Organosolv pretreatment of Sitka spruce wood: conversion of hemicelluloses to ethyl glycosides

A range of organosolv pretreatments, using ethanol:water mixtures with dilute sulphuric acid, were applied to Sitka spruce sawdust with the aim of generating useful co-products as well as improving saccharification yield. The most efficient of the pretreatment conditions, resulting in subsequent saccharification yields of up to 86%, converted a large part of the hemicellulose sugars to their ethyl glycosides as identified by GC/MS. These conditions also reduced conversion of pentoses to furfural, the ethyl glycosides being more stable to dehydration than the parent pentoses. Through comparison with the behaviour of model compounds under the same reaction conditions it was shown that the anomeric composition of the products was consistent with a predominant transglycosylation reaction mechanism, rather than hydrolysis followed by glycosylation. The ethyl glycosides have potential as intermediates in the sustainable production of high-value chemicals

Isolation of high quality lignin as a by-product from ammonia percolation pretreatment of poplar wood

A two-step process combining percolation-mode ammonia pretreatment of poplar sawdust with mild organosolv purification of the extracted lignin produced high quality, high purity lignin in up to 31% yield and 50% recovery. The uncondensed fraction of the isolated lignin was up to 34%, close to that the native lignin (40%). Less lignin was recovered after pretreatment in batch mode, apparently due to condensation during the longer residence time of the solubilised lignin at elevated temperature. The lignin recovery was directly correlated with its molecular weight and its nitrogen content. Low nitrogen incorporation, observed at high ammonia concentration, may be explained by limited homolytic cleavage of -O-4 bonds. Ammonia concentrations from 15% to 25% (w/w) gave similar results in terms of lignin structure, yield and recovery

Catalytic depolymerisation of isolated lignin to fine chemicals: part 2 – process optimisation

The depolymerisation of an ammonia treated lignin to alkylphenols over a Pt/alumina catalyst was investigated under a range of process parameters including, pressure, mass of lignin, solvent and gas atmosphere. The depolymerisation was shown to be under kinetic control and orders of reaction in hydrogen and lignin were determined as 0.4 and 0 respectively. Hydrogen was shown to be necessary under our reaction conditions as when helium was used as the gas atmosphere poor conversion was obtained. A clear solvent effect was observed with 100% methanol being more effective than 100% water or any combination of the two with a yield of alkylphenols >40% with a selectivity of >40% to substituted 4-propyl-2,6-dimethoxyphenol compounds. This high yield using methanol as a solvent was thought to be due to the ability of the methanol to inhibit re-polymerisation. IPA/water was also found to be an effective solvent combination with a yield of alkylphenols of >20%. The depolymerisation reaction was also studied over Rh/alumina and Ir/alumina catalysts. The rhodium catalyst was found to be the most active on a weight basis being slightly more active than platinum, however on a molar basis the platinum was much more active

Investigation of the chemocatalytic and biocatalytic valorization of a range of different lignin preparations: The importance of β-O-4 content

A set of seven different lignin preparations was generated from a range of organosolv (acidic, alkaline, ammonia-treated, and dioxane-based), ionic liquid, autohydrolysis, and Kraft pretreatments of lignocelluloses. Each lignin was characterized by 2D HSQC NMR spectroscopy, showing significant variability in the β-O-4 content of the different lignin samples. Each lignin was then valorised using three biocatalytic methods (microbial biotransformation with Rhodococcus jostii RHA045, treatment with Pseudomonas fluorescens Dyp1B or Sphingobacterium sp. T2 manganese superoxide dismutase) and two chemocatalytic methods (catalytic hydrogenation using Pt/alumina catalyst, DDQ benzylic oxidation/Zn reduction). Highest product yields for DDQ/Zn valorization were observed from poplar ammonia percolation-organosolv lignin, which had the highest β-O-4 content of the investigated lignins and also gave the highest yield of syringaldehyde (243 mg L -1 ) when using R. jostii RHA045 and the most enzymatic products using P. fluorescens Dyp1B. The highest product yield from the Pt/alumina hydrogenation was observed using oak dioxasolv lignin, which also had a high β-O-4 content. In general, highest product yields for both chemocatalytic and biocatalytic valorization methods were obtained from preparations that showed highest β-O-4 content, while variable yields were obtained with preparations containing intermediate β-O-4 content, and little or no product was obtained with preparations containing low β-O-4 content

A flexible adaptive optics concept for general purpose high angular resolution science on the DAG 4m telescope

