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

Characteristics of starch-based films with different amylose contents plasticised by 1-ethyl-3-methylimidazolium acetate

Starch-based films plasticised by an ionic liquid, 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]), were prepared by a simple compression moulding process, facilitated by the strong plasticisation effect of [Emim][OAc]. The effects of amylose content of starch (regular vs. high-amylose maize) and relative humidity (RH) during ageing of the samples on a range of structural and material characteristics were investigated. Surprisingly, plasticisation by [Emim][OAc] made the effect of amylose content insignificant, contrary to most previous studies when other plasticisers were used. In other words, [Emim][OAc] changed the underlying mechanism responsible for mechanical properties from the entanglement of starch macromolecules (mainly amylose), which has been reported as a main responsible factor previously. The crystallinity of the plasticised starch samples was low and thus was unlikely to have a major contribution to the material characteristics, although the amylose content impacted on the crystalline structure and the mobility of amorphous parts in the samples to some extent. Therefore, RH conditioning and thus the sample water content was the major factor influencing the mechanical properties, glass transition temperature, and electrical conductivity of the starch films. This suggests the potential application of ionic liquid-plasticised starch materials in areas where the control of properties by environmental RH is desired

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

Facile preparation of starch-based electroconductive films with ionic liquid

Here, we discovered that starch could be straightforwardly processed into optically-transparent electroconductive films, by compression molding at a relatively mild temperature (55 °C or 65 °C), much lower than those commonly used in biopolymer melt processing (typically over 150 °C). Such significantly-reduced processing temperature was achieved with the use of an ionic liquid plasticizer, 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]). A higher [C2mim][OAc] content, lower processing temperature (55 °C), and/or higher relative humidity (RH) (75%) during the sample post-processing conditioning, suppressed the crystallinity of the processed material. The original A-type crystalline structure of starch was eliminated, although small amounts of B-type and V-type crystals were formed subsequently. The starch crystallinity could be linked to the mechanical properties of the films. Moreover, the processing destroyed the original lamellar structure of starch, and the amorphous starch processed with [C2mim][OAc]/water could aggregate on the nanoscale. The films displayed excellent electrical conductivity (> 10−3 S/cm), which was higher with a lower processing temperature (55 °C) and a higher conditioning RH (75%). The incorporation of [C2mim][OAc] reduced the thermal decomposition temperature of starch by 30 °K, while the formulation and processing conditions did not affect the film thermal stability

Characteristics of starch-based films plasticised by glycerol and by the ionic liquid 1-ethyl-3-methylimidazolium acetate : a comparative study

This paper reports the plasticisation effect of the ionic liquid, 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]), as compared with the traditionally used plasticiser, glycerol, on the characteristics of starch-based films. For minimising the additional effect of processing, a simple compression moulding process (which involves minimal shear) was used for preparation of starch-based films. The results show that [Emim][OAc] was favourable for plasticisation, i.e., disruption of starch granules (by scanning electron microscopy), and could result in a more amorphous structure in the starch-based materials (by X-ray diffraction and dynamic mechanical analysis). 13C CP/MAS and SPE/MAS NMR spectroscopy revealed that not only was the crystallinity reduced by [Emim][OAc], but also the amorphous starch present was plasticised to a more mobile form as indicated by the appearance of amorphous starch in the SPE/MAS spectrum. Mechanical results illustrate that, when either glycerol or [Emim][OAc] was used, a higher plasticiser content could contribute to higher flexibility. In spite of the accelerated thermal degradation of starch by [Emim][OAc] as shown by thermogravimetric analysis, the biodegradation study revealed the antimicrobial effect of [Emim][OAc] on the starch-based materials. Considering the high-amylose starch used here which is typically difficult to gelatinise in a traditional plasticiser (water and/or glycerol), [Emim][OAc] is demonstrated to be a promising plasticiser for starch to develop “green” flexible antimicrobial materials for novel applications

Pulping of Crustacean Waste Using Ionic Liquids: To Extract or Not To Extract

Ionic liquids (ILs), such as hydroxylammonium acetate ([NH₃OH]­[OAc]), can reactively demineralize and remove proteins from shrimp shells in an efficient one-pot pulping process, thus allowing the isolation of native chitin with >80% purity and a high degree of acetylation and crystallinity. Compared to a previously reported IL extraction using 1-ethyl-3-methylimidazolium acetate, [C₂mim]­[OAc], these less expensive ILs can achieve comparable chitin yields and purity, at up to ten times the biomass loading, although potentially result in lower molecular weight (MW) chitin. Because the IL is not recovered or recycled, the cost can additionally be further reduced by the sequential addition of hydroxylamine and acetic acid (or <i>vice versa</i>) to conduct the pulping process <i>in situ.</i> Though each methodology results in a comparable yields and purity of chitin material, the varying production costs and process safety issues are still unknown. This work presents a step toward narrowing the choices for chitin isolation technologies that can lead to an economically and environmentally sustainable process replacing the current hazardous, energy consuming, and environmentally unsafe process

State Intervention into the Lives of Single Mothers and Their Children: Toward a Resolution of Maternal Autonomy and Children\u27s Needs

With increased awareness of global sustainability, there has been growing interest in the preparation of materials from natural, eco-friendly polymers (i.e., biopolymers). Nonetheless, despite their enormous application potential, biopolymers (starch, etc.) have a native semicrystalline structure with strong hydrogen bonding, and require use of solvents to improve their processability. However, the dissolution/processing of natural biopolymers such as starch often requires heating and thus significant energy input. Herein, we report an aqueous ionic liquid for fast and facile dissolution of starch, a typical semicrystalline natural polymer, under ambient conditions. The ionic liquid used is 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]). In particular, it is revealed that 0.15:1 mol/mol [C2mim][OAc]:water mixture disintegrates the sophisticated granule structure of native starch without apparently decreasing the molecular mass within 1 h at room temperature (i.e., 28 °C). In addition, this process did not result in any undesired derivatization. The discovery of this phenomenon could provide guidance for rationally designing “green” processes for chemical and biological engineering for the utilization of promising natural biopolymers