CO2 Valorization in Deep Eutectic Solvents.

The deep eutectic solvent (DES) has emerged in recent years as a valuable medium for converting CO2 into valuable chemicals because of its easy availability, stability, and safety, and its capability to dissolve carbon dioxide. CO2 valorization in DES has evolved rapidly over the past 20 years. As well as being used as solvents for acid/base-promoted CO2 conversion for the production of cyclic carbonates and carbamates, DESs can be used as reaction media for electrochemical CO2 reduction for formic acid and CO. Among these products, cyclic carbonates can be used as solvents and electrolytes, carbamate derivatives include the core structure of many herbicides and pesticides, and formic acid and carbon monoxide, the C1 electrochemical products, are essential raw materials in the chemical industries. An overview of the application of DESs for CO2 valorization in recent years is presented in this review, followed by a compilation and comparison of product types and reaction mechanisms within the different types of DESs, and an outlook on how CO2 valorization will be developed in the future.

A carbon-promoted galvanic replacement method to synthesize efficient PdNi nanoalloy catalyst.

PdNi nanoalloy catalysts were prepared by a carbon-promoted galvanic replacement method. Characterizations and control experiments show the increased replacement rate of metal Ni with Pd2+ ion can be attributed to the higher electrode potential and smaller crystalline sizes caused by carbon doping. Introduction of carbon (C) into Ni particles not only accelerates the formation process of PdNi nanoalloys, but also enables C atoms to successfully enter the lattice interstices of PdNi nanoalloys. C regulates the surface electronic properties of PdNi nanoalloys by the electron transfer between different elements and improves their activity. The PdNi@C-650 exhibits extraordinary activity and long-term stability for hydrogenation reduction of hexavalent chromium (Cr (VI)) and hydrodechlorination of chlorophenols in comparison with PdNi/CNTs (carbon nanotubes) and commercial Pd/C. Density functional theory calculations together with investigations of mechanism reveal that the high electron-deficient PdNi nanoalloys from the redistribution of electron between Ni, Pd and C of the PdNi@C-650 promote the surface adsorption of substrate molecules and H2, which accordingly enhances the hydrogenation activity. This study brings a new method for the design and preparation of high active noble metal nanoalloy.

Anion-Bridged Dual Hydrogen Bond Enabled Concerted Addition of Phenol to Glycal.

A noncovalent organocatalytic concerted addition of phenol to glycal is developed for the stereoselective and regioselective construction of biologically important phenolic 2-deoxyglycosides, featuring wide substrate tolerance. The method relies on an anion-bridged dual hydrogen bond interaction which is experimentally proved by Nuclear Magnetic Resonance (NMR), Ultraviolet and visible (UV-vis), and fluorescence analysis. Experimental evidence including kinetic analysis, Kinetic Isotope Effect (KIE) studies, linear free energy relationship, Hammett plot, and density functional theory (DFT) calculations is provided for a concerted mechanism where a high-energy oxocarbenium ion is not formed. In addition, the potential utility of this method is further demonstrated by the synthesis of biologically active glycosylated flavones. The benchmarking studies demonstrate significant advances in this newly developed method compared to previous approaches.

Hydrogen Bond Networks Stabilized High-Capacity Organic Cathode for Lithium-Ion Batteries.

High-capacity small organic materials are plagued by their high solubility. Here we proposed constructing hydrogen bond networks (HBN) via intermolecular hydrogen bonds to suppress the solubility of active material. The illustrated 2, 7- diamino-4, 5, 9, 10-tetraone (PTO-NH2 ) molecule with intermolecular hydrogen (H) bond between O in -C=O and H in -NH2 , which make PTO-NH2 presents transverse two-dimensional extension and longitudinal π-π stacking structure. In situ Fourier transform infrared spectroscopy (FTIR) has tracked the reversible evolution of H-bonds, further confirming the existence of HBN structure can stabilize the intermediate 2-electron reaction state. Therefore, PTO-NH2 with HBN structure has higher active site utilization (95 %), better cycle stability and rate performance. This study uncovers the H-bond effect and evolution during the electrochemical process and provides a strategy for materials design.

Treated activated carbon as a metal-free catalyst for effectively catalytic reduction of toxic hexavalent chromium.

In this work, activated carbon treated in N2 atmosphere, as a non-metallic catalyst, exhibits excellent catalytic performance in reduction of Cr (VI) to Cr (III) using HCOOH as the reducing agent at room temperature. A series of characterizations and control experiments were carried out to deduce the possible reaction mechanism. The results showed that the improved catalytic performance can be attributed to the enhanced graphitization degree and basic sites such as pyrone-like, which favor electron transferring and activation of reactant. The reaction rate constant observed herein for the C-800 was 22 and 6 times more than that for C-0 and Pd/C catalyst, respectively. In addition, C-800 showed good recycle performance, and no loss of activity was observed after 5 cycles. This study broadens the application of nonmetallic catalyst and provides an easy-available and cost-effective catalytic material for removing toxic Cr (VI).

