THE INS AND OUTS OF YOUR SKIN. Emma Sparr Physical Chemistry Lund University
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1 THE INS AND OUTS OF YOUR SKIN Emma Sparr Physical Chemistry Lund University
2 The skin - A Responding Barrier Membrane stratum corneum (10 20 µm) Water CO 2 Temperature ph 5.5 O 2 Moisturizers, Drugs etc ph 7.4
3 The skin - A Responding Barrier Membrane stratum corneum (10 20 µm) Water Water flux across stratum corneum versus RH (Blank et al J Invest Dermatol 1984) RESPONDING MEMBRANE - Protects from evaporation!
4 Responding membranes? Non-responding membrane
5 Responding membranes? Non-responding membrane Responding membrane
6 The skin - A Responding Barrier Membrane stratum corneum (10 20 µm) Water Water flux across stratum corneum versus RH (Blank et al J Invest Dermatol 1984) RESPONDING MEMBRANE - Protects from evaporation!
7 Water The skin - A Responding Barrier Membrane a skin <0.9 P skin low Impermeable SC a skin >0.9 P skin high SC more permeable
8 Stratum Corneum Brick & Mortar Corneocytes in a lipid matrix Stacked lipid bilayers Lipid
9 Mortar... Scale indicator = 250 Å = 250*10-10 m [Swartzendruber et al., J. Invest. Dermatolgy1989]
10 Small size domains Domain Mosaic Model (B Forslind 1994) Atomic force microscopy (AFM) on model mixtures of skin lipids 1 1 µm (Sparr, Eriksson, Bouwstra, Ekelund., Langmuir, 2001; Ekelund, Eriksson, Sparr, BBA, 2000)
11 Questions Why do we not evaporate during a dry day? How can we understand skin occlusion? What can moisturizers do to dry skin?
12 APPROACH Coupling between structure & transport Model membranes Theoretical model Stratum corneum n=n n=n-1 n=2 n=1 (Sparr, Åberg, Nilsson, Wennerström, Soft Matter 2009)
13 Responding membranes
14 Responding membranes Water
15 Responding membranes Water Membrane Respond to Water Gradient Inhomogeneous swelling
16 Responding membranes Water Membrane Respond to Water Gradient Inhomogeneous swelling Isothermal sorption calorimetry sc corneocytes lipids Silva, Topgaard, Kocherbitov, Pais, Sousa, Sparr, BBA 2007]
17 Responding membranes Water Membrane Response to Water Gradient Inhomogeneous swelling Phase transitions dehydration e.g. phospholipids, ceramides
18 Responding membranes Water Membrane Response to Water Gradient Inhomogeneous swelling Phase transitions Extracted skin lipids, NMR FID 35 C 40 C (Silva, Topgaard, Sparr, Manuscript)
19 (Sparr & Wennerström, Biophys. J. 2001) Transport in responding membranes Constant gradient in model susbtance (ex nicotine) Vary water gradient
20 Transport in responding membranes Constant gradient in model susbtance (ex nicotine) Vary water gradient (Sparr & Wennerström, Biophys. J. 2001) The water gradient regulate the barrier properties (compare skin occlusion)
21 Water flux as a function of RH Exp. data for stratum corneum (Blank et al J Invest Dermatol 1984)
22 Why do we not evaporate on a dry day? Water flux vs water gradient Water flux ( 10 4 mol m -2 s -1 ) Water flux ( 10 6 mol m -2 s -1 ) RH (%) Model calculations (Sparr & Wennerström, Biophys. J. 2001) Exp. data for stratum corneum (Blank et al J Invest Dermatol 1984)
23 Responding membranes The skin: a membrane that is exposed to several different gradients and different environments (not equilibrium!) Stratum corneum behave as a responding membrane - Cannot be described by a simple permeability but depends on the external conditions (eg hydration) The membrane barrier properties can be regulated by an external gradient- Switch
24 Questions Why do we not evaporate during a dry day? How can we understand skin occlusion? What can moisturizers do to dry skin?
25 dehydration Fluid membranes More permeable Swell in water More flexible / elastic Solid membranes Impermeable Minor swelling in water Less flexible / elastic
26 MOISTERIZERS & LIPID MEMBRANES dehydration Fluid membranes More permeable Swell in water More flexible / elastic Solid membranes Impermeable Minor swelling in water Less flexible / elastic Add moisterizer; Urea or Glycerol What happens?
