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The Diels–Alder cycloaddition of bio-based 2,5-dimethylfuran (DMF) and ethylene and the subsequent dehydration of the cycloadduct intermediate hold promise to produce renewable p-xylene (PX) from biofeedstocks.

Oxygen vacancy-enriched ultrafine tetragonal ZrO2 was introduced as a support for copper nanoparticles to enhance the energy effici- ency of CO2 hydrogenation for methanol synthesis. This approach generates the critical...

Background: Multi-phenotype analysis of genetically correlated phenotypes can increase the statistical power to detect loci associated with multiple traits, leading to the discovery of novel loci. This is the first study to date to comprehensively analyze the shared genetic effects within different hemostatic traits, and between these and their associated disease outcomes. Objectives: To discover novel genetic associations by combining summary data of correlated hemostatic traits and disease events. Methods: Summary statistics from genome wide-association studies (GWAS) from seven hemostatic traits (factor VII [FVII], factor VIII [FVIII], von Willebrand factor [VWF] factor XI [FXI], fibrinogen, tissue plasminogen activator [tPA], plasminogen activator inhibitor 1 [PAI-1]) and three major cardiovascular (CV) events (venous thromboembolism [VTE], coronary artery disease [CAD], ischemic stroke [IS]), were combined in 27 multi-trait combinations using metaUSAT. Genetic correlations between phenotypes were calculated using Linkage Disequilibrium Score Regression (LDSC). Newly associated loci were investigated for colocalization. We considered a significance threshold of 1.85 × 10−9 obtained after applying Bonferroni correction for the number of multi-trait combinations performed (n = 27). Results: Across the 27 multi-trait analyses, we found 4 novel pleiotropic loci (XXYLT1, KNG1, SUGP1/MAU2, TBL2/MLXIPL) that were not significant in the original individual datasets, were not described in previous GWAS for the individual traits, and that presented a common associated variant between the studied phenotypes. Conclusions: The discovery of four novel loci contributes to the understanding of the relationship between hemostasis and CV events and elucidate common genetic factors between these traits.

Development of efficient and affordable catalytic systems for direct H2O2 production from abundant resources is necessary to replace the current anthraquinone process and also to enable broader use...

We describe herein that the quasi-one-dimensional confinement effect of functionalized nanoporous supports is particularly advantageous for boosting formic acid (FA) dehydrogenation efficiency over palladium nanoparticles (NPs). Benefiting from their unique structural merits that lead to significant lowering of the entropic barrier for FA activation, the Pd NPs interiorly located on the amino-modified MCM-41 offer the promise of more than an order of magnitude speedup of the initial activity in H2 production from FA over their exterior analogs. Under mild and additive-free conditions, ultrafine Pd NPs confined in amino-modified MCM-41 channels exhibit an initial turnover frequency as high as 46,677 h−1 and a turnover number up to 1,060,000 at 60°C. In conjunction with the enhancement and robust performance for efficient regeneration of FA via CO2 hydrogenation, the presented approach greatly contributes to the development of FA-based hydrogen storage and related technologies as viable means of enabling sustainable future energy prospects.

Sulfuric acid was used in the pretreatment of corn stover to obtain xylose as a value-added by-product, and the pretreated corn stover (Pre-CS) was hydrolyzed to produce glucose for butanol fermentation. The aim of this work is to achieve high xylose accumulation and reduced wastewater by recycling the pretreatment solution. The pretreatment conditions were optimized as follows: 180 °C, 15 min, 1:7 solid–liquid ratio (w/w), 0.6% H2SO4 (w/w, first batch)/0.9% H2SO4 (w/w, second and third batches), in which pretreatment solution was recycled for three times. Under above conditions, pretreatment solution containing 56.3 g/L xylose and 4.5 g/L glucose was obtained. Pre-CS residue was further hydrolyzed by cellulase to achieve 35.7–39.9 g/L glucose. The condensed corn stover hydrolysate was subjected to simultaneous detoxification and sterilization using 1% (w/w) activated carbon and then applied in butanol fermentation. The highest butanol titer of 9.5 g/L was obtained in 72 h. The results provide a practical approach for coproducing xylose and biobutanol from corn stover.

