Advanced Sun

protection
with Titanium Dioxides and Functional Fillers

Pigments & Functional Materials (PM-PFC-RT)

June 2017
Agenda

1 Introduction

3.1
Effects of near infrared light on

2.1
skin
Effects of visible light/
HEV on skin

3.2
Performance of titanium dioxides in

2.2
Performance of titanium dioxides in the near- infrared light range
the HEV light range

3.3
Performance of functional fillers in
the near-infrared light range

2.3
Performance of functional fillers in
the HEV light range

Appendix:

4 Conclusion
5 References/ Test
Materials
2 Advanced Sun Protection | Comprehensive Information
Introduction
Solar radiation spectrum
Impact on skin

Content in sunlight 5% 50% 45%

Photoaging

ROS/ RNS generation

DNA
oxidation Heat

Sunburn
DNA damage
Immune Oxidative damage to DNA
Blocked by atmosphere suppression and other molecules

UVC UVB UVA2 UVA1 Visible light Infrared light

200 280 290 320 340 400 800 (nm) 1 (mm)

Source [1]: Int. Journal Cos. Science 2013, 35, 224-232

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Solar radiation spectrum
Impact on skin layers

Ultraviolet light (100-400 nm)

• UVC (100-280 nm) absorbed by ozone in the atmosphere

• UVB (280-320 nm) absorbed by epidermis and keratinocyte DNA

• UVA (320-400 nm) penetration to dermis

Visible light (400-800 nm) penetration to dermis

• Blue/violet light or HEV (400-500 nm)

Infrared light
• IR-A (800-1450 nm) penetration to dermis
• IR-B (1450-3000 nm) absorbed by epidermis
• IR-C (3000 nm- 1 mm) absorbed by epidermis
Source [13] : SCENIHR, Health Effects of Artificial Light, 2012

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Market trend (Mintel Database)

Cream Gel, SPF Sun Cream SPF UV sunscreen, Dry Touch Gel, Energizing Invisible Face
40, Thailand 50, Spain SPF 40, Japan SPF 50+, Protective Milk, Gel, SPF 30,
Argentina SPF 30, France Netherlands
- UVB/ UVA/ HEV - UVB/ UVA/ HEV - UVB/UVA/ blue/ - UVB/ UVA/ IR - UVB/ UVA/ VIS/ - UVB/ UVA/ VIS/
far- infrared IR IR + tan

- Formulated with - org. UV filters, - Enriched with 5 - enriched with XL- - Fractionated - org. UV filters,
HEV shield TiO2, extracts and ceramides Protect melanin AO and extracts
antioxidants absorbing VIS
- org. UV filters, - org. UV filters, - org. UV filter and
and reducing
TiO2, extracts extracts TiO2
free radicals

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UV, VIS and IR
protection
Second defense line:
Extracts and antioxidants only catch the free
radicals already formed due to over exposure
to UV, HEV (blue light) and IR-A light. It’s a
responsive action.

First defense line:

To prevent the skin from harmful damage due
to over exposure, absorption, scattering,
reflection in UV as well as in HEV (blue light)
and IR-A light should be the first choice.
A combination of both would be perfect.
Visible light
(VIS)/
high energy
visible light
(HEV)
 2.1 Effects of
VIS / HEV light
on skin

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Effect of visible light/ HEV on skin
Radical formation by sun

Radical formation in
human skin – ex vivo,
determination by ESR in
the range 300 – 700 nm

• 50% of radicals formed

in the UVA range and
approx. 50% in visible
light.
• ~ 35% in the region of
high energy visible
light (HEV)

Source [15] : Skin Pharmcol Physiol, 2009, 22: 31-44

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Effect of visible light/ HEV on skin
Overexposure

Harmful effects on skin

Effects [6,10] Signs of premature aging

• Production of ROS, pro-inflammatory • Wrinkles

cytokines, MMP-1 and (MMP)-9 • Sagging skin
expression
• Increased dryness
• Decreased type 1 procollagen • Inflammation and redness
expression
• Hyperpigmentation at 415 nm [3]
 Depressed immunity and suppressed
healing

