锌配体化合物选择性诱导、稳定、荧光检测G-四联体

通过两步简单的合成反应,制备了锌的配体化合物（ZSC）.并将其与不同构型的G-四联体作用,发现其可以很好的选择性荧光打开检测G-四联体.通过荧光,圆二色谱（CD）等实验的深入研究,表明这个化合物兼具诱导、稳定和荧光打开检测G-四联体的优点.这是第一次报道既可以诱导稳定G-四联体,又可以进行荧光打开检测定量分析G-四联体的锌的salen配体复合物.此外,这个化学试剂还可以将Z型G-四联体转变成平行的G-四联体.这是一个针对G-四联体的选择性的、敏感的和拓扑特异性的探针.这个探针与不同G-四联体的序列之间的相互作用的研究,展示了它可能作为一种抗癌药物的潜力,并且,有望将其用于基于G-四联体的检测方法检测其他生物物质的领域.     

Synthesis,Structure and Properties of a Zinc(II) Complex with the Lapacholate Anion and Ethanol as Ligands

The reaction of lapachol, 2-hydroxy-3-(3-methyl-2-butenyl)-1,4-naphtoquinone, C₁₅H₁₄O₃, with zinc acetate, in ethanol, produces a chelate formula Zn(C₁₅H₁₃O₃)₂(C₂H₆O)₂, whose structure has been determined by single crystal X-ray diffraction. It pertains to the triclinic system, space group P I (No. 2), a = 8.2380(3) Å, b = 9.4900(2) Å, c = 11.0110(4) Å, α = 112.536(2)°, β = 91.204(2)°, γ = 92.664(2)°, Z = 1. Some spectroscopic and chemical properties of the complex are also reported.     

Spectrophotometric Simultaneous Determination of Zinc(II), Manganese(II) and Iron(II) in Pharmaceutical Preparations Using OSC-PLS

The purpose of this paper is to develop a fast and sensitive spectrophotometric method for the simultaneous determination of zinc(II), manganese(II) and iron(II) in pharmaceutical preparations. The method presented in this work is based on the well-known reaction of these ions with 4-(pyridylazo)resorcinol (PAR)1. The application of quantitative chemometric methods, particularly PLS to multivariate chemical data is becoming more widespread owing to the availability of digitized spectroscop…     

Urothermal Syntheses of two New Luminescent Zinc(II) Compounds via Dual-ligand Strategy

Urothermal reaction of Zn(NO₃)₂ · 6H₂O, Htrz and NH₂H₂pdc or H₂pdc affords two new compounds, namely [Zn₂(NH₂bdc)(trz)₂]_n · 2n(e-urea) ( 1 ) and [Zn₄(bdc)₂(trz)₄(H₂O)(e-urea)]_n · n(e-urea) ( 2 ) (Htrz = 1,2,4-triazole, NH₂H₂bdc = 2-aminoterephthalic acid, H₂bdc = terephthalic acid, e-urea = 1,3-ethyleneurea). X-ray structural analyses revealed that both compounds 1 and 2 feature e-urea-templated 3D pillar-layer framework with 2D Zn^II-triazole layer and 6-connected pcu topological network. These two compounds not only have high thermal stabilities but also show intense luminescence at room temperature.     

活性炭自溶液吸附锌(II)离子及其配合物

近年来，有人提出通过表面处理提高活性炭表面电荷，加强对无机离子吸附力等观点，但活性炭对无机离子的吸附活性点，表面含氧基团及配体对吸附的影响等重要问题仍众说纷经[1－4]为此，本文提出用氧化一负离子化法处理活性炭，以表面酸度表征表面含氧基团的量，探讨活性炭对Zn（Ⅱ）及其配合物的吸附特性．1试验（1）试验材料活性发由北京光华木材厂出品，分析纯．过20－30目，BET法测得比表面为1316m2·g-1．在2．5×10－2mlo·dm－3的NaNO3中，测得等电点pHIEP为7．75[5]，元素含量（质量分数）为C（83．9％），N（0．07％），H（1…     

Formation of Zinc(II) and Cadmium(II) Complexes with Pyridine Oxime Ligands in Aqueous Solution

Complex formation equilibria involving pyridine-2-carboxaldehyde oxime (1), 1-(2-pyridinyl)ethanone oxime (2) and 6-methylpyridine-2-carboxaldehyde oxime (3), HL, with zinc(II) and cadmium(II) ions were studied in aqueous 0.1 M NaCl solution at 25° C by potentiometric titrations with a glass electrode. Experimental data were analysed with the least-squares computer program SUPERQUAD to determine the complexes formed and their stability constants. With Ligands 1 and 2 the sets of complexes for Zn(II) and Cd(II) are essentially the same, mono- and dinuclear oxime complexes and their deprotonated/hydrolysed products H_pM_q(HL)^2q+p _r. Owing to the steric requirements of the 6-methyl group, sets of complexes formed with 3 are distinctly different. For zinc(II), only dinuclear oximato species H_pZn₂(HL)^4q+p ₂ ( p = ? 2, ? 3, ? 4) are found, while for the larger cadmium(II) ion mononuclear oximato species CdL⁺ and CdL₂ are detected in addition to the dinuclear complex H_pCd₂(HL)^4q+p ₂ ( p = ? 3).     

