进样阀(I)

高效液相色谱进样阀（或进样器）的作用是将一定量的样品送入色谱仪。样品在流动相的带动下进入色谱柱系统完成分离过程。现代高效液相色谱仪对于进样阀的要求如下：（１）耐高压,因为高效液相色谱通常要在３５．０ＭＰａ或更高的压力下工作;（２）进样量精确;（３）进样重复性好;（４）方便、适用,且可根据需要选择不同的进样量;（５）价格低廉;（６）保证在色谱柱中心进样,操作时不产生流量或压力波动。到目前为止,液相色谱进样阀共有３种形式：１．手动注射进样器;２．手动进样阀;３．自动进样器。从原理上讲,自动进样器是在…     

Small Gold(I) and Gold(I)–Silver(I) Clusters by C−Si Auration

Auration of o-trimethylsilyl arylphosphines leads to the formation of gold and gold–silver clusters with ortho-metalated phosphines displaying 3c–2e Au−C−M bonds (M=Au/Ag). Hexagold clusters [Au₆L₄](X)₂ are obtained by reaction of (L−TMS)AuCl with AgX, whereas reaction with AgX and Ag₂O leads to gold–silver clusters [Au₄Ag₂L₄](X)₂. Oxo-trigold(I) species [Au₃O]⁺ were identified as the intermediates in the formation of the silver-doped clusters. Other [Au₅], [Au₄Ag], and [Au₁₂Ag₄] clusters were also obtained. Clusters containing PAu−Au−AuP structural motif display good catalytic activity in the activation of alkynes under homogeneous conditions.     

Lumineszierende Cu(I)-, Ag(I)- und Tl(I)-Komplexe mit N-Butyl-N′-benzolsulfonylthioharnstoff- Tetra- und hexamere (ML)x-Cluster

Zusammenfassung Das Säureanion von N-Butyl-N-benzolsulfonylthioharnstoff (BuBsT) bildet mit Cu(I) einen lumineszierenden hexameren und einen nicht lumineszierenden tetrameren Cluster (Cu(BuBsT))_x; x=6, 4. Röntgenstrukturanalysen belegen für x=6 eine verzerrt oktaedrische und für x=4 eine verzerrt tetraedrische Anordnung der Cu-Atome. Die Liganden beider Cluster sind über den Thioharnstoff-Schwefel und den Sulfonamid-Stickstoff mit den Cu-Atomen verknüpft (S,N-Koordination). Jeweils ein Sulfonyl-Sauerstoffatom pro Ligand bildet eine intramolekulare Wasserstoffbrücke zu der NHC₄H₉-Gruppe der gleichen Ligandeinheit aus. Ag(BuBsT) tritt in Form von drei lumineszierenden Modifikationen auf, von denen eine (Ag(BuBsT)-II) hexamer ist (isotyp mit (Cu(BuBsT))₆). Tl(BuBsT) liegt in CHCl₃-Lösung überwiegend als Dimer vor.

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Luminescent Cu(I)-, Ag(I)- and TI(I)-complexes with N-Butyl-N-benzenesulfonylthiourea-tetramer and hexamer (ML)_x-clusters

Summary The acid anion of N-butyl-N-benzenesulfonylthiourea (BuBsT) forms numerous 1/1 complexes with the univalent ions Cu(I), Ag(I) and Tl(I). The crystal structures of two different copper(I) clusters (Cu(BuBsT))_x, (x=6, 4) are discussed. The hexamer containing a distorted Cu₆ octahedron is luminescent, while the analogous tetramer containing a distorted Cu₄ tetrahedron is not. The copper atoms of both clusters form coordinate linkages with the sulfonamide nitrogen and the thiourea sulphur of the ligands (S,N-coordination). One sulfonyl oxygen per ligand is bound to the NHC₄H₉ group of the same ligand through a hydrogen bond. Ag(BuBsT) forms three different luminescent modifications. One of them (Ag(BuBsT)-II) is isotype to (Cu(BuBsT))₆ and therefore hexamer, too. Tl(BuBsT) mainly forms dimers in CHCl₃ solution.

