Copper(II), nickel(II), cobalt(II) and oxovanadium(IV) complexes of substituted β-hydroxyiminoanilides

Complexes of the general formula, ML₂ [M = Cu^II, Ni^II, Co^II and OV^IV; L = 1,2,3,5,6,7,8,8a-octahydro-3-hydroxyimino-N-(4-X-phenyl)-l-phenyl-5-(phenylmethylene)-2-naphthalenecarboxamide (X = H, Me, OMe, Cl)] have been prepared and characterized on the basis of elemental analysis, magnetic moments and i.r., e.p.r. and electronic spectra. These metal complexes contain the N₄ chromophore with the ligand coordinating through nitrogens of the azomethine and deprotonated anilide functions. C.v. measurements indicate that the copper(II) complexes are quasi-reversible in acetonitrile solution. Square planar and square pyramidal structures are assigned respectively to the copper(II) and oxovanadium(IV) complexes, whereas tetrahedral geometry is assigned to the nickel(II) and cobalt(II) complexes. Deprotonated anilide nitrogen is involved in coordination and the presence of an electron-donating group para to the anilide function decreases the ΔE values of the d–d transitions while the value is found to increase when electron-withdrawing groups are substituted. Line spacing in the e.p.r. spectra of the copper(II) and oxovanadium(IV) complexes increases when methyl group is para to the anilide group, and decreases when this group is replaced by methoxy or chloro. The ν(C–N) of the anilide group and the ν(C-N) of the azomethine function of the oxime metal complexes are metal-sensitive and the blue shift for the above stretching frequencies follows the order: copper(II) > oxovanadium(IV) > nickel(II) ≈ cobalt(II). This revised version was published online in June 2006 with corrections to the Cover Date.     

Temperature dependent absorption spectra of Br(-), Br2(•-), and Br3(-) in aqueous solutions

The absorption spectra of Br(2)(?-) and Br(3)(-) in aqueous solutions are investigated by pulse radiolysis techniques from room temperature to 380 and 350 °C, respectively. Br(2)(?-) can be observed even in supercritical conditions, showing that this species could be used as a probe in pulse radiolysis at high temperature and even under supercritical conditions. The weak temperature effect on the absorption spectra of Br(2)(?-) and Br(3)(-) is because, in these two systems, the transition occurs between two valence states; for example, for Br(2)(-) we have (2)Σ(u) → (2)Σ(g) transition. These valence transitions involve no diffuse final state. However, the absorption band of Br(-) undergoes an important red shift to longer wavelengths. We performed classical dynamics of hydrated Br(-) system at 20 and 300 °C under pressure of 25 MPa. The radial distribution functions (rdf's) show that the strong temperature increase (from 20 to 300 °C) does not change the radius of the solvent first shell. On the other hand, it shifts dramatically (by 1 ?) the second maximum of the Br-O rdf and introduces much disorder. This shows that the first water shell is strongly bound to the anion whatever the temperature. The first two water shells form a cavity of a roughly spherical shape around the anion. By TDDFT method, we calculated the absorption spectra of hydrated Br(-) at two temperatures and we compared the results with the experimental data.     

Extraction behavior of uranium(VI), plutonium(IV), zirconium(IV), ruthenium(III) and europium(III) with γ-pre-irradiated solutions of N,N′-methylbutyl substituted amides in n-dodecane