Development of a highly efficient and robust catalyst with reduced usage of noble metals is extremely desirable for selective hydrogenations of furan-containing bio-based feedstocks, which represents an attractive and sustainable alternative to petrochemical resources. Herein, we describe a new type of well-dispersed Ru subnanoclusters (ca. 0.50 wt%) supported on commercial P25 TiO2 material obtained from a facile and effective amino acid-assisted deposition–precipitation strategy. The as-synthesized catalyst exhibits superior catalytic activity and selectivity for direct hydrogenation of industrially important furfural as well as a range of structurally diverse bio-based furanic compounds to their corresponding fully hydrogenated derivatives. An average turnover frequency (ATOF) value as high as 367 h−1 at 80 °C and 4 MPa H2 is obtained, which is the highest reported value. This catalyst also shows stable furfural total hydrogenation in 5 reaction cycles conducted at 80 °C (52 mmol-scale, turnover number up to 12 500). In terms of the kinetic and structural characterizations, the key performances of the ultrasmall Ru clusters are proposed to mainly originate from an enhanced number of unsaturated surface Ru atoms and change in local coordination environment. Our work highlights the importance of the subnanometric size of Ru clusters in the advancement of efficient and affordable approaches towards bio-based chemical production.

Background Anlotinib hydrochloride is an oral small molecule multi-target tyrosine kinase inhibitor, and it has been approved as third-line therapy for patients with advanced non-small cell lung cancer (NSCLC) in China. This dose-exploration study was designed to investigate the feasibility of anlotinib in combination with chemotherapy in patients with non-squamous NSCLC. Methods This phase I study followed a 3 + 3 dose reduction design with three dose levels of anlotinib (12mg, 10mg, 8mg). Anlotinib was given at an initial dose of 12mg with pemetrexed (500mg/m2) plus cisplatin (75mg/m2) or carboplatin (AUC = 5) on 21-day cycles for 4 cycles. The primary goal of the study was to identify the maximum tolerated dose (MTD) and secondary endpoints included progression free survival (PFS) and overall survival (OS). Results A total of eight participants were enrolled. DLTs were observed in two patients (pts) at anlotinib 12mg (grade 3 hand-foot syndrome and grade 3 appetite loss). No DLTs occurred at anlotinib 10mg and the MTD was 10mg. Among seven pts evaluable, four achieved confirmed partial response (PR) and three had stable disease (SD). With a median follow-up of 10.05 months, the median PFS was 7.00 months (95%CI: 2.76 to NE). Grade 3 treatment-related adverse events (TRAEs) included appetite loss (n = 2), hypertension (n = 2), thrombocytopenia (n = 1), diarrhea (n = 1) and hand-foot syndrome (n = 1). No grade 4 or grade 5 TRAEs observed during the treatment. Conclusion The feasible dose of anlotinib in combination with platinum-pemetrexed as first-line therapy was 10 mg, which was well tolerated and showed promising antitumor activity in advanced non-squamous NSCLC.

BACKGROUND Hepatic stellate cell (HSC) hyperactivation is a central link in liver fibrosis development. HSCs perform aerobic glycolysis to provide energy for their activation. Focal adhesion kinase (FAK) promotes aerobic glycolysis in cancer cells or fibroblasts, while FAK-related non-kinase (FRNK) inhibits FAK phosphorylation and biological functions. AIM To elucidate the effect of FRNK on liver fibrosis at the level of aerobic glycolytic metabolism in HSCs. METHODS Mouse liver fibrosis models were established by administering CCl4, and the effect of FRNK on the degree of liver fibrosis in the model was evaluated. Transforming growth factor-β1 was used to activate LX-2 cells. Tyrosine phosphorylation at position 397 (pY397-FAK) was detected to identify activated FAK, and the expression of the glycolysis-related proteins monocarboxylate transporter 1 (MCT-1) and enolase1 (ENO1) was assessed. Bioinformatics analysis was performed to predict putative binding sites for c-myc in the ENO1 promoter region, which were validated with chromatin immunoprecipitation (ChIP) and dual-luciferase reporter assays. RESULTS The pY397-FAK level was increased in human fibrotic liver tissue. FRNK knockout promoted liver fibrosis in mouse models. It also increased the activation, migration, proliferation and aerobic glycolysis of primary hepatic stellate cells (pHSCs) but inhibited pHSC apoptosis. Nevertheless, opposite trends for these phenomena were observed after exogenous FRNK treatment in LX-2 cells. Mechanistically, the FAK/Ras/c-myc/ENO1 pathway promoted aerobic glycolysis, which was inhibited by exogenous FRNK. CONCLUSION FRNK inhibits aerobic glycolysis in HSCs by inhibiting the FAK/Ras/c-myc/ENO1 pathway, thereby improving liver fibrosis. FRNK might be a potential target for liver fibrosis treatment.

