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71.
Science China Chemistry - Cellular metabolism in multiple organelles utilizes compartmentalized multienzyme efficient catalysis to realize substance metabolism, energy conversion and immune... 相似文献
72.
Qiang Fu Xianjie Wang Jiecai Han Jun Zhong Tongrui Zhang Tai Yao Chengyan Xu Tangling Gao Shibo Xi Ce Liang Lingling Xu Ping Xu Bo Song 《Angewandte Chemie (International ed. in English)》2021,60(1):259-267
To ensure sustainable hydrogen production by water electrolysis, robust, earth‐abundant, and high‐efficient electrocatalysts are required. Constructing a hybrid system could lead to further improvement in electrocatalytic activity. Interface engineering in composite catalysts is thus critical to determine the performance, and the phase‐junction interface should improve the catalytic activity. Here, we show that nickel diphosphide phase junction (c‐NiP2/m‐NiP2) is an effective electrocatalyst for hydrogen production in alkaline media. The overpotential (at 10 mA cm?2) for NiP2‐650 (c/m) in alkaline media could be significantly reduced by 26 % and 96 % compared with c‐NiP2 and m‐NiP2, respectively. The enhancement of catalytic activity should be attributed to the strong water dissociation ability and the rearrangement of electrons around the phase junction, which markedly improved the Volmer step and benefited the reduction process of adsorbed protons. 相似文献
73.
电化学水分解制氢作为重要的生产氢能的新能源技术,包括氢气析出反应(HER)和氧气析出反应(OER).然而,OER进行的是多步电子转移过程,动力学过程缓慢且过电位高,严重制约了电解水制氢的发展.因此开发低成本、高效稳定的非贵金属催化剂替代贵金属催化剂(RuO2,IrO2)来降低过电位,减少能源消耗十分必要.Ni3S2由于其高导电性、高活性、低成本等优点,具有作为贵金属催化剂替代品的广阔应用前景,但其OER性能仍需进一步提高.对已有的有效OER催化剂进行表界面调控是提高催化剂性能的一种有效策略.CeO2中的Ce3+和Ce4+价态之间可以灵活过渡,使其具有良好的电子/离子导电性、可逆的表面氧离子交换和较高的储氧能力.CeO2的多价性使其有机会与其它基质产生强烈的电子相互作用,良好的电子/离子导电性和较高的储氧能力是提高催化剂析氧活性的有利因素.因此,用CeO2对Ni3S2进行修饰是提高其析氧活性的有效途径.基于此,本文运用水热和电沉积相结合的方法将CeO2修饰到Ni3S2纳米片上,制备得到生长于泡沫镍上的Ni3S2-CeO2纳米片阵列(Ni3S2-CeO2/NF),并运用X射线粉末衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、X射线光电子能谱(XPS)等手段进行了表征,以三电极系统测试了其电催化析氧性能及稳定性,并通过密度泛函理论计算进行了验证.XRD结果表明,复合材料中确实存在Ni3S2和CeO2.通过SEM发现,泡沫镍基底上均匀分布着Ni3S2纳米片阵列;电沉积CeO2后,Ni3S2-CeO2仍保持其纳米片特性,但表面变得粗糙.Ni3S2-CeO2的TEM结果也证实了纳米片结构的形成,高分辨率TEM图像清晰的显示出Ni3S2和CeO2之间具有明显的界面.XPS结果表明,Ni3S2-CeO2的Ni 2p的结合能与Ni3S2相比出现负位移.与纯CeO2的Ce 3d谱图相比,Ni3S2-CeO2杂化体系中Ce4+的比例明显增加,表明Ce的价态发生了重排,部分电子转移给了Ni元素.这些结果均说明Ni3S2与CeO2之间存在着较强的电子相互作用.相应的电催化测试结果显示,在1.0 M KOH中,当电流密度达到20 mA cm–2时,Ni3S2/NF需提供356 mV的过电位,Ni3S2-CeO2/NF只需264 mV的过电位,仅次于RuO2/NF.而且,Ni3S2-CeO2/NF在中性条件下也显示出了较理想的析氧活性.Ni3S2-CeO2/NF的Tafel斜率明显低于CeO2/NF和Ni3S2/NF,表明其具有良好的OER反应动力学.循环伏安法和计时电位法结果均表明,Ni3S2-CeO2/NF具有良好的电化学稳定性.电化学阻抗谱测试结果表明,与Ni3S2/NF和CeO2/NF相比,Ni3S2-CeO2/NF明显具有更小的半圆直径,说明其电荷转移阻抗更小,进一步表明CeO2的修饰有助于催化过程中电子的快速转移.在非法拉第区域的循环伏安扫描曲线以及拟合扫描速度对电容电流曲线结果显示,Ni3S2-CeO2/NF的最大电容值大于CeO2/NF和Ni3S2/NF,表明其暴露了更多的活性位点,具有更大的电化学活性表面积;而且,Ni3S2-CeO2/NF在400和500 mV时的电催化析氧转换频率明显高于Ni3S2/NF和CeO2/NF,进一步说明Ni3S2-CeO2/NF具有更高的本征催化活性.密度泛函理论计算表明,由于*OH,*O和*OOH与Ni3S2-CeO2中的Ni和Ce原子相互作用的存在,使得反应中间产物与Ni3S2-CeO2之间的结合强度较纯Ni3S2或CeO2强,使其显示出了更高的OER性能.在经过24 h连续电解后,SEM和TEM结果均表明,Ni3S2-CeO2/NF材料仍保持了其纳米片形貌.稳定性测试后的XPS结果表明,Ni 2p对应的峰强度降低,而与氧化镍物种对应的峰强度增强;S元素在Ni3S2-CeO2表面的信号强度明显降低.根据文献报道,在强烈的氧化环境下,过渡金属硫化物会部分转化为氧化物或氢氧化物,这通常被认为是OER过程的实际催化物种. 相似文献
74.
