牛磺酸双核铜络合物为载体的高选择性硫氰酸根离子电极的研究

本文报道了一种以牛磺酸双核铜络合物为中性载体的硫氰酸根PVC膜电极。该电极对硫氰酸根有良好的电位响应并呈现出anti-Hofmeister行为,其选择性顺序SCN^->I^->ClO₄^->Sal^->NO₃^-> NO₂^-> Br^- > Cl^- > SO₃^-> SO₄ ^2-。在20℃ pH 5.0的磷酸缓冲溶液中,其线性范围为1.0´10 ^-1~ 1.0´10^-6mol×L-1,检测线为8.0×10 ^-7mol•L^-1,斜率为 -56.5 mV/pcSCN^-。紫外、红外和交流阻抗研究表明电极的高选择性与载体的立体结构和分析物与中心金属离子的作用相关。将该电极用于废水和人体尿液中硫氰酸根的测定,获得了较满意的结果。     

New Copper(II) Ion-Selective Membrane Electrode Based on Erythromycin Ethyl Succinate as a Neutral Ionophore

Abstract

The potentiometric response characteristics of a new copper(II) ion-selective PVC membrane electrode based on erythromycin ethyl succinate (EES) as ionophore were investigated. The electrode exhibited a Nernstian response to Cu²⁺ ions over the activity range of 1.5 × 10^?2 to 2.0 × 10^?6 mol L^?1 with a limit of detection of 6.3 × 10^?7 mol L^?1. Stable potentials were obtained in the pH range of 5.5–6.5. The potentiometric selectivity coefficients were calculated by using fixed interference method and revealed no important interferences except for Ag⁺. This electrode was successfully applied as an indicator electrode in determination of copper ions in real water samples.     

Anion-Selective Membrane Electrodes Based on Polymer-supported Metalloporphyrins

Prepared polystyrene pyridine copolymer supported metallo-protoporphyrin IX structures (MPPIX-PSP4) were applied as an ionophore for ion selective electrodes.     

Selective Transport of Copper(II) Ion across a Polymer Membrane Incorporating a Difunctional Schiff-base Ionophore

The selective polymer membrane transport of Cu(II) from an aqueous solution containing seven metal cations, Co(II), Ni(II), Cu(II), Zn(II), Ag(II), Cd(II) and Pb(II), was studied .The source phase contained equimolar concentrations of the above-mentioned cations, with the source and receiving phases being buffered at pH 4.9 and 3.0, respectively. Cu(II) ion transport occurred (J=2.82 × 10⁻⁷ mol/h at 25 °C) from the aqueous source phase across the polymer membrane (derived from cellulose triacetate) containing ligand (I) as the ionophore, into the aqueous receiving phase. Clear transport selectivity for Cu(II) was observed.     

水杨醛肟铜络合物中性载体高选择性水杨酸根电极的研究

采用合成的Schiff碱金属络合物水杨醛肟铜(Ⅱ)、锌(Ⅱ)、镍(Ⅱ)为中性载体制备阴离子选择性电极。结果表明水杨醛肟铜(Ⅱ)对水杨酸根(Sal-)具有高选择性及优良的电位响应性能,电极呈现反Hofmeister选择性行为,其选择性次序为Sal->ClO4->SCN->I->NO2->NO3->Br->Cl->OAc->SO42-。采用交流阻抗技术和紫外可见光谱技术研究了电极的响应机理。该电极具有响应快、重现性好、检出限低和制备简单等优点。将电极用于药品及人体尿液分析,结果令人满意。     

Ionophore Properties of Schiff Base Compounds as Ion Sensing Molecules for Fabricating Cu(II) Ion-Selective Electrodes

Bis(2-hydroxybenzaldehyde)-1,2-diaminoethane (L^I), bis(2-hydroxybenzaldehyde)-1,3-diaminopropane (L^II) and bis(2-hydroxybenzaldehyde)-4,4'-methylendianiline (L^III) were examined as ionophores for fabrication of polyvinylchloride (PVC) membrane Cu(II) ion-selective potentiometric sensors. The optimum composition (%) for the sensors was: 5 L^I, 30 PVC, 6 sodium tetraphenylborate (NaTPB), 59 ortho-nitrophenyloctyl ether (NPOE); 4 L^II, 30 PVC, 5 NaTPB, 61 dibutyl phthalate; 6 L^III, 30 PVC, 5 NaTPB, 59 NPOE. The linear response range of the electrodes was 5 × 10^–4–0.05 (L^I), 5 × 10^–4–0.1 (L^II) and 1 × 10^–6–0.01 M (L^III), and the corresponding detection limits were 4 × 10^–4, 4 × 10^–4 and 2 × 10^–7 M, respectively. The sensors were showed rapid response time (≈10 s). Their responses were independent on pH in the range 2.5–5.0 (L^I), 3.2–4.7 (L^II) and 4.0–5.0 (L^III). The selectivity of the prepared electrodes towards copper ions over some mono-, di- and trivalent metal ions was evaluated. The sensors were used as indicator electrode in potentiometric titration of copper ions in aqueous solutions.     