The extraction of plutonium(IV), uranium(VI), zirconium(IV), europium(III) and ruthenium(III) with -pre-irradiated n-dodecane solutions of methylbutyl substituted hexanamide (MBHA), octanamide (MBOA) and decanamide (MBDA) from 3.5M HNO₃ has been studied as a function of absorbed dose up to 184×10⁴ Gray. The distribution ratios (K_d) of uranium(VI) decreased gradually up to a dose of 50×10⁴ Gray and became almost constant thereafter, while ruthenium(III) and europium(III) were not extracted in the entire dose range studied. The K_d values of Pu(IV) decreased gradually up to 10×10⁴ Gray, for MBOA, and 30×10⁴ Gray for MBHA and MBDA and then increased up to a dose of 72×10⁴ Gray, indicating the synergistic effect of radiolytic products at higher doses. The extraction of zirconium(IV) was found to increase gradually up to 72×10⁴ Gray. However, the steep fall in K_d values of plutonium(IV), zirconium(IV) beyond a dose of 72×10⁴ Gray was atrributed to third phase formation. The radiolytic degradation of amides was monitored by quantitative IR spectroscopy and was found to follow the order MBOA>MBDA>MBHA at 184×10⁴ Gray having the amines and carboxylic acids as the main radiolytic products.     

Über die Identifizierung der Lokalanaesthetica (L-A) Butacain (1), Butethamin (2), Chloroprocain (3), Dyclonin (4), Äthylaminobenzoat (5), Lidocain (6), Meprylcain (7), Metalbutethamin (8), Metabutoxycain (9), Naepain (10), Parethoxycain (11), Piperocain (12), Procain (13), Proparacain (14), Propoxycain (15) und Tetracain (16)

Analytical and Bioanalytical Chemistry -     

Complex formation of hexakis(2,6-di-O-methyl)-α-cyclodextrin with substituted benzenes in aqueous solution

The host-guest interaction of hexakis(2,6-di-O-methyl)--cyclodextrin (DM--CDx) with substituted benzenes in aqueous solution has been investigated by circular dichroism spectra. From the resemblance of the spectra, it is concluded that the guest molecules are included in the DM--CDx ring in a manner similar to that of corresponding -cyclodextrin complexes. Thermodynamic parameters of the complex formation were determined on the basis of the temperature dependent intensity change of the spectra. In spite of the considerable variation in H and AS values, the free energy does not change much among complexes because of the strong compensation effect. The compensation temperature was 309 ± 11K. Negative values of H and S, suggesting that the complex formation is not governed by the hydrophobic interaction, can be interpreted in terms of the tight binding of the guest molecule within the host cavity.     

Thermodynamics of Copper(II), Zinc(II), Cobalt(II), Mercury(II), and Nickel(II) Complexation with α,α-Dipyrrolylmethene in DMF

Thermodynamics of complexation reactions between Zn(II), Ni(II), Hg(II), Co(II), and Cu(II) acetates and 3,35,5-tetramethyl-4,4-dibutyldipyrrolylmethene in DMF at 298.15 K is studied by calorimetric and spectrophotometric methods. The replacement of Zn²⁺, Ni²⁺, and Hg²⁺ ions by Co²⁺ and Cu²⁺ ions was found to increase the equilibrium constants of reactions of complex formation with dipyrrolylmethene by more than two orders of magnitude. The role of solvation interactions in coordination of dipyrrolylmethene by d-metal ions is established.     

Complexes of N-phenyl-N′-2-furanthiocarbohydrazide with oxovanadium(IV), manganese(III), iron(III), cobalt(II), nickel(II), copper(II) and zinc(II)

A new ligand, N-phenyl-N -2-furanthiocarbohydrazide (HPhfth), and its complexes with VO^IV, Mn^III, Fe^III, Co^II, Ni^II, Cu^II and Zn^II have been prepared and characterized by elemental analyses, magnetic susceptibility measurements, i.r., n.m.r., u.v.–vis., mass and FAB mass spectral data. The room temperature e.s.r. spectra of the VO^IV, Fe^III and Cu^II complexes yield <g> values characteristic of square pyramidal VO^IV, octahedral Fe^III and square planar Cu^II, respectively. The Ni^II and Cu^II complexes semiconduct, but the Zn^II complex is an insulator at room temperature. However, the conductivity increases as the temperature increases from 303–383 K, with a band gap of 0.21–1.01 eV. HPhfth and its soluble complexes have been screened against several bacteria and fungi.     