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Effect of visible light/ HEV on skin
Sources of high energy visible light (HEV)

1 white daylight

2
lights sources
Replacement of traditional light bulbs by LEDs, electronic devices

3
reflective surfaces
like snow, concrete, sand, water, glass

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 2.2
Performance
of TiO2 in
VIS/ HEV range

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Performance of TiO2 in visible light/ HEV range
Test Design

Products Placebo emulsions: (I) o/w, (II) w/si and (III) gel
Test emulsions (I), (II), (III) with Titanium Dioxide (5 - 25 %)

Method Photometric measurements of the transmission T (%) with Perkin Elmer

Lambda 900 in short cut cuvettes:
- Defined film thickness of 0.1 mm
- Wavelength: VIS: 400 – 800 nm
HEV: 400 – 500 nm

Read out Protection (%)= [1- T(emulsion with TiO2)/ T(base emulsion)] x 100

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(I) O/W test formulation

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(I) Transmission/ Reflection/ Absorption in o/w emulsion
Visible light protection HEV protection

o/w placebo emulsion without pigment o/w placebo emulsion without pigment
Transmission/ Reflection/ Absorption [%]

70
60

Transmission/ Reflection/ Absorption [%]

60
50
50
40
40
30
30
20
20

10 10

0 0
400 500 600 700 800 400 425 450 475 500

Wavelength [nm] Wavelength [nm]

Transmission [%] Reflection [%] calc. Absorption [%] Transmission [%] Reflection [%] calc. Absorption [%]

~ 60% Transmission ~ 55% Transmission

~ 30% Reflection (including Scattering) ~ 32% Reflection (including Scattering)
~ 12% calculated Absorption ~ 12% calculated Absorption

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VIS protection vs. HEV protection
(I) Performance of 5% Titanium Dioxide in o/w formulation

80%

60%
• In this o/w emulsion
Transmisssion [%]

59%
55% system, good

Protection
protection against VIS
45% 46%
40% 43% and same ranking in
38% HEV light can be
33%
achieved with 5%
27%
20% Titanium Dioxide
UV filters –
in HEV, up to 50%
protection with
0%
Placebo Eusolex® T-AVO Eusolex® T-PRO Eusolex® T-S
Eusolex® T-PRO vs.
basis emulsion
VIS HEV

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HEV protection
(I) Performance of 5-10% Titanium Dioxide in o/w formulation

60%

55%

• Increased HEV
Transmisssion [%]

40%

Protection
protection can be
achieved with
33%
increased
27% concentrations of
20% Eusolex® T-AVO and
18%
Eusolex® T-PRO –
11% up to 80% vs. basis
emulsion
0%
Placebo Eusolex® T-AVO Eusolex® T-PRO

5% 10%

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(II) W/Si test formulation

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HEV protection
(II) Performance of Titanium Dioxide in w/si formulation

80%
73%

• TiO2 UV filters could

Transmisssion [%]

Protection
reduce HEV
transmission up to
40% 37%
34%
36% 85% compared to the
31% placebo emulsion.
23%
• Performance
18% 19%
16% dependent on use
12%
level, coating/ surface
treatment of TiO2
0%
Placebo Eusolex® T- Eusolex® T- Eusolex® T-S Eusolex® T-
AVO PRO 2000

5% 10% 20% 25%

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(III) Gel test formulation

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HEV protection
(III) Performance of 5% Titanium Dioxide in gel formulation

60%

52%

Protection
• In this gel system,
Transmisssion [%]

40%
TiO2 UV filters at
5% use level could
30% reduce HEV
26% 26% transmission up to
20% 50% compared to the
basis emulsion.

0%
Placebo Eusolex® T-AVO Eusolex® T-EASY Eusolex® T-PRO

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Summary VIS/HEV protection
Performance of titanium dioxides

➢ It could be shown that titanium dioxides give an excellent

protection against visible light (400-800 nm), with the focus
on HEV range (400-500 nm).

