The Structural and Electronic Engineering of Molybdenum Disulfide Nanosheets as Carbon-Free Sulfur Hosts for Boosting Energy Density and Cycling Life of Lithium-Sulfur Batteries.

The compact sulfur cathodes with high sulfur content and high sulfur loading are crucial to promise high energy density of lithium-sulfur (Li-S) batteries. However, some daunting problems, such as low sulfur utilization efficiency, serious polysulfides shuttling, and poor rate performance, are usually accompanied during practical deployment. The sulfur hosts play key roles. Herein, the carbon-free sulfur host composed of vanadium-doped molybdenum disulfide (VMS) nanosheets is reported. Benefiting from the basal plane activation of molybdenum disulfide and structural advantage of VMS, high stacking density of sulfur cathode is allowed for high areal and volumetric capacities of the electrodes together with the effective suppression of polysulfides shuttling and the expedited redox kinetics of sulfur species during cycling. The resultant electrode with high sulfur content of 89 wt.% and high sulfur loading of 7.2 mg cm-2 achieves high gravimetric capacity of 900.9 mAh g-1 , the areal capacity of 6.48 mAh cm-2 , and volumetric capacity of 940 mAh cm-3 at 0.5 C. The electrochemical performance can rival with the state-of-the-art those in the reported Li-S batteries. This work provides methodology guidance for the development of the cathode materials to achieve high-energy-density and long-life Li-S batteries.

A 3D COF constructed by interlayer crosslinking of 2D COF as cathode material for lithium-sulfur batteries.

The design and construction of three-dimensional covalent organic frameworks (3D COF) remains a major challenge, and it is necessary to explore new strategies to synthesize 3D COF with ideal structure. Here, we utilize two-dimensional covalent organic framework (2D COF) with allyl side chain to achieve interlayer crosslinking through olefin metathesis reaction, thereby constructing a 3D COF with cage-like structures. This new material named CAGE-COF has larger specific surface area and more open pore structure than the original 2D COF. The cathode material with CAGE-COF retained 78.7% of its initial capacity after 500 cycles, and the fading rate is 0.04% each cycle.

Stereospecific Nucleophilic Substitution with Arylboronic Acids as Nucleophiles in the Presence of a CONH Group.

Stereospecific nucleophilic substitution was achieved for the first time with arylboronic acids as nucleophiles. This transition-metal-free coupling between chiral α-aryl-α-mesylated acetamides and arylboronic acids provided access to a series of chiral α,α-diaryl acetamides with excellent enantioselectivity and moderate to good yields. The CONH functionality proved to be crucial for bridging the reactants and promoting the reaction. Efficient syntheses of a cannabinoid CB1 receptor ligand, the antidepressant (S)-diclofensine, and a key chiral building block of the inhibitor implitapide were successfully accomplished by using this method.

Influencing factors of hydrogen bonding intensity in beer.

The hydrogen bonding was prone to be formed by many components in beer. Different sorts of flavor substances can affect the Chemical Shift due to their different concentrations in beer. Several key factors including 4 alcohols, 2 esters, 6 ions, 9 acids, 7 polyphenols, and 2 gravity indexes (OG and RG) were determined in this research. They could be used to investigate the relationship between hydrogen bonding intensity and the flavor components in bottled larger beers through the Correlation Analysis, Principal Component Analysis and Multiple Regression Analysis. Results showed that ethanol content was the primary influencing factor, and its correlation coefficient was 0.629 for Correlation Analysis. Some factors had a positive correlation with hydrogen bonding intensity, including the content of original gravity, ethanol, isobutanol, Cl(-), K(+), pyruvic acid, lactic acid, gallic acid, vanillic acid, and Catechin in beer. A mathematic model of hydrogen bonding Chemical Shift and the content of ethanol, pyruvic acid, K(+), and gallic acid was obtained through the Principal Component Analysis and Multiple Regression Analysis , with the adjusted R(2) being 0.779 (P = 0.001). Ethanol content was proved to be the most important factor which could impact on hydrogen bonding association in beer by Principal Component Analysis. And then, a multiple non-linearity model could be obtained as follows: [Formula: see text]. The average error was 1.23 % in the validated experiment.

