Binjia Zhang

Understanding the structural disorganization of starch in water-ionic liquid solutions

Using synchrotron X-ray scattering analyses and Fourier transform infrared spectroscopy, this work provides insights into the solvent effects of water : [C2mim][OAc] solutions on the disorganization of a starch semi-crystalline structure. When a certain ratio (10.2 : 1 mol/mol) of water : [C2mim][OAc] solution is used, the preferential hydrogen bonding between starch hydroxyls and [OAc](-) anions results in the breakage of the hydrogen bonding network of starch and thus the disruption of starch lamellae. This greatly facilitates the disorganization of starch, which occurs much easier than in pure water. In contrast, when 90.8 : 1 (mol/mol) water : [C2mim][OAc] solution is used, the interactions between [OAc](-) anions and water suppress the solvent effects on starch, thereby making the disorganization of starch less easy than in pure water. All these differences can be shown by changes in the lamellar and fractal structures: firstly, a preferable increase in the thickness of the crystalline lamellae rather than that of the amorphous lamellae causes an overall increase in the thickness of the semi-crystalline lamellae; then, the amorphous lamellae start to decrease probably due to the out-phasing of starch molecules from them; this forms a fractal gel on a larger scale (than the lamellae) which gradually decreases to a stable value as the temperature increases further. It is noteworthy that these changes occur at temperatures far below the transition temperature that is thermally detectable as is normally described. This hints to our future work that using certain aqueous ionic liquids for destructuration of the starch semi-crystalline structure is the key to realize green processes to obtain homogeneous amorphous materials.

Understanding the structure and digestibility of heat-moisture treated starch.

To rationalize the effects of heat-moisture treatment (HMT) on starch digestibility, the HMT-induced alterations in the mesoscopic and molecular scale structures of regular and high-amylose maize starches, as well as in their digestibility, were evaluated. Accompanying the supramolecular structural disorganizations and certain molecular degradation induced by HMT, somewhat molecular rearrangements occurred to probably form densely packed starch fractions, which eventually weakened starch digestion and thus transformed RDS into SDS and RS for regular and high-amylose starches. Interestingly, due to its larger amount of inter-helical water molecules that could be induced by HMT, B-polymorphic high-amylose starch was more susceptible to HMT (relative A-polymorphic regular starch), causing more prominent structural evolutions including molecular re-assembly and thus increasingly slowed digestion. In particular, the treated high-amylose starch with 30% moisture content showed a high SDS+RS content (48.3%). The results indicate that HMT-treated starch may serve as a functional ingredient with adjustable enzymatic digestibility for various food products.

Effects of amylose and phosphate monoester on aggregation structures of heat-moisture treated potato starches.

For three cultivars of potato starch, heat-moisture treatment (HMT) displayed an influence on the aggregation structures at different scale levels. With HMT, the granular morphology of potato starch granules remained similarly, and an increase in the average repeat distance of semi-crystalline lamellae was observed. The crystalline structure and birefringence were also affected. Moreover, the polymorphic transformation (B → A+B) could be related to dehydration, whereas the decrease in the degree of crystallinity might be resulted from the rupture of hydrogen bonds. Interestingly, amylose could act as the backbone of the aggregation structures of potato starch to provide resistance to HMT, but phosphate monoester could promote the destruction during HMT. In addition, compared with amylose, phosphate monoester played a more significant role in changing the average repeat distance of semi-crystalline lamellae (long period) during HMT.

Different characteristic effects of ageing on starch-based films plasticised by 1-ethyl-3-methylimidazolium acetate and by glycerol

The focus of this study was on the effects of plasticisers (the ionic liquid 1-ethyl-3-methylimidazolium acetate, or [Emim][OAc]; and glycerol) on the changes of starch structure on multiple length scales, and the variation in properties of plasticised starch-based films, during ageing. The films were prepared by a simple melt compression moulding process, followed by storage at different relative humidity (RH) environments. Compared with glycerol, [Emim][OAc] could result in greater homogeneity in [Emim][OAc]-plasticised starch-based films (no gel-like aggregates and less molecular order (crystallites) on the nano-scale). Besides, much weaker starch-starch interactions but stronger starch-[Emim][OAc] interactions at the molecular level led to reduced strength and stiffness but increased flexibility of the films. More importantly, [Emim][OAc] (especially at high content) was revealed to more effectively maintain the plasticised state during ageing than glycerol: the densification (especially in the amorphous regions) was suppressed; and the structural characteristics especially on the nano-scale were stabilised (especially at a high RH), presumably due to the suppressed starch molecular interactions by [Emim][OAc] as confirmed by Raman spectroscopy. Such behaviour contributed to stabilised mechanical properties. Nonetheless, the crystallinity and thermal stability of starch-based films with both plasticisers were much less affected by ageing and moisture uptake during storage (42 days), but mostly depended on the plasticiser type and content. As starch is a typical semi-crystalline bio-polymer containing abundant hydroxyl groups and strong hydrogen bonding, the findings here could also be significant in creating materials from other similar biopolymers with tailored sensitivity and properties to the environment.