➢ The effect is dependent on the type of Titanium Dioxide,

use level and type of formulation.

➢ Best performance in the HEV range could be achieved by

Eusolex® T-PRO in an o/w emulsion but also Eusolex®
T-AVO and Eusolex® T-S showed good results.

➢ In the w/si emulsion Eusolex® T-S showed the best ability

to reduce the transmission in the HEV light, close to
Eusolex® T-PRO, T-2000 and T-AVO

➢ Only Eusolex® T-AVO, Eusolex® T-PRO and Eusolex®

T-EASY lead to stable gel formulations. They all showed a
good protection against HEV light.

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 2.3
Performance
of Functional
Fillers in
VIS/ HEV range

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Performance of fillers in visible light/ HEV range
Test Design

Products o/w Placebo emulsions

o/w Test emulsions with functional fillers (3-5 %) (I)

Method Photometric measurements of transmission T (%) with Perkin Elmer Lambda

900 in short cut cuvettes:
- Defined film thickness of 0.1 mm
- Wavelength: VIS: 400 – 800 nm
HEV: 400 – 500 nm

Read out Protection (%)= [1- T(emulsion with TiO2)/ T(base emulsion)] x 100

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(I) o/w test formulation

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(I) Transmission/ Reflection/ Absorption in o/w emulsion
Visible light protection HEV protection

o/w placebo emulsion without pigment o/w placebo emulsion without pigment
Transmission/ Reflection/ Absorption [%]

Transmission/ Reflection/ Absorption [%]

70
60

60
50
50
40
40
30
30
20
20

10 10

0 0
400 500 600 700 800 400 425 450 475 500
Wavelength [nm] Wavelength [nm]

Transmission [%] Reflection [%] calc. Absorption [%] Transmission [%] Reflection [%] calc. Absorption [%]

~ 60% Transmission ~ 55% Transmission

~ 30% Reflection (including Scattering) ~ 32% Reflection (including Scattering)
~ 12% calculated Absorption ~ 12% calculated Absorption

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VIS protection vs. HEV protection
(I) Performance of 5% filler in o/w formulation

60
59

Protection
55

47
Transmission [%]

44
42 • In this o/w emulsion
39 38
37 37 system, good
30
protection against VIS
29
and HEV light can be
achieved with 5%
filler –
in HEV, up to 50%
protection with
0 RonaFlair® Balance
Placebo 5% Balance 5% Balance 5% Balance 5% Balance
Gold Red Blue Green
Blue vs. basis
emulsion
VIS HEV

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HEV protection
(I) Performance of 3-5% filler in o/w formulation

60

55

Protection
50
Transmission [%]

47 48

42
38 37 37
30
29

0
Placebo Balance Blue Balance Red Balance Gold Balance Green

3% 5%

Increased HEV protection can be achieved by increased concentration of

RonaFlair® Balance Blue.

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HEV protection
(I) Performance of filler + titanium dioxide in o/w formulation

53%
Transmision [%]

• Tandem Eusolex® T-PRO /

30% RonaFlair® Balance Blue
31%
achieved an exceptional
transmission reduction
of HEVL of ~ 90%, which
90 %
corresponds to the addition
15% protection
of the protection effects of
9% both single materials
6%
(72% for Eusolex® T-PRO
0%
Placebo 10% T-PRO 5% Balance 10% T-PRO+ 10% T-PRO+ PLUS 42% for RonaFlair®
Blue 5% B. Blue 5% B. Blue Balance Blue)
(measured) (calculated)

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Summary VIS/HEV protection
Performance of functional fillers

➢ It could be shown that RonaFlair® Balance Colors give an

excellent protection against visible light (400-800 nm) with
focus on HEV range from 400-500 nm.

➢ The effect is dependent on the type of functional filler and

use level.

➢ Excellent performance in the HEV range could be achieved

by RonaFlair® Balance Blue in an o/w emulsion but also
RonaFlair® Balance Red, Balance Gold and Balance
Green are effective.