     

Natriummetaphosphat (I) in Metaphosphors?ure (II)

Ohne Zusammenfassung     

Au(I)、Ag(I)、Cu(I)氰合离子在大孔强碱性阴离子交换树脂中的传质研究

测定了不同温度下Au(Ⅰ)、Ag(Ⅰ)、Cu(Ⅰ)氰合离子分别在大孔强碱性苯乙烯系CN、Cl、OH型离子交换树脂中的内扩散系数和扩散活化能。从结果得出,氰合离子在树脂相中扩散传质异常缓慢并非由于过高的活化能,而可能是由于过低的活化熵所致。     

Die Extrahierbarkeitvon Thallium- (I) -komplexen mit 8-Hydroxychinolin(I), Di?thyldithiocarbamidat(II) und 8-Mercaptochinolin(III)

Ohne Zusammenfassung     

Review: Multimetallic silver(I)–pyridinyl complexes: coordination of silver(I) and luminescence

This review highlights some structural features and luminescent properties of homo- and hetero-multinuclear silver(I)–pyridinyl complexes. It focuses on the coordination and geometry of the silver(I) ions to the pyridinyl-nitrogen. For this reason, we have considered only pyridinyl-N–Ag(I) complexes whose crystal data are available. In addition, this review does not consider mononuclear silver(I)–pyridinyl complexes as these have been reviewed elsewhere. This is motivated by the fact that multinuclear silver(I)–pyridinyl complexes have been shown to be more stable in solution, possess enhanced properties, and have fascinating structures compared to their mononuclear counterparts. The introduction highlights pyridinyl ligands used in complexation of silver(I) ions. The main body highlights complexation of silver(I) through pyridinyl nitrogen and the interactions found in the multinuclear silver(I)–pyridinyl complexes as well as the coordination number and geometry of silver(I) centers. Though silver(I) has been flaunted to prefer linear twofold coordination geometry, from this review, it is clear that higher coordination numbers in varied geometries are possible. These include distorted trigonal planar, T-shaped, distorted tetrahedral, trigonal bipyramidal, and octahedral geometries. Coordination of silver(I) to pyridinyl ligands and their metalloligands has been observed to impart or enhance luminescent properties in the ensuing complexes.     

鬼灯檠化学成分的研究(I)

鬼灯檠(Rodgersia aesculifolia batal),亦名黄药子(Huang Yaozi),系虎耳草科(Saxifragaceae)鬼灯檠属植物,分布于甘肃、陕西、四川、河北等省区,甘肃省陇南地区分布尤广。民间常用作收敛止血、消炎解热以及湿热腹泻、痢疾、血崩、外伤出血、疮疖等病患的治疗。所含的化学成分有抑菌和广谱性的抗病毒作用。     

Pyrazolate bridged ruthenium(I) complexes. A convenient synthesis of ruthenium(I) compounds. The X-ray structure of bis-μ-(3,5-dimethylpyrazolate)bis(tricarbonyl-ruthenium(I)) (RuRu)

RuCl₃·nH₂O reacts with carbon monoxide in boiling 2-methoxyethanol to give a solution which upon treatment with pyrazole-type ligands (HPz) in the presence of zinc and carbon monoxide yields the complexes [Ru(μ-Pz)(CO)₃]₂. This provides an easy high-yield route to ruthenium(I) complexes. In the crystal structure of [Ru(μ-dpmz)(CO)₃]₂ (dpmz = 3,5-dimethylpyrazolate) the Ru₂N₄ framework adopts a boat conformation with a RuRu distance of 2.705(2) Å.     