Single-walled carbon nanotube gutter layer supported ultrathin zwitterionic microporous polymer membrane for high-performance lithium-sulfur battery.

Development of efficient lithium-sulfur (Li-S) battery requires the need to develop an appropriate functional separator that allows strong facilitation and transport of lithium ions together with limited passage of polysulfides. In this work, a multifunctional separator (TB-BAA/SWCNT/PP) is developed through spin coating of a novel zwitterionic microporous polymer (TB-BAA) on the gutter layer constructed from single-walled carbon nanotubes (SWCNT), where commercially available polypropylene (PP) separator is used to act as the mechanical support. SWCNT in this study serves as the first modification layer to decrease the size of the macropores in the PP separator, while the ultrathin TB-BAA top barrier layer with the presence of zwitterionic side chains allows the creation of confined ionic channels with both lithiophilic and sulfophilic groups. Due to the presence of available chemical interactions with lithium polysulfides, selective ion transport can be foreseen through such separator. In this regard, shuttle effect that is frequently encountered in Li-S battery can be suppressed effectively via implementing the as-obtained functional separator, resulting in the creation of credible and stable sulfur electrochemistry. The TB-BAA/SWCNT/PP-based Li-S battery has been investigated to possess high cycling ability (capacity fading per cycle of 0.055% over 500 cycles at 1 C) together with decent rate capability (736.6 mAh g-1 at 3 C). In addition, a high areal capacity retention of 5.03 mAh cm-2 after 50 cycles can be also obtained under raised sulfur loading (5.4 mg cm-2).

A one-pot process for the enantioselective synthesis of tetrahydroquinolines and tetrahydroisoquinolines via asymmetric reductive amination (ARA).

Asymmetric reductive amination for the synthesis of both chiral tetrahydroquinolines (THQs) and tetrahydroisoquinolines (THIQs) has been realized with an Ir/ZhaoPhos catalytic system via a one-pot N-Boc deprotection/intramolecular asymmetric reductive amination (ARA) sequence. Control experiments reveal that HCl plays a vital role to the success of this transformation. The HCl acid assists the removal of the N-Boc protecting group and also provides chloride ions to interact with the thiourea moiety in ZhaoPhos, thus leading to excellent reaction enantiocontrol.

Enantioselective and Diastereoselective Ir-Catalyzed Hydrogenation of α-Substituted ß-Ketoesters via Dynamic Kinetic Resolution.

An iridium/f-amphol catalytic system for the enantioselective hydrogenation of α-substituted ß-ketoesters via dynamic kinetic resolution is reported. The desired anti products were obtained in high yields (up to 98%) with good diastereoselectivity (up to 96:4 diastereometic ratio (dr)) and excellent enantioselectivity (up to >99% enantiomeric excess (ee)). A catalytic model is proposed to explain the stereoselectivity.

Rhodium-catalyzed asymmetric hydrogenation of ß-cyanocinnamic esters with the assistance of a single hydrogen bond in a precise position.

With the assistance of hydrogen bonds, the first asymmetric hydrogenation of ß-cyanocinnamic esters is developed, affording chiral ß-cyano esters with excellent enantioselectivities (up to 99% ee). This novel methodology provides an efficient and concise synthetic route to chiral GABA-derivatives such as (S)-Pregabalin, (R)-Phenibut, (R)-Baclofen. Interestingly, in this system, the catalyst with a single H-bond donor performs better than that with double H-bond donors, which is a novel discovery in the metalorganocatalysis area.

Asymmetric hydrogenation of maleic anhydrides catalyzed by Rh/bisphosphine-thiourea: efficient construction of chiral succinic anhydrides.

Asymmetric hydrogenation of various 3-substituted maleic anhydrides catalyzed by Rh/bisphosphine-thiourea (ZhaoPhos) under mild conditions was successfully developed. A wide range of 3-alkyl and 3-aryl maleic anhydrides were hydrogenated well to provide the desired products 3-substituted succinic anhydrides in one hour with excellent results (full conversions, up to 99% yield, 99% ee, 3000 TON). Importantly, we developed a creative and efficient synthetic route to construct the key intermediate of the hypoglycemic drug mitiglinide through our catalytic system.