27 Lipid dehydration in the presence of urea 20 hydration 15 L β L α n w /n l RH (%) Sorption microbalance + X-ray scattering (SAXS, WAXS)
28 Lipid dehydration in the presence of urea L β hydration +urea L α n w /n l % urea 0 % urea RH (%) FLUID MEMBRANE PRESENT AT LOWER RH
29 Lipid dehydration in the presence of urea / glycerol T ( C) Lipid in water RH (%)
30 Lipid dehydration in the presence of urea / glycerol T ( C) 40 T ( C) 40 Pure lipid 30 with urea 30 T ( C) RH (%) RH (%) RH (%)
31 MOISTERIZERS & LIPID MEMBRANES dehydration Fluid membranes More permeable Swell in water More flexible / elastic Solid membranes Impermeable Minor swelling in water Less flexible / elastic Add moisterizer; Urea or Glycerol
32 MOISTERIZERS & LIPID MEMBRANES In the presence of urea or glycerol the properties of the fully hydrated system is retained also under dehydration Urea and glycerol protects the fluid membrane structure under dehydration Moisturizing properties: fluid membranes that are also able to swell in water
33 CONCLUSIONS The stratum corneum is a clear non-equilibrium system - Many parallel transport processes Stratum corneum behave as a responding membrane - Cannot be described by a simple permeability but depends on the external conditions (eg hydration) Switch: The responding membrane barrier properties can be regulated by an external gradient Moisturizers like urea or glycerol can protect the fluid membrane structure under dehydration
34 Acknowledgements Christoffer Åberg (Physical Chemistry, Lund) Fatima Costa-Balogh (Physical Chemistry, Lund; Dept Pharmacy, Coimbra) Stephane Douzane (Physical Chemistry, Lund; ESPCI, Paris) Håkan Wennerström (Physical Chemistry, Lund) Johan Engblom (Malmö University) Lars Wadsö (Building Materials, Lund) Claudia Silva (Dept Pharmacy, Coimbra) Daniel Topgaard (Physical Chemistry 1, Lund) Vitaly Kocherbitov (Malmö University) Craaford foundation
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37 Water profile of skin No hydration After 45 min hydration with wet bandage SC Viable epidermis In vivo determination of water concentration profiles in human skin by depth-scanning confocal Raman microspectrometry Caspers et. el. J. Raman Spectrosc. 31, (2000)
38 How does small polar molecules, like urea or glycerol, protect lipid membranes against osmotic stress? dehydration Urea or Glycerol Model system: DMPC, urea (or glycerol), water Techniques: Calorimetry, X-ray scattering (SAXS+WAXS), MAS NMR, Sorption microbalance
39 Lipid dehydration in the presence of urea DSC DMPC, in excess water-urea 40 % urea 86.0 %RH 30 % urea 90.5 %RH T ( C) 40 no urea Phase diagram 20 % urea 94.1 %RH Endothermic 10 % urea 97.2 %RH 30 5 % urea 98.6 %RH 0 % urea 100 %RH Temperature ( o C) with urea RH (%) (Costa-Balogh, Wennerström, Wadsö, Sparr, J. Phys. Chem. 2006)
40 Lipid dehydration in the presence of urea Urea - A polar molecule with low vapor pressure Urea replaces water in an almost ideal way - Retains the properties of the fully hydrated system Urea protects the liquid crystalline phase upon dehydration T ( C) no urea with urea RH (%)
41 CONCLUSIONS The stratum corneum is a clear non-equilibrium system - Many parallel transport processes The membrane barrier properties can be regulated by an external gradient - Switch - A possible explanation for non-linear transport behavior in stratum corneum Transport of water and CO 2 across the bilayer membrane can give rise to a ph gradient Urea can replace water and protect the fluid structures - possible mechanism also for skin care products and urea naturally present in the stratum corneum.
42 Acknowledgements Christoffer Åberg (Physical Chemistry 1, Lund) Fatima Costa-Balogh (Physical Chemistry 1, Lund; Dept Pharmacy, Coimbra) Cécile Pairin (Physical Chemistry 1, Lund; ENSCP Paris) Lars Wadsö (Building Materials, Lund) Håkan Wennerström (Physical Chemistry 1, Lund)
43
44 Stratum corneum lipids Sorption calorimetry sc SC lipids Δh w corneocytes lipids Δµ w Swelling of both lipids and corneocytes Exothermic transitions in SC lipids at %RH (Silva, Topgaard, Kocherbitov, Pais, Sousa, Sparr, BBA 2007)
45 MODEL SYSTEM Phospholipid (DMPC) and urea The overall phase behavior is hardly affected by the presence of urea Urea replaces the water in an almost ideal way lamellar repeat distance Replace water by urea (Costa-Balogh, Wennerström, Wadsö, Sparr (2006) J Phys Chem B)
46 Lipid dehydration in the presence of urea L β hydration +urea L α 20 % urea 10 % urea 1 % urea 10 0 % urea Urea protects the liquid crystalline (L α ) phase upon dehydration Sorption microbalance + X-ray scattering (SAXS, WAXS) (Costa-Balogh, Wennerström, Wadsö, Sparr, J. Phys. Chem. 2006)
47 Cell membrane Stratum corneum LIPID MEMBRANE Alveolar membrane Drug delivery system
48 Temperature-induced transition DMPC in excess urea-water solution 20 % urea 20 C 25 C 20 C 25 C T m L β L α The overall phase behavior is hardly affected by the presence of urea The weakening of hydrophobic interactions caused by urea is by far not sufficient to solubilize / disturb the lamellar phases (compare protein denaturation)
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