Cu(I), Ag(I) complexes containing (η 5-cyclopentadienyl) [η 5-1-(diphenylphosphino) cyclopentadienyl] cobaltocenium

{Cu₄Br₅[(η ⁵-C₅H₄PPh₂)(η ⁵-C₅H₅)Co]₄}[PF₆]₃, [(η ⁵-C₅H₄PPh₂)(η ⁵-C₅H₅)Co]⁺ = ((η ⁵-cyclopentadienyl)[η ⁵-1-(diphenylphosphino) cyclopentadienyl] cobaltocenium) and {Ag(NO₃)(CH₃COCH₃)[(η ⁵-C₅H₄PPh₂)(η ⁵-C₅H₅)Co]} _n [PF₆] _n have been synthesized and characterized by elemental analyses, infrared spectroscopy, X-ray diffraction techniques, and by cyclic voltammetry. {Cu₄Br₅[(η ⁵-C₅H₄PPh₂)(η ⁵-C₅H₅)Co]₄}[PF₆]₃ contains four coplanar copper atoms bridged by four μ-Br and one central μ ₄-Br occupying the apex of a square pyramid, and {Ag(NO₃)(CH₃COCH₃)[(η ⁵-C₅H₄PPh₂)(η ⁵-C₅H₅)Co]} _n [PF₆] _n affording a 1-D coordination zigzag polymer.     

Luminescent copper(I) halide adducts of [Au(im(CH2py)2)2]PF6 exhibiting short Au(I)···Cu(I) separations and unusual semibridging NHC ligands

The picolyl-substituted NHC complex [Au(im(CH(2)py)(2))(2)]PF(6) (1) reacts with two equivalents of copper(I) halides, affording compounds [Au(im(CH(2)py)(2))(2)(CuX)(2)]PF(6) (X = Cl, 2; Br, 3; I, 4). Each complex contains a nearly linearly coordinated [Au(NHC)(2)](+) center where the two picolyl groups on each im(CH(2)py)(2) ligand chelate a single copper atom. The Cu(I) center resides in a distorted tetrahedral environment and is coordinated to two pyridyl groups, a halide ion, and a gold metalloligand. The Au(I)-Cu(I) separations measure 2.7030(5), 2.6688(9), and 2.6786(10) ? for 2-4, respectively. Additionally, each Cu(I) center is further coordinated by a semibridging NHC ligand with short Cu-C separations of ~2.3 ?. In solution, these complexes dissociate the Cu(I) ion. In the solid state, 2-4 are photoluminescent with respective emission maxima of 512, 502, and 507 nm. The reaction of [Au(im(CH(2)py)(2))(2)]PF(6) with four equivalents of CuBr afforded the coordination polymer {[AuCu(2)Br(2)(im(CH(2)py)(2))(2)]Br·3CH(3)CN}(n) (5). This polymeric complex contains [Au(NHC)(2)](+) units interconnected by Cu(2)Br(2) dimers. In 5, the Au-Cu separations are long at 4.23 and 4.79 ?, while the Cu-Cu distance is considerably shorter at 2.9248(14) ?. In the solid state, 5 is photoluminescent with a broad band appearing at 533 nm.     

Structure and Properties Characteristic of Dimeric Silver(I) Complex: Dinuclear Bis(O,O′-Diphenyldithiophosphato)bis(1,10-phenanthroline) Ag(I)

The complex bis(O,O-diphenyldithiophosphato)bis(1,10-phenanthroline) silver(I), Ag₂[(PhO)₂PS₂]₂(Phen)₂, has been synthesized and structurally characterized. Its crystal structure has been determined by X-ray crystallography. It crystallizes in the monoclinic system, space group P2₁/c, with unit cell parameters a = 11.140(2) Å, b = 10.044(2) Å, c = 23.006(6) Å, = 113.36(3)° V = 2363.1(9) ų, _calcd = 1.600 g/cm³, and Z = 4 for R ₁ = 0.0961. The coordination geometry of each Ag atom, by two N atoms from 1,10-phenanthroline ligand and by two S atoms from two O,O-diphenyldithio phosphate anions, is that of a tetrahedron. The two diphenyldithiophosphato ligands each bridge two silver atoms to form an eight-membered Ag₂S₄P₂ ring, while the 1,10-phenanthroline molecule coordinates to a silver atom to complete the local tetrahedral geometry. The Ag···Ag separation is 3.185(2) Å. The data of elemental analysis, IR and UV-vis spectroscopies are in good agreement with the crystal structure. The thermal gravimetry data indicate that there are two decomposition steps with one intense endothermical peak and one weak exothermical peak. The final product of the thermal decomposition is AgS.     

