Turning on Asymmetric Catalysis of Achiral Metal-Organic Frameworks by Imparting Chiral Microenvironment

The development of heterogeneous asymmetric catalysts has attracted increasing interest in synthetic chemistry but mostly relies on the immobilization of homogeneous chiral catalysts. Herein, a series of chiral metal–organic frameworks (MOFs) have been fabricated by anchoring similar chiral hydroxylated molecules (catalytically inactive) with different lengths onto Zr-oxo clusters in achiral PCN-222(Cu). The resulting chiral MOFs exhibit regulated enantioselectivity up to 83 % ee in the asymmetric ring-opening of cyclohexene oxide. The chiral molecules furnished onto the catalytic Lewis sites in the MOF create multilevel microenvironment, including the hydrogen interaction between the substrate and the chiral −OH group, the steric hindrance endowed by the benzene ring on the chiral molecules, and the proximity between the catalytic sites and chiral molecules confined in the MOF pores, which play crucial roles and synergistically promote chiral catalysis. This work nicely achieves heterogeneous enantioselective catalysis by chiral microenvironment modulation around Lewis acid sites.     

Slug-flow microextraction coupled with paper spray mass spectrometry for rapid analysis of complex samples

Analysis of trace compounds in small-volume complex samples is of importance for forensic, clinical, pharmaceutical, environmental, and life science investigation. In this study, we reported the coupling of slug-flow microextraction with paper spray mass spectrometry for rapid analysis of trace analytes in small volume of complicated biological samples such as whole blood, milk, and body fluid, etc. The method is performed by applying a disposable glass capillary for rapid extraction of a small amount of complex samples using a small amount of organic solvent; the loaded organic solvent was then spotted onto a paper triangle and dried out; subsequently, a high voltage and some spray solvent were applied onto the paper triangle for mass spectrometric analysis. By using the proposed method, high sensitivity and satisfactory precision for quantitative analysis of trace macrolide antibiotics in whole bloods and milks as well as perfluorinated compounds in individual small organisms have been successfully achieved. In addition, investigation of bioaccumulation of perfluorinated compounds in individual small organisms has been reached.     

Pomegranate rind-derived activated carbon as electrode material for high-performance supercapacitors

In this paper, activated carbon materials were synthesized from pomegranate rind through carbonization and alkaline activation processes. The effects of pyrolytic temperature on the textual properties and electrochemical performance were investigated. The surface area of the activated carbon can reach at least 2200 m² g^?1 at different pyrolytic temperatures. It was found that, at the range of 600–900 °C, decreasing the carbonization temperature leads to the increase of t-plot micropore area, t-plot micropore volume, and capacitance. Further decreasing the carbonization temperature to 500 °C also leads to the increase of t-plot micropore area and t-plot micropore volume, but the capacitance is slightly poorer. The activated carbon carbonized at 600 °C and activated at 800 °C possesses very high specific area (2931 m² g^?1) and exhibits very high capacitance (～268 F g^?1 at 0.1 A g^?1 and ～242 F g^?1 at 1 A g^?1). There is no capacitance fading after 2000th cycle.     

Obacunone Attenuates Liver Fibrosis with Enhancing Anti-Oxidant Effects of GPx-4 and Inhibition of EMT

Obacunone, a limonin triterpenoid extracted from Phellodendronchinense Schneid or Dictamnus dasycarpusb Turcz plant, elicits a variety of pharmacological effects such as anti-inflammatory, anti-neoplastic, anti-oxidation, and anti-lung-fibrosis ones. However, the anti-fibrotic effect of obacunone and the detailed underlying mechanism in liver fibrosis remain unclear. Liver fibrosis is a debilitating disease threatening human health. Transforming growth factor (TGF)-β/P-Smad is a major pathway of fibrosis featured with epithelia mesenchymal transformations (EMT) and collagen depositions, accompanying with excessive oxygen-free radicals. Nrf-2 acts as a key anti-oxidative regulator driving the expressions of various antioxidant-related genes. Glutathionperoxidase-4 (GPx-4) is a member of the glutathione peroxidase family that directly inhibits phospholipid oxidation to alleviate oxidative stress. In the present study, we aimed to explore the role of obacunone in mouse liver fibrosis model induced by carbon tetrachloride (CCl4) and in hepatic stellate cells (LX2 cell line) challenging with TGF-β. Obacunone demonstrated potent ameliorative effects on liver fibrosis both in activated LX2 and in mice liver tissues with reduced levels of α-SMA, collagen1, and vimentin. Obacunone also remarkably suppressed the TGF-β/P-Smad signals and EMT process. Meanwhile, obacunone exerted a potent anti-oxidation effect by reducing the levels of reactive oxygen species (ROS) in both models. The antioxidant effect of obacunone was attributed to the activation of GPx-4 and Nrf-2. In addition, the therapeutic effect of obacunone on LX2 cells was significantly removed in vitro plus with GPx-4 antagonist RSL3, in parallel with the re-elevated levels of ROS. Thus, we demonstrate that obacunone is able to attenuate liver fibrosis via enhancing GPx-4 signal and inhibition of the TGF-β/P-Smad pathway and EMT process.     

