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  • Jiapeng Zhang, Fanzhen Lin, Lijing Yang, Hua Dong
    Chinese Chemical Letters. 2020, 31(9): 2512-2515.

    Ru and Co are highly dispersed on the surface of TiO2 nanoparticles with an easy coprecipitation method to fabricate a novel Ru-based catalyst (Ru/Co-TiO2). The fabricated Ru/Co-TiO2 catalyst exhibits superior catalytic performance for promoting NaBH4 hydrolysis in alkaline medium, showing an impressive hydrogen generation rate per gram Ru as high as 172 L min-1 gRu-1, which is better than most of recently reported Ru-based catalysts. In addition, the fabricated Ru/Co-TiO2 catalyst also shows excellent durability in cycle use, with only 2.9% activity loss after being used for 5 cycles.These advantages make the developed Ru/ Co-TiO2 catalyst a potential choice for promoting hydrogen generation from NaBH4 hydrolysis.

  • Waseem Muhammad, Jie Ni, Zvonko Jagličić, Ping Cui, Linna Gao, Di Sun
    Chinese Chemical Letters. 2020, 31(9): 2503-2506.

    An iron (Ⅲ) cluster, namely [Fe10(μ3-O)8L8(NO3)6] (1), has been synthesized by treatment of Fe (NO3)3·9H2O with 3, 5-dimethyl-1-(hydroxymethyl)-pyrazole (HL) under ambient temperature. The core skeleton of {Fe10} can be regarded as a pear-like cage with eight triangular {Fe3(μ3-O)} units, in which each three Fe centers is held together by one μ3-O2- group with Fe centers as corner-sharing triangle units. Importantly, {Fe10} cluster is not only stable in solid state but also in solution, which is confirmed by powder X-ray diffraction (PXRD) pattern and electrospray ionization mass spectrometry (ESI-MS), respectively. Furthermore, 1 shows antiferromagnetic exchange behavior arising from the interactions between the iron(Ⅲ) centers.

  • Ying Li, Xiuxiu Cao, Changlin Tian, Ji-Shen Zheng
    Chinese Chemical Letters. 2020, 31(9): 2365-2374.

    D-peptides are recognized as a new class of synthetic chemical drugs and they possess many interesting advantages such as high enzymatic stability, improved oral bioavailability, as well as high binding affinity and specificity. Recently, D-peptide drugs have been attracting increasing attention in both academic and industrial researches over recent years. One D-peptide etelcalcetide has even entered the market that targets the calcium (Ca2+)-sensing receptor (CaSR) to fight secondary hyperparathyroidism. Effective discovery and optimization of D-peptide ligands that can bind to various disease-related targets with high specificity and potency is of great importance for the development of D-peptide drugs. This review surveys the recent method development in this area especially the chemical protein synthesis-assisted high-throughput screening strategies for D-peptide ligands and their application in drug discovery.

  • Lifen Wang, Jiajia Song, Xiaofei Wang, Honglan Qi, Qiang Gao, Chengxiao Zhang
    Chinese Chemical Letters. 2020, 31(9): 2520-2524.

    A highly sensitive electrochemiluminescence (ECL) biosensing method was developed for monitoring casein kinase Ⅱ (CK2) at subcellular level via bio-bar-code assay. A bio-bar-code probe (h-DNA/AuNPs/pDNA) prepared by conjugating phosphorylated DNA (p-DNA) and hairpin DNA (h-DNA) onto gold nanoparticles (AuNPs) was used as a carrier for ECL signal reagent (Ru(phen)32+) while a specific peptide was used as a recognition substance. A gold ultramicroelectrode with a diameter of 400 nm was fabricated and then modified with the specific peptide via self-assembly technique to obtain peptide modified gold ultramicroelectrode. The peptide on gold ultramicroelectrode was phosphorylated in the presence of CK2 and adenosine 5'-triphosphate, and then the phosphorylated peptide was integrated with the h-DNA/AuNPs/p-DNA through a process mediated by zirconium cations (Zr4+), and finally Ru(phen)32+ was intercalated into h-DNA. A "signal on" ECL method was developed for the detection of CK2 in the range of 0.005-0.2 U/mL with a detection limit of 0.001 U/mL. Additionally, combined efficient subcellular phosphorylation in vivo with bio-bar-code-based ECL biosensing method, the ECL method was further applied to monitor CK2 at subcellular level without tedious subcellular fractionation. It was found that the concentration of CK2 by inserting the peptide modified gold ultramicroelectrode into the nucleus was higher than that into cytoplasm of HeLa cells. A distinct heterogeneity among CK2 concentrations in single cells was observed for cellular heterogeneity assessment.

