Synthesis and Characterization of Silica@Copper Core–Shell Nanoparticles: Application for Conjugate Addition Reactions

Silica@copper (SiO₂@Cu) core–shell nanoparticles were synthesized and well characterized by XRD, TEM, AFM, XPS, UV/Vis, TGA–MS, and ICP–AES techniques. The synthesized SiO₂@Cu core–shell nanoparticles were employed as catalysts for the conjugate addition of amines to α,β‐unsaturated compounds in water to obtain β‐amino carbonyl compounds in excellent yields in shorter reaction times. Furthermore, the catalyst works well for hetero‐Michael addition reactions of heteroatom nucleophiles such as thiols to α,β‐unsaturated compounds. As the reaction is performed in water, it allows for easy recycling of the catalyst with consistent activity.     

铜蒸汽激光器双闸流管触发系统的研究

研制成用于钢蒸汽激光器的双间流管触发系统。用两个闸流管并联进行交替触发，总输入电功率达7．8kW。低功率运行时，激光器的效率为0．6％与单间流管激光器的效率一致。     

Surface-enhanced Raman scattering study of polymer on metals. III. Chemisorbed polybenzimidazole and its corrosion-inhibiting properties at high temperature

Chemisorption of polybenzimidazole on silver and copper etched with nitric acid has been observed by surface-enhanced Raman scattering (SERS). The polymer is found to react chemically with silver, forming a complexed film on the surface. The SERS spectra show that polybenzimidazole film inhibits oxidation of the metal at high temperature, unlike chemisorbed benzimidazole, benzotriazole, and poly(4-vinyl pyridine). © 1992 John Wiley & Sons, Inc.     

Click chemistry in materials synthesis. III. Metal‐adhesive polymers from Cu(I)‐catalyzed azide–alkyne cycloaddition

1,2,3‐Triazole‐based polymers generated from the Cu(I)‐catalyzed cycloaddition between multivalent azides and acetylenes are effective adhesive materials for metal surfaces. The adhesive capacities of candidate mixtures of azide and alkyne components were measured by a modified peel test, using a customized adhesive tester. A particularly effective tetravalent alkyne and trivalent azide combination was identified, giving exceptional strength that matches or exceeds the best commercial formulations. The addition of Cu catalyst was found to be important for the synthesis of stronger adhesive polymers when cured at room temperature. Heating also accelerated curing rates, but the maximum adhesive strengths achieved at both room temperature and high temperature were the same, suggesting that crosslinking reaches the same advanced point in all cases. Polytriazoles also form adhesives to aluminum, but copper is bound more effectively, presumably because active Cu(I) ions may be leached from the surface to promote crosslinking and adhesion. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5182–5189, 2007     

Air‐stable and recoverable catalyst for copper‐catalyzed controlled/living radical polymerization of styrene; In situ generation of Cu(I) species via electron transfer reaction

Copper‐catalyzed controlled/living radical polymerization (LRP) of styrene (St) was conducted using the silica gel‐supported CuCl₂/N,N,N′,N′,N″‐pentamethyldiethylenetriamine (SG‐CuCl₂/PMDETA) complex as catalyst at 110 °C in the presence of a definite amount of air. This novel approach is based on in situ generation and regeneration of Cu(I) via electron transfer reaction between phenols and Cu(II). Sodium phenoxide or p‐methoxyphenol was used as a reducing agent of Cu(II) complexes in LRP. The number–average molecular weight, M_n,GPC, increases linearly with monomer conversion and agrees well with the theoretical values up to 85% conversion The molecular weight distribution, M_w/M_n, decreases as the conversion increases and reaches values below 1.2. The catalyst was recovered in aerobic condition and reused in copper‐catalyzed LRP of St. For the second run, the number–average molecular weights increased with monomer conversion and the polydispersities decreased as the polymerization proceeded and reached to the value <1.3 at 81% conversion. The recycled catalyst retained 90% of its original activity in the subsequent polymerization. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 77–87, 2006     

Ligand Design in Atomically Precise Copper Nanoclusters and Their Application in Electrocatalytic Reactions

Metal nanoclusters (MNCs) are compositionally well-defined and also structurally precise materials with unique molecule-like properties and discrete electronic energy levels. Atomically precise ligand-protected Cu nanoclusters (LP-CuNCs) are one category of typical MNCs that usually demonstrate unique geometric and electronic structures to serve as electrocatalysts. However, the synthesis, application, as well as structure-performance relationship of LP-CuNCs are not adequately studied. Significantly, the ligands are essential to the geometric structure, crystal structure, size, and electronic structure of LP-CuNCs, which determine their physiochemical properties and applications. In this review, significant progress in the ligand design of LP-CuNCs, and their application in electrocatalytic reactions is introduced. The general basics of ligand-protected MNCs (LP-MNCs) are first introduced and the functions of ligands are emphasized. Subsequently, a series of different ligands for LP-CuNCs including thiolates, phosphines, alkynyl, polymers, and biomolecules are highlighted. Thereafter, their applications in different electrocatalytic reactions are discussed. It is believed that this review will not only inspire the design and synthesis of novel LP-CuNCs, but also contribute to the extension of their applications in electrocatalytic reactions and the establishment of accurate structure-performance relationships.     

电化学合成铜配合物的研究

采用金属铜为"牺牲"阳极,首次在无隔膜电解槽中,电化学溶解金属铜一步制备了纳米CuO前体Cu(OEt)2, Cu(OBu)2, Cu(acac)2, Cu(OEt)(acac), Cu(OBu)(acac) (acac为乙酰丙酮基).产物通过红外光谱(FT-IR)、拉曼光谱(Raman spectrum)进行表征.同时讨论了影响电合成铜醇盐及其配合物的关键因素.实验表明,防止阳极钝化,温度控制在30～50 ℃,采用有机胺溴化物为导电盐, 电极电位控制在0.8～1.2 V之间,可以提高电合成效率.实验同时表明Cu(acac)2, Cu(OEt)(acac), Cu(OBu)(acac)可作为制备含铜纳米材料前驱体.     

硫胺的燐光研究

硫胺无燐光，在碱中氧化后才产生燐光。 λ激发＝３００ｎｍ，λ发射＝４１０ ｎｍ，燐光寿命为１．３ｓ．硫胺燐光受溶剂极性影响甚小，１５种金属离子中只有铜离子可增强流胺燐光，寿命变短为 ０． ９４ ｓ，但不影响燐光光谱。在开始３０ｍｉｎ内有ＣｕＳＯ４的作用较快，以后逐渐变慢，到 ４ｈ后达平衡与不用ＣｕＳＯ４的燐光相近，启示ＣｕＳＯ４具有催化硫胺的氧化作用，建立了硫胺的燐光分析方法，用于两种维生素Ｂ１片的分析，分别为９８．５％与９８％。     

Copper—A “Modern” Bioelement

Copper is a bioessential element in biology with truly unique chemical characteristics in its two relevant oxidation states +I and +II. Significant progress has been made in recent years in the elucidation of the frequently surprising biochemistry of this trace element. Those advances were especially furthered through mutual stimulation involving results from biochemistry, molecular biology, and medicine on one hand and the synthesis as well as the structural and spectroscopic characterization of low molecular weight model complexes on the other. The most notable features of protein-bound active copper are its almost exclusive function in the metabolism of O₂ or N/O compounds (NO, N₂O) and its frequent association with oxidizing organic and inorganic radicals such as tyrosyl, semiquinones, superoxide, or nitrosyl. This unique biological role of copper can be rationalized given its chemical and assumed evolutionary background.