Physical characterisation of high amylose maize starch and acylated high amylose maize starches.

The particle size, water sorption properties and molecular mobility of high amylose maize starch (HAMS) and high amylose maize starch acylated with acetate (HAMSA), propionate (HAMSP) and butyrate (HAMSB) were investigated. Acylation increased the mean particle size (D(4,3)) and lowered the specific gravity (G) of the starch granules with an inverse relationship between the length of the fatty acid chain and particle size. Acylation of HAMS with fatty acids lowered the monolayer moisture content with the trend being HAMSB

Water sorption properties, molecular mobility and probiotic survival in freeze dried protein-carbohydrate matrices.

The moisture uptake and molecular mobility of freeze-dried powders containing whey protein isolate-carbohydrate matrices (1WPI:2maltodextrin; 1WPI:1maltodextrin:1d-glucose; and 1WPI:1maltodextrin:1l-glucose) and encapsulated Lactobacillus rhamnosus GG (LGG) in these matrices were investigated at 25 °C and 33% and 70% relative humidity (RH). The inactivation rate constant for probiotics in freeze-dried matrices were positively correlated (R(2) = 0.98) to moisture uptake and molecular mobility measured by NMR relaxometry. The stability of probiotics in glassy protein-carbohydrate matrices was dependent on the composition of the matrix. The partial substitution of maltodextrin with glucose (d- or l-) which improved microbial survival at 33% RH was related to the reduced molecular mobility and lower water uptake of the matrix. This study suggests that moisture uptake properties and molecular mobility of the matrix composition, as opposed to the relative humidity of the environment, are better determinants of probiotic viability during storage. Dynamic vapour sorption and NMR relaxometry are promising tools to assist in the selection of protein-carbohydrate matrices for enhancing probiotic viability during storage.

Extraction of silver(I) from aqueous solutions in the absence and presence of copper(II) with a methimazole-based ionic liquid.

The ionic liquid (IL) 2-butylthiolonium bis(trifluoromethanesulfonyl)amide, [mimSBu][NTf(2)], facilitates the efficient extraction of silver(I) from aqueous media via interaction with both the cation and anion components of the IL. Studies with a conventional aqueous-IL two phase system as well as microextraction of silver(I) by a thick IL film adhered to an electrode monitored in situ by cyclic voltammetry, established that [mimSBu][NTf(2)] can extract electroactive silver(I) ions from an aqueous solution. The pH of the aqueous phase decreases upon addition of [mimSBu](+), which is attributed to partial release of the hydrogen attached to the N(3) nitrogen atom of the imidazolium ring. The presence of silver(I) further increase the acidity of the aqueous phase as a consequence of coordination with the IL cation component. Voltammetric and (1)H and (13)C NMR techniques have been used to establish the nature of the silver(I) complexes extracted, and show that the form of interaction with the IL differs from that outlined previously for the extraction of copper(II). Insights on the competition established when silver(I) is extracted in the presence of copper(II) are provided. Finally, it is noted that metallic silver can be directly electrodeposited at the electrode surface after extraction of silver(I) into [mimSBu][NTf(2)] and that back extraction of silver(I) into aqueous media is achieved by addition of an acidic aqueous solution.

Comparison of diffusivity data derived from electrochemical and NMR investigations of the SeCN¯/(SeCN)2/(SeCN)3¯ system in ionic liquids.

Electrochemical studies in room temperature ionic liquids are often hampered by their relatively high viscosity. However, in some circumstances, fast exchange between participating electroactive species has provided beneficial enhancement of charge transport. The iodide (I¯)/iodine (I(2))/triiodide (I(3)¯) redox system that introduces exchange via the I¯ + I(2) ⇌ I(3)¯ process is a well documented example because it is used as a redox mediator in dye-sensitized solar cells. To provide enhanced understanding of ion movement in RTIL media, a combined electrochemical and NMR study of diffusion in the {SeCN¯-(SeCN)(2)-(SeCN)(3)¯} system has been undertaken in a selection of commonly used RTILs. In this system, each of the Se, C and N nuclei is NMR active. The electrochemical behavior of the pure ionic liquid, [C(4)mim][SeCN], which is synthesized and characterized here for the first time, also has been investigated. Voltammetric studies, which yield readily interpreted diffusion-limited responses under steady-state conditions by means of a Random Assembly of Microdisks (RAM) microelectrode array, have been used to measure electrochemically based diffusion coefficients, while self-diffusion coefficients were measured by pulsed field gradient NMR methods. The diffusivity data, derived from concentration and field gradients respectively, are in good agreement. The NMR data reveal that exchange processes occur between selenocyanate species, but the voltammetric data show the rates of exchange are too slow to enhance charge transfer. Thus, a comparison of the iodide and selenocyanate systems is somewhat paradoxical in that while the latter give RTILs of low viscosity, sluggish exchange kinetics prevent any significant enhancement of charge transfer through direct electron exchange. In contrast, faster exchange between iodide and its oxidation products leads to substantial electron exchange but this effect does not compensate sufficiently for mass transport limitations imposed by the higher viscosity of iodide RTILs.