A study of complex equilibria of phenylglycine with nickel(II), copper(II) and zinc(II) in water and in water - methanol solution

The complex equilibria of the systems phenylglycine — nickel(II), copper(II) and zinc(II) in water and in water — methanol solution have been studied by computer analysis of potentiometric data. The mode of coordination has been established by¹³C-NMR and IR studies.

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Gleichgewichtsuntersuchungen der Komplexbildung von Phenylglycin mit Nickel(II), Kupfer(II) und Zink(II) in Wasser und Wasser - Methanol-Lösung

Zusammenfassung Anhand einer Computer-Analyse von potentiometrischen Daten wurden die Bildungsgleichgewichte in den Systemen Phenylglycin — Nickel(II), Kupfer(II) und Zink(II) untersucht. Der Koordinationstyp wurde mittels¹³C-NMR und IR festgestellt. Die Lösungsmittel waren Wasser und Wasser — Methanol.

     

Complex formation equilibria of some β-amino-alcohols with lead(II) and cadmium(II) in aqueous solution

A study of complex formation equilibria of some β-amino-alcohols with lead(II) and cadmium(II) ions at 25°C and in 0.5 M KNO₃ is reported. The amino-alcohols considered are 2-amino-1-propanol, 2-amino-1-butanol, 2-amino-1-pentanol and 2-amino-1,3-propanediol. sec-Buthylamine and 2-amino-1-methoxy-propane have been also considered for comparison. The results are discussed in terms of ligand structure, paying attention to the number of hydroxyl groups and to the length of the alkyl residual. A weak contribution of the alcoholic oxygen in the coordination of cadmium(II) and the presence of a mixed hydroxyl species in lead(II) containing systems are hypothesized.     

Zinc(II) and cadmium(II) complexes with PDT: study of the effect of weak interactions on crystal packing

Two new zinc(II) and cadmium(II) complexes, [Zn(PDT)₂(NCS)₂] (1) and [Cd((PDT)₂I_1.6(H₂O)_0.4(OH)_0.4] · 0.4H₂O (2) (“PDT” is the abbreviation of 3-(2-pyridyl)-5, 6-diphenyl-1,2,4-triazine), have been synthesized and characterized by elemental analysis, IR, ¹H NMR spectroscopy, and studied by X-ray crystallography. Zinc(II) in 1 is six coordinate ZnN₆. 2 is a co-crystal with cadmium(II) being 60% six-coordinated with a CdN₄I₂ environment and 40% seven-coordinated with a CdN₄O₂I environment. The supramolecular features in these complexes are guided/controlled by weak directional intermolecular S ··· π, C–H ··· π, C–H ··· I, and π ··· π interactions.     

Spectrophotometric study of Cd(II), Pb(II), Hg(II) and Zn(II) complexes with 5,10,15,20-tetrakis(4-carboxylphenyl)porphyrin

The reaction of 5,10,15,20-tetrakis(4-carboxylphenyl)porphyrin (TCPP) with Cd(II), Pb(II), Hg(II) and Zn(II) was studied spectrophotometrically and kinetics, equilibrium constants as well as photodecomposition of complexes were determined. It was verified that these metal ions with large radius accelerate the incorporation reaction of zinc into TCPP. On the basis of the mechanism and kinetics of this reaction, a sensitive method for the spectrophotometric determination of trace amounts of Zn(II) has been developed. The molar absorptivity of examined Zn-TCPP complex and Sandell's sensitivity at 423 nm were 3.5×10⁵ M⁻¹ cm⁻¹ and 18.3 ng cm⁻². The detection limit for the recommended procedure was 1.4×10⁻⁹ M (0.9 ng ml⁻¹) and precision in range 20-100 ng ml⁻¹ not exceeds 2.7% RSD. The proposed method applied for zinc determination in natural waters and nutritional supplement was compared with AAS results and declared value.     

Synthesis and Crystal Structure of an Mn(II) Complex with Benzoylacetone

The complex (benzoato)benzoylacetonato(bipyridine)Mn(II) has been prepared and its crystal structure determined by X-ray diffraction methods. Benzoic acid, benzoylacetone (bzac) and 2,2'-bipyridine all chelate to Mn(II) to form a six coordinate complex. As bond angles around the Mn(II) atom greatly deviate from those expected for an octahedron, the coordination geometry may be described as distorted pyramidal with a bidentate carboxyl group occupying the apex of the pyramid. Although the Mn atom deviates by 0.550 Å from the enol ring plane of bzac, Mn-O distances [2.105(2) and 2.098(2) Å] are normal. This suggests the existence of electrostatic interactions between Mn(II) and the bzac ligand.     

