Nickel(II) 1,10-Phenanthroline complexes: cis-[Aqua(Bromo) bis (1,10-Phenanthroline)Nickel(II)] Bromide Trihydrate and ( tris (1,10-Phenanthroline)Nickel(II)] Bromide Octahydrate

[Ni(phen)₂(H₂O)Br]Br·3H₂O where phen is 1,10-phenanthroline, is a light-blue material which crystallizes in the monoclinic space group P2₁/c with Z = 4, a = 10.4300(4), b = 25.310(2), c = 9.7790(9)?Å and β = 102.932(6)°. The structure was determined at ambient temperature from 5161 reflections with R = 0.0643 and R _w = 0.1306. The structure consists of a complex cation, a bromide anion and three waters of hydration. The Ni atom is pseudo-octahedral with a cis arrangement of Br and H₂O. This cis geometry persists in solution, as evidenced by ¹H NMR spectroscopy, although the Br may be replaced by another H₂O. [Ni(phen)₃]Br₂·8H₂O is a light-red material which crystallizes in the monoclinic space group C2/m with Z = 8, a = 23.6320(11), b = 21.4880(13), c = 15.5470(9)?Å and β = 107.927(3)°. The structure was determined at 120?K from 6820 reflections with R = 0.0733 and R _w = 0.1022. The structure consists of a complex cation, two bromide anions and eight waters of hydration. The anions and waters are extensively disordered. The Ni atom is pseudo-octahedral.     

马来腈二硫纶·邻菲咯啉镍(II)配合物的电子光谱和理论研究

测量了标题配合物Ni(mnt)(phen)在多种介质中的电子吸收光谱和发射光谱, 使用密度泛函理论的B3LYP方法和分子轨道理论的PM3方法研究了其气态分子几何构型、电子结构和成键, 用ZINDO/S方法通过多组态的组态相互作用(CI)计算解释了实验光谱. 结果表明: 该配合物分子为平面结构, 对称性属于点群C_2v, 基态为自旋三重态, 配位键Ni—N和Ni—S为典型的共价结合, Ni的3d电子反馈效应较显著; 可见区的吸收带和发射带(对应于基态电子组态到较低能量激发态组态的跃迁)本质上属于配体phen到mnt^2－的荷移跃迁(LL'CT), 紫外区的吸收带本质上属于配体的π→π*跃迁.     

Determination of Iron in Calf Serum Using Bathophenanthroline and Thermal Lens Spectrometry

ABSTRACT

Thermal lens spectrometry has been used for the determination of iron in calf serum. The method is based on dissociation of Fe³⁺ from proteins, reduction of Fe³⁺ to Fe²⁺ and formation of a coloured complex between Fe²⁺ and bathophenanthroline. Contrary to the spectrophotometric method, it is shown that thermal lens spectrometry is less sensitive to scattering caused by the presence of small particles remaining in the test solution after the deproteinization step. The background signal is very small and the response is only slightly dependent on the amount of scattering particles. The method is reliable, sensitive and reproducible. The limit of detection for iron is 4 ppb and the relative standard deviation is around 2%. It is expected that the volume of serum sample necessary for an analysis can be reduced to less than 100 μl.     

Synthesis and Crystal Structure of a Copper(II) Complex with Benzilic Acid and 1,10-Phenanthroline

A new complex [Cu(phen)3][(C6H5)2C(OH)COO]2·6H2O was prepared by self-assembly of benzilic acid, 1,10-phenanthroline (phen), and copper perchlorate. It crystallizes in triclinic, space group P1, with a = 1.14661(17), b = 1.6455(2), c = 1.6457(2) nm, α = 74.779(2), β = 74.904(3), γ = 84.424(3)o, V = 2.8914(7) nm3, Dc = 1.340 g/cm3, Z = 2, F(000) = 1218, GOOF = 1.018, the final R = 0.0643 and wR = 0.1633. The crystal structure shows that the copper ion is coordinated with six nitrogen atoms from six 1,10-phenanthroline molecules, forming a distorted octahedral coordination geometry.     

