Microwave-assisted alkali pre-treatment medium for fractionation of rice straw and catalytic conversion to value-added 5-hydroxymethyl furfural and lignin production.

In the current study, the use of microwave-assisted sodium hydroxide medium (MWSH) for pre-treatment and saccharification of rice straw to obtain sugar syrup for the production of 5-hydroxymethyl furfural (5-HMF) was investigated. The optimization of the MWSH pre-treatment was carried out using central composite methodology, resulting in a maximum reducing sugar yield of 350 mg/g of treated rice straw (TRS) and a glucose yield of 255 mg/g of TRS under the conditions of a microwave power of 681 W, a NaOH concentration of 0.54 M, and a pre-treatment time of 3 min. Additionally, the microwave assisted transformation of sugar syrup with titanium magnetic silica nanoparticle as catalyst, producing 41.1 % yield of 5-HMF from the sugar syrup after 30 min microwave irradiation at 120 °C with catalyst loading of 2.0:200 (w/v)). The structural characterization of the lignin was analysed using 1H NMR techniques, and the surface carbon (C1s spectra) and oxygen (O1s spectra) composition changes of the rice straw during pre-treatment were analysed using X-ray photoelectron spectroscopy. The rice straw based bio-refinery process which contains MWSH pretreatment followed by dehydration of sugars achieved high efficiency of 5-HMF production.

Impact of CO2-solvent separators on the degradation of benzyl-2,3-dihydroxypiperidine-1-carboxylate during preparative supercritical fluid chromatographic (SFC) purification.

During a preparative separation of the cis enantiomeric pair of benzyl-2,3-dihydroxypiperidine-1-carboxylate using supercritical-fluid chromatography (SFC) with methanol modifier, significant degradation of the products in the collected fractions was observed when a Waters SFC-350® (Milford, MA, USA) was used, but same was not observed when a Waters SFC-80q® (Milford, MA, USA) was used. Through a systematic investigation, we discovered that the compound degraded over time under an acidic condition created by the formation of methyl carbonic acid from methanol and CO2. The extent of the product degradation was dependent on the time and the concentration of CO2 remained in the product fraction, which was governed by the efficiency of CO2-methanol separation during the fraction collection. Hence, we demonstrated that the different designs of CO2-solvent separator (high pressurized cyclone in Waters SFC-350® and low-pressurized vortexing separator in Waters SFC-80q®®) had a significant impact on the degradation of an acid-sensitive compound. The acidity caused by CO2 in methanol was supported by diminished degradation after a nitrogen purging or after neutralizing the collected fractions with a base. Three different solutions to overcome the degradation problem of the acid sensitive compounds using SFC-350® with the high pressurized separator were investigated and demonstrated. The degraded products were isolated as four enantiomers and their relative stereochemistry were established based on 2D NMR data along with the plausible mechanism of degradation.