Nitrile functionalized methimazole-based ionic liquids.

The alkylation reaction of 2-mercapto-1-methylimidazole 1b with 2-chloroacetonitrile and 2-chloropropionitrile produced S-alkyl methimazole chlorides 2a and 2b which were subjected to anion metathesis with lithium bis(trifluoromethanesulfonyl)amide, LiNTf(2), to afford nitrile functionalized methimazole-based room temperature ionic liquids 3a and 3b in 94% and 89% yields, respectively. Ionic liquids 3a and 3b have reasonably wide electrochemical windows. The efficient extraction of Ag(+) from aqueous media into 3a and 3b is also reported.

NMR relaxation and self-diffusion study at high and low magnetic fields of ionic association in protic ionic liquids.

NMR relaxation and diffusion characterization of several protic ionic liquids at high and low magnetic fields are reported. The dynamics of cations and anions were similar at both frequencies, with similar trends and magnitudes for a fixed component paired with oppositely charged species. An Arrhenius relationship was displayed between the molecular motion and the glass transition temperature. The diffusion of ions showed a strong degree of ion correlation between cation and anion, and Arrhenius plots of relaxation and diffusion indicated that the ions diffused as a pair. At high field diffusion was dominated by mobile species that followed Stokes-Einstein behavior. Conversely, diffusion observed at low field emphasized relatively immobile species that displayed fractional Stokes-Einstein behavior. No evidence was found to indicate the influence of magnetic field on structural and dynamic properties of the studied ILs; however, variation between diffusion coefficients at different magnetic fields indicated dynamic heterogeneities (or temporal aggregates) within the ionic liquid.

Synthesis, X-ray structure and electrochemical oxidation of palladium(II) complexes of ferrocenyldiphenylphosphine.

Four new complexes, [PdX(κ(2)-2-C(6)R(4)PPh(2))(PPh(2)Fc)] [X = Br, R = H (1), R = F (2); X = I, R = H (3), R = F (4)], containing ferrocenyldiphenylphosphine (PPh(2)Fc) have been prepared and fully characterised. The X-ray structures of complexes trans-1, cis-2 and cis-4, and that of a decomposition product of 4, [Pd(κ(2)-2-C(6)F(4)PPh(2))(µ-I)(µ-2-C(6)F(4)PPh(2))PdI(PPh(2)Fc)] (5), have been determined. These complexes show a distorted square planar geometry about the metal atom, the bite angles of the chelate ligands being about 69°, as expected. The cis/trans ratio of 1-4 in solution is strongly dependent on solvent. The new complexes and the uncoordinated PPh(2)Fc ligand were electrochemically characterised by cyclic and rotating disk voltammetry, UV-visible spectroelectrochemistry, and bulk electrolysis in dichloromethane and acetonitrile. In both cases, oxidation occurs at both the ferrocene and phosphine centres, but the complexes oxidise at more positive potentials than uncoordinated PPh(2)Fc; subsequently, the metal-phosphorus bond is cleaved, leading to free PPh(2)Fc(+), which undergoes further chemical and electrochemical reactions.

Extraction of copper(II) ions from aqueous solutions with a methimazole-based ionic liquid.

The recently synthesized ionic liquid (IL) 2-butylthiolonium bis(trifluoromethanesulfonyl)amide, [mimSBu][NTf(2)], has been used for the extraction of copper(II) from aqueous solution. The pH of the aqueous phase decreases upon addition of [mimSBu](+), which is attributed to partial release of the hydrogen attached to the N(3) nitrogen atom of the imidazolium ring. The presence of sparingly soluble water in [mimSBu][NTf(2)] also is required in solvent extraction studies to promote the incorporation of Cu(II) into the [mimSBu][NTf(2)] ionic liquid phase. The labile copper(II) system formed by interacting with both the water and the IL cation component has been characterized by cyclic voltammetry as well as UV-vis, Raman, and (1)H, (13)C, and (15)N NMR spectroscopies. The extraction process does not require the addition of a complexing agent or pH control of the aqueous phase. [mimSBu][NTf(2)] can be recovered from the labile copper-water-IL interacting system by washing with a strong acid. High selectivity of copper(II) extraction is achieved relative to that of other divalent cobalt(II), iron(II), and nickel(II) transition-metal cations. The course of microextraction of Cu(2+) from aqueous media into the [mimSBu][NTf(2)] IL phase was monitored in situ by cyclic voltammetry using a well-defined process in which specific interaction with copper is believed to switch from the ionic liquid cation component, [mimSBu], to the [NTf(2)] anion during the course of electrochemical reduction from Cu(II) to Cu(I). The microextraction-voltammetry technique provides a fast and convenient method to determine whether an IL is able to extract electroactive metal ions from an aqueous solution.

