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Lab Course Renewable Resources: Starch-based nano-particles

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1 Lab Course Renewable Resources: Starch-based nano-particles
CePoL/MC - Central Polymer Lab / Molecular Characteristics @ IfC - Inst. f. Chemie, KFU - Karl-Franzens-Univ. Graz / Austria / Europe Lab Course Renewable Resources: Starch-based nano-particles Anton HUBER, Shazia JUNA In a number of lectures in the last days the importance of supermolecular structures have been claimed, in particular to understand biosynthesis of cellulose. In the next minutes I try to show you, that this claim holds not only for cellulose but micht be a gerneral propertiy of glucans or PS in general. description of audience + status of knowledge + needs + goals motivation of the lecture with respect to results for the audience ntroduction with an interesting (new, controversial, ...) topic, either as statement or question e.g.: Nothing new but maybe something somehow different Outline / Content European Polysaccharide Network of Excellence wwww.epnoe.org

2 Material Characteristics
body surface interface technology:domains hydro colloids supermolecular structures crystalline amorphous gel / glass chemistry: states dissolved a lot has been told and written in the book of abstracts about sources and occurence of cellulose and callose (b-1-4, and b1-3). maybe this slide is some supplumentary information, where glucans might be found: functionality: structure, storage, metabolic products sources basic chemistry

3 Starch: granules formed by molecules
a lot has been told and written in the book of abstracts about sources and occurence of cellulose and callose (b-1-4, and b1-3). maybe this slide is some supplumentary information, where glucans might be found: functionality: structure, storage, metabolic products sources basic chemistry Serge Perez, CNRS Grenoble, F / Eric Bertoft, Abo Akademi Univ, Turku / SF

4 Carbohydrates Aldoses aldo-triose, aldo-tetraoses, aldo-pentoses, aldo-hexoses Ketoses keto-triose, keto-tetraoses, keto-pentoses, keto-hexoses a lot has been told and written in the book of abstracts about sources and occurence of cellulose and callose (b-1-4, and b1-3). maybe this slide is some supplumentary information, where glucans might be found: functionality: structure, storage, metabolic products sources basic chemistry cyclic form: hemi-acetals cyclic form: hemi-ketals polymerization: formation of (full)acetals / (full)ketals by glycosidic linkages

5 Polysaccharides: Made by Nature®
glycosidic linkage -D-Glcp- (14)--D -Glcp -D-glycopyranosyl- (14)--D -glucopyranose ( maltose ) -D-Glcp- (12)--D -Fruf -D-glucopyranosyl- (12)--D -fructofuranosid ( sucrose ) a lot has been told and written in the book of abstracts about sources and occurence of cellulose and callose (b-1-4, and b1-3). maybe this slide is some supplumentary information, where glucans might be found: functionality: structure, storage, metabolic products sources basic chemistry

6 Polysaccharides: Made by Nature®
modified unimers oxidation @ C6-position  uronic acid oxidation / substitution @ C2-position → acetate oxidation / C2-position  glucosyl-2-amine basic (14) linked glycosyl residue oxidation / activation @ C6-position  glucosyl-6-phosphate oxidation / substitution / C2-position  glucosyl-2-N-acetyl oxidation / substitution / C4-position → glycosyl-4-sulfate a lot has been told and written in the book of abstracts about sources and occurence of cellulose and callose (b-1-4, and b1-3). maybe this slide is some supplumentary information, where glucans might be found: functionality: structure, storage, metabolic products sources basic chemistry

7 Symmetry / conformation of starch glucans
→4)-αD-Glcp-(1→4)-αD-Glcp-(1→ non-branched starch component nb-glucans / amylose-type helical conformation D(14)-glucans + (16) Glcx branches lcb / scb glucans / amylopectin-type (long-chain-branched / short-chain-branched) irregular / globular conformation oxidation / activation @ C6-position  glucosyl-6-phosphate a lot has been told and written in the book of abstracts about sources and occurence of cellulose and callose (b-1-4, and b1-3). maybe this slide is some supplumentary information, where glucans might be found: functionality: structure, storage, metabolic products sources basic chemistry

8 Starch glucan populations
homogeneous scb glucan cereal starch amaranth up to °C in DMSO scb + lcb heterogeneous glucan cereal starch wheat up to °C in DMSO a lot has been told and written in the book of abstracts about sources and occurence of cellulose and callose (b-1-4, and b1-3). maybe this slide is some supplumentary information, where glucans might be found: functionality: structure, storage, metabolic products sources basic chemistry

9 Managing Heterogeneity by Fractionation
LC afFFF/ AF4 Entropy controlled separation (S/k) due to differences in excluded volume (Ve) Size Exclusion Chromatography (SEC) Diffusion mobility controlled separation due to 1st approach: differences in excluded volume (Ve) asymmetric flow field flow fractionation (afFFF or AF4)

10 Distributions and Mean values by Separation and Detetection

11 asym flow Field Flow Fractionation: AF4

12 asymmetric Field Flow Fractionation: AF4
objects are separated according to differences in their diffusion coefficient / difusive mobility

13 Diffusive Mobilty DT Hydrodynamic Radius Rh
Stokes-Einstein: DT from retention times (tr) of AF4 t0 (void time), Fcr (cross-flow), w (channel thickness), V0 (void volume) and tr (retention time) T (temp), k (Boltzmann const), η (intrinsic visc)

14 Light Scattering Detection: Scattering vs. Spectroscopy
probing soft matter by radiation (typically electromagnetic, but also neutrons). The electromagnetic radiation introduces dipole oscillations. Part of the energy will be absorbed when close to resonance → spectroscopy Any acceleration of charges leads to emission of secondary radiation → scattering field. Analysis of the scattered field provides information about local structure (due to interference) and mobility (time dependence of the signal) of the sample At short wavelengths (X-rays) we are far above most resonance frequencies (spectroscopy), all electrons are polarized and emit a secondary wave, i.e. the signal will depend on the electron density At much larger wavelengths (visible light) we are below most resonances, but we only polarize the valence electrons. The polarizablility is a function of the wavelength and is related to the refractive index.

15 Static and Dynamic Scattering

16 Scattering facts Zimm plot x-axis: sin2(Θ/2) + k c  q2 + k c
y-axis: K c / RΘ intercept: 1 / Mw slope (q2  0): Rg slope (c  0): A2


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