➢ Depending on the final formulation also a combination can

be recommended: best results are obtained with a
combination of RonaFlair® Balance Blue and
Eusolex® T-PRO

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 Near- infrared
light

32
 3.1 Effects of
near-infrared
light on skin

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Effect of near infrared light on skin
Why infrared light protection?

Near-infrared light or IR-A ranges from 800-1450 nm.

Cells Skin

IR radiation has the lowest energy, but its

contribution to solar spectrum reaching human Photoaging
Metabolism of
skin is about 45%. [1] extracellular matrix

Erythema
Destruction of Ca2+
ion homeostasis
At low doses IR-A (1-10 J/cm²) stimulates therapeutic Dermatitis

effects (treatment of inflammatory processes), but at

Upregulation of
high doses (>120 J/cm²) harmful effects are apoptosis Carcinogenesis

reported.[12]

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Effect of near infrared light (n-IR) on skin
Why infrared light protection?

• IR-A radiation (800 - 1450 nm)

 Direct (dose dependent) and secondary (heat generated) formation of dermal mitochondrial ROS and active
nitric oxides (NO) in dermal fibroblasts [16]
 Direct and indirect increase in MMP-1 (collagen degradation), MMP-9 Adapted from Int. Journal Cos. Science 2013, 35, 224-232
(elastin degradation) expression in dermal fibroblasts [12]
 Decrease type I procollagen expression (COL1A1) [6]

 Alteration in expression of genes involved in skin aging [16]

PHOTOAGING
Clinical signs: wrinkle formation,
loss of skin tone,…
ROS
MMPs COL1A1
• IR-B (1450-3000 nm) and IR-C (3000nm- 1mm) mainly
absorbed by water in epidermal layers – heat formation Retrograde
signaling

35 Advanced Sun Protection | Comprehensive Information

IR light sources

1 Natural sunlight

2 Fire

3 Radiators

4 IR heating Source: conrad.electronic.co.uk

Quartz IR Radiator 1500 W 9m²

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 3.2
performance
of TiO2 in
near-infrared
light range

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Performance of TiO2 in IR-A range
Test Design

Products Placebo emulsions: (I) o/w, (II) w/si

Test emulsions (I), (II) with Titanium Dioxide (5 - 25 %)

Method Photometric measurements of transmission T (%) with Perkin Elmer Lambda

900 in short cut cuvettes:
- Defined film thickness of 0.1 mm
- Wavelength: 800 – 1450 nm

Read out Protection (%)= [1- T(emulsion with TiO2)/ T(base emulsion)] x 100

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(I) o/w test formulation

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IR-A protection
(I) Transmission/ Reflection/ Absorption in o/w emulsion

o/w placebo emulsion without any filter/ pigment

70
Placebo:
Transmission/ Reflection/ Absorption [%]

60

50 ~ 65% Transmission
40 ~ 25% Reflection (including
Scattering)
30

20
~ 8% calculated Absorption
10

0
800 900 1000 1100 1200 1300 1400
Wavelength [nm]

Transmission [%] Reflection [%] calc. Absorption [%]

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IR-A protection
(I) Performance of Titanium Dioxide in o/w formulation

80%

64%

Protection
60% 63%
• In this o/w emulsion
Transmisssion [%]

59%
system,
51%
47% Eusolex® T-PRO and
40%
Eusolex® T-AVO
could reduce
IR-A transmission at a
20% use level of 10%.

0%
Placebo Eusolex® T-AVO Eusolex® T-PRO

5% 10%

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(II) w/si test formulation

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IR-A protection
(II) Performance of Titanium Dioxide in w/si formulation

80%
80%
74%

Protection
70%

60% 62% • In this w/si emulsion

Transmisssion [%]

61%
system, TiO2 UV
53%
49% filters could reduce
40%
IR-A transmission up
40%
37%
to 55% compared to
the basis emulsion.

20%
• Performance
dependent on use
level, coating/ surface
treatment of TiO2
0%
Placebo Eusolex® T-AVO Eusolex® T-PRO Eusolex® T-S

5% 10% 20% 25%

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IR-A protection – Summary
Performance of titanium dioxides

➢ It could be shown that titanium dioxides protect

against IR-A light (800-1450 nm).

