A procedure is described to estimate the persistence length and related properties of a persistent polymer by MD simulations of a small fragment, including solvent effects. The procedure is applied to cellulose in aqueous solution, which leads to an upper limit of the persistence length of 145 ± 10 Å. The occurrence of small amounts of folded conformations seems to be indicated by comparison of the theoretical with experimental data. The behavior of the cellulose chain is consistent with the Kratky−Porod wormlike model.

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Ageing of gelatinised and partly gelatinised potato starch and wheat starch were investigated in the presence of plasticisers with increasing size and number of OH groups (ethylene glycol, glycerol, threitol, xylitol, glucose, and for potato starch also maltose). The influences of these plasticisers and of granular remnants (ghosts) on recrystallisation were determined by using X-ray diffraction. Recrystallisation of potato starch samples in the presence of plasticisers resulted in crystallinity indices of ,0.5. The largest reduction in potato starch recrystallisation is found for threitol (4 OH) and xylitol (5 OH). In the plasticiser range examined, the crystallisation inducing effect of granular potato starch remnants is reduced better when the plasticiser contains more OH groups. Wheat starch recrystallises to a lesser extent than potato starch, resulting in crystallinity indices of , 0.4. The results for wheat starch do not show clear trends for the influences of plasticiser size and of ghosts. The difference in behaviour of the two starches is probably caused by wheat starch having shorter amylopectin chains. Resulting from these shorter amylopectin chains, the remaining structure in wheat starch ghosts may resemble A-type crystallinity, making it more difficult to form B-type crystals. Alternatively, the trends as found for potato starch may occur, but are less manifest for wheat starch, due to the lower total extent of recrystallisation. Solid state CP/MAS NMR spectra of the wheat starch samples containing ethylene glycol were obtained, in order to compare completely and partly gelatinised systems. The spectra were identical, confirming that the ghost structures do not influence wheat starch recrystallisation. Apparently, wheat starch ghosts do not act as nuclei for crystallisation.Similarly, the influence of various malto-oligosaccharides in combination with granular remnants (ghosts) was investigated on wheat starch ageing. Gelatinised and partly gelatinised wheat starch were plasticised with maltose, maltotriose, maltotetraose, maltopentaose or maltohexaose. This resulted in crystallinity indices of , 0.2, with the largest reduction in recrystallisation for maltotriose and maltotetraose. No trend was found for the influence of ghosts. The presence of ghosts did not influence the 13 C solid state HP/DEC NMR spectra. Less recrystallisation took place than with the previously mentioned smaller plasticisers that resulted in crystallinity indices of ,0.4. The finding that maltose was able to reduce retrogradation better than glucose could be of practical importance. q

The interaction between amylopectin, a starch polysaccharide, and ethylene glycol (EG) was investigated using broad-band dielectric relaxation spectroscopy. Water-free amylopectin (AP) was mixed with 21 wt % ethylene glycol. This resulted in a continuous ethylene glycol phase, as well as a molecularly mixed AP/EG fraction. After storage at room temperature or annealing, the mixture shows dynamic properties typical of a polymer with weak intermolecular interactions, suggesting that EG binds preferentially to AP and forms intrachain H-bridges leading to increased chain stiffness and thus an increased glass transition temperature. This structure evolution is accompanied by a sharp reduction in the size of the ethylene glycol droplets to a few nanometers, as revealed by pronounced confinement effects in the R-relaxation of the dispersed EG.

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The interaction of crystalline and amorphous amylopectin with the plasticisers glycerol and ethylene glycol in the absence of water was studied with differential scanning calorimetry (DSC) and solid state NMR. At room temperature glycerol interacts mainly with the amorphous regions, while for ethylene glycol the amylopectin crystallinity does not effect the interaction. After heating the mixtures, an additional immobilisation of the plasticiser occurs.