Syntheses and crystal structures of nickel(II), copper(II), and zinc(II) complexes with a biphenyl-bridged bis(pyrrole-2-yl-methyleneamine) ligand

The reactions of nickel(II), copper(II), and zinc(II) acetate salts with a potentially tetradentate biphenyl-bridged bis(pyrrole-2-yl-methyleneamine) ligand yielded three complexes with different coordination geometries. X-ray crystal structural analysis reveals that in the nickel(II) complex each nickel is five-coordinate, distorted trigonal bipyramid. In the copper(II) complex, each copper is four-coordinate, between square planar and tetrahedral. In the zinc(II) complex, each zinc is four-coordinate with a distorted tetrahedral geometry and the molar ratio of the zinc and ligand is 1 : 2.     

Synthesis,structure and properties of three one-dimensional coordination polymers {[M(II)L(NCS)2](DMF)2} n (M(II)=cadmium(II), zinc(II), manganese(II); L=1,4-bis[2-(2-pyridyl)benzimidazolato]butane)

A tetradentate N-donor ligand 1,4-bis[2-(2-pyridyl)benzimidazolato]butane (L) was prepared for construction of a coordination framework. Three one-dimensional coordination polymers {[M(II)L(NCS)₂](DMF)₂} _n (M(II) = cadmium(II), 1, zinc(II), 2, manganese(II), 3) were obtained by reaction of metal ions and L in the presence of KSCN in DMF/water. The complexes are isostructural and consist of 1D zigzag [M(II)L(NCS)₂] _n chains and DMF molecules. Within the chains, the metal atoms are each octahedrally coordinated by four N atoms of L and two N atoms of the SCN^? anions. Complexes 1 and 2 in the solid state at room temperature exhibit intense photoluminescence at 453 and 433 nm, respectively.     

Synthesis,Crystal Structure and Fluorescence of A 1-D Polymeric Zinc(Ii) Complex with Pyrazine-2-Carboxylate as a Bridging Ligand

A one-dimensional chain complex {[Zn(pyz)(SCN)(H₂O)₂]·H₂O}_∞ (pyz = pyrazine-2-carboxylic anion) has been synthesized and its crystal structure determined by X-ray crystallography. The complex crystallizes in an orthorhombic system and the space group is P2 ₁2₁2₁ with a = 6.873(3), b = 9.847(4), c = 16.466(7) Å. The Zn(II) ion is located in a distorted octahedral environment with two oxygen atoms O(3) and O(4) from terminal ligands of two water molecules, another oxygen atom O(1) from the carboxylate group of pyz, and three nitrogen atoms, N(1), and N(2A) from two different pyz and N(3) from a terminal thiocyanate anion, in which a chelated five-membered ring is formed by coordination of O(1) and N(1) to the Zn(1) atom. Therefore, an infinite zigzag chain consisting of Zn(II) ions and pyz anions is constructed and the chains are linked together with hydrogen bonding from coordinated and uncoordinated water molecules. The fluorescence spectra for the bridging ligand Na(pyz) and the complex were measured at room temperature in aqueous solution and in the solid state.     

Complex compounds of Cu(II) and Zn(II) withN,N-dimethylglycine andN,N-diethylglycine in water and in water—Methanol system

The complex equilibria of the systems: copper—N,N-dimethylglycine, zinc—N,N-dimethylglycine, copper—N,N-diethylglycine, and zinc—N,N-diethylglycine have been studied by computer analysis of potentiometric data. The stability constants of the complexes formed in these systems are reported. A discussion is presented about the influence of the substituent and the solvent on the dissociation constants of the amino acids and the stability constants of their complexes with metals.¹H NMR and IR studies indicate that both functional group of the ligands are involved in complex formation.

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Cu(II)- und Zn(II)-Komplexe mitN,N-Dimethylglycin undN,N-Diethylglycin in Wasser und Wasser—Methanol-Lösung

Zusammenfassung Anhand der Computer-Analyse von potentiometrischen Daten wurden die Bildungsgleichgewichte von Kupfer(II)- und Zink(II)-Komplexen mitN,N-Dimethylglycin undN,N-Diethylglycin untersucht. Die Beständigkeitskonstanten der gebildeten Komplexe wurden angegeben. Der Einfluß von Liganden und Lösungsmitteln auf Beständigkeit und Dissoziationskonstanten dieser Komplexe wurde diskutiert. Es wurde mittels¹H-NMR- und IR-Untersuchungen festgestellt, daß bei der Bildung der Komplexe beide funktionellen Gruppen der Liganden teilnehmen.