Preparation of protic ionic liquids with minimal water content and (15)N NMR study of proton transfer.

Low-molecular-weight Brønsted acids and amine bases were used to reproducibly prepare very dry, high-purity room-temperature protic ionic liquids (PILs). A series of eight amine bases and six Brønsted acids were combined to produce 48 mixtures, of which 18 were liquid at room temperature. The phase transitions and thermal decomposition temperatures were determined for each mixture; whereas viscosity, density and conductivity were determined for the room-temperature liquids. By utilising (15)N NMR it was possible to distinguish between neutral and ionised amine bases (ammonia vs. ammonium-type ion), which indicated that the protic ionic liquids were completely ionised when made as a stoichiometric mixture. However, a Walden plot comparison of fluidity and molar conductivity indicated the majority of PILs had much lower conductivity than predicted by viscosity unless the base contained excess proton-donating groups. This disparity is indicative of protic ionic molecules forming neutral aggregates or non-Newtonian fluid hydrogen-bonded networks with a secondary Grotthuss proton-hopping mechanism arising from polyprotic bases.

Microencapsulated Lactobacillus rhamnosus GG powders: relationship of powder physical properties to probiotic survival during storage.

Freeze-dried commercial Lactobacillus rhamnosus GG (LGG) were encapsulated in an emulsion-based formulation stabilized by whey protein and resistant starch and either spray-dried or freeze-dried to produce probiotic microcapsules. There was no difference in loss of probiotics viability after spray drying or freeze drying. Particle size, morphology, moisture sorption, and water mobility of the powder microcapsules were examined. Particle size analysis and scanning electron microscopy showed that spray-dried LGG microcapsules (SDMC) were small spherical particles, whereas freeze-dried LGG microcapsules (FDMC) were larger nonspherical particles. Moisture sorption isotherms obtained using dynamic vapor sorption showed a slightly higher water uptake in spray-dried microcapsules. The effect of water mobility, as measured by nuclear magnetic resonance (NMR) spectroscopy, at various water activities (a(w) 0.32, 0.57, and 0.70) and probiotic viability during storage at 25 °C was also examined. Increasing the relative humidity of the environment at which the samples were stored caused an increase in water mobility and the rate of loss in viability. The viability data during storage indicated that SDMC had better storage stability compared to FDMC. Although more water was adsorbed for spray-dried than freeze-dried microcapsules, water mobility was similar for corresponding storage conditions because there was a stronger water-binding energy for spray-dried microcapsule. This possibly accounted for the improved survival of probiotics in spray-dried microcapsules.

Physical and electrochemical properties of thioether-functionalized ionic liquids.

The preparation and characterization of a series of ionic liquids based on S-alkyl thiolonium, S-alkyl thiotetrazolium, or S-alkyl thiobenzolium cations coupled with bis(trifluoromethanesulfonyl)amide, trifluoromethanesulfonate, alkyl phosphate, chloride, and hexafluorophosphate anions are reported. All are liquid at room temperature, except the chloride salt, which has a melting point of 92 degrees C. The electrochemical characteristics of this class of ionic liquid have been determined by cyclic voltammetry. Potential windows of the ionic liquids have been obtained at glassy carbon, platinum, and gold electrodes and found to be the largest at glassy carbon, but are limited by oxidation of the thioether-functionalized cation. The voltammetry of IUPAC reference potential scale systems, ferrocene/ferrocenium, cobaltocenium/cobaltocene, and decamethylferrocene/decamethylferrocenium have been evaluated, with the last being most widely applicable. Nonadditivity of Faradaic current is found in the voltammograms of decamethylferrocene in the presence of ferrocene and cobaltocenium. Diffusion coefficient, viscosity, ionic conductivity, double layer capacitance, and other physical properties have also been measured. The dependence of the diffusion coefficient vs viscosity follows the Stokes-Einstein relationship. The properties of the ionic liquids are compared with the related imidazolium family of ionic liquids.

