materials and methods
To test the effect of different external
influences on skin some tests were done.
The basis of these tests were measurements of the RSF (11) of skin after external treating.
Generated free radicals were detected
with
• ESR Spectrometer Mini Scope 200
Magnettech, Germany
External treatments were performed with
• UV Solar Simulator 300 W
Newport 91260 USA
•
IR lamp Osram Thera 250 W E27
Germany
•
wIRA lamp Hydrosun 501
Medizintechnik Müllheim, Germany
Increased moisture in skin –
moisturizers
Hydration of skin during UV-irradiation
can have a detrimental effect on the UV
protection of skin. This detrimental effect is correlated with the generation of
free radicals. The radical generation depends on the properties of the skin (water content, see Fig. 1) and the applied
formulation (water content, penetration
behavior, among others). Hydration of
skin can be achieved by using moisturizers. Naturally occurring skin lipids and
sterols as well as artificial or natural oils,
humectants, emollients, lubricants, etc.
may be part of the composition of commercial skin moisturizers.
The amount of generated free radicals
in moisturized skin is higher than in dry
skin.
The effect of different moisture contents
on the RSF of skin was tested by using
different skin moisturizing formulations
Four different formulations were applied
on the skin and the Radical Status Factor (RSF) was determined (Fig. 6).
Generally, all skin treatments that influence the hydration degree of the skin
and/or its barrier function may have a
measurable influence on the radical gen-
Chemical Irritant
Examples
Found in
Effects
Strong acid
Hydrochloric acid
Fertilizers
Dyes
Paint pigments
Severe burns
Brief or prolonged
Effects
Sulfuric acid
Battery acid
Phosphate
Fertilizers
Nitric acid
Fertilizers
Metal working
Sodium hydroxide
Soaps, detergents
Cleaning products
Adhesives
Paint remover
Desinfectants
Potassium hydroxide
Desinfectants
Sterilizing agents
Dichlormetane
Paint remover
Prolonged dermatitis
N-Methylpyrrolidine
Alcohol
Prolonged acne
Strong caustics
Strong solvents
Severe burns
Brief or prolonged Effects
Table 2 Types and effects of chemical irritants
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Fig. 6 Free radical formation in the skin during UV radiation with and without
application of placebo formulations.
(Spray = 50% EtOH, Lotion = 70% H2O, Cream = 50% H2O, Glycerine = 50% H2O)
eration. The highest effect was measured, when a solution of glycerine and
water (50:50, w/w) was applied on the
skin. The amount of free radicals compared to untreated skin was nearly doubled. The lowest effect showed an ethanolic spray formulation (28 % more free
radicals compared to untreated skin). The
measured RSF values are the mean values of 6 samples.
Electromagnetic Radiation –
Interactions
Ultraviolet Interactions
The acute reactions of human skin to solar ultraviolet radiation (280 - 400 nm)
are recognised as a form of inflammation reactions that are mediated by several possible mechanisms (12) including
(a) direct action of photons on DNA; (b)
generation of reactive free radicals and
reactive oxygen species (ROS) involving
the formation of O2-., O2, H2O2, .OH, ROO.,
ecc.; (c) generation of prostaglandins,
histamine, leucotrienes, and other inflammatory mediators. It is conceivable
that UV-induced reactions represent oxidative stress mediated by the formation
of free radicals, reactive oxygen species
(ROS), lipid peroxidation, liberation of
membrane phospholipids, and subsequent formation of prostaglandins by
cyclooxygenase pathway.
While the energy of photons of the UVB
range seems to be sufficient to damage
directly the DNA, the photon energy of
UVA radiation generates more free radicals It has been suggested that skin exposure to UVA involves the production
of free radicals (reactive oxygen species)
which may be the first step of the multiple damages induced by UVA (13). It has
also been reported that irradiation with
UVA produces a decrease in the levels of
antioxidants (14), inactivation of antioxidant enzymes (15) and an increase in the
markers of lipid peroxidation in skin (16).
Recent studies have shown that UVA can
induce epidermal tumours (17), and contributes to erythema caused by solar exposure (18).
Infrared Interactions
Contrary to UV part of the solar spectrum concerning the generation of free
radicals in skin the effect of IR on the
skin is under debate.
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Two classes point out the generation of
free radicals/ROS in skin (cell culture
material, biopsies, forearms) (19-23) during IRA radiation.
In addition to this opinion T. Jung et al.
(24) have measured how infrared A acts
on skin cells. They have demonstrated
that in human dermal fibroblasts the reactive oxygen species generation is dependent on heat formation by infrared A
and can be reproduced by thermal exposure. On the other hand wIRA (water filtered IR) irradiation had no detectable
effect if the temperature in cells kept
constant, even if irradiance exceeded the
extraterrestrial solar irradiance in the IR
range by a factor of about 4 and the
maximum at noontime in the tropics by
factor up to about 6.
Incandescent lamp
Incandescent lamps with an red filter are
commonly used as a source of infrared
light (IRA, IRB,IRC). A special red filter removes the visible and ultraviolet part of
the spectrum.
Fig. 7 shows a typical energy curve for
an incandescent lamp. As it is seen, energy emission is mostly in the infrared,
with only a small amount in the visible
region. As with natural daylight, this
curve is strictly a continuous spectrum,
without the narrow band emissions of
fluorescent lighting. Unlike natural daylight (other than direct sunlight at sunrise and sunset), most of the visible emissions consist of red wavelengths.
wIRA ( water filtered infrared A)
Using only the higher penetrating IRA
(penetration window for near IR, see
Fig. 2) a special radiator was used.
