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1.
In this paper, a flower-like molybdenum disulfide material was prepared by hydrothermal method and was first used as adsorbents in the solid-phase extraction process for enriching N-nitrosoamines. Molybdenum disulfide exhibited three-dimensional petal-like microspheres with about 500 nm in diameter. The relevant analyte extraction and elution parameters (sample volumes, solution pH, washing solvents, elution solvents, and elution volumes) were optimized to improve the solid-phase extraction efficiency. The solid-phase extraction process coupled with high-performance liquid chromatography-tandem mass spectrometry for determining N-nitrosoamines in environmental water samples was established. The limits of detection were in the range of 0.01–0.05 ng/mL. The satisfactory recoveries (68.9–106.1%) were obtained at three different spiked concentrations (2, 5, and 8 ng/mL) in water samples, and the relative standard deviations were between 1.96 and 8.38%. This proposed method not only showed high sensitivity and good reusability but also provided a new adsorbent for enriching trace N-nitrosoamines in environmental water samples.  相似文献   
2.
Yutuo Guo 《中国物理 B》2022,31(7):76105-076105
Direct visualization of the structural defects in two-dimensional (2D) semiconductors at a large scale plays a significant role in understanding their electrical/optical/magnetic properties, but is challenging. Although traditional atomic resolution imaging techniques, such as transmission electron microscopy and scanning tunneling microscopy, can directly image the structural defects, they provide only local-scale information and require complex setups. Here, we develop a simple, non-invasive wet etching method to directly visualize the structural defects in 2D semiconductors at a large scale, including both point defects and grain boundaries. Utilizing this method, we extract successfully the defects density in several different types of monolayer molybdenum disulfide samples, providing key insights into the device functions. Furthermore, the etching method we developed is anisotropic and tunable, opening up opportunities to obtain exotic edge states on demand.  相似文献   
3.
The first total synthesis of glycocin F, a uniquely diglycosylated antimicrobial peptide bearing a rare S‐linked N‐acetylglucosamine (GlcNAc) moiety in addition to an O‐linked GlcNAc, has been accomplished using a native chemical ligation strategy. The synthetic and naturally occurring peptides were compared by HPLC, mass spectrometry, NMR and CD spectroscopy, and their stability towards chymotrypsin digestion and antimicrobial activity were measured. This is the first comprehensive structural and functional comparison of a naturally occurring glycocin with an active synthetic analogue.  相似文献   
4.
电催化水分解制氢是可以形成闭环的生产过程, 起始原料与副产物均为水、 过程清洁无污染, 是极具希望的产氢策略. 目前制约其发展的瓶颈之一是价格昂贵的Pt基贵金属催化剂. 为推动电催化分解水制氢的普及, 亟待开发低成本非贵金属催化剂. 在众多备选非贵金属催化材料中, 纳米层状结构二硫化钼(MoS2)因催化效果可期、 价格低而获得了广泛关注. 然而, 通常条件下易于获得的层状结构2H相MoS2大面积的基面部分显示惰性, 仅在片层边缘处存在少量活性位点, 且导电性较差, 因而尚不能替代Pt基催化剂, 而如何增加其活性位点数量和提高其导电性成为亟待解决的问题; 另一方面, 1T相MoS2虽然活性高、 导电性好, 但却存在制备困难及稳定性差的问题. 鉴于此, 研究者通过对纳米MoS2进行掺杂改性实现了其活性与稳定性的有效提升. 本文对非贵金属纳米MoS2催化剂掺杂改性的方法、 机理及其电催化水解制氢性能的相关研究进行了总结与讨论. 作为典型的非贵金属电解水析氢催化剂, MoS2具有巨大发展潜力, 本文能够对相关非贵金属催化剂的研发提供有益的参考.  相似文献   
5.
We investigated the electronic properties of armchair MoS2 nanoribbons with vacancy defects using a first-principles method based on density functional theory. It was found that defects reduced the stability of armchair MoS2 nanoribbons. Mo vacancies and MoS2 triple vacancies can both change the band structures of nanoribbons from semiconductor to metallic, whereas S vacancies, 2S divacancies, and MoS divacancies only decrease the bandgap. The densities of states and eigenstates of the nanoribbons indicated that impurity bands near the Fermi level basically contributed to the defect states. The relationships between the bandgap and width of four types of semiconducting nanoribbons were simulated. Nanoribbons with no defects have a bandgap that oscillates with width in a period of three, but the bandgap changes nonperiodically for nanoribbons with S vacancies, 2S divacancies, and MoS divacancies. We also found that when the concentration of defects decreased, the vacancy defects did not destroy the nanoribbon semiconducting behavior but only decreased the bandgap. These results open up possibilities for MoS2 nanoribbon applications in novel nanoelectronic devices.  相似文献   
6.