Nonadditivity of Faradaic currents and modification of capacitance currents in the voltammetry of mixtures of ferrocene and the cobaltocenium cation in protic and aprotic ionic liquids.

Unexpected nonadditivity of currents encountered in the electrochemistry of mixtures of ferrocene (Fc) and cobaltocenium cation (Cc(+)) as the PF(6)(-) salt has been investigated by direct current (dc) and Fourier-transformed alternating current (ac) cyclic voltammetry in two aprotic (1-butyl-3-methylimidazolium tetrafluoroborate and 1-butyl-3-methylimidazolium hexafluorophosphate) and three protic (triethylammonium formate, bis(2-hydroxyethyl)ammonium acetate, and triethylammonium acetate) ionic liquids (ILs). The voltammetry of the individual Fc(0/+) and Cc(+/0) couples always exhibits near-Nernstian behavior at glassy carbon and gold electrodes. As expected for an ideal process, the reversible formal potentials and diffusion coefficients at 23 +/- 1 degrees C in each IL determined from measurement on individual Fc and Cc(+) solutions were found to be independent of electrode material, concentration, and technique used for the measurement. However, when Fc and Cc(+) were simultaneously present, the dc and ac peak currents per unit concentration for the Fc(0/+) and Cc(+/0) processes were found to be significantly enhanced in both aprotic and protic ILs. Thus, the apparent diffusion coefficient values calculated for Fc and Cc(+) were respectively found to be about 25 and 35% larger than those determined individually in the aprotic ILs. A similar change in the Fc(0/+) mass transport characteristics was observed upon addition of tetrabutylammonium hexafluorophosphate (Bu(4)NPF(6)), and the double layer capacitance also varied in distinctly different ways when Fc and Cc(+) were present individually or in mixtures. Importantly, the nonadditivity of Faradaic current is not associated with a change in viscosity or from electron exchange as found when some solutes are added to ILs. The observation that the (1)H NMR T(1) relaxation times for the proton resonance in Cc(+) also are modified in mixed systems implies that specific interaction with aggregates of the constituent IL ionic species giving rise to subtle structural changes plays an important role in modifying the mass transport, double layer characteristics, and dynamics when solutes of interest in this study are added to ILs. Analogous voltammetric changes were not observed in studies in organic solvent media containing 0.1 M added supporting electrolyte. Implications of the nonadditivity of Faradaic and capacitance terms in ILs are considered.

Methimazole-based ionic liquids.

The alkylation reaction of 2-mercapto-1-methylimidazole 1a with iodoethane and chlorobutane produced S-alkylmethimazole halides 2a and 2b which were subjected to anion metathesis with two different metal salts (MA) to afford methimazole-based room-temperature ionic liquids 3a, 3b, and 3c in 82%, 85%, and 87% yields, respectively. S-Alkylation giving 2a and 2b suggests that methimazole reacts through the thione tautomer.

Wheat-gluten-based natural polymer nanoparticle composites.

A series of wheat-gluten-based nanocomposites were produced by dispersing Cloisite-30B nanoclay particles into plasticized wheat gluten systems under thermal processing conditions. The exfoliation of the nanoparticles as confirmed by wide-angle X-ray diffraction and transmission electron microscopy has resulted in significant enhancement of the mechanical properties for both deamidated proteins and vital gluten systems under 50% relative humidity (RH). Such strength improvement was also pronounced for wheat gluten (WG) systems under a high humidity condition (RH = 85%). A similar level of further strength enhancement was obtained for the WG systems that had been strengthened by blending with poly(vinyl alcohol) (PVA) and cross-linking with glyoxal. Although the nanoclay modifier, a quaternary ammonium, caused an additional plasticization to the materials, the interactions between the gluten matrix and the nanoparticles were predominant in all of these nanocomposites. A solid-state NMR study indicated that the polymer matrix in all of these nanocomposites displayed a wide distribution of chain mobilities at a molecular level (less than 1 nm). The interactions between the nanoparticles and the natural polymer matrix resulted in motional restriction for all components in the mobile phases including lipid, plasticizers, and plasticized components, although no significant influence from the nanoparticles was obtained in the mobility of the rigid phases (unplasticized components). On a scale of 20-30 nm, the deamidated protein systems tended to be homogeneous. The small domain size of the matrix resulted in modifications of the spin-lattice relaxation of these systems via spin diffusion. The residual starch seemed to remain in a relatively larger domain size in WG systems. The nanoparticles could enhance the miscibility between the starch and the other components in the WG nanocomposite, but such miscibility enhancement did not occur in the WG/PVA blend and the cross-linked system. These polymer matrixes were still heterogeneous on a scale of 20-30 nm.

pH effect on the mechanical performance and phase mobility of thermally processed wheat gluten-based natural polymer materials.