Hydrosun® 501 (Medizintechnik Müllheim, Germany) is a radiator, emitting
water-filtered infrared-A (wIRA) and visible light (VIS), spectrum shown in Fig. 8.
The principle of operation involves the
use of a water-filter in the radiation path
that absorbs or decreases those infrared
wavelengths emitted by conventional infrared lamps that would otherwise lay a
thermal burden on the skin (especially
infrared-B and -C and water absorption
bands within infrared-A (19-21)). With
wIRA high irradiation intensities are perceived as pleasant and therapeutic heating of deeper tissue layers over longer
30
Fig. 7 Spectrum of incandescent lamp
periods of time can be achieved. 10 mm
water cuvette, standard orange filter,
water-filtered spectrum 550 - 1400 nm,
see Fig. 8 had approximately 185 mW/cm2
total irradiation intensity (wIRA(+VIS))
with approximately 140 mW/cm2 waterfiltered infrared-A (wIRA) and approximately 45 mW/cm2 visible light (VIS) at
a distance of 25 cm.
Generated Free Radicals during electromagnetic irradiation
Using the UV and IR part of the electromagnetic spectrum skin was irradiated
by different irradiances to generate free
radicals. Fig. 9 shows clearly that free
radicals are exclusively induced by the UV
part of the solar spectrum. The amount of
generated free radicals is advised as the
rate constant factor k measuring the differential radical increase. It is seen that
k correlates with higher radiation frequencies implicating higher photon energy. The results are the mean values of
six skin samples.
Sun light is polychromatic, its final effect on human skin is the result of not
only the action of each wavelength individually, but also the interaction between these wavelengths (25).
Fig. 8 Spectrum with spectral irradiation intensity E (mW/cm2 · (10 nm)-1 = W · m-2 · nm-1
of a wIRA radiator (Hydrosun® 501)
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Fig. 9 Rate constant k (normalized Radicals / min) of generated free radicals in skin
during electromagnetic radiation with the following irradiances:
E UVB = 1,2 mW/cm2 , EUVAB = 22,2 mW/cm2, EUVA= 21,0 mW/cm2, EIR1 = 15 mW/cm2
(T = 32 °C) , EIR2 = 150mW/cm2 (T = 42 °C), EwIRA = 150 mW/cm2 (T = 44 °C)
Corresponding to its wavelength different radical increases / time unit are seen.
The radical increase / time unit is expressed by the rate constant k which
correlates with the photon energy of
the applied light. The used light spectrum simulated by the UV Solar Simulator 300 W Newport shows the highest
rate constant for the UVB part followed
by UVAB and UVA. IR and wIRA generated by Osram Thera 250 W E27 and Hydrosun 501 show only minor influences
on the generation of free radicals.
No free radicals could be detected for
electromagnetic radiation with wavelength > 400 nm. This result corresponds
to the theoretical assumptions made in
(26).
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Zastrow et al (27) represented an action
spectrum over the range from 280 nm –
700 nm for the generation of an absolute
amount of free radicals in the used skin
biopsy. This spectrum shows the highest
amount of free radicals for the UVA
range considering the higher penetration depth of UVA versus UVB. Radicals
generated in the range over 400 nm inclusive the whole range of IR radiation
show a minor intensity.
UVA generates primary oxygen radicals
followed by secondary lipid radicals. The
high power UVB damages additionally
and directly cell structures inclusive
DNA.
The lower photon energy of IRA is not
sufficient to generate any kind of free
radicals in skin. The influence of temperature, which is in the physiological range,
can be neglected for the generation of
free radicals.
Finally it is a fact that the feasibility of
the generation of free radicals correlates
with the photon energy depending on
the atomic surrounding of biological object (skin cells). The amount and quality
of free radicals is determined by the intensity (wave length) of the photon and
only in the case of thermal destruction
of the object by long irradiation times
(dose), relevant changes may occur.
Résumé
In a three-part series the Radical Status
Factor RSF was represented beginning
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CO S M ET I C S
R A D I C A L S K I N STAT U S FAC TO R ( R S F )
with its measurement and calculation
continuing with topical applications of
different formulations and ending with
external physical and chemical influences. The possibility of measuring the
protecting and promoting influences
on skin and the presentation as 2D factor (quality – protection/promotion, and
quantity - intensity) offers a comprehensive classification and comparison of dermal applied products and treatments.
After presentation of the technique in
part I the application of the RSF was
tested on various examples and was
shown in part II and III. A wide range of
different applications of this technique
is shown. The universality of the RSF enables comparing and assessing of various
products and treatments with each other. A simple number determines the redox-status of the skin. It offers the possibility of a comparative classification of
all products and treatments. So that selective or complex activities for prevention of radical damages in skin are possible.
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Address of the authors’:
* • Thomas Herrling
Department of Medical Physics
University of Applied Sciences
TFH Berlin
Katinka Jung
Thomas Herrling
GEMATRIA Test Lab
Pestalozzistrasse 5-8
13187 Berlin
Germany
Email: email@gematria-test-lab.com
•
SOFW-Journal | 136 | 10-2010