ABSTRACT
Solid-state NMR is a nondestructive and noninvasive technique used to study the chemical structure and dynamics of starch-based materials and to bridge the gap between structure-function relationships and industrial applications. The study of crystallinity, chemical modification, product blending, molecular packing, amylose-amylopectin ratio, end chain motion, and solvent-matrix interactions is essential for tailoring starch product properties to various applications. This article aims to provide a comprehensive and critical review of research characterizing starch-based materials using solid-state NMR, and to briefly introduce the most advanced and promising NMR strategies and hardware designs used to overcome the sensitivity and resolution issues involved in structure-function relationships.
ABSTRACT
Solid state nuclear magnetic resonance (ssNMR) is a powerful and attractive characterization method for obtaining insights into the chemical structure and dynamics of a wide range of materials. Current interest in cellulose-based materials, as sustainable and renewable natural polymer products, requires deep investigation and analysis of the chemical structure, molecular packing, end chain motion, functional modification, and solvent-matrix interactions, which strongly dictate the final product properties and tailor their end applications. In comparison to other spectroscopic techniques, on an atomic level, ssNMR is considered more advanced, especially in the structural analysis of cellulose-based materials; however, due to a dearth in the availability of a broad range of pulse sequences, and time consuming experiments, its capabilities are underestimated. This critical review article presents the comprehensive and up-to-date work done using ssNMR, including the most advanced NMR strategies used to overcome and resolve the structural difficulties present in different types of cellulose-based materials.
ABSTRACT
The role of water as highly effective hydrogen-bond donor (HBD) for promoting the coupling reaction of CO2 with a variety of epoxides was demonstrated under very mild conditions (25-60 °C, 2-10â bar CO2 ). Water led to a dramatic increase in the cyclic carbonate yield when employed in combination with tetrabutylammonium iodide (Bu4 NI) whereas it had a detrimental effect with the corresponding bromide and chloride salts. The efficiency of water in promoting the activity of the organic halide was compared with three state-of-the-art hydrogen bond donors, that is, phenol, gallic acid and ascorbic acid. Although water required higher molar loadings compared to these organic hydrogen-bond donors to achieve a similar degree of conversion of CO2 and styrene oxide into the corresponding cyclic carbonate under the same, mild reaction conditions, its environmental friendliness and much lower cost make it a very attractive alternative as hydrogen-bond donor. The effect of different parameters such as the amount of water, CO2 pressure, reaction temperature, and nature of the organic halide used as catalyst was investigated by using a high-throughput reactor unit. The highest catalytic activity was achieved with either Bu4 NI or bis(triphenylphosphine)iminium iodide (PPNI): with both systems, the cyclic carbonate yield at 45 °C with different epoxide substrates could be increased by a factor of two or more by adding water as a promoter, retaining high selectivity. Water was an effective hydrogen-bond donor even at room temperature, allowing to reach 85 % conversion of propylene oxide with full selectivity towards propylene carbonate in combination with Bu4 NI (3â mol %). For the conversion of epoxides in which PPNI is poorly soluble, the addition of a cyclic carbonate as solvent allowed the formation of a homogeneous solution, leading to enhanced product yield.