[Cu（L-Ⅱe）（Phen）（H2O）（ClO4）]的合成、结构及稳定性研究

合成了三元混配配合物[Cu(L-Ile)(Phen)(H_2O)(ClO_4)](L-Ile=L=异亮氨酸,phen=1,10-邻菲咯啉),通过红外光谱、紫外-可见光谱、摩尔电导率、X射线单晶结构分析,对配合物进行了表征。该晶体属单斜晶系,P2_1空间群,晶胞参数:a=1.1704(5)nm,b=0.8090(5)nm,c=2.1822(5)nm,β=98.061(5)°,Z=2,D_x=1.60Mg·m~(-3),R_1=0.0462,wR_2=0.1225。每个配合物分子中Cu(Ⅱ)离子与一个L-Ile(N,O)配体、一个Phen(N,N)配体、一个H_2O(O)配体及一个Cl_O~-(O)形成六配位的畸变八面体构型。本文还用电位滴定法测定了配合物的稳定常数,结果表明,配合物具有高的稳定性。     

双核铕-苯甲酸-邻菲咯啉三元络合物非等温热分解动力学研究

采用TG-DTG和DTA技术研究了Eu2(BA)6(PHEN)2 (BA苯甲酸根离子;PHEN1,10-邻菲咯啉)在静态空气中的热分解过程,根据TG曲线确定了热分解过程中的中间产物及最终产物,运用Acher法、Madhusudanan-Krishnan-Ninan (MKN)法和Flynn-Wall-Ozawa法对非等温动力学数据进行分析,推断出第一步热分解反应的动力学方程为dα/dt=Aexp(-E/RT)(1-α)2, 第一步热分解反应的活化能为135 kJ/mol, 活化自由能ΔG为149 kJ/mol, 活化焓ΔH为129 kJ/mol, 活化熵ΔS为-33 J/(mol·k), 同时用等温TG法得到失重10%为寿终指标的寿命方程为lnτ=-22.66+1.646×104/T.     

三邻菲咯啉合亚钌-亚硫酸根-过二硫酸钾化学发光法测定空气中的二氧化硫

提出了－菲咯啉）化学发光测定亚硫酸盐的方法。亚硫酸盐的浓度与化学发光强度在1．75×10－7～1．25×10-4mol／L范围内呈正比。检出限为6×10－9mol／L,4×10－5mol／L亚硫酸盐溶液9次测定的相对标准偏差为1．4％。该方法用三乙醇胺作为吸收液成功地测定了空气中的二氧化硫。     

铜(Ⅱ)-邻菲咯啉-(邻菲咯啉-5,6-二酮)络合物的合成及其同脱氧核糖核酸的作用

以邻菲咯啉（phen)、邻菲咯啉－5，6－二酮（dione)为配体首次合成了高氯酸邻菲咯啉－邻菲咯啉－5，6－二酮（Ⅱ）。用荧光光谱，摩尔比，粘度，MLCT减色效应，平衡常数以及荧光能量转移研究了各合物与鱼精子DNA的结合情况，证实了该络合物与DNA存在插入作用。基于络合物对DNA能量转移造成荧光量子产率比值（Φλ/Φ320）的降低，解释了不同波长激发光下，荧光发射峰在加入DNA后产生猝灭和增强两种绝然不同的现象。     

Synthesis,Characterization and Crystal Structure of a Ternary Cu(II) Complex with 1,10-Phenanthroline and l-Leucinate

The complex [Cu(l-Leu)(phen)(H₂O)]NO₃ has been synthesized and characterized by elemental analysis, molar conductivity, spectroscopic and X-ray diffraction methods, where phen = 1,10-phenanthroline and l-Leu = l-leucinate. The complex crystallizes in the triclinic space group Pī with two molecules in a unit cell of dimensions a = 7.288(4) Å, b = 11.588(7) Å, c = 12.349(3) Å, α = 86.388(10)^o, β = 76.175(11)°, γ = 72.132(3)°, V = 963.8(10) ų, Z = 2, D _c = 1.564 g/cm³, μ = 1.177 mm^?1, F(000) = 470, R ₁ = 0.0611, and wR ₂ = 0.0711. The copper(II) is ligated in a distorted square-pyramidal geometry by the two nitrogen atoms of phen and the amino nitrogen atom and one carboxylate oxygen atom from each independent l-Leu moiety in the basal plane, and one water oxygen at the apical position. A supramolecular configuration is formed from strong phen-phen stacking interactions between neighboring [Cu(l-leu)(phen)(H₂O)]⁺cations in the crystal.     