维库溴铵、罗库溴铵和泮库溴铵是一类广泛使用的非去极化肌松剂,使用过程中引起过敏反应甚至死亡的情况时有发生,快速检测血液中该类肌松剂的浓度,可为临床早期诊断提供有价值的信息。该类肌松剂为强极性的季铵盐类化合物,在反相色谱柱上难以保留,主要采用离子对色谱法进行分离。采用离子对色谱法时,加入的离子对试剂有离子抑制作用,可降低质谱灵敏度,还会污染质谱系统。该文建立了高效液相色谱-串联质谱(HPLC-MS/MS)同时检测血液中3种季铵盐类肌松剂的检测方法。血液样品经稀释、高速离心后,上清液过Bond Elut AL-N固相萃取柱净化,用0.45 μm的微孔滤膜过滤后检测。采用ZIC-cHILIC色谱柱(50 mm×2.1 mm, 3.0 μm)分离,以乙腈和0.1%甲酸水溶液为流动相,梯度洗脱,在ESI+、多反应检测(MRM)模式下检测。3种季铵盐类肌松剂在血液中的基质效应为88.1%~95.4%,在各自范围内线性关系良好,相关系数(R2)均大于0.996,检出限为0.2~0.8 ng/mL,定量限为0.5~2.0 ng/mL,加标回收率为92.8%~110.6%,相对标准偏差(RSD)为3.2%~9.4%。该方法灵敏度高,准确性好,操作简便,可用于血液样品中维库溴铵、罗库溴铵和泮库溴铵的快速检测。 相似文献
75.
Balancing the Rate of Cluster Growth and Etching for Gram‐Scale Synthesis of Thiolate‐Protected Au25 Nanoclusters with Atomic Precision 下载免费PDF全文
Xun Yuan Bin Zhang Zhentao Luo Qiaofeng Yao Prof. David Tai Leong Prof. Ning Yan Prof. Jianping Xie 《Angewandte Chemie (International ed. in English)》2014,53(18):4623-4627
We report a NaOH‐mediated NaBH4 reduction method for the synthesis of mono‐, bi‐, and tri‐thiolate‐protected Au25 nanoclusters (NCs) with precise control of both the Au core and thiolate ligand surface. The key strategy is to use NaOH to tune the formation kinetics of Au NCs, i.e., reduce the reduction ability of NaBH4 and accelerate the etching ability of free thiolate ligands, leading to a well‐balanced reversible reaction for rapid formation of thermodynamically favorable Au25 NCs. This protocol is facile, rapid (≤3 h), versatile (applicable for various thiolate ligands), and highly scalable (>1 g Au NCs). In addition, bi‐ and tri‐thiolate‐protected Au25 NCs with adjustable ratios of hetero‐thiolate ligands were easily obtained. Such ligand precision in molecular ratios, spatial distribution and uniformity resulted in richly diverse surface landscapes on the Au NCs consisting of multiple functional groups such as carboxyl, amine, and hydroxy. Analysis based on NMR spectroscopy revealed that the hetero‐ligands on the NCs are well distributed with no ligand segregation. The unprecedented synthesis of multi‐thiolate‐protected Au25 NCs may further promote the practical applications of functional metal NCs. 相似文献
76.
水杨羟肟酸对氟碳铈矿的捕收机制研究 总被引:2,自引:0,他引:2
以水杨羟肟酸为捕收剂,通过浮选试验、溶液化学计算、动电位和红外光谱检测分析研究了氟碳铈矿的可浮性及药剂与矿物的作用机制。当水杨羟肟酸浓度为5×10-4mol·L-1时,氟碳铈矿在pH=7~10较宽的范围内有较好的可浮性,与矿物表面的稀土阳离子的水解产物种类及其浓度有关。pH=8~9范围内,稀土阳离子水解优势组分RE(OH)2+和RE(OH)+2吸附在氟碳铈矿表面是主要的正活性质点,有利于药剂的化学吸附。在pH=8.3时,水杨羟肟酸对氟碳铈矿捕收是化学吸附作用生成五元环螯合物的结果。 相似文献
77.