Enantioselective Iridium-Catalyzed Hydrogenation of α-Keto Amides to α-Hydroxy Amides.

A highly enantioselective iridium-catalyzed hydrogenation of α-keto amides to form α-hydroxy amides has been achieved with excellent results (up to >99% conversion and up to >99% ee, TON up to 100 000). As an example, this protocol was applied to the synthesis of (S)-4-(2-amino-1-hydroxyethyl)benzene-1,2-diol, the enantiomer of norepinephrine, which is widely used as an injectable drug for the treatment of critically low blood pressure. Density functional theory (DFT) calculations were also carried out to reveal the reaction mechanism.

Effects of extraction solvent mixtures on antioxidant activity evaluation and their extraction capacity and selectivity for free phenolic compounds in barley (Hordeum vulgare L.).

Four kinds of solvent extracts from three Chinese barley varieties (Ken-3, KA4B, and Gan-3) were used to examine the effects of extraction solvent mixtures on antioxidant activity evaluation and their extraction capacity and selectivity for free phenolic compounds in barley through free radical scavenging activity, reducing power and metal chelating activity, and individual and total phenolic contents. Results showed that extraction solvent mixtures had significant impacts on antioxidant activity estimation, as well as different extraction capacity and selectivity for free phenolic compounds in barley. The highest DPPH* and ABTS*+ scavenging activities and reducing power were found in 80% acetone extracts, whereas the strongest *OH scavenging activity, O2*- scavenging activity, and metal chelating activity were found in 80% ethanol, 80% methanol, and water extracts, respectively. Additionally, 80% acetone showed the highest extraction capacity for (+)-catechin and ferulic, caffeic, vanillic, and p-coumaric acids, 80% methanol for (-)-epicatechin and syringic acid, and water for protocatechuic and gallic acids. Furthermore, correlations analysis revealed that TPC, reducing power, DPPH* and ABTS*+ scavenging activities were well positively correlated with each other (p < 0.01). Thus, for routine screening of barley varieties with higher antioxidant activity, 80% acetone was recommended to extract free phenolic compounds from barley. DPPH* scavenging activity and ABTS*+ scavenging activity or reducing power could be used to assess barley antioxidant activity.

Effects of molecular weight and concentration of arabinoxylans on the membrane plugging.

In this paper, arabinoxylans from wheat were isolated, purified, and degraded into four fractions with different molecular weight. The distribution of particle size was employed to evaluate the membrane plugging by beer. These arabinoxylans fractions were added into arabinoxylan-free beer to investigate the effects of molecular weight and concentration on the distribution of particle size in beer. Results showed that the fraction of arabinoxylans retained by a 0.22-mum pore size membrane was more easily affected by shearing and arabinoxylan concentration than the fraction of arabinoxylans retained by a 0.45-mum membrane. The effects of shearing, pH, and ethanol concentration of beer on the particle size distribution of the highest molecular weight arabinoxylan fraction in beer were also examined. General linear models (GLM) equations indicated that there was a positive correlation between the particle size distributions of arabinoxylans and shearing and ethanol content, while high molecular weight arabinoxylans particle size retained by the 0.45-mum membrane was not significantly (p > 0.05) influenced by pH value. Scanning electron microscope (SEM) photos showed that membrane plugging was significantly affected by the molecular weight of the arabinoxylans.

Discovery and structural insight of a highly selective protein kinase inhibitor hit through click chemistry.

Novel bisaryl maleimide derivatives to mimic natural kinase inhibitors were prepared through click chemistry. A highly selective hit was discovered in a 124-kinase-assay, and docking studies revealed a π-π stacking interaction with the Phe67 at the P-loop of GSK-3ß kinase.

Discovery and extensive in vitro evaluations of NK-HDAC-1: a chiral histone deacetylase inhibitor as a promising lead.