Bis(4‐picoline‐κN)gold(I) dibromidoaurate(I) and bis(4‐picoline‐κN)gold(I) dichloridoaurate(I): space‐group ambiguity?

Bis(4‐picoline‐κN)gold(I) dibromidoaurate(I), [Au(C₆H₇N)₂][AuBr₂], (I), crystallizes in the monoclinic space group P2₁/n, with two half cations and one general anion in the asymmetric unit. The cations, located on centres of inversion, assemble to form chains parallel to the a axis, but there are no significant contacts between the cations. Cohesion is provided by flanking anions, which are connected to the cations by short Au...Au contacts and C—H...Br hydrogen bonds, and to each other by Br...Br contacts. The corresponding chloride derivative, [Au(C₆H₇N)₂][AuCl₂], (II), is isotypic. A previous structure determination of (II), reported in the space group P with very similar axis lengths to those of (I) [Lin et al. (2008). Inorg. Chem. 47 , 2543–2551], might be identical to the structure presented here, except that its γ angle of 88.79 (7)° seems to rule out a monoclinic cell. No phase transformation of (II) could be detected on the basis of data sets recorded at 100, 200 and 295 K.     

STUDY ON BINUCLEAR COPPER(I)COMPLEXES III.SYNTHESIS,CHARACTERIZATION AND ELECTROCHEMISTRY OF DICHLORO-TRIS(4-VINYLPYRIDINE)-DICOPPER(I)COMPLEX

Recent years,many novel complexes have been prepared by usinghetero-bidentate ligands.However,complexes with such ligands as 4-vinylpyridinewhich has two different coordinating sites have not been reported,and only a fewcomplexes of Cu(I)have been published~(1-3).The title complex Cu_2(C_5H_4N·CH=CH_2)_3Clwas prepared and characterized by elemental analyses,ICP,IR,and electronicspectra.Its conductivity,oxidation potential and reduction potential weremeasured.     

月光花素甲(I)、(II)整体分子结构的测定

测定了月光花素甲的整体分子结构分析, 它由月光花素甲I和月光花素甲II组成.它们分别含有三个鼠李糖, 1个3-位碳上有取代基的鼠李糖和一个甙元. 三个鼠李糖和取代鼠李糖的构型, 取代基的结构和位置以及糖之间的连接方式在二个分子中对应相同, 在二个糖甙中存在有二个糖元和糖取代基的结构证明为2-羟基-3-甲基丁酸, 11-羟基十六羧酸基和11-羟基十四羧酸基, 并证明了每个糖甙的六个分子片段的连接方式.     

Zur Bestimmung von Phenoxyessigs?ure (I) neben Phenoxymethylpenicillin (II)

Ohne Zusammenfassung     

Zur Untersuchung von H?matoporphyrin (I) und Cytochrom (II)

Ohne Zusammenfassung     

2,4′-Bipyridyl complexes with silver(I) and copper(II)

Summary Ag^I and Cu^II complexes with 2,4-bipyridyl (2,4-bipy or L) with the general formulae AgL₂X (where X = NO _inf3 ^sup– or ClO₄ ^-), CuL₂X₂·2H₂O (X = Cl^- or Br^-), CuL₄SO₄·4H₂O, CuL₄(NO₃)₂·2H₂O and CuL₄(ClO₄)₂·H₂O have been isolated pure and characterized by analytical, spectral and magnetic measurements. The thermal decomposition of these complexes was studied under non-isothermal conditions in air.