The utilization of compounds from natural sources to prepare functional materials is of great importance. Herein, we describe for the first time the preparation of organic-inorganic hybrid catalysts by using natural phytic acid as building block. Zirconium phosphonate (Zr-PhyA) was synthesized by reaction of phytic acid and ZrCl4 and was obtained as a mesoporous material with pore sizes centered around 8.5 nm. Zr-PhyA was used to catalyze the mild and selective Meerwein-Ponndorf-Verley (MPV) reduction of various carbonyl compounds, e.g., of levulinic acid and its esters into γ-valerolactone. Further studies indicated that both Zr and phosphate groups contribute significantly to the excellent performance of Zr-PhyA.

The effect of water on CO2 hydrogenation to produce higher alcohols (C2-C4) was studied. Pt/Co3O4, which had not been used previously for this reaction, was applied as the heterogeneous catalyst. It was found that water and the catalyst had an excellent synergistic effect for promoting the reaction. High selectivity of C2-C4 alcohols could be achieved at 140 °C (especially with DMI (1,3-dimethyl-2-imidazolidinone) as co-solvent), which is a much lower temperature than reported previously. The catalyst could be reused at least five times without reducing the activity and selectivity. D2O and (13)CH3OH labeling experiments indicated that water involved in the reaction and promoted the reaction kinetically, and ethanol was formed via CH3OH as an intermediate.

Alzheimer’s disease (AD) is characterized by progressive dementia, especially in episodic memory, and amnestic mild cognitive impairment (aMCI) is associated with a high risk of developing AD. Hippocampal atrophy/shape changes are believed to be the most robust magnetic resonance imaging (MRI) markers for AD and aMCI. Radiomics, a method of texture analysis, can quantitatively examine a large set of features and has previously been successfully applied to evaluate imaging biomarkers for AD. To test whether radiomic features in the hippocampus can be employed for early classification of AD and aMCI, 1692 features from the caudal and head parts of the bilateral hippocampus were extracted from 38 AD patients, 33 aMCI patients and 45 normal controls (NCs). One way analysis of variance (ANOVA) showed that 111 features exhibited statistically significant group differences (P < 0.01, Bonferroni corrected). Among these features, 98 were significantly correlated with Mini-Mental State Examination (MMSE) scores in AD and aMCI subjects (P < 0.01). The support vector machine (SVM) model demonstrated that radiomic features allowed us to distinguish AD from NC with an accuracy of 86.75% (specificity = 88.89% and sensitivity = 84.21%) and an area under curve (AUC) of 0.93. In conclusion, these findings provide evidence showing that radiomic features are beneficial in detecting early cognitive decline, and SVM classification analysis provides encouraging evidence for using hippocampal radiomic features as a potential biomarker for clinical applications in AD.

ARTICLEThis journal is Catalytic transfer hydrogenation (CTH) of ethyl levulinate (EL) to γ-valerolactone (GVL) is a very attractive reaction in the field of biomass transformation. In this work, a new porous Zrcontaining catalyst with phenate group in its structure was prepared by the coprecipitation of 4hydroxybenzoic acid dipotassium salt and ZrOCl 2 (Zr-HBA) in water and characterized by powder X-Ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N 2 adsorption-desorption, and Fourier transform infrared spectroscopy. The Zr-HBA was used as the catalyst for CTH of EL to GVL in the presence of isopropanol, and the effects of temperature, time, and amount of the catalyst on the reaction were studied. It was found that Zr-HBA was very active for the reaction and a GVL yield of 94.4% could be achieved. Meanwhile, the Zr-HBA could be reused at least five times without notable decrease in activity and selectivity. The main reason for the high catalytic activity of the Zr-HBA was that the existence of phenate in the structure of Zr-HBA increased the basicity of the catalyst, which is favourable to the CTH of EL.

Benzene is a widely used commodity chemical, which is currently produced from fossil resources. Lignin, a waste from lignocellulosic biomass industry, is the most abundant renewable source of benzene ring in nature. Efficient production of benzene from lignin, which requires total transformation of Csp2-Csp3/Csp2-O into C-H bonds without side hydrogenation, is of great importance, but has not been realized. Here, we report that high-silica HY zeolite supported RuW alloy catalyst enables in situ refining of lignin, exclusively to benzene via coupling Bronsted acid catalyzed transformation of the Csp2-Csp3 bonds on the local structure of lignin molecule and RuW catalyzed hydrogenolysis of the Csp2-O bonds using the locally abstracted hydrogen from lignin molecule, affording a benzene yield of 18.8% on lignin weight basis in water system. The reaction mechanism is elucidated in detail by combination of control experiments and density functional theory calculations. The high-performance protocol can be readily scaled up to produce 8.5 g of benzene product from 50.0 g lignin without any saturation byproducts. This work opens the way to produce benzene using lignin as the feedstock efficiently.

Ionic liquid 1-benzyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BnMIm][NTf2]) can promote the generation of the ˙OOH free radical and thereby efficiently transformed the β-O-4 lignin model compound 2-phenoxyacetophenone into benzoic acid and phenol using O2 as the oxidant. Furthermore, the IL-based metal-free catalytic system can also depolymerize other lignin model compounds and organosolv lignin effectively.

γ-Valerolactone acts as both a solvent and catalyst for N-formylation of various amines with CO2 to formamides in the presence of phenylsilane without any additional catalysts.

Cyclohexanone and its derivatives are very important chemicals, which are currently produced mainly by oxidation of cyclohexane or alkylcyclohexane, hydrogenation of phenols, and alkylation of cyclohexanone. Here we report that bromide salt-modified Pd/C in H2O/CH2Cl2 can efficiently catalyse the transformation of aromatic ethers, which can be derived from biomass, to cyclohexanone and its derivatives via hydrogenation and hydrolysis processes. The yield of cyclohexanone from anisole can reach 96%, and the yields of cyclohexanone derivatives produced from the aromatic ethers, which can be extracted from plants or derived from lignin, are also satisfactory. Detailed study shows that the Pd, bromide salt and H2O/CH2Cl2 work cooperatively to promote the desired reaction and inhibit the side reaction. Thus high yields of desired products can be obtained. This work opens the way for production of ketones from aromatic ethers that can be derived from biomass.