Thanks to the availability of high actuator density deformable mirrors (ALPAO 468 DM), the high versatility of the pyramid wavefront sensor and above all, the venue of essentially no noise EMCCD detectors, it becomes possible to fully adapt the degree of correction of an adaptive optics system for a given guide star brightness and atmospheric condition. Indeed, when the conditions are very good, the high actuator density of the DM allows to reach a high Strehl by using all the modes, and when the conditions are less favorable, the spatial sampling, i. the number of modes, and the sensitivity of the detector allows to maximize the Strehl beyond what would be possible with a classical, frozen SH-WFS based system. Beside, oversampling the detector allows to relax the specification on the pupil images given by the pyramid on the detector, which in turn relaxes the pyramid prism manufacturing specifications. We are now designing an AO system for the DAG 4 m telescope that will allow, on the same system, ExAO as well as low order improved seeing observations. This article reports on the AO performance analysis, the final optical design and the design of the double prism achromatic pyramid.Publisher's Versio

Recent Advances in the Catalytic Depolymerization of Lignin towards Phenolic Chemicals : A Review

The efficient valorization of lignin could dictate the success of the 2nd generation biorefinery. Lignin, accounting for on average a third of the lignocellulosic biomass, is the most promising candidate for sustainable production of value-added phenolics. However, the structural alteration induced during lignin isolation is often depleting its potential for value-added chemicals. Recently, catalytic reductive depolymerization of lignin has appeared to be a promising and effective method for its valorization to obtain phenolic monomers. The present study systematically summarizes the far-reaching and state-of-the-art lignin valorization strategies during different stages, including conventional catalytic depolymerization of technical lignin, emerging reductive catalytic fractionation of protolignin, stabilization strategies to inhibit the undesired condensation reactions, and further catalytic upgrading of lignin-derived monomers. Finally, the potential challenges for the future researches on the efficient valorization of lignin and possible solutions are proposed

Bosutinib plus capecitabine for selected advanced solid tumours: results of a phase 1 dose-escalation study

Background: This phase 1 study evaluated the maximum tolerated dose (MTD), safety, and efficacy of bosutinib (competitive Src/Abl tyrosine kinase inhibitor) plus capecitabine. Methods: Patients with locally advanced/metastatic breast, pancreatic, or colorectal cancers; cholangiocarcinoma; or glioblastoma received bosutinib plus capecitabine at eight of nine possible dose combinations using an ‘up-down' design to determine the toxicity contour of the combination. Results: Among 32 enrolled patients, none of the 9 patients receiving MTD (bosutinib 300 mg once daily plus capecitabine 1000 mg m−2 twice daily) experienced dose-limiting toxicities (DLTs). Overall, 2 out of 31 (6%) evaluable patients experienced DLTs (grade 3 neurologic pain (n=1); grade 3 pruritus/rash and increased alanine aminotransferase (n=1)). Most common treatment-related adverse events (AEs) were diarrhoea, nausea, vomiting, palmar-plantar erythrodysesthesia (PPE), fatigue; most frequent grade 3/4 AEs: PPE, fatigue, and increased alanine/aspartate aminotransferase. Although diarrhoea was common, 91% of affected patients experienced maximum grade 1/2 events that resolved. Best overall confirmed partial response or stable disease >24 weeks (all tumour types) was observed in 6 and 13% of patients. Conclusions: In this population of patients with advanced solid tumours, bosutinib plus capecitabine demonstrated a safety profile similar to that previously reported for bosutinib or capecitabine monotherapy; limited efficacy was observed

Combining steam distillation with microwave-assisted pyrolysis to maximise direct production of levoglucosenone from agricultural wastes

The favourable impact of using a wet waste stream of agricultural residues in a biorefinery was studied through a combination of pyrolysis and self-induced steam distillation of hemicellulose depleted barley straw. The results showed that steam distillation provided both selective isolation and higher yields of polysaccharide-derived products such as levoglucosenone (LGO). The acid content of pretreated barley straw had the highest impact on the products selectivity. Both hydrolytic and pyrolytic pathways contributed to the products distribution, with higher selectivity toward pyrolytic products such as levoglucosan and LGO when less than 0.8 wt% acid was used. Interestingly, the increase of water content increased the overall products yields but had no impact on the products selectivity suggesting that the water did not directly impact on the decomposition pathway. In situ vaporisation of the water generates a microwave transparent steam environment preventing the distilled products for further degradation. The observation of the selective microwave activation of the polysaccharides in the presence of lignin offers significant opportunities for subsequent conversion of lignocellulosic biomass