Background and Purpose Two Chinese herbal medicines Huang Qi (HQ, Astragalus mongholicus) and Dan Shen (DS, Salvia miltiorrhiza) are often combined to treat coronary heart disease (CHD). The purpose of this study was to identify the underlying synergistic effects and mechanisms of HQ and DS against CHD. Methods The active components and targets of HQ and DS, CHD-related genes, and the biological progression were analysed by network pharmacology. The myocardial infarction (MI) rat model was established by ligating the left anterior descending coronary artery. Cardiac function was detected by ultrasonic electrocardiography. The MI size, fibrosis, cardiac hypertrophy, lipid metabolism, blood viscosity, and coagulation indexes were analysed by histological staining or chemical methods, respectively. Results A total of 170 shared and specific seed genes of HQ and DS against CHD were identified. The shared and specific biological processes of HQ and DS against CHD were obtained. The LVEF and LVFS values significantly increased, the myocardium infarct size and fibrosis significantly decreased, the values of lipid metabolism indexes and blood viscosity indexes significantly reduced in the HQ + DS treatment group vs HQ or DS single treatment (P < 0.05); the LVEDd, LVEDs, and the CSA values significantly reduced in HQ single and HQ + DS treatment groups vs MI group (P < 0.05); the coagulation index (APTT, PT, TT, and FIB) values decreased significantly in the DS single and HQ + DS treatment groups vs MI group (P < 0.05). Conclusion In MI rats, HQ and DS exhibited synergistic effects on improving cardiac function, reducing MI size, fibrosis, regulating hyperlipidaemia, and maintaining circulatory system homeostasis; HQ had the specific advantage of alleviating cardiac remodelling; DS had the specific advantage of regulating hypercoagulability. This study revealed that HQ and DS not only exerted synergistic effects but also exhibited complementary effects on CHD.

Site-selective deoxygenation of hydroxyl groups represents essential processes to access valuable functionalized bio-based compounds with industrial potential. One of the challenging tasks in this context is to convert biodiesel-derived glycerol in the presence of abundant water directly to 1,3-propanediol (1,3-PDO), a key component of the emerging polymer industry. Herein, a monometallic iridium supported on H-ZSM-5 in the absence of Re oxophilic metal oxides was prepared via grinding-assisted impregnation procedures and attempted as an effective and recyclable catalyst for the aqueous-phase selective hydrogenolysis of glycerol toward 1,3-PDO in the absence of acid additives. The results revealed the necessity to control the Ir domain dispersions, Ir0/Ir3+ ratio and the amounts of overall acid/Bronsted acid sites. Activity depended linearly on the amount of overall and Bronsted acid sites, and 1,3-PDO selectivity increased in the presence of Ir-induced Bronsted acid sites, denoted as Ir-O(H)-H-ZSM-5. We speculate that Ir-O(H)-H-ZSM-5 are generated by the interfacial synergistic interaction between IrOx and H-ZSM-5 through hydrogen spillover and reverse hydrogen spillover according to the reported literatures. The reaction mechanism to elucidate the role of Ir-O(H)-H-ZSM-5 sites in glycerol hydrogenolysis was also postulated based on extensive characterization and catalytic reaction results.

The development of function-integrated catalysts to enable scalable and efficient biomass valorization is an important topic. Here, a stepwise methodology was developed to fabricate novel supported Au–Pd bimetallic catalysts featuring immobilized well-defined on-surface nanoarchitectures (Pd∧Au). This was achieved by an atomic decoration of a trace amount of Pd (Pd/Au molar ratio of 0.01–0.02) on the surface of 2 nm Au nanoparticle (NP, 0.86 wt %) preanchored to titania. Benefiting from their unique structural merits and the cooperative interplay among the selective hydrogenation activity furnished by the ultrasmall Pd∧Au NPs and prominent Lewis acidity endowed by TiO2, Pd0.02∧Au/TiO2 exhibits excellent activity with 100% conversion and over 90% selectivity and stability (turnover number up to 48 300) toward controlled ring-opening conversion of 5-hydroxymethylfurfural and related furanic compounds to the corresponding di- and triketone-type products under mild conditions (120 °C, 10 bar of H2). The resul...