  • Huaming Xiao, Ping Liu, Shujian Zheng, Xian Wang, Jun Ding, Yuqi Feng
    Chinese Chemical Letters. 2020, 31(9): 2423-2427.

    Direct infusion mass spectrometry (DIMS) is a powerful technique in clinical diagnosis for screening neonatal amino acid metabolic disorders from dried blood spots (DBS). However, DIMS sometimes generated false-positive results for analysis of amino acids. In this work, we utilized a stable isotope derivatization method, combining with liquid chromatography tandem mass spectrometry (SID-LC-MS), to improve the specificity for screening amino acids in DBS specimens. A pair of isotope reagents, p-(dimethylamino)phenyl isothiocyanate (DMAP-NCS) and 4-isothiocyanato-N, N-bis(methyl-[2H2])aniline ([2H4]DMAP-NCS), was synthesized and used to label amino acids in DBS specimens. The [2H4]DMAP-NCS labelled amino acid standards were used as internal standards to compensate the matrix effect. This method was validated by measuring linearity, recovery and accuracy. The results showed that the developed SID-LC-MS method can be used for sensitive and selective determination of 12 diagnostically important amino acids in DBS specimens.

  • Fengfeng Xiao, Bing Cao, Liewei Wen, Yanhong Su, Meixiao Zhan, Ligong Lu, Xianglong Hu
    Chinese Chemical Letters. 2020, 31(9): 2516-2519.

    Pathogen infection is the main cause of human morbidity and death. Traditional antibiotics usually sterilize bacteria in chemical ways, which tends to develop serious antibiotic resistance. Cationic polymers exhibit good bacterial inhibition with less resistance, but often face severe cytotoxicity toward normal cells. The optimization of polymeric antimicrobials for enhanced bactericidal capacity and improved biocompatibility is quite meaningful. In addition, photodynamic therapy (PDT) is a therapeutic modality with less susceptibility to develop resistance. Herein, a typical commercial polymeric antimicrobial, polyhexamethylene guanidine (PHMG) was selected for current proof-of-concept optimization due to its excellent bactericidal capacity but moderate biocompatibility. Eosin-Y (EoS) was copolymerized to afford EoS-labeled polymer conjugates, poly(2-(dimethylamino) ethyl methacrylate-co-eosin), P(DMAEMA-co-EoS), which was conjugated with PHMG to afford a novel polymeric antimicrobial, P(DMAEMA-co-EoS)-b-PHMG-b-P(DMAEMA-co-EoS), noted as PEoS-PHMG. It could efficiently kill broad-spectrum bacteria by physical damage and photodynamic therapy. Compared with PHMG, the bacterial inhibition of PEoS-PHMG was potentiated after the functionalization. Furthermore, PEoS-PHMG exhibited low cytotoxicity and minimal hemolysis, which was demonstrated by cell viability assays toward LO2 cells and RAW 264.7 cells as well as hemolytic assays against red blood cells. These results confirmed that the resultant PEoS-PHMG could act as promising alternative antibacterial materials with excellent broad-spectrum bacterial inhibition and favorable biocompatibility.

  • Haibo Mei, Attila Márió Remete, Yupiao Zou, Hiroki Moriwaki, Santos Fustero, Lorand Kiss, Vadim A. Soloshonok, Jianlin Han
    Chinese Chemical Letters. 2020, 31(9): 2401-2413.

    Eleven new fluorine-containing FDA-approved drugs have been profiled and details of their discovery and preparation are discussed. Therapeutic areas include schizophrenia, migraine, multiple sclerosis, insomnia, rheumatoid arthritis, anti-tuberculosis, breast cancer, lymphoma kinase inhibitor, serotonin receptor antagonist. New pharmaceuticals feature four examples of aromatic fluorine, three aromatic CF3 group, three aliphatic CF3 and one compound with aromatic CF3O group. Furthermore, among the new compounds, six are chiral and seven are derived from tailor-made amino acids.