2,9-二甲基-1,10-菲咯啉的α-氨甲基吡啶衍生物的合成表征及其Mn(II),Co(II),Ni(II),Cu(II),Zn(II)配合物稳定性研究

以2,9-二甲基-1,10-菲咯啉为初始原料,合成了2,9-二甲基-1,10-菲咯啉的α-氨甲基吡啶衍生物-N,N'-二(2'-吡啶基)甲基-1,10-菲咯啉-2,9-二甲胺(L).该配体经过元素分析、红外光谱、核磁共振氢谱表征.在25±0.1℃、I=0.1mol·dm-3NaNO3的条件下,用pH电位滴定法测定了该配体在水溶液中的质子化常数及其分别与Mn(II),Co(II),Ni(II),Cu(II)和Zn(II)的配合物的稳定常数,提出了配合物的可能结构.进一步讨论了相应稳定常数较大的内在原因.     

Complexes of N-nicotinoyl-N′-2-furanthiocarbohydrazide with oxovanadium(IV), manganese(II), iron(II & III), cobalt(II), nickel(II), copper(II) and zinc(II)

A new potential tetradentate ligand, N-nicotinoyl-N-2-furanthiocarbohydrazide (H₂Nfth), and its complexes with VO^IV, Mn^II, Fe^II,III, Co^II, Ni^II, Cu^II and Zn^II have been prepared and characterized by elemental analyses, magnetic susceptibility measurements, u.v.–vis, i.r., n.m.r., ES⁺ and FAB mass spectral data. The room temperature e.s.r spectra of the VO^IV and Fe^III complexes yield g values, characteristic of octahedral complexes. The Mössbauer spectra of [Fe(HNfth)₂] and [Fe₂(Nfth)₃] at room temperature and at 78 K suggest the presence of high-spin iron(II) and iron(III), respectively. The complexes are electrically insulating at room temperature, however, their conductivities increase as the temperature increases from 333–383 K, with a band gap of 0.46–0.77 eV, indicating their semiconducting behaviour. H₂Nfth and its soluble complexes have been screened against several bacteria and fungi.     

Cyclization of 2-methoxy-6-(substituted benzyloxy)acetophenone hydrazones in the presence of polyphosphoric acid(PPA)

Cyclization of 2-methoxy-6-benzyloxy acetophenone hydrazone gave 3-methyl-4-meth-oxy indazole and 3-methyl-4-methoxy-7-benzyl indazole in the presence of polyphosphoric acid(PPA).The hydrazone was probably converted to 2-hydroxy-6-methoxy acetophenone hydra-zone and 2-hydroxy-3-benzyl-6-methoxy acetophenone hydrazone followed by cyclization to thecorresponding indazoles in acidic conditions.Cyelization of 2-methoxy-6-(halo or alkyl or arylbenzyloxy)acetophenone hydrazones gave similar products.Cyclization of 2-methoxy-6-(p-nitrobenzyloxy)acetophenone hydrazone gave 2-(p-nitrophenyl)-3-methyl-4-methoxy benzo-furan and 3-methyl-4-methoxy indazole while 2-methoxy-6-(m-nitrobenzyloxy)acetophenonehydrazone gave 3-methyl-4-methoxy indazole,3-methyl-4-methoxy-7-(m-nitrophenyl)indazole and3-methyl-4-(m-nitrobenzyloxy)indazole.     