Structural features and thermal property of propionylated starches with different amylose/amylopectin ratio

This work concerned the effects of amylose/amylopectin ratio on the structure and thermal stability of propionylated starches with high degree of substitution (DS). Four starches with different amylose content were used to obtain propionylated starches. Acylation partly disrupted granule morphology of native starches, and the imperfection and porous structures of starch granule were intensified along with the increased amylose content. It was noted that the crystalline structure of starch was destroyed and thus intense acylation occurred in both amorphous and crystalline regions. The acylated starch with high-amylose content displayed more ordered region compared to low-amylose starch. Acylation enhanced the thermal stability of starch, and this effect became more evident as the amylose content increased. Thus, the amylose/amylopectin ratio has been confirmed capable of affecting the structure and thermal behaviors of hydrophobic propionylated starch, which is of value for the design of starchy materials with tailored thermal stability.

Effects of concurrent ball milling and octenyl succinylation on structure and physicochemical properties of starch

This work concerns the effects of concurrent ball milling (BM) and octenyl succinic anhydride (OSA) modification on the starch microstructure and physicochemical properties (swelling, emulsifying, and rheological). Unlike normal OSA-modified starches, the BM/OSA-modified starch displayed new features such as reduced viscosity and rigidity but increased paste stability during shearing, heating and cooling, regardless of the substitution degree. More interestingly, while the physicochemical properties could be regulated by simply altering the BM treatment time, BM/OSA was more efficient and effective at modulating starch properties during the initial period (approx. 10h), as seen by the rapid evolutions in starch structural disruption and OSA esterification. Thus, the BM/OSA modification can serve as a viable and cost-effective approach for producing octenyl succinate starches where low viscosity (at relatively high concentrations) and high paste stability are desired.

Multi-scale structure, pasting and digestibility of heat moisture treated red adzuki bean starch

The pasting and digestibility of a red adzuki bean starch were simultaneously modulated by heat-moisture treatment (HMT) through altering the multi-scale structure. HMT, especially at high moisture content, could disrupt the granule integrity, semicrystalline lamellae, molecular order (crystallites) and molecular chains. Also, certain rearrangement of starch molecules occurred to form ordered structures with increased thermal stability as shown by DSC. This concomitant disordering and reassembly in the multi-scale structure converted the fractions of resistant starch (RS) and rapidly digestible starch (RDS) into that of slowly digestible starch (SDS). Furthermore, the emergence of thermally-stable orders increased the pasting temperature but suppressed the swelling of granules during heating. Hence, HMT-modified red adzuki starch may serve as a potential thickener/gelling agent with slow digestion rate for various foods.

Multi-scale structural changes of starch-based material during microwave and conventional heating

This work revealed the influence of thermal processing on the microstructural, mesoscopic and molecular scale structures and thus the plasticizer migration of the starch ester films. Thermal processing promoted the permeation of water molecules to hinder the shrink of the amorphous macromolecules. That is, the swelling of the amorphous macromolecules diminished the ordered regions to a certain degree, resulting in the enlarged amorphous regions. Along with slight degradation of the macromolecules, the crystallites were partially disorganized, as indicated by a reduced relative crystallinity. These multi-scale structural changes of the films and the thermally enhanced mobility of plasticizer molecules synergistically enhanced the plasticizer migration. This study not only enables a well understanding of how thermal treatment alters the plasticizer migration of starch-based films from a multi-scale structural view, but also hints to our future work that rationally modulating the structural features of starch-based film may effectively control the migration of chemicals.

Hydration-induced crystalline transformation of starch polymer under ambient conditions

With synchrotron small/wide-angle X-ray scattering (SAXS/WAXS), we revealed that post-harvest hydration at ambient conditions can further alter the starch crystalline structure. The hydration process induced the alignment of starch helices into crystalline lamellae, irrespective of the starch type (A- or B-). In this process, non-crystalline helices were probably packed with water molecules to form new crystal units, thereby enhancing the overall concentration of starch crystallinity. In particular, a fraction of the monoclinic crystal units of the A-type starches encapsulated water molecules during hydration, leading to the outward movement of starch helices. Such movement resulted in the transformation of monoclinic units into hexagonal units, which was associated with the B-type crystallites. Hence, the hydration under ambient conditions could enhance the B-polymorphic features for both A-type and B-type starches. The new knowledge obtained here may guide the design of biopolymer-based liquid crystal materials with controlled lattice regularity and demanded features.

Effect of growth period on the multi-scale structure and physicochemical properties of cassava starch

Starches were isolated from South China 5 (SC5) cassava harvested for 7, 8, 9, 10 and 11 months. During growth, the granule size, lamellar structure, crystalline structure and digestibility changed slightly, while the amylose content varied between 20.93% and 22.61%. However, the molecular weight showed an obvious increase as the harvesting time increased to 9 months, and then decreased during 9-11 months. The pasting behaviors were greatly affected by harvesting time. A shorter growth time led to higher pasting temperature, and lower peak, breakdown and setback viscosities. This trend became contrary when the growth time prolonged from 9 to 11 months. Hence, the starch harvested at 9 months showed the lowest pasting temperature (64.6°C), but highest paste viscosity (2105cP) and retrogradation tendency. All these results confirm that the growth time of 9 months was the turning point for the physicochemical features of SC5 during growth. This study provides fundamental data for rationally tailoring cassava starch properties by simply controlling the harvest time.