     

Synthesis and Characterization of Ni(II), Cu(II), Zn(II) and Cd(II) Complexes of a New Vic-Dioxime Ligand

In this study, 1,2-dihydroxyimino-3,7-di-aza-9,10-O-α-methyl benzal decane (LH₂) was synthesized starting from 1,2-O-α-methyl benzal-4-aza-7-amino heptane (RNH₂) and antichloroglyoxime. With this ligand, complexes were synthesized using Ni(II) and Cu(II) salts with a metal:ligand ratio of 1:2. However, the reaction of the ligand with salts of Zn(II) and Cd(II) gave products with metal:ligand ratio of 1:1. Structures of the ligand and its complexes are proposed based on elemental analyses, IR, ¹³C- and ¹H-NMR spectra, magnetic susceptibility measurements and thermogravimetric analyses (TGA).     

Synthesis and Characterization of A Nickel(II) Complex With Bis(Benzimidazol-2-Ylmethyl) (2-Hydroxyethyl)Amine

This paper reports the synthesis, crystal structure and properties of two new mononuclear nickel(II) complexes, [NiL(phen)][ClO₄]₂(1) and [NiL(bpy)][ClO₄]₂(2), where L is bis(benzimidazol-2-ylmetheyl)(2-hydroxyethyl)amine and phen and bpy are 1,10-phenanthroline and 2,2'-bipyridine, respectively. The crystal structure of 1 ·2EtOH has been determined by single-crystal X-ray analysis. It crystallizes in the monoclinic system, space group C2/c, a= 24.279(2), b= 20.864(2), c= 17.635(1)Å, g = 121.730(2)°, Z= 8, R ₁= 0.064, wR ₂= 0.167. The Ni(II) ion in 1 ·2EtOH is coordinated to three nitrogen atoms and one oxygen atom of the ligand L and two nitrogen atoms of phen to form a distorted octahedron. Spectroscopic properties of 1 and 2 are reported.     

Highly Charged Ruthenium(II) Polypyridyl Complexes as Effective Photosensitizer in Photodynamic Therapy

A comparative study between two novel, highly water soluble, ruthenium(II) polypyridyl complexes, [Ru(phen)₂ L ′] and [Ru(phen)₂Cu(II) L ′] ( L and L -Cu^II), containing the polyaazamacrocyclic unit 4,4′-(2,5,8,11,14-pentaaza[15])-2,2′-bipyridilophane ( L ′), is herein reported. L and L -Cu^II interact with calf-thymus DNA and efficiently cleave DNA plasmid when light-activated. They also possess great penetration abilities and photo-induced biological activities, evaluated on an A375 human melanoma cell line, with L -Cu^II being the most effective. Our study highlights the key role of the Fenton active Cu^II center within the macrocycle framework, that would play a synergistic role with light activation in the formation of cytotoxic ROS species. Based on these results, an optimal design of Ru^II polypyridyl systems featuring specific Cu^II-chelating polyamine units could represent a suitable strategy for the development of novel and effective photosensitizers in photodynamic therapy.     

Syntheses and characterization of nickel(II), zinc(II) and palladium(II) complexes derived from three pyrazole-based polydentate ligands

Two pyrazole-based polydentate ligands, 1,3-bis(5-methyl-3-phenylpyrazol-1-yl)-propan-2-ol (Hmppzpo) and 1,3-bis(5-methyl-3-p-isopropylphenylpyrazol-1-yl)-propan-2-ol (Hmcpzpo), have been synthesized. A third ligand, 1,3-bis(3,5-dimethylpyrazol-1-yl)-propan-2-ol (Hdmpzpo), has been synthetically modified. Seven new M(II) coordination compounds of general formula M₂L₂X₂ (M?=?Zn, Ni; X?=?NO₃ or ClO₄; L?=?dmpzpo, mppzpo or mcpzpo) or MLX (M?=?Pd; L?=?dmpzpo; X?=?Cl) were synthesized and structurally characterized by elemental analysis and FT-IR analysis. The crystal structures of [Zn₂(μ-dmpzpo-O,N,N′)₂(NO₃)₂]?·?2H₂O (1?·?2H₂O), [Ni₂(μ-dmpzpo-O,N,N′)₂(CH₃CN)₂](ClO₄)₂ (2) and Pd(μ-dmpzpo-N,N′)Cl₂ (4) were determined by single-crystal X-ray crystallography. The crystal structures show that complexes 1?·?2H₂O and 2 are center-symmetric dinuclear compounds, with two metal ions bridged by two alkoxo groups and each metal ion with a distorted square-pyramidal environment. The palladium complex, 4, displayed square-planar coordination geometry around the Pd(II) ion with trans arrangement.