ROPERS Marie-Hélène 1, MEISTER Annette 2, RALET Marie-Christine 1
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1 ROPERS Marie-élène 1, MEISTER Annette 2, RALET Marie-Christine 1 1 Institut National de la Recherche Agronomique, Unité Biopolymères, Interactions, Assemblages, Nantes (France 2 Institute of Physical Chemistry, Marthin Luther University alle- Wittenberg, alle (Germany
2 What are Pectins? O Polysaccharides from fruits and vegetables ROOC O O O O n>50 omogalacturonan α- D- (1 4 galacturonic acid R =, C 3 DM RhamnoGalacturonan omogalacturonan Visser & Voragen, Pectins and pectinases, Elsevier 1996 Propriétés : sugar composition, DM, M w, polydispersity pka (dissociation, DM, viscosity (C, DM gelation : Food applications (E440 pastry, jellies, jams milk drinks Neutral sugars (arabinans, galactans (~ 5% Polyelectrolyte Interactions +/- Charge distribution
3 Modified Pectines Chemical or enzymatical de-esterification of highly methylated pectins Ralet M.C., Dronnet V., Buchholt.C. and Thibault J.-F., Carbohydr. Res., 336 ( base (series B : random distribution of charge (COO - fungus PME (series F : plant PME (series P : random like distribution block distribution ow does the charge distribution affect the interfacial properties of surface active molecules? surfactant (C N + (C 3 2 DODAB Pectin B34, F31 or P32 air water Langmuir films at the air/water interface isothermes de compression / BAM IRRAS
4 Interface air-eau (BAM Langmuir Films Principle of the Brewster angle microscope BAM Laser (p Capteur de Pression camera vidéo barrière Analyseur p barrière lumière polarisée parallèlement au plan d incidence: tan (θ = n liquide / n air
5 Interface air-eau (BAM Langmuir Films Principle of the Brewster angle microscope BAM Laser (p Capteur de Pression camera vidéo barrière Analyseur p barrière
6 Air-water interface (BAM Isotherms of compression and morphology of DODAB/pectin films 60 Surface tension, mn/m Α ~ 105Å 2 π ~ 10-20mN/m P32 F31 water B Molecular Area, Å 2 500µm Modification of the lipid film properties at the air-water interface shift to higher areas and pressures discrimination of the interfacial behavior through the charge distribution (P32-block < F31-random like, B34 random hairy (F31, B34 and smooth aggregates (P32 pectin/lipid assembly charge distribution
7 Air-water interface (IRRAS Spectres IRRA des films DODAB/pectine IR (s, p Capteur de pression détecteur MCT barrière barrière Films spread in the same conditions as R for BAM measurements R 0 IRRA spectra measured on the filmcovered surface (R et on the film-free surface (R 0
8 Air-water interface (IRRAS IRRA spectra of DODAB/pectin film π=35mn/m - Log (R/R 0 0,020 0,015 0,010 0,005 ν s (OCO δ (C 2 ν as (C 2 water F31 B34 P32 0,000-0,005 Galacturonane wavenumber, cm -1 Separate modes of vibration allowing a separated evaluation of the binding effect
9 Air-water interface (IRRAS C Asymmetric stretching vibration mode of C 2 ν as (C 2, cm water unordered P32 F31 B34 DODAB more ordered Film pressure, mn/m The decrease in wavenumber of the asymmetric stretching vibration mode ν as (C 2 = increased ordering of alkyl chains (ν as >2920cm -1 : non ordered phase Pectins induce a higher disorder (B34<F31<P32
10 Air-water interface (IRRAS C δ(c 2, cm P32 F31 B34 2 peaks orthorhombic 1 peak hexagonal Bending mode δ(c Film pressure, mn/m The bending mode δ(c 2 gives the local ordering (100 molecules. 1 peak = hexagonal, 2 peaks = orthorhombic packing the charge distribution affects the ordering : the transition pressure (orth. hex. increases in the order eau< B34<F31. P32 prevents the formation of the hexagonal packing.
11 Air-water interface (IRRAS O O δ (C 2 C Symmetric stretching vibration mode of COO - groups - Log (R/R 0 0,000 water F31 B34 P32 ν s (OCO wavenumber, cm -1 The symmetric and asymmetric vibration mode ν s (OCO and ν as (OCO of pectin splits into two peaks = 2 COO- around N+
12 Conclusion The properties of DODAB at the air-water interface are modified by pectins visible at the microscopic scale by surface tension and BAM visible at the molecular scale by IRRAS. The structure of the film depends on the pectin charge distribution Film morphology (B34, F31 P32 DODAB film more disordered on pectin subphases (disorder pressure Orthorhombic-to-exagonal transition appearing at increased film pressure in the order water>b34>f31>p32 (no transition for P32 Splitting of the stretching vibration mode of COO - : two kinds of environment. Pectin may act on film structure at interfaces
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