Improvement of Photocatalytic CO Reduction with Conjugated Organic Polymers by Rational Modulation of Donor, Acceptor and Bonding Method.

The use of metal-free catalysts to convert CO into valuable chemicals is very challenging. Here, we synthesized a conjugated organic polymer (TpTf-1) featuring 2,4,6-Triphenyl-1,3,5-Triazine as the acceptor unit, triphenylamine as the donor unit, and vinylidene bond as the linkage. The local structure of donor-acceptor (D-A) forms an intramolecular electric field that can promote the separation of photogenerated electrons and charges, meanwhile, the vinylidene bond can further change the charge distribution to promote exciton dissociation.

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.

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.

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.

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.

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.

Rhodium-catalyzed asymmetric hydrogenation of β-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 β-cyanocinnamic esters is developed, affording chiral β-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 ()-Pregabalin, ()-Phenibut, ()-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.

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

An iridium/f-amphol catalytic system for the enantioselective hydrogenation of α-substituted β-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.

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.

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.

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.

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.

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-3β kinase.

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.

[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.

[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.

[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.

[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.

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.

[Improvement of beer anti-staling capability by genetically modifying industrial brewing yeast with high glutathione content].

Based on homologous recombination, recombinant plasmid pRKG was constructed by replacing the internal fragment of 18S rDNA of pRJ-5 with a copy of gamma-glutamylcysteine synthetase gene (GSH1) from the industrial brewing yeast strain G03 and a copy of G418 resistance gene (Kan) used as the dominant selection marker respectively. The fragment 18s rDNA::( Kan-GSH1) obtained through the PCR reaction was integrated to the chromosomal DNA of G03 strain, and recombinants were screened by G418 resistance. It was shown that the GSH content of beer fermented with the recombinant strain SG1 was 16.

[Determination of isomerized alpha-acids in beer using solid phase extraction-high performance liquid chromatography].

An analytical method for four isomerized a-acids in beer was developed using solid phase extraction (SPE) coupled with high performance liquid chromatography (HPLC). The method for solid phase extraction was systematically optimized. The optimal conditions were determined as follows: 2 mL of acidic methanol as eluting solvent through a Sep-Pak C18 cartridge and the pH value of beer was adjusted to 2.

[Study on application of rep-PCR fingerprint in rapid identification of beer-spoilager].

The application potential of rep-PCR in typing beer-spoilage isolates was studied. The effects of different factors, including DNA templates and primers, on the quality and reproducibility of fingerprints were investigated. The CTAB protocol was shown to be the feasible method for DNA extraction.

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.

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.

Mathematical modeling for prediction of endo-xylanase activity and arabinoxylans concentration during mashing of barley malts for brewing.

A mathematical model describing the degradation of arabinoxylans by endo-xylanase during mashing process was developed. Endo-xylanase activities and arabinoxylans concentrations in laboratory scale mashing process at different temperature profiles were measured and then used for identifying the model parameters for Harrington barley malt. The modeling errors range for the final concentration of arabinoxylans in wort was -4% to +11.