二-(2,4,4-三甲基戊基)膦酸浸渍树脂分离Tb~(3 ),Dy~(3 ),Ho~(3 ),Er~(3 )的研究

研究了大孔网状树脂XAD 4 ,XAD 7,XAD 1 1 80对二 -( 2 ,4 ,4 三甲基戊基 )膦酸 (Cyanex 571 )浸渍树脂的吸附及制备方法 ,并对Cyanex571浸渍树脂分离稀土的性能进行了研究 ,发现在盐酸介质中Cyanex 571 /XAD 7具有最强的萃取能力 ,树脂中的萃取剂含量在 0 35～ 0 4 5g·g- 1时 ,其萃取性能最好。将上述浸渍树脂装入色层柱对稀土元素 (Tb3 ,Dy3 ,Ho3 ,Er3 )进行了分离 ,且降低负载量和流速分离效果更好。     

Zn(Ⅱ),Cd(Ⅱ),Mn(Ⅱ)与3-吡啶-4-苯甲酸二元配位聚合物的合成与性质

本文采用了3-吡啶-4苯甲酸作为配体,与过渡金属离子Zn(II)、Cd(II)和Mn(II)组装,通过溶剂热合成法获得了三例配位聚合物. 单晶结构分析表明,配合物1具有由四面体配位的Zn(II)离子与?-OH组成的一维之字链,通过3-吡啶-4苯甲酸与相邻的其它四条之字链连接,形成了具有钻石网拓扑的配位聚合物;配合物2和3为异质同晶,它们都具有由八面体配位的Cd(II)或Mn(II)离子和?-OH2组成的二核金属簇,通过3-吡啶-4苯甲酸与相邻的其它四个二核金属簇连接,也形成了具有钻石网拓扑的配位聚合物. 本文还对配体以及配合物1和2的荧光性质进行了表征. 配合物3的磁学性质测试表明,二核金属Mn(II)簇之间存在着反铁磁交换作用,而且表现出自旋反转的行为,并归属于短程相关而不存在长程有序.     

Elektrophorese der halogenokomplexe von Hg(II), Bi(III), Cd(II), Pb(II) und -Cu(II) : Chlorokomplexe in chlorwasserstoffsäure

An apparatus for heavy-current and high-tension electrophoresis on filter paper is described This apparatus enables one to avoid the difficulties that occur in electrophoresis in base electrolytes that are highly concentrated or show greater electric conductivity The zones migrate along the paper strips with constant speed and, consequently, it is possible to measure the mobility The effective length of the filter paper strips is 660 mm Correction of the apparent mobility in the porous adsorbent is treated thoroughly.Diagrams of the electrophoretic mobility of the chloro-complexes of Hg(II), Bi(III), Cd(II), Pb(II), and Cu(II) in hydrochloric acid, are given in the experimental part The concentration of the hydrochloric acid varied between 0.1N and 6N In 6N HCl all the metals investigated are present asani onic complexes. Hg, Bi.Cd, and Pb chloro-complexes show a pronounced maximum of mobility in the anionic range. The sequence of the zones in the direction anode to cathode is Hg, B1, Cd, Pb, Lu al 0.1–2.3N HCl and B1, Hg, Cd, Pb.Cu at2.3–6N HCl.Finally, the electrophoretic separation of a mixture of Hg, Bi, Cd, Pb, Cu in 1N, 2N and 4N HCl is illustrated Complete separation of the zones was achieved in each experiment     

Inclusion of chemotherapeutic agents in substituted ��-cyclodextrin derivatives

The stabilities of the inclusion compounds of three chemotherapeutic agents, camptothecin (CPT), docetaxel (DOC) and idarubicin (IDA), plus a model compound 1,4-dihydroxyanthraquinone (DHA) with several ??-cyclodextrin (??-CD) derivatives were investigated by solubility measurements, isothermal titration microcalorimetry and fluorescence anisotropy measurements. Ionic heptakis-(6-deoxy-6-thioethers) of ??-CD were found to exhibit very high binding potentials for these drugs making them to good candidates for advanced drug delivery.     