Stellera chamaejasme is one of the most serious weeds in Qinhai-Tibetan Plateau, the rapid expansion of which exerts an increasing effect on the alpine meadow ecosystem. With high-throughput sequencing technology, geostatistics and GIS method, the spatial heterogeneity of soil fungal diversity in Stellera occurrence area and the spatial correlation between Stellera coverage and soil fungal diversity were investigated in a typical degraded alpine meadow of the Qilian Mountain. Compared to no-Stellera area, the fungi richness in Stellera area decreased, the dominance increased, and the α-diversity reduced. The difference of fungal species composition enhanced and β-diversity significantly increased. The spatial pattern of soil fungal diversity was affected by the invasion of Stellera, resulting in higher fragmentation in occurrence area. Spatial heterogeneity of species composition increased remarkably, and spatial stability of α-diversity and β-diversity decreased. The portion of positive correlation and negative correlation interlaced, indicating no clear spatial correlation between Stellera coverage and soil fungal diversity. Our results indicate that the spatial pattern of soil fungal diversity was affected by the interaction of soil and vegetation in Stellera invaded meadows.狼毒是青藏高原危害最严重的毒草种类之一,其快速蔓延对高寒草甸生态系统的影响日益严重。选取祁连山中段退化高寒草甸为研究区,综合采用高通量测序技术、地统计学和GIS空间分析方法,分析狼毒发生区土壤真菌多样性的空间变异特征,研究狼毒群落与土壤真菌多样性的空间相关性。结果表明: 与非发生区相比,狼毒发生区土壤真菌群落物种丰富度下降而优势度显著增加,α多样性降低;土壤真菌群落物种构成差异增强,β多样性明显升高。狼毒入侵对土壤真菌多样性的空间格局有一定扰动,发生区各多样性指数的斑块破碎化程度增加,土壤真菌群落物种构成的空间异质性明显增强,α和β多样性的空间稳定性降低。狼毒盖度与土壤真菌α和β多样性指数呈现显著正相关及显著负相关的区域交错镶嵌分布,空间相关性规律不明显,表明狼毒入侵草甸土壤真菌多样性的空间变异可能受地上植被和土壤环境的共同作用。.

Summary The use of biomass as a solution to satisfy the pressing needs for a fully sustainable biocommodity industry has been explored for a long time. However, limited success has been obtained. In this study, a highly effective two-stage procedure for the direct preparation of para-xylene (PX) from 5-hydroxymethylfurfural (HMF) and formic acid in one pot is described; these chemicals are two of the major bio-based feedstocks that offer the potential to address urgent needs for the green, sustainable production of drop-in chemical entities. The use of a robust, efficient heterogeneous catalyst, namely, bimetallic Pd-decorated Au clusters anchored on tetragonal-phase zirconia, is crucial to the success of this strategy. This multifunctional catalytic system can not only facilitate a low-energy-barrier H2-free pathway for the rapid, nearly exclusive formation of 2,5-dimethylfuran (DMF) from HMF but also enable the subsequent ultraselective production of PX by the dehydrative aromatization of the resultant DMF with ethylene.

Here, S237 was identified to be important in fine tuning the substrate specificity and enantioselectivity of alcohol dehydrogenase from Kluyveromyces polysporus (KpADH). In the reduction of a diaryl ketone, (4-chlorophenyl)-(pyridin-2-yl)-methanone (1a), the highest and lowest enantioselectivity of 96.1% and 27.0% e.e. (R) were obtained with S237A and S237C. Kinetic parameters analysis revealed that S237G, S237A, S237H and S237D displayed improved kcat/Km toward 1a. Various prochiral ketones, including acetophenone, 4-chloroacetophenone and ethyl 2-oxo-4-phenylbutyrate could be asymmetrically reduced by S237C, S237G and S237E with > 99% e.e. This study provides guidance for the application of KpADH in the preparation of chiral secondary alcohols.