Herein, further SAR studies of lead compound NSC746457 (Shen, J.; Woodward, R.; Kedenburg, J. P.; Liu, X. W.; Chen, M.; Fang, L. Y.; Sun; D. X.; Wang. P. G. J. Med. Chem. 2008, 51, 7417-7427) were performed, including the replacement of the trans-styryl moiety with a 2-substituted benzo-hetero aromatic ring and the introduction of a substituent onto the central methylene carbon. A promising chiral lead, S-(E)-3-(1-(1-(benzo[d]oxazol-2-yl)-2-methylpropyl)-1H-1,2,3-triazol-4-yl)-N-hydroxyacrylamide (12, NK-HDAC-1), was discovered and showed about 1 order of magnitude more potency than SAHA in both enzymatic and cellular assays. For the in vitro safety tests, NK-HDAC-1 was far less toxic to nontransformed cells than tumor cells and showed no significant inhibition activity against CYP-3A4. The pharmaceutical properties (LogD, solubility, liver micrsomal stability (t1/2), plasma stability (t1/2), and apparent permeability) strongly suggested that NK-HDAC-1 might be superior to SAHA in bioavailability and in vivo half-life.

Structure-based optimization of click-based histone deacetylase inhibitors.

Previously, we reported a click-chemistry based approach to the synthesis of a novel class of histone deacetylase (HDAC) inhibitors [1]. The lead compound NSC746457 was found to be as potent as SAHA (Vorinostat). Further optimization of NSC746457 by using the HDAC2-TSA crystal structure is described herein. Docking of NSC746457 into HDAC2 binding domain suggested that the hydrophobic residue Phe210 flanking the cap-group binding-motif could be exploited for structural optimization. Substitution on the methylene group of cinnamic cap region led to identification of more potent HDAC inhibitors: isopropyl derivative 5 and tert-butyl derivative 6, with an IC(50) value of 22 nM and 18 nM, respectively.

[Improvement of thermostability of beta-1,3-1,4-glucanase from Bacillus amyloliquefaciens BS5582 through in vitro evolution].

In vitro evolution methods are often used to modify protein with improved characteristics. We developed a directed evolution protocol to enhance the thermostability of the beta-1,3-1,4-glucanase. The thermostability of the enzyme was significantly improved after two rounds of directed evolution. Three variants with higher thermostability were obtained. The mutant enzymes were further analyzed by their melting temperature, halftime and kinetic parameters. Comparing to intact enzyme, the T50 of mutant enzymes 2-JF-01, 2-JF-02 and 2-JF-03 were increased by 2.2 degrees C, 5.5 degrees C and 3.5 degrees C, respectively, the halftime (t1/2, 60 degrees C) of mutant enzymes 2-JF-01, 2-JF-02 and 2-JF-03 were shortened by 4,13 and 17 min, respectively, the V(max) of mutant enzymes were decreased by 8.3%, 2.6% and 10.6%, respectively, while K(m) of mutant enzymes were nearly unchanged. Sequence analysis revealed seven single amino acid mutant happened among three mutant enzymes, such as 2-JF-01 (N36S, G213R), 2-JF-02 (C86R, S115I, N150G) and 2-JF-03 (E156V, K105R). Homology-modeling showed that five of seven substituted amino acids were located on the surface of or in hole of protein. 42.8% of substituted amino acids were arginine, which indicated that arginine may play a role in the improvement of the thermostability of the beta-1,3-1,4-glucanase.This study provide some intresting results of the structural basis of the thermostability of beta-1,3-1,4-glucanase,and provide some new point of view in modifying enzyme for future industrial use.

[Determination of xanthohumol in beer by solid-phase extraction-high performance liquid chromatography].

A method for the determination of xanthohumol in beer using solid-phase extraction-high performance liquid chromatography (SPE-HPLC) has been developed. A Waters Sep-Pak C18 column was used to extract and clean-up the sample. The separation was achieved on a reversed-phase Agilent Zorbax Eclipse XDB-C18 (250 mm x 4.6 mm, 5 microm) in a linear gradient, and the mobile phases were consisted of water (containing 0.1% formic acid) (A) and methanol (B) with a flow rate of 0.4 mL/min. In addition, the column temperature was maintained at 25 degrees C. The detection wavelength was set at 370 nm. There was a good linear relationship (r2 = 1) in the range of 0.5 - 500 microg/L. The average recoveries were between 91.21% and 95.58% with the relative standard deviations less than 2%. The limit of detection was 0.24 microg/L and the limit of quantification was 0.80 microg/L. It was proved to be a convenient and accurate method for the analysis of xanthohumol content in beer.