Nitroxide‐Mediated Polymerization of 2‐Hydroxyethyl Methacrylate (HEMA) Controlled with Low Concentrations of Acrylonitrile and Styrene

Nitroxide‐mediated controlled radical polymerization of 2‐hydroxyethyl methacrylate (HEMA) is achieved using the copolymerization method with a small initial concentration of acrylonitrile (AN, 5–16 mol%)) or styrene (S, 5–10 mol%). The polymerization is mediated by N‐tert‐butyl‐N‐(1‐diethyl phosphono‐2,2‐dimethyl propyl) nitroxide (SG1)‐based BlocBuilder unimolecular alkoxyamine initiator modified with an N‐succinimidyl ester group (N‐hydroxysuccinimide‐BlocBuilder). As little as 5% molar feed of acrylonitrile results in a controlled polymerization, as evidenced by a linear increase in number average molecular weight M _n with conversion and dispersities (? ) as low as 1.30 at 80% conversion in N ,N‐dimethylformamide (DMF) at 85 °C. With S as the controlling comonomer, higher initial S composition (≈10 mol%) is required to maintain the controlled copolymerization. Poly(HEMA‐ran‐AN)s with M _n ranging from 5 to 20 kg mol^?1 are efficiently chain extended using n‐butyl methacrylate/styrene mixtures at 90.0 °C in DMF, thereby showing a route to HEMA‐based amphiphilic block copolymers via nitroxide‐mediated polymerization.

     

Anharmonic Effect in CH<Subscript>3</Subscript>CH<Subscript>2</Subscript>C(=O)OCH<Subscript>2</Subscript>CH<Subscript>3</Subscript> Decomposition

In this paper, using the B3LYP functional and CCSD(T) method with 6-311++G** basis set, the harmonic and anharmonic rate constants in the unimolecular dissociation of ethyl propanoate have been calculated using Rice–Ramsperger–Kassel–Marcus theory. The anharmonic rate constants of the title reaction have also been examined, the comparison shows that, the anharmonic effect especially in the case of high total energies and temperature for channels 3 to 6 is significant, so that the anharmonic effect cannot be neglected for unimolecular dissociation reaction of CH₃CH₂C(=O)OCH₂CH₃ both in microcanonical and canonical systems.     

电化学还原制备铂-氢钨青铜阳极

用电化学还原法在炭布上电沉积铂-氢钨青铜复合催化剂作为质子交换膜燃料电池(PEMFC)阳极。 利用X射线衍射、扫描电子显微镜、单电池极化性能测试以及电化学阻抗谱(EIS)法研究了催化剂的组成、分散性及其对氢氧化的电催化性能。 实验结果表明,阴极还原顺序对催化剂的形貌及分散有较大的影响。 采用分步还原法制备的HxWO3/Pt电极(先沉积铂,后沉积氢钨青铜)对氢氧化具有较高的催化活性,氢钨青铜与铂形成协同催化效应,提高了铂对氢氧化的催化活性。 而共沉积制备的Pt-HxWO3催化剂的电催化活性较差,这是因为共沉积过程中,由于受到2种电解液共存的影响,电极催化层中没有或较少得到氢钨青铜,且铂催化剂出现明显的团聚现象。     

A replaceable dual-enzyme capillary microreactor using magnetic beads and its application for simultaneous detection of acetaldehyde and pyruvate

A novel replaceable dual-enzyme capillary microreactor was developed and evaluated using magnetic fields to immobilize the alcohol dehydrogenase (ADH)- and lactate dehydrogenase (LDH)-coated magnetic beads at desired positions in the capillary. The dual-enzyme assay was achieved by measuring the two consumption peaks of the coenzyme β-nicotinamide adenine dinucleotide (NADH), which were related to the ADH reaction and LDH reaction. The dual-enzyme capillary microreactor was constructed using magnetic beads without any modification of the inner surface of the capillary, and showed great stability and reproducibility. The electrophoretic resolution for different analytes can be easily controlled by altering the relative distance of different enzyme-coated magnetic beads. The apparent K(m) values for acetaldehyde with ADH-catalyzed reaction and for pyruvate with LDH-catalyzed reaction were determined. The detection limits for acetaldehyde and pyruvate determination are 0.01 and 0.016 mM (S/N = 3), respectively. The proposed method was successfully applied to simultaneously determine the acetaldehyde and pyruvate contents in beer samples. The results indicated that combing magnetic beads with CE is of great value to perform replaceable and controllable multienzyme capillary microreactor for investigation of a series of enzyme reactions and determination of multisubstrates.