Objective: To investigate the effects of methotrexate and hydroxychloroquine sulfate and prednisone on inflammatory response, immune function, liver and renal function in patients with systemic lupus erythematosus (SLE). Methods: A total of 80 cases of SLE patients according to the random data table were divided into the control group (n=40) and observation group (n=40), the control group were treated with hydroxychloroquine sulfate and prednisone treatment, on the basis of treatment of the control group, patients in the observation group in the control group were treated with methotrexate, the levels of inflammatory factors, immune function, liver and kidney function indexes in the two groups between the before treatment and after treatment were compared. Results: Comparison of the levels before treatment, the difference of the CRP, WBC, ESR, IgA, IgG, complement C3, complement C4, ALT, AST, SCr and BUN levels were not statistically significant. After treatment, the levels of CRP, ESR, IgA, IgG, ALT, AST, SCr and BUN in the observation group were significantly lower than those in the control group, and the difference was statistically significant. The levels of WBC and complement C4 in the observation group [(5.18±1.08)伊10 9 /L, (0.22±0.05) g/L] were significantly higher than those in the control group [(4.51±0.52)伊10 9 /L, (0.18±0.03) g/L], and there was no significant difference in the level of complement C3 between the two groups after treatment. Conclusion: Methotrexate combined with hydroxychloroquine sulfate and prednisone for the treatment of SLE can effectively reduce inflammation, improve immune function, has little effect on kidney function, high safety, which has an important clinical value.

Ya-Lan Wu,1,2,* Rui-Zhan Tong,1,* Yan Zhang,1,* Bin-bin Hu,1 Ke Zheng,3 Zhen-Yu Ding,1 Feng Peng,1 You-Ling Gong,1 Yong-Mei Liu,1 You Lu1 1Department of Thoracic Oncology, Cancer Center, 2Department of Oncology, Chengdu Shang Jin Nan Fu Hospital, 3Department of Pathology, West China Hospital, Sichuan University, People’s Republic of China *These authors contributed equally to this work Abstract: Blood biopsy has many advantages over tissue biopsy for diagnosing acquired T790M mutation in patients with non-small-cell lung cancer, such as being less risky and painful. New techniques with high sensitivity (eg, droplet digital PCR) show promising results during blood biopsy, but the positive rates of identification are still quite unclear. Whether there are other factors, except technology, affecting the results of blood biopsy is unclear. In this study, we used conventional amplification refractory mutation system to detect tumor tissue or blood for T790M mutation in patients clinically resistant to tyrosine kinase inhibitors. A total of 45 patients treated at West China Hospital between 2014 and 2016 were analyzed. The positive rate of T790M mutation was 70.8% based on tissue biopsy and 37.5% based on blood biopsy. Of the 24 patients whose epidermal growth factor receptor gene was genotyped through tissue and blood biopsy, 10 (41.7%) were concordant for T790M mutation status (κ=0.006). Of the 17 patients positive for T790M by tissue biopsy, 7 (41.2%) were positive for T790M by blood biopsy, and 3 of these 7 were only weakly positive. Of the 7 patients negative for T790M by tissue biopsy, 2 (28.6%) were positive by blood biopsy. Our T790M detection rate is higher than that reported by other studies using digital droplet PCR. These results suggest that other factors (eg, clinical features), intrinsically connected with circulating tumor DNA level, also affect the results of blood biopsy, and thus cannot be controlled through technological optimization. Keywords: non-small-cell lung cancer, T790M mutation, re-biopsy, liquid biopsy&nbsp

The discovery that supported gold catalysts can promote CO/H2O-mediated reduction at ambient temperatures is important to chemoselective synthesis and has gained significant attention in recent years. Whether the alternative Pt group metal (PGM) catalysts can exhibit such exceptional performance is thus an interesting research issue. So far, no PGM catalyst shows activity for CO/H2O-mediated reduction at ambient temperatures. Here, we demonstrate that it is possible to transform nonactive into highly active and selective catalysts for CO/H2O-mediated reduction by modulating the interfacial structure and electronic properties at the metal-support interfaces. Thus, highly active and chemoselective hydrogenation Pt, Ir, Rh and Pd catalysts can be prepared by decorating the exposed metal faces with partially reduced support species by means of a simple catalyst activation procedure. In this way, it has been possible to dramatically facilitate the previously unappreciated PGM-catalyzed activation of CO molecules under mild conditions, which can make a significant contribution not only to reveal the intrinsic catalytic potential of supported PGMs but also to establish a more sustainable and industrially-relevant process.