The implementation of covalent adaptable networks (CANs) in general resin system is becoming attractive. In this work, we propose a simple post-curing strategy based on the core-shell structured acrylate latex for the achievement on both the improved general performance and the CANs characteristics in latex films. The building to the CANs was relied on the introduction of 4,4′-diaminophenyl disulfide as the curing agent, which cured the acetoacetoxy decorated shell polymer through the ketoamine reaction. The metathesis reaction of aromatic disulfides in the crosslinking segments enabled the thermally induced dynamic behavior of the network as revealed in the stress relaxation tests by comparison with other diamine crosslinking agents without the incorporation of disulfide. The synergism of the dynamic crosslinking of the shell polymer and static crosslinking in the core polymer contributed to the improved mechanical strength (15 MPa, strain% = 250%) and the suppressed water adsorption (~1% in 24 h of soaking) of the latex film, which exhibited above 90% of recovery in both strength and strain from a cut-off film damage within 1 h at 80°C. Moreover, the cured latex film could be recycled, and 75% of the mechanical performance was regained after three fragmentation-hot-pressing cycles. These, in addition with the feasible and environmental friendly characteristics, suggest a sustainable paradigm toward the smart thermosetting latex polymers.  相似文献   
7.
Molybdenum disulfide (MoS2) has been regarded as one of the most promising candidates for replacing Pt group noble metals as an efficient electrocatalyst to enhance the hydrogen evolution reaction (HER) in consideration of its relatively high earth abundance. Recent studies show that the catalytic efficiency of MoS2 for HER can be promoted by the presence of 1T-phase MoS2. It is hard to precisely control the formation of 1T-MoS2, however, due to its metastability relative to 2H-MoS2. Elevating the stability of 1T phase allotrope is therefore of great importance and could be realized by replacing divalent S with monovalent elements or groups according to crystal field theory, which has been demonstrated through our first-principles density functional theory (DFT) calculation results. Differential Gibbs free energy analysis for hydrogen adsorption (ΔGH*) suggest that 1T and 1T′ MoSO (O doped MoS2) might be taken as potential candidate catalysts for HER process with better performance than 1T and 1T′ MoS2. We also propose a probable approach to synthesize 1T and 1T′ MoSO under oxidation circumstance environment of graphene oxide.  相似文献   
8.
Thermoset polymer elastomers that are capable of autonomous repairability upon physical damage at ambient temperature are highly desirable because of their thermal and environmental resistance, outstanding mechanical toughness and stability. To aim at this goal, we demonstrated that tris(diethylamino)phosphine was initially proven as an efficient catalyst for the aliphatic disulfide exchange at mild condition. By making use of the aliphatic disulfide bond reshuffling and elasticity of polyurethane elastomers, the inherently cross-linked polysulfide-based poly(thiourethane-urethane) elastomers were prepared and exhibited the ability to mend without extrinsic stimuli in the presence of phosphorus catalyst at room temperature after artificially damaged. The self-healing efficiency via the mechanical recovery approach was investigated to be mainly dependent upon the cross-linking density of polysulfide and hard segments chemistry, which in turns determined the molecular chain diffusion and reshuffling that was corroborated by the stress-relaxation study. The thermoset elastomer based on asymmetric diisocynate showed a maximum self-healing efficiency of 85.6% compared to 71.6% for the elastomer with symmetric monomer building blocks. The self-healable polymer was confirmed to be recyclable and reprocessable through a cut-compression processing cycle under a quite mild pressure and temperature thanks to the disulfide bond reshuffling. Meanwhile, the recycled thermoset elastomer well maintained the mechanical properties to its original material.  相似文献   
9.
Insulin is a small protein crucial for regulating the blood glucose level in all animals. Since 1922 it has been used for the treatment of patients with diabetes. Despite consisting of just 51 amino acids, insulin contains 17 of the proteinogenic amino acids, A- and B-chains, three disulfide bridges, and it folds with 3 α-helices and a short β-sheet segment. Insulin associates into dimers and further into hexamers with stabilization by Zn2+ and phenolic ligands. Selective chemical modification of proteins is at the forefront of developments in chemical biology and biopharmaceuticals. Insulin's structure has made it amenable to organic and inorganic chemical reactions. This Review provides a synthetic organic chemistry perspective on this small protein. It gives an overview of key chemical and physico-chemical aspects of the insulin molecule, with a focus on chemoselective reactions. This includes N-acylations at the N-termini or at LysB29 by pH control, introduction of protecting groups on insulin, binding of metal ions, ligands to control the nano-scale assembly of insulin, and more.  相似文献   
10.
Density functional studies of the edges of single-layer 1H-MoS2 are presented. This phase presents a rich variability of edges that can influence the morphology and properties of MoS2 nano-objects, play an important role in industrial chemical processes, and find future applications in energy storage, electronics and spintronics. The so-called Mo-100 %S edges vertical S-dimers were confirmed to be stable, however the authors also identified a family of metastable edges combining Mo atoms linked by two-electron donor symmetrical disulfide ligands and four-electron donor unsymmetrical disulfide ligands. These may be entropically favored, potentially stabilizing them at high temperatures as a “liquid edge” phase. For Mo-50 %S edges, S-bridge structures with 3× periodicity along the edge are the most stable, compatible with a Peierls’ distortion arising from the d-bands of the edge Mo atoms. An additional explanation for this periodicity is proposed through the formation of 3-center bonds.  相似文献   
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