Nantes

Morphologies de grains d’amidon

Spherulitic organization of the starch granule

NantesPositive birefringence, average radial orientation

Amylose

OH

H

H

O

CH 2OH

HO OHH

OH

H

H

O

CH2OH

HO OHH

OH

H

H

O

CH2OH

HO OHH

OH

H

H

α(1-4)linkages

Nantes

Mw ~106 -107

Amylopectin

OH

H

H

OHO OH

H

OH

H

H

O

CH2OH

HO OHH

OH

H

H

O

CH2OH

HO OHH

OH

H

H

CH2

H

2CH OH

HH

H

H

HO

OH

O

Ø

cluster

Short chains average DP ~ 15-20,Long chains average DP ~ 40-45,

Average molecular weight around 107-108

5-6% α(1,6) linkages

D ~1 6P 5 ( nm)

α(1-6)linkage

α(1-4)linkage

Nantes

A. Buleon, P. Colonna, V. Planchot and S. Ball (1998) Int. J. Biol. Macromol., 23, 85-112.Nantes

µWAXS

SAXS

Solid state NMR

(0.25 - 2nm)

µMicrobeam diffraction

(1-2 m2)

9-10 nm

Granule1 - 100 m

Amorphousbackground

Growth ring

Amorphous

CrystallineAmorphousCrystallineAmorphousCrystalline

Amorphous

Semi-crystalline structure of starch

(Thickness 150-500nm)

Crystalline type in native starches - WAXS

0 5 10 15 20 25 30

Diffracted Intensity

Diffraction angle

B-type

A-type

Nantes

50556065707580859095100105110115

Chemical shift in ppm

C1

C-2,3,4,5

C6A-type15% H2O

A-type20% H2O

B-type16% H2O

B-type24% H2O

Crystalline type in native starches - solid state NMR

M. Paris, H. Bizot, J. Emery, J.Y. Buzare and A. Buleon (1999)Carbohydr. Polym., 39, 327-339Nantes

Internal polymorphism within a C-type starch granule (pea)

DiffractedIntensity

Bragg angle (2 thetas)

Pea starch60%A/ 40%B

5 10 1 5 2 0 25 30

A. Buleon, C. Gerard, C. Riekel, R. Vuong and H. Chanzy (1998). Macromolecules, 31, 6605-6610Nantes

Synchrotron microbeam (1µm) mapping

Main enzymes involved in the starch granule formation

Soluble Starch Synthases : SSSGranular Bound Starch Synthases : GBSSBranching Enzyme : BEDebranching Enzymes : DBEDisproportionating Enzyme : D

Genetic control and crystalline structure

5 10 15 20 25 30

0 100

0100208050507030

aewxaeaeduduwx

% A % B

Polymorphictype

2θ(Bragg Angle)

Diffracted Intensity

wx ae

wxwx duWM

1520

25

30

35

40

4550

0 20 40 60 80 100

AMaeduae

su2dusu2

du

NM

Crystallinity (±4%)

Amylopectin content (%)

Nantes Gerard c., Planchot v., Buleon a. Colonna p. in “ Biopolymer Science :Food and Non Food Applications ”, INRA Ed., n°91, 1999, p 59-63.

5 10 15 20 25 30

10°C

20°C

30°C

Bragg angle

Diffracted Intensity

A/B100/0

20/80

70/30

Growth temperature and crystalline structure

Nantes

7.521Tex + 5

14.520Tex

1921Tex - 5

B/ACrystallinity

± 5%

T °C / T

external

Wheat starch

Pea starch

Easily Degradable

Fraction

0

0.1

0.2

0.3

0.4

0 10 20 30 40Time (days)

log 100/(100-X)

0 5 10 15 20 25Repeat (nm)

ScatteredIntensity Native

Hydrolysed 12 days

Normal maize - SAXS

8.8 nm

6.6 nm

Amorphousbackground

A m o rp h o u sC ry s ta llin e

A m o rp h o u s

A m o rp h o u s

A m o rp h o u sC rys ta llin e

C ry s ta llin e

Mild acid hydrolysis of native starch (lintnerization)

Nantes

Crystalline lamellae prepared by acid hydrolysis (waxy maize starch)

Nantes Pohu, A; Putaux, J.-L.; Planchot, V.; Colonna, P.; Buleon, A. Biomacromolecules, 2004, 5(1), 119-125.

A-type amylose lamellar crystals

Imberty, H. Chanzy, S. Perez, A. Buleon & V. Tran (1988). J. Mol. Biol.,201, 365-378. Nantes

Nantes

Helical conformation and starch or recrystallized amylose

6 monomers per turnPitch : 2.13 nm

6 monomers per turnPitch : 0.8 nm

Stacking of lamellae with a common chain axis

A-type low DP crystals : negative staining and morphology

Pohu, A; Putaux, J.-L.; Planchot, V.; Colonna, P.; Buleon, A. Biomacromolecules, 2004, 5(1), 119-125.Nantes

B-type amylose lamellar crystals

A. Imberty, A. Buleon, V. Tran and S. Perez (1991). Starch/Staerke, 43, 375-384. Nantes

Nantes Oostergetel G.T. and van Bruggen E.F. Carbohydr. Polym. 1993, 21:7.

Schematic model for the arrangement of amylopectin in potato starch in a ‘super-helical’ organisation (from Oostergetel & van Bruggen ).

The « super helical » model

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The Blocklet model

Gallant D., Bouchet B. and Baldwin P. Carbohydr. Polym 1997, 32:177.Nantes

DRY GLASSY NEMATIC STRUCTURE

Glassy nematic helices

Glassy backbone and spacers

HYDRATED SMECTIC STRUCTURE

Highly plasticized liquidbackbone and spacers

Lamellarperiodicity

Nantes

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sont requis pour visionner cette image.

Waigh T., Perry P., Riekel C., Gidley M., Donald A. (1998), Macromolecule 31, 7980.

The side chain liquid crystal model