Dynamic and Quantitative Control of the DNA‐Mediated Growth of Gold Plasmonic Nanostructures 下载免费PDF全文
Dr. Jianlei Shen Lifeng Xu Dr. Chunpeng Wang Dr. Hao Pei Prof.Dr. Renzhong Tai Prof.Dr. Shiping Song Prof.Dr. Qing Huang Prof.Dr. Chunhai Fan Prof.Dr. Gang Chen 《Angewandte Chemie (International ed. in English)》2014,53(32):8338-8342
Reproducible and controllable growth of nanostructures with well‐defined physical and chemical properties is a longstanding problem in nanoscience. A key step to address this issue is to understand their underlying growth mechanism, which is often entangled in the complexity of growth environments and obscured by rapid reaction speeds. Herein, we demonstrate that the evolution of size, surface morphology, and the optical properties of gold plasmonic nanostructures could be quantitatively intercepted by dynamic and stoichiometric control of the DNA‐mediated growth. By combining synchrotron‐based small‐angle X‐ray scattering (SAXS) with transmission electron microscopy (TEM), we reliably obtained quantitative structural parameters for these fine nanostructures that correlate well with their optical properties as identified by UV/Vis absorption and dark‐field scattering spectroscopy. Through this comprehensive study, we report a growth mechanism for gold plasmonic nanostructures, and the first semiquantitative revelation of the remarkable interplay between their morphology and unique plasmonic properties. 相似文献
78.
Jong Young Joung Ha Yeon Lee Jongil Park Jee-Young Lee Byung Ha Chang Kyoung Tai No Ky-Youb Nam Jae Sung Hwang 《Applied biochemistry and biotechnology》2014,172(4):1882-1897
Melanocytes are unique cells that produce specific melanin-containing intracellular organelles called melanosomes. Melanosomes are transported from the perinuclear area of melanocytes toward the plasma membrane as they become more melanized in order to increase skin pigmentation. In this vesicular trafficking of melanosomes, Rab27a, melanophilin, and myosin Va play crucial roles in linking melanosomes to actin-based motors. To identify novel compounds to inhibit binding interface between Rab27a and melanophilin, a pharmacophore model was built based on a modeled 3D structure of the protein complex that describes the essential binding residues in the intermolecular interaction. A pharmacophore model was employed to screen a chemical library database. Finally, 25 virtual hits were selected for biological evaluations. The biological activities of 11 analogues were evaluated in a second assay. Two compounds were identified as having concentration-dependent inhibitory activity. By analyzing structure–activity relationships of derivatives of BMD-20, two hydroxyl functional groups were found to be critical for blocking the intermolecular binding between Rab27a and melanophilin. 相似文献
79.
Chin-Kuen Tai Pao-Ling Yeh Chun-Chi Chang Wen-Hao Chen Rong-Hou Wu Yu-Ma Chou Bo-Cheng Wang 《Research on Chemical Intermediates》2014,40(6):2355-2362
Recently, the organic synthesis and electronic device applications of π-conjugated polymer-based materials with low energy band gap (below 2 eV) and high values of incident photon to current efficiency have been presented. In the present study, the physical properties of polythiophene (PTH) and its derivative systems (PTs) were investigated as π-conjugated low energy band gap polymers. Density functional theory with periodic boundary condition (PBC), the B3LYP functional, and the 6-31G(d) basis set was applied to determine their geometric and electronic structures and corresponding energies (E HOMO, E LUMO, and E g = E LUMO ? E HOMO) from the monomer of thiophene and its derivatives for one-dimensional (1D) extension to polymer. The effects of 3-substitution in PTs including electron-donating (CH3–, C6H13–, OH–, Cl–, OCH3–, and CHO–) and electron-withdrawing groups (Cl–, CHO–, CN–, NO2–, CF3–, and COOH–) compared with PTH were investigated. According to the calculation results, PTs with electron-donating and electron-withdrawing substituents should exhibit red- and blue-shifts, respectively, compared with PTH. These calculation results show good agreement with experimental data and provide further information for molecular design considerations. 相似文献
80.
A new tripodal ligand, N,N′,N″-tri(salicylaldehyde)triaminotriethylamine (1) has been synthesized and characterized by elemental analysis, IR and UV spectroscopy, MS, and X-ray crystallography. X-ray diffraction analysis reveals that the three chains of the ligand form a cup-like structure. The ligand’s magnesium(II) complex has been synthesized and characterized by elemental analysis, conductivity, and IR and UV spectroscopy. The luminescence properties of the ligand and its magnesium(II) complex were investigated in DMF, CH3OH, and CH3CH2OH solution and in the solid state at room temperature. 相似文献