Direct coupling of Si–H bonds has emerged as a promising strategy for designing chemically and biologically useful organosilicon compounds. Heterogeneous catalytic systems sufficiently active, selective, and durable for dehydrosilylation reactions under mild conditions have been lacking to date. Herein, we report that the hydrophobic characteristics of the underlying supports can be advantageously utilized to enhance the efficiency of palladium nanoparticles (Pd NPs) for the dehydrogenative coupling of organosilanes. As a result of this prominent surface wettability control, the modulated catalyst showed a significantly higher level of efficiency and durability characteristics toward the dehydrogenative condensation of organosilanes with water, alcohols, or amines in comparison to existing catalysts. In a broader context, this work illustrates a powerful approach to maximize the performance of supported metals through surface wettability modulation under catalytically relevant conditions.

Reductive amination (RA) constitutes an attractive and practical strategy for discovering protocols capable of converting biomass into valuable N-containing compounds. Described herein is a versatile and sustainable RA of 5-hydroxymethyl-furfural (HMF), an important biomass-derived aldehyde, using abundant and cheaply available CO and water as reductants. A single phase rutile titania supported gold (Au/TiO2-R) catalyst is shown to efficiently catalyze this CO/H2O-mediated RA under mild and convenient conditions. With this system, a broad spectrum of primary and secondary amines can be used as suitable substrates and the desired reaction can proceed favourably in a highly chemoselective, efficient and atom-economical fashion. In particular, this protocol can also allow convenient access to bis(hydroxylmethylfurfuryl)-amines, a new group of furan-based monomers with great potential to form functional biopolymers with tunable properties. Moreover, this CO-assisted RA is more efficient (higher TON and TOF) and more eco-friendly (increased resource efficiency) than the previous state-of-the-art technique.

It was shown for the first time that cyclohexanone oxime (CHO) can be selectively produced by heterogeneous copper-catalyzed hydrogenative transformation of nitrocyclohexane (NC). The combination of Cu0 and Cu+ and their cooperative interaction with weakly acidic SiO2 supports elicited a significantly unique and selective catalysis in the hydrogenation of NC to CHO.

Given the wide applications of pyrroles in agriculture, pharmaceuticals, and supramolecular and materials chemistry, a mild and eco-friendly route to produce functionalized pyrroles from bioderived feedstocks is highly desirable. Described herein is a mild and convenient synthesis of pyrroles via direct condensation of an equimolar amount of structurally diverse anilines with biobased furans catalyzed by a simple and efficient solid acid H form zeolite Y catalyst. The protocol tolerates a large variety of functional groups and offers a general and versatile method for scale-up synthesis of a variety of N-substituted pyrrole compounds. Most importantly, the bioactive pyrrole-derived drug pyrvinium, which has lately been confirmed as highly effective in curing colon cancer, can be obtained by this method.

Decomposition of formic acid (FA) to hydrogen and carbon dioxide through catalysis holds great promise for clean energy in fuel cells designed for portable use, but the selective and efficient dehydrogenation of FA by a robust heterogeneous catalyst under ambient conditions remains a major challenge. We report herein that a new FA dehydrogenation system comprising liquid FA and amines with high boiling point as hydrogen storage material can be efficiently decomposed for ultrapure H2 release under mild reaction conditions. Of significant importance is that a high turnover frequency (TOF) of up to 1166 h−1 can be readily attained at 60 °C in FA-dimethylethanolamine system using gold nanoparticles supported on amphoteric zirconia (Au/ZrO2). The amine acts as a proton scavenger can facilitate the O H bond cleavage in the key step of FA deprotonation in Au–ZrO2 interface resulting in high catalytic activity. The versatile gold catalyst displayed excellent stability for dimethylethanolamine-assisted FA dehydrogenation as well as a typical particle-size-dependent effect.

Mercury (Hg) is generally considered as a toxic metal; yet the biological outcomes of Hg-containing compounds are highly dependent upon their chemical forms. We hypothesize that mercury sulfide (HgS) is different from HgCl

