title: Simultaneous and in situ analysis of thermal and volumetric properties of starch gelatinization over wide pressure and temperature ranges.
abstract: A method for simultaneous and in situ analysis of thermal and volumetric properties of starch gelatinization from 0.1 to 100 MPa and from 283 to 430 K is described. The temperature of a very sensitive calorimetric detector containing a starch-water emulsion at a selected pressure is programmed to rise at a slow rate; volume variations are performed automatically to keep the selected pressure constant while the heat exchange rate and the volume are recorded. The method is demonstrated with a novel investigation of pressure effects on a sequence of three phase transitions in an aqueous emulsion of wheat starch (56 wt % water). The volume changes during the main endothermic transition (M), associated with melting of the crystalline part of the starch granules and a helix-coil transformation in amylopectin, but also with an important swelling, were separated into a volume increase associated with swelling and a volume decrease associated with the transition itself. Thermodynamic parameters for this transition together with their pressure dependencies have been obtained from four independent experiments at each pressure. The data are thermodynamically consistent, but are poorly described by the Clapeyron equation. The negative volume change of the slow exothermic transition (A) appearing just after the main endothermic transition (M) is small, spread out over a wide temperature interval, and occurs at higher temperatures with increasing pressures. This transition is probably associated with reassociation of the unwound helixes of amylopectin with parts of amylopectin molecules other than their original helix duplex partner. The positive volume change of the high-temperature, endothermic transition (N) with a small enthalpy change is probably associated with a nematic-isotropic transformation ending the formation of a homogeneous SOL phase (in the sense of Flory), and is also pushed to higher temperatures with increasing pressures. Knowledge of the state of wheat starch as a function of pressure and temperature is important in extruder processing. The data also provide a basis for the elliptic phase diagram for starch gelatinization. The method is easily adapted to determine similar data for other macromolecular materials.
authors.affiliation: Institute of Physical Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warsaw, Poland. randzio@ichf.edu.pl
authors.forename: Stanislaw L
authors.initials: SL
authors.lastname: Randzio
authors.forename: Marta
authors.initials: M
authors.lastname: Orlowska
mesh_terms: D000687:Amylopectin / Q000737:chemistry; D000688:Amylose / Q000737:chemistry; D001672:Biocompatible Materials / Q000737:chemistry*; D002138:Calibration; D002151:Calorimetry; D002152:Calorimetry, Differential Scanning; D004655:Emulsions; D006358:Hot Temperature; D046911:Macromolecular Substances / Q000737:chemistry*; D011208:Powders; D011312:Pressure; D013213:Starch / Q000737:chemistry*; D013696:Temperature; D013816:Thermodynamics; D014908:Triticum / Q000378:metabolism
chemical_list: D001672:Biocompatible Materials; D004655:Emulsions; D046911:Macromolecular Substances; D011208:Powders; D013213:Starch; D000688:Amylose; D000687:Amylopectin