Pd-promoting reduction of zinc salt to PdZn alloy catalyst for the hydrogenation of nitrothioanisole.

Catalytic hydrogenation of sulfur-containing substrates is an important and challenging reaction in the chemical industry. In this work, active carbon supported PdZn alloy catalyst was prepared by self-reduction method using zinc acetate as precursor without H2 atmosphere. During the process of self-reduction, Zn2+ was firstly reduced to Zn0 at 300 °C by active carbon and reducing gas from the decompose of acetate under the promotion of metal Pd, and Zn0 further reacted with metal Pd to form PdZn alloy phase at 500 °C. These PdZn/AC-X catalysts showed the higher conversion and stability for the hydrogenation of 4-nitrothioanisole than the Pd/AC-600 catalyst. The excellent catalytic performance of PdZn/AC-600 catalyst can be attributed to formation of PdZn alloy, in which electron-rich Pd atoms weaken the binding ability between Pd and S and enhance the sulfur-resistance of catalyst. On the other hand, H2-TPR and DFT theory calculation further indicated that the PdZn alloy phase weakens the adsorption capacity of S. Compared with the Pd/AC-600 catalyst, the PdZn alloy phase in PdZn/AC-600 catalyst has not changed and only a small amount of sulfur-containing substrates deposited on the catalyst surface after three cycles. PdZn/AC-600 catalyst exhibited improved stability in the hydrogenation of 4-nitrothioanisole and can be used three cycles with little decrease in activity.

A hepatocyte-targeting fluorescent probe for imaging isoniazid-induced hydrazine in HepG2 cells and zebrafish.

A hepatocyte-targeting fluorescent N2H4 probe, GHP, was first designed and synthesized employing N-acetylgalactosamine (GalNAc) as the hepatocyte-targeting group and 3-nitrophthalimide as the recognition moiety. The probe can be used to selectively image N2H4 produced by the hydrolysis of isoniazid in HepG2 cells and the liver of zebrafish in situ.

A coumarin-fused 'off-on' fluorescent probe for highly selective detection of hydrazine.

Hydrazine is a kind of widely used industrial raw material and a toxic biochemical reagent. Due to its toxic to organisms, hydrazine has been classified to be a hazardous environmental pollutant. It is urgent to develop fluorescent probe tools for selective sensitivity detection of hydrazine in the environment and the body. We developed here a new coumarin-based fluorescent probe for hydrazine detection. The probe can selectively detect hydrazine over other environmental and endogenous interfering analytes with a large off-on fluorescence response. The detection limit is 8.55 ppb, which is well below the allowed threshold limit value. The sensing mechanism is hydrazine-induced pyrazole ring formation, which is confirmed by HRMS and DFT calculation methods. Additionally, the probe could also be applied for hydrazine imaging in living HeLa cells.

Design, synthesis and evaluation of novel (S)-tryptamine derivatives containing an allyl group and an aryl sulfonamide unit as anticancer agents.

A series of (S)-tryptamine derivatives containing an allyl group and an aryl sulfonamide unit were designed, synthesized and evaluated for their potential application as anticancer agents. The structures of the synthesized compounds were characterized by 1H NMR, 13C NMR and ESI-MS spectral analyses. The target compounds were evaluated for their in vitro cytotoxicity against HepG2, HeLa, CNE1 and A549 human cancer cell lines. Some of the synthesized compounds showed moderate to good anticancer activities against four selected cancer cell lines, among of which 6ag was found to be the most active analogue possessing IC50 values 16.5-18.7 µM. Further mechanism studies revealed that compound 6ag could significantly induce HepG2 cell cycle arrest at G1 phase, promote cell apoptosis, and inhibit the colony formation as well.

Design, synthesis, biological evaluation, and molecular docking of chalcone derivatives as anti-inflammatory agents.

In this study, two series of 35 new chalcone derivatives containing aryl-piperazine or aryl-sulfonyl-piperazine fragment were synthesized and their structures were characterized by 1H, 13C and ESI-MS. The in vivo and in vitro anti-inflammatory activities of target compounds were evaluated by using classical para-xylene-induced mice ear-swelling model and ELISA assays. Furthermore, docking studies were performed in COX-2 (4PH9). The in vivo anti-inflammatory assays indicated that most of the target compounds showed significant anti-inflammatory activities. Docking results revealed that the anti-inflammatory activities of compounds correlated with their docking results. Especially, compound 6o exhibited the most potent anti-inflammatory activity in vivo with the lowest docking score of -17.4kcal/mol and could significantly inhibit the release of LPS-induced IL-6 and TNF-α in a dose-dependent manner in vitro.