Comment inThe yin and yang of magnesium and calcium: New genetic insights for stroke? [Neurology. 2019]; International audience; Objective To determine whether serum magnesium and calcium concentrations are causally associated with ischemic stroke or any of its subtypes using the mendelian randomization approach. Methods Analyses were conducted using summary statistics data for 13 single-nucleotide polymorphisms robustly associated with serum magnesium (n = 6) or serum calcium (n = 7) concentrations. The corresponding data for ischemic stroke were obtained from the MEGASTROKE consortium (34,217 cases and 404,630 noncases). Results In standard mendelian randomization analysis, the odds ratios for each 0.1 mmol/L (about 1 SD) increase in genetically predicted serum magnesium concentrations were 0.78 (95% confidence interval [CI] 0.69-0.89; p = 1.3 × 10 −4) for all ischemic stroke, 0.63 (95% CI 0.50-0.80; p = 1.6 × 10 −4) for cardioembolic stroke, and 0.60 (95% CI 0.44-0.82; p = 0.001) for large artery stroke; there was no association with small vessel stroke (odds ratio 0.90, 95% CI 0.67-1.20; p = 0.46). Only the association with cardioembolic stroke was robust in sensitivity analyses. There was no association of genetically predicted serum calcium concentrations with all ischemic stroke (per 0.5 mg/dL [about 1 SD] increase in serum calcium: odds ratio 1.03, 95% CI 0.88-1.21) or with any subtype. Conclusions This study found that genetically higher serum magnesium concentrations are associated with a reduced risk of cardioembolic stroke but found no significant association of genetically higher serum calcium concentrations with any ischemic stroke subtype.

Biobutanol is attracting increasingly interest as a source of renewable energy and biofuels because of its many advantages over bioethanol that include higher energy density, fuel efficiency, and reduced engine damages. Currently, there is a growing interest in producing biobutanol from bioethanol, in view of the tremendous potential benefits of this transformation for the bulk production of biobutanol in a target specific manner. This perspective paper describes recent progress for the ethanol to butanol process. The different catalysts, including homogeneous and heterogeneous catalytic systems, for ethanol to butanol are outlined and compared, and the key issues and requirements for future developments are highlighted. A major challenge for further development and application of ethanol to butanol process is to find an optimal balance between different catalytic functions and to suppress the formation of side products that has plagued most catalytic bioethanol upgrading systems.

Formic acid (FA) has attracted considerable attention as a safe and convenient hydrogen storage material for renewable energy transformation. However, development of an efficient heterogeneous catalyst for selective FA decomposition for ultraclean H2 gas in the absence of any alkalis or additives under mild conditions remains a major challenge. Based on our previous work on Au/ZrO2 as a robust and efficient catalyst for FA dehydrogenation in amine system, we report here ZrO2 with different nanocrystal polymorphs supported Au nanoparticles can achieve near completion of FA dehydrogenation in base-free aqueous medium. Of significant importance is that an excellent rate of up to 81.8 L H2 gAu−1 h−1 in open system and highly pressurized gas of 5.9 MPa in closed one can be readily attained at 80 °C for Au/m-ZrO2. In situ diffuse reflectance infrared Fourier transform (DRIFT) and CO2-temperature programmed desorption (TPD) techniques revealed that Au/m-ZrO2 exhibits a higher density of surface basic sites than Au/t-ZrO2 and Au/a-ZrO2. Basic sites in surface can substantially facilitate crucial FA deprotonation process which appears to be a key factor for achieving high dehydrogenation activity. The H/D exchange between solvent of H2O and substrate of FA was observed by the kinetic isotope effect experiments.

The reductive transformation of furfural (FAL) into furfuryl alcohol (FOL) is an attractive route for the use of renewable bio-sources but it suffers from the heavy use of H 2 . We describe here a highly efficient reduction protocol for converting aqueous FAL to FOL. A single phase rutile TiO 2 support with a gold catalyst (Au/TiO 2 -R) that used CO/H 2 O as the hydrogen source catalyze this reduction efficiently under mild conditions. By eliminating the consumption of fossil fuel-derived H 2 , our process has the benefit afforded by using CO as a convenient and cost competitive reducing reagent.

The use of formic acid (FA) to produce molecular H2 is a promising means of efficient energy storage in a fuel-cell-based hydrogen economy. To date, there has been a lack of heterogeneous catalyst systems that are sufficiently active, selective, and stable for clean H2 production by FA decomposition at room temperature. For the first time, we report that flexible pyridinic-N-doped carbon hybrids as support materials can significantly boost the efficiency of palladium nanoparticle for H2 generation; this is due to prominent surface electronic modulation. Under mild conditions, the optimized engineered Pd/CN0.25 catalyst exhibited high performance in both FA dehydrogenation (achieving almost full conversion, and a turnover frequency of 5530 h(-1) at 25 °C) and the reversible process of CO2 hydrogenation into FA. This system can lead to a full carbon-neutral energy cycle.