➢ The effect is dependent on the type of Titanium

Dioxide, use level and type of formulation.

➢ Best performance could be achieved by Eusolex®

T-PRO in an o/w emulsion. Additionally only this
titanium dioxide type works also as second defense
line due to its antioxidative properties.

➢ In a w/si emulsion, Eusolex® T-S showed the best

ability to reduce the transmission in the IR-A light.

44 Advanced Sun Protection | Comprehensive Information

 3.3
Performance
of functional
Fillers in
near-infrared
light range

45 Advanced Sun Protection | Comprehensive Information

Performance of fillers in IR-A range
Test Design

Products o/w Placebo emulsions

o/w Test emulsions with functional fillers (3-5 %) (I)

Method Photometric measurements of transmission T (%) with Perkin Elmer Lambda

900 in short cut cuvettes:
- Defined film thickness of 0.1 mm
- Wavelength: 800 – 1450 nm

Read out Protection (%)= [1- T(emulsion with TiO2)/ T(base emulsion)] x 100

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(I) o/w test formulation

47 Advanced Sun Protection | Comprehensive Information

IR-A protection
(I) Transmission/ Reflection/ Absorption in o/w emulsion

o/w placebo emulsion without any filter/ pigment

70
Placebo:
Transmission/ Reflection/ Absorption [%]

60

50 ~ 65% Transmission
40 ~ 25% Reflection (including
Scattering)
30

20
~ 8% calculated Absorption
10

0
800 900 1000 1100 1200 1300 1400
Wavelength [nm]

Transmission [%] Reflection [%] calc. Absorption [%]

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 IR-A protection
(I) Performance of functional fillers in o/w formulation

64

Protection
54
52
Transmission [%]

47 48
• In this o/w emulsion
44 44
40
system,
35 38 RonaFlair® Balance
Blue and Balance
Red could reduce
IR-A transmission up
to 40% at 5% use
level.

0
Placebo Balance Red Balance Blue Balance Gold Balance Green

3% 5%

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IR-A protection
(I) Performance of filler + titanium dioxide in o/w formulation

60%
60%

45% 50 % • Combination Eusolex®

protection
Transmission [%]

T-PRO / RonaFlair®
36%
30% Balance Blue provided
30% a superb transmission
27%
reduction of 50% of
IR-A light.
• Additive effects:
25% for Eusolex® T-PRO
PLUS 40% for RonaFlair®
0%
Balance Blue
Placebo 10% T-PRO 5% Balance 10% T-PRO+ 10% T-PRO+
Blue 5% B. Blue 5% B. Blue
(measured) (calculated)

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Summary IR-A protection
Performance of functional fillers

➢ It could be shown that functional fillers protect

against IR-A light (800-1450 nm).

➢ The effect is dependent on the type of functional

filler and the use level.

➢ Excellent performance could be achieved by

RonaFlair® Balance Blue and Balance Red in an
o/w emulsion.

➢ A combination of RonaFlair® Balance Blue and

Eusolex® T-PRO gives an additional protection.

51 Advanced Sun Protection | Comprehensive Information

Conclusion
Protective solution for
N-IR and HEV protection as
first defense line through

Titanium dioxide &

Functional Fillers
alone or in combination
depending on formulations and claims
Appendix
Test materials
Titanium dioxides

Merck name INCI Properties Description

Eusolex® T-AVO Titanium dioxide (nano), Silica Hydrophilic powder, can also Alumina free, nature-identical,
be added to oil phase for ‚green‘ cosmetics, pushes
Avobenzone efficacy
Eusolex® Titanium Dioxide (nano), Silica, Hydrophobic powder, can also Alumina free, excellent
T-EASY* Cetyl Phosphate be added to water phase compatibility with demanding
raw materials
Eusolex® T-PRO Titanium Dioxide (nano), Hydrophilic powder, can also The transparent anti-aging
Alumina, Manganese Dioxide be added to oil phase pigment, nature-identical, for
‚green‘ cosmetics
Eusolex® T-S Titanium Dioxide (nano), Hydrophobic powder Vegetable derived surface
Alumina, Stearic Acid coating, nature-identical, for
‚green‘ cosmetics