铅-邻菲罗啉络合吸附波的研究

在0.06MHAc-0.14MNaAc(pH=5.1)和2×10^-5M邻菲罗啉(phen)溶液中,用单扫示波极谱法可得到Pb(Ⅱ)-phen络合波,峰电位在-0.49V处。其导数峰高与铅在5×10^-8-5×10^-6M范围内的浓度有线性关系,最低检出限2.5×10^-8M。此波可用于测定铅。研究确定该波为1:1铅-邻菲罗啉络合物的吸附波。     

Multispectroscopic Studies on the Interaction of a Platinum(II) Complex Containing l-Histidine and 1,10-Phenanthroline Ligands with Bovine Serum Albumin

The mechanism of the interaction between bovine serum albumin (BSA) and [Pt(phen) (histidine)]⁺ complex was studied employing ultraviolet (UV) absorption, circular dichroism (CD), FT-IR, differential pulse voltammetry (DPV), and fluorescence spectral methods. Fluorescence data showed that the intrinsic fluorescence of BSA was strongly quenched by Pt(II) complex in terms of an untypical static quenching process. The corresponding number of binding sites (n) and binding constant (K _b) of BSA and complex at 283, 298, and 310 K were calculated to be 0.61?×?10⁶, 19?×?10⁶, and 42?×?10⁶ M^?1, respectively. The results showed that the increasing temperature improves the stability of the complex–BSA system, which results in a higher binding constant and the number of binding sites of the complex–BSA system. The positive ΔH and positive ΔS indicated that hydrophobic forces might play a major role in the binding between complex and BSA. Based on Forster’s theory of non-radiation energy transfer, the binding distance (r) between the donor (BSA) and acceptor (Pt(II) complex) was evaluated. The results of CD, UV–vis, DPV, and FT-IR spectroscopy showed that the binding of Pt(II) complex to BSA induced conformational changes in BSA     

Sorption–Spectrophotometric and Test Determination of Zinc(II) as the Mixed-Ligand Complex of 1,10-Phenanthroline and Bromophenol Blue

The interaction of Zn(II), Cd(II), and Pb(II) with 1,10-phenanthroline noncovalently immobilized on silica in the presence of Bromophenol Blue was studied. The optimum conditions of the reaction and the composition of mixed-ligand complexes that are formed at the surface were found, and a scheme was proposed for the interaction at the interface. A sorption–spectrophotometric procedure and a test scale were developed for the determination of zinc with detection limits of 0.011 and 0.018 mg/L, respectively. The procedure was used for the determination of labile zinc species in soil.     

[双-(N-苯基水杨醛亚胺)](二氮杂菲)合钴(II)的合成与结构

Bis(N-Phenylsalicylaldiminato)(1,10-Phenanthroline) Co(Ⅱ), C38H28N4O2Co,was synthesized and its crystal structure as been determined by X-ray diffraction method. The crystallographic data are as follows: monoclinic, space group C2/c, α=21.402(7), b=10.060(2), c=14.830(4)Å. β=109.19(2)°, V=3015.8 Å3, Z=4, M=631.57, Dc=1.39g•cm-3, μ=6.35cm-1, F(000)=1308, R=0.061, Rw=1.065. Two N and two O atoms from two bidentate ligands (L), other two N atoms from phen molecule coordinate the central Co(Ⅱ) ion forming octahedral configuration. Co-O, Co-N and Co-N(Phen) bond lengths are 1.995(5), 2.147(5) and 2.224(6) Å, respectively.     

Synthesis and crystal structure of BIS(DI-n-Butyldithiocarbamato)(1,10-Phenanthroline)cadmium(II)

A new mixed-ligand complex, Cd(S₂CN(C₄H₉)₂)₂ Phen, is synthesized and investigated by thermal, element, and IR analyses and by diffractometry of polycrystals (DRON-3M, CuK_α radiation, Ni filter). The crystal structure was determined on a CAD-4 Enraf-Nonius automatic diffractometer (MoK_α radiation, θ from 1.5 to 25°, 2325 nonzero independent reflections, 190 refined parameters, R = 0.036 for I > 2σ(I)). Crystal data for C₃₀H₄₄CdN₄S₄: a = 15.592(3), b = 22.724(5), c = 9.922(2) Å, space group Pbcn, V = 3515.5(12) ų, Z = 4, M= 701.33, d_calc = 1.325 g/cm³. The structure involves monomeric molecules in which the cadmium atom has a distorted octahedral environment.     