  • Juan Yang, Dan Xu, Ruilin Hou, Junwei Lang, Zhaoli Wang, Zhengping Dong, Jiantai Ma
    Chinese Chemical Letters. 2020, 31(9): 2239-2244.

    Lithium-ion hybrid capacitors (LIHCs) is a promising electrochemical energy storage devices which combines the advantages of lithium-ion batteries and capacitors. Herein, we developed a facile multistep pyrolysis method, prepared an amorphous structure and a high-level N-doping carbon nanotubes (NCNTs), and by removing the Co catalyst, opening the port of NCNTs, and using NCNTs as anode material. It is shows good performance due to the electrolyte ions enter into the electrode materials and facilitate the charge transfer. Furthermore, we employ the porous carbon material (APDC) as the cathode to couple with anodes of NCNTs, building a LIHCs, it shows a high energy density of 173 Wh/kg at 200 W/kg and still retains 53 Wh/kg at a high power density of 10 kW/kg within the voltage window of 0-4.0 V, as well as outstanding cyclic life keep 80% capacity after 5000 cycles. This work provides an opportunity for the preparation of NCNTs, that is as a promising high-performance anode for LIHCs.

  • Tao Zhu, Yongrui Yang, Suyuan Zhou, Xiang Yao, Lei Liu, Wenping Hu, Xiong Gong
    Chinese Chemical Letters. 2020, 31(9): 2249-2253.

    In the past ten years, perovskite solar cells were rapidly developed, but the intrinsic unbalanced charge carrier diffusion lengths within perovskite materials were not fully addressed by either a planar heterojunction or meso-superstructured perovskite solar cells. In this study, we report bulk heterojunction perovskite solar cells, where perovskite materials CH3NH3PbI3 is blended with solution-processed n-type TiOx nanoparticles as the photoactive layer. Studies indicate that one-step solution-processed CH3NH3PbI3:TiOx bulk-heterojunction thin film possesses enhanced and balanced charge carrier mobilities, superior film morphology with enlarged crystal sizes, and suppressed trapinduced charge recombination. Thus, bulk heterojunction perovskite solar cells by CH3NH3PbI3 mixed with 5 wt% of TiOx, which is processed by one-step method rather than typical two-step method, show a short-circuit current density of 20.93 mA/cm2, an open-circuit voltage of 0.90 V, a fill factor of 80% and with a corresponding power conversion efficiency of 14.91%, which is more than 30% enhancement as compared with that of perovskite solar cells with a planar heterojunction device structure. Moreover, bulk heterojunction perovskite solar cells possess enhanced device stability. All these results demonstrate that perovskite solar cells with a bulk heterojunction device structure are one of apparent approaches to boost device performance.

  • Hao Li, Jiangfeng Gong, Jing-Chang Li, Xincheng Zhang, Chunmei Tang, Hongbing Yao, Qingping Ding
    Chinese Chemical Letters. 2020, 31(9): 2275-2279.

    As a significant semiconductor, nickel selenide shows enormous potential and extensive application prospects in the field of sensor, photocatalysis and supercapacitor. In this paper, nickel selenide (Ni3Se2, NiSe) thin films were successfully fabricated on stainless-steel sheet using a facile, effective electrodeposition technique. The morphologies, microstructures and chemical compositions of the thin films are characterized systematically. Electrochemical tests exhibit that the Ni3Se2 and NiSe possess high specific capacitance of 581.1 F/g and 1644.7 F/g, respectively. A flexible, all-solid-state asymmetric supercapacitor is assembled by utilizing NiSe film as positive electrode and activated carbon as negative electrode. The solid device delivers a high areal capacitance of 27.0 mF/cm2 at the current density of 0.7 mA/cm2. The maximum volumetric energy density and power density of the NiSe//AC asymmetric SCs can achieve 0.26 mWh/cm3 and 33.35 mW/cm3, respectively. The device shows robust cycling stability with 84.6% capacitance retention after 10, 000 cycles, outstanding flexibility and satisfactory mechanical stability. Moreover, two devices in series can light up a red light-emitting diode, which displayed great potential applications for energy storage.

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