*not available for Europe

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Test materials
Filler

Merck name INCI Properties Description

RonaFlair® Titanium dioxide, Bluish- white powder Helps to compensate a rather yellowish skin
Balance® Blue Mica, Tin oxide medium coverage base, e.g. of Asian skin alone or in
combination with Balance Gold and Red.
RonaFlair® Titanium dioxide, Reddish white powder Adds natural freshness and luminosity to
Balance® Red Mica, Tin oxide medium coverage any skin type. Can be combined with
Balance Gold and Blue to modify any
existing skin tone.
RonaFlair® Titanium dioxide, Greenish-white powder Provides a visible effect due to its intensive
Balance® Green Mica, Tin oxide medium coverage interference. Effective in compensating
reddish parts of the skin.
RonaFlair® Titanium dioxide, Yellowish white powder Provides high Chroma. Helps to balance out
Balance® Gold Mica, Tin oxide high coverage slightly reddish skin. Darker skin types will
be brightened nicely.

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Literature

1. Dupont et al: Beyond UV radiation: A skin under challenge, Int. Journal Cos. Science 2013, 35: 224-232
2. Schieke et al: Cutaneous effects of infrared radiation: from clinical observations to molecular response mechanisms,
photodermal photoimmunol Photomed 2003, 19: 228-234
3. Duteil et al: Differences in visible light-induced pigmentation according to wavelengths: a clinical and histological
study in comparison with UVB exposure, Pigment Cell Melanoma Res, 27: 822-826
4. Sklar et al: Effects of ultraviolet radiation, visible light, and infrared radiation on erythema and pigmentation: a
review, Photochem Photobiol Sci, 2013, 12: 54
5. Mahmoud et al: Effects of visible light on the skin, Photochem and Photobio, 2008, 84:450-462
6. Cho et al: Infrared plus visible light and heat from natural sunlight participate in the expression of MMPs and type I
procollagen as well as infiltration of inflammatory cell in human skin in vivo, Journal of Dermatological Science 2008,
50: 123-133
7. Schieke et al: Infrared-A radiation-induced matrix metalloproteinase 1 expression is mediated through extracellular
signal-regulated kinase ½ activation in human dermal fibroblasts, Society of Investigative Dermatology 2002, 1323-
1329
8. Calles et al: Infrared-A radiation influences the skin fibroblast transcriptome: mechanisms and consequences, Journal
of Investigative Dermatology 2010, 130: 1524-1536

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Literature

9. Shaath et al: Infrared radiation & skin protection, The Sunscreen Filter 2012, www.happi.com
10. Liebel et al: Irradiation of skin with visible light induces reactive oxygen species and matrix degrading enzymes,
Journal of Investigative Dermatology 2012, 132: 1901-1907
11. Mahmoud et al: Impact of long-wavelength UVA and visible light on melanocompetent skin, Journal of Investigative
Dermatology 2010, 130: 2092-2097
12. Akhalaya et al: Molecular action mechanisms of solar infrared radiation and heat on human skin, Ageing Research
Reviews 2014, 16: 1-11
13. Mattsson et al: Scientific Committee on Emerging and Newly Identified Health Risks SCENIHR, Health Effects of
Artificial Light, 2012
14. James et al: Sunscreens: Myths, controversy and photo protection beyond UV, www.dermascope.com
15. Zastrow et al: The missing link – light-induced (280-1600 nm) free radical formation in human skin, Skin Pharmacol
Physiol 2009, 22:31-44
16. Schroeder et al: The role of near infrared radiation in photoaging of the skin, Experimental Gerontology 2008, 43:
629-632
17. Randhawa et al: Visible light induces melanogenesis in human skin through a photoadaptive response, Johnson and
Johnson Skin Research Center 2015

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