The mechanical properties, phase composition, and molecular motions of thermally processed wheat gluten- (WG-) based natural polymer materials were studied by mechanical testing, dynamic mechanical analysis (DMA), and solid-state NMR spectroscopy. The performance of the materials was mainly determined by the denaturization and cross-linking occurring in the thermal processing and the nature or amount of plasticizers used. The pH effect also played an important role in the materials when water was used as the only plasticizer (WG-w). Alkaline conditions modified the chemical structure of WG, possibly via deamidation; enhanced the thermal cross-linking of WG macromolecules to form a more stable aggregation structure; and promoted intermolecular interactions between water and all components in WG (proteins, starch, and lipid), resulting in a strong adhesion among different components and phases. The saponification of lipid under alkaline conditions also enhanced the hydrophilicity of lipid and the miscibility among lipid, water, and WG components. However, when glycerol was used with water as a plasticizer (WG-wg), the phase mobility and composition of the materials mainly depended on the content of glycerol when the water content was constant. During thermal processing under either acidic or alkaline conditions, glycerol was unlikely to thermally cross-link with WG as suggested previously. The advanced mechanical performance of the WG-wg materials was attributed to the nature of hydrogen-bonding interactions between glycerol and WG components in the materials. This caused the whole material to behave like a strengthened "cross-linked" structure at room temperature due to the low mobility of glycerol. The pH effect on phase mobility and compositions of WG-wg systems was not as significant as that for WG-w materials.

Chemical modification of wheat protein-based natural polymers: cross-linking effect on mechanical properties and phase structures.

Chemical modification of wheat protein-based natural polymer materials was conducted using glyoxal as cross-linker, and the cross-linking effect was studied on mechanical properties under different humidity conditions, the molecular motions of each component, and the phase structures/components of the whole materials. The cross-linking significantly enhanced the mechanical strength of wheat gluten (WG) materials under RH = 50%. The elongation of materials was also increased, which was in contrast to many cross-linked protein systems. The reaction mainly occurred in proteins and starch components, resulting in the formation of a stable cross-linked network with restricted molecular motions and modified motional dynamics. Although the plasticizer glycerol could also take part in the reaction with glyoxal or other components in WG especially when the glyoxal content was higher, the amount of glycerol involved in such reactions was very little. Glycerol was predominantly hydrogen-bonded with the network. The lipid component did not seem to take part in the cross-linking reaction; its mobility was promoted while its interaction with the protein-starch network was weakened after cross-linking. The formation of the cross-linked network did not enhance the hydrophobicity of the materials; the materials still adsorbed a high level of moisture under high humidity conditions (ca. RH = 85%) with no improvement in mechanical strength. In addition, further increasing the amount of glyoxal did not generate an additional strength improvement even at RH = 50%, possibly because the enhanced mobility of lipid promoted the component to be phase-separated from the WG system. To improve the water-resistant properties, the hydrophobicity of the protein macromolecules requires enhancement by other chemical modifications.

Intermolecular interactions and phase structures of plasticized wheat proteins materials.

The intermolecular interactions and phase structures of thermally processed wheat proteins with glycerol and water as plasticizers were studied by dynamic mechanical analysis and solid-state high-resolution NMR spectroscopy. The results of phase structures at scales of molecular level to tens of nanometers were correlated with the mechanical properties of the materials. The strong hydrogen bonding intermolecular interactions between the components in wheat proteins and the plasticizers resulted in a significant change in molecular motions of wheat protein materials. The plasticized systems, however, still presented a wide distribution of chain mobility at a scale from the molecular level to 20-30 nm, and the plasticizing effect was different for each wheat protein system. High protein content systems tended to be plasticized relatively easily especially when lipid content is high, but the existence of residual starch would require more plasticizers to reach a similar level of chain mobility. On a scale of 20-30 nm, plasticized vital wheat gluten (WG) and the deamidated wheat proteins (WP-I) were heterogeneous with each component exhibiting its individual mobility, whereas the plasticized insoluble protein system (WP-II) with poor mechanical properties was homogeneous. Both WG and WP-I systems showed excellent mechanical polymeric properties in tensile strength and elasticity despite the heterogeneity. The strong intermolecular hydrogen bonding interactions and soluble protein components in the materials could provide an adhesion among different components and act as a continuous matrix in the systems. Therefore, these materials displayed excellent mechanical properties via coordination effects among different components.