Synthesis and Crystal Structure of a New Ternary Complex of Nickel(II) with L-Aspartic Acid and 1,10-Phenanthroline

1 INTRODUCTION Amino acid is the fundamental structure unit ofbiomacromolecules, such as protein and enzyme, andit is also the important biomicromolecular ligandinside the life body. Study on the metal-amino acidcomplex is the basis of understanding …     

Copper(II) Complex Containing 4-Fluorophenoxyacetic Acid Hydrazide and 1,10-Phenanthroline: A Prostate Cancer Cell-Selective and Low-Toxic Copper(II) Compound

Prostate Cancer (PCa) is the second leading cause of cancer-related deaths among men worldwide. The treatment of advanced cases is based on chemotherapy, which lacks specificity and efficacy, due to severe side effects and resistance to the traditional drugs. Copper complexes have shown antitumoral efficacy and low toxicity, being considered a promising class of metal-based drugs for the treatment of malignant neoplasms. Thus, the present study aimed to evaluate the cellular effects of a copper(II) complex with 4-fluorophenoxyacetic acid hydrazide and 1,10-phenanthroline (1) on PCa cell lines, as well as the mutagenic/recombinogenic and anticarcinogenic potential of 1 in Drosophila melanogaster. PNT-2 (non-tumorigenic), LNCaP (hormone-responsive PCa) and PC-3 (androgen-independent PCa) cells were cultured, and cytotoxicity was assessed using the MTT assay. The expression levels of the proliferation markers Ki-67 and Cyclin D1 were analyzed by flow cytometry. Furthermore, the Somatic Mutation and Recombination Test (SMART) and the Epithelial Tumor Test (ETT) were performed. Complex 1 was selective to LNCaP cells, significantly reducing Ki-67 and Cyclin D1 expression levels. Sub-toxic concentrations of complex 1 were defined by the toxicity test in D. melanogaster, and no mutagenic/recombinogenic/carcinogenic effects were observed. Anticarcinogenic potential was observed in D. melanogaster, suggesting modulating activity of the complex 1 against Doxorubicin, a drug used as control by its carcinogenic properties. Therefore, complex 1 is a possible starting point for the development of new antitumor agents for the treatment of PCa.     

聚1,10-菲络啉合钴(Ⅱ)化学修饰电极对一氧化氮测定的研究

报道了电化学聚合 1 ,1 0 -菲络啉合钴 ( )化学修饰电极的制备 ,对 NO的响应范围及机理作了初步的探讨。研究发现 :用电化学方法聚合制备的该电极涂加Nafion后对 NO的检测有高的灵敏度和好的选择性 ;NO的浓度在 4.2× 1 0 - 5～ 2 .4× 1 0 - 7mol/L范围内氧化电流与浓度呈良好的线性关系 ,检出限达 4.8× 1 0 - 8mol/L;生物体内常见的物质如 NO- 2 、NO- 3、抗坏血酸、多巴胺、葡萄糖、L-精氨酸等物质不干扰测定。该修饰电极可望用于 NO的在体实时检测     

Structure and Reactivity of the 1,10-Phenanthroline Complex with Nitrenium Cation

According to the X-ray diffraction data, the cationic fragment in 1-amino-1,10-phenanthrolinium mesitylenesulfonate is a unidentate n-complex whose asymmetric structure is retained in solution. Quantum-chemical calculations by the AM1 method and ab initio (6-31G, 6-31G*, MP2/6-31G) give geometric parameters of the cation, which are similar to those determined experimentally. No dynamic processes involving intra- or intermolecular transfer of the NH2 group was observed up to 100°C by NMR spectroscopy. 1-Amino-1,10-phenanthrolinium cation does not react with 4-methylpyridine and 4-methyl-1,10-phenan-throline with transfer of the amino group, and it fails to react with mesitylene and anthracene at elevated temperature.