[Optimization of cloning and expression of beta-glucanase gene from Bacillus amyloliquefaciens].

To compare of performance of beta-1,3-1,4-glucanase gene (bgl) in different expression systems, the beta-1,3-1,4-glucanase gene (GenBank Accession No. EU623974) was amplified from Bacillus amyloliquefaciens BS5582 by PCR and was cloned into three vectors pEGX-4T-1, pET20b(+) and pET28a(+) to construct pEGX-4T-1-bgl, pET20b(+)-bgl and pET28a(+)-bgl recombinant plasmids. The pEGX-4T-1-bgl was transformed into three different Escherichia coli host strains. The pET20b (+)-bgl and pET28a (+)-bgl were transformed into E. coli BL21 (DE3) respectively. Recombinant beta-glucanase was expressed by IPTG inducement in these recombinants. E. coli BL21 (DE3)-pET28a (+)-bgl had the highest enzyme activity. In Luria-Bertani medium, the total enzyme activity was (322.0 +/- 8.8) U/mL, which was 40.1% of original strain in optimal shaking flask condition. This recombinant's performance was studied in Terrific Broth medium under inducement of IPTG and lactose at the same time., and the highest total enzyme activity could reach (1883.3 +/- 45.8) U/mL (818.8% of the original), which indicate that the recombinant strain has a good value in industry application.

Multivariate modeling of aging in bottled lager beer by principal component analysis and multiple regression methods.

Data collected from the sensory test score evaluation of bottled lager beer, together with the chemical components related to aging, including carbonyl compounds, higher alcohols, unsaturated fatty acid, organic acids, alpha-amino acids, dissolved oxygen, and staling evaluation indices, including lag time of electron spin resonance (ESR) curve, 1,1'-diphenyl-2-picrylhydrazyl (DPPH) scavenged amounts, and thiobarbituric acid (TBA) values, were used to predict the extent of aging in bottled lager beer, using both multiple linear regression and principal component analysis methods. Carbonyl compounds, higher alcohols, and TBA value were significantly and positively correlated with sensory evaluation of staling flavor. While lag time and DPPH scavenging amount were negatively correlated with taste test score. Multiple regression analysis was used to fit the sensory test data using the above chemical compound aging related parameters and evaluation indices as predictors. A variable selection method based on high loadings of varimax rotated principal components was used to obtain subsets of the predominant predictor variables to be included in the regression model of beer aging, so as to eliminate the multicollinearity of the original nine variables. It was found that staling extent was influenced significantly by higher alcohols, TBA value, and DPPH scavenging amount, and the multicollinearity of the regression model was found to be weak by examining the variance inflation factors of the new predictor variables. A mathematic model of the organoleptic test score for beer aging using these three predictors was obtained by multiple linear regression, showing that the major contributors to the sensory taste of beer aging were higher alcohols, TBA index, and DPPH scavenging amount, with the adjusted R(2) of the model being 0.62.

[Effects of knockout ECM25/YJL201W gene in brewing yeast on beer flavor stability].

The ECM25 deletion mutant of industrial brewing yeast, G03/a, was constructed by replacing the ECM25 gene with the kanMX gene. The transformant was verified to be genetically stable. The PCR analysis showed that ECM25 gene in the G-03/a was deleted. Under aerobic conditions of ll degrees C and 28 degrees C, compared with the host strain G-03, the excretive glutathione concentration of G-03/a increased by 21.4% and 14.7%, respectively. Strains G-03 and G-03/a were inoculated in flasks and cultivated continuously for 4 generations. Compared with the host strain G-03, the glutathione concentration in the main fermentation broth and final beer of strain G-03/a increased by 32.1% and 13.8%, the stability index (SI) increased by 7.7% and 5.3%, respectively, and the flavor resistance staling value (RSV value) in final beer increased by 45.0%. During EBC fermentation, the glutathione concentration in the main fermentation broth of strain G-03/a increased by 34.0%, compared with the host strain G-03. Furthermore, no significant difference in routine fermentation parameters was found. The strain G-03/a is proved to be an excellent anti-staling brewing yeast to improve beer flavor stability.