乙醇-水混合溶液中1-苯基-3-甲基-4-苯甲酰基吡唑酮-5对Nd(Ⅲ), Eu(Ⅲ),Ho(Ⅲ)的萃取及其机理

在乙醇－水混合溶液中，1－苯基－3－甲基－4－苯甲酰基吡唑酮－5与Nd(Ⅲ）,Eu(Ⅲ）,Ho(Ⅲ）等及乙醇形成了萃合物，使萃取分配比明显提高。利用斜率法研究了萃取机理。借助红外（IR）、元素分析、热分析（TG－DTA）等手段对萃合物进行了表征。     

SO_3~(2-),S~(2-),S_2O_3~(2-)的高效离子交换色谱法的分离和测定

用国产高效离子交换色谱仪及国产阴离子交换树脂研究了分离SO_3~(2-),S~(2-),S_2O_3~(2-)的色谱条件。以硝酸钠为洗脱液,可在九分钟内完全分离上述离子。进行了一些样品的定量测定,用无换向阀的预柱富集测定了污水中PPm级的S~(2-)及定量回收了ppb级的S_2O_3~(2-)。从色谱动力学的观点试讨论了SO_3~(2-),S~(2-)及S_2O_3~(2-)的色谱行为,得出了用结构参数及实验条件估算分配系数D的经验式: 式中a是与离子性质及交换条件有关的常数,k为硫化物阴离子中硫原子的数目,Z为硫的平均氧化数,B为洗脱液浓度。     

Cu(Ⅱ),Ni(Ⅱ),Co(Ⅱ),Mn(Ⅱ),Zn(Ⅱ)和Cd(Ⅱ)的乙基3-(2-氨硫化亚肼基)-2-(羟胺基)丁烯酸酯配合物:合成、表征和细胞毒性(英文)

合成了Cu(Ⅱ),Ni(Ⅱ),Co(Ⅱ),Mn(Ⅱ),Zn(Ⅱ)和Cd(Ⅱ)的乙基3-(2-氨硫化亚肼基)-2-(羟胺基)丁烯酸酯配合物(H2L)并用元素分析,DTA热分析,IR,UV-Vis,1H-NMR,质谱,顺磁共振以及磁矩,电导率测量等对合成的配合物进行表征。摩尔电导率测量结果证明合成的配合物为非电解质。光谱数据表明配体分别表现为一元的三齿配体,一元的二齿配体,中性的二齿配体,中性的三齿配体,一元的四齿配体或二元的四齿配体通过席夫碱的氮原子,氨基硫脲中的氮原子,肟中的氮原子和硫酮中的硫原子与金属离子键合生成围绕金属离子的四面体或平面正方形构型。固态Cu(Ⅱ)(2),(3),(4)和(5)的配合物顺磁共振谱表明其为轴向对称,但(10~15)的配合物却为各向异性。配体和配合物(2),(3),(10),(13),(16)和(19)由于它们对乳腺癌(MCF-7细胞系)和肝癌(HePG-2细胞系)的抑制作用而表现出潜在的抗癌活性。     

Competitive bulk liquid membrane transport of Co(Ⅱ),Ni(Ⅱ),Zn(Ⅱ),Cd(Ⅱ),Ag(Ⅰ),Cu(Ⅱ)and Mn(Ⅱ),cations using 2,2'-dithio(bis)benzothiazole as carrier

A series of competitive metal-ion transport experiments has been performed.Each involved transport from an aqueous source phase across an organic membrane phase into an aqueous receiving phase.The source phase contained equimolar concentration of Co（Ⅱ）,Ni（Ⅱ）,Zn（Ⅱ）,Cd（Ⅱ）,Ag（Ⅰ）,Cu（Ⅱ） and Mn（Ⅱ） metal cations.The transport experiments of metal cations were carried out by 2,2’-dithio（bis）benzothiazole（DTB） in chloroform（CHCl₃）.The source phase being buffered at range pH of 4-6.5 and receiving phase being buffered at pH 3.The obtained results show that the selectivity and the efficiency of Ag（I） transport from aqueous solutions are observed in this investigation.The effect of concentration of palmitic acid in the transport efficiency of Ag（Ⅰ） ion was also conformed.