Study of Cobalt(III) Corrole as the Neutral Ionophore for Nitrite and Nitrate Detection via Polymeric Membrane Electrodes

Cobalt(III) 5,10,15‐tris(4‐tert‐butylphenyl) corrole was synthesized and incorporated into plasticized poly(vinyl chloride) membranes and studied as a neutral carrier ionophore via potentiometry. This cobalt(III) complex has binding affinity to nitrite, and the resulting membrane electrode yields reversible and Nernstian response toward nitrite. Enhanced nitrite selectivity is observed over other anions, including lipophilic anions such as thiocyanate and perchlorate when an appropriate amount of lipophilic cationic sites are added to the membrane phase. Detection limit to nitrite is ca. 5 µM. Using tributylphosphate as the plasticizer with the cobalt(III) corrole species yields electrodes with enhanced nitrate selectivity.     

Binuclear Copper(II) Complexes in which other copper(II) complexes are coordinated as bidentate ligands

Twelve new copper(II) complexes in which N,N′-bis-(2-pyridylmethyl)-oxamidatocopper(II) or N,N′-bis(2-pyridylethyl)-oxamidatocopper(II) coordinates as a bidentate ligand have been isolated and characterized. These complexes have a structure bridged by the oxamide group (including two tetranuclear complexes formed by olation of two binuclear complexes, of. Fig. 1), and possess Cu? Cu interaction resulting in a sub-normal magnetic moment at room temperature. In one of them, [Cu₂(PMoxd) (bipy)₂] (NO₃)₂ (cf. Fig. 2), each copper(II) ion has a five-coordinated environment.     

Organoselenide as a Novel Ionophore for a Silver-Selective Membrane Electrode

Abstract

Three selenium-containing compounds, diphenyl selenide, benzyl phenyl selenide and dibenzyl selenide were used as neutral carriers to make a Ag⁺-selective membrane electrode. All three compounds exhibited higher sensitivity to Ag⁺ than the corresponding sulfides and ethers. The highest sensitivity was obtained by dibenzyl selenide and an electrode constructed using this carrier and bis(l-butylpentyl) adipate as a membrane solvent in a poly(vinyl chloride) membrane matrix exhibited a near-Nernstian response to Ag⁺ in the concentration range from 1 x 10^?5 to 1 x 10^?2 M with a slope of 52 mV per concentration decade. The lower limit of detection was around 1 μM. The ion selectivity of this electrode for Ag⁺ was over 10⁴ times that for other metal cations. Dibenzyl selenide and Ag⁺ interactions were examined by ¹H-NMR spectroscopy.     

Asymmetrical Schiff Bases as Carriers in PVC Membrane Electrodes for Cadmium (II) Ions

5‐[((4‐Methyl phenyl) azo)‐N‐(6‐amino‐2‐pyridin) salicylaldimine] (S₁), and 5‐[((4‐methyl phenyl) azo)‐N‐(2‐diamino‐2‐cyano‐1‐ethyl cyanide) salicylaldehyde] (S₂) with N and O donor atoms are effective ionophores to make Cd²⁺‐selective membrane electrodes. The electrodes based on S₁ and S₂ exhibits a Nernstian or near‐Nernstian response for cadmium ion over a wide concentration range 1.5×10^?1–7.5×10^?7 with a slope of 28 and 2.0×10^?1–4.0×10^?7 with a slope of 22, respectively. They have quick response and can be used for three or four months without any divergence in potential. The proposed sensors show fairly good selectivity over some alkali, alkaline earth, transition and heavy metal ions. The electrodes based on S₁ and S₂ can be used in the pH range 3.5–9. These electrodes were used as an indicator electrode in potentiometric titration of cadmium ion with EDTA and in the direct determination of cadmium ion in aqueous solutions.     

草酰胺桥联双核铜配合物结构单元的从头算

运用Gaussian 94W量子化学程序包 ,采用LanL2DZ基组 ,对草酰胺桥联双核铜配 (聚 )合物结构单元Cu2 (oxen) (OH) 2 [H2 oxen =N ,N' 二 ( 2 胺乙基 )草酰胺 ](包括顺、反构型及其单、三重态电子组态 )进行从头算研究 ,探讨该配合物结构单元的稳定性 ,并从电荷布居及分子轨道组成等电子结构特征分析这种配合物反式三重态比较稳定的原因 .计算结果与实验规律相符合 .     

Binuclear Copper(II) Complexes with Hydrazones Containing Spiropyran Fragment

New hydrazones were prepared by the reaction of new spiropyran of benzoxazine series and aliphatic acid hydrazides; their binuclear complexes were synthesized.     

Binuclear Copper(II) Complexes. N,N′-bis(3-aminopropyl)-oxamidatocopper(II) coordinated as a bidentate ligand

Four new binuclear copper(II) complexes having sub-normal magnetic moment have been synthesized by reaction of N, N′-bis(3-aminopropyl)-oxamidatocopper(II) with another copper(II) compound such as mono- and bis-(2,2′-bipyridine)-copper(II) nitrate, cupric mono-malonate, or cupric chloride. One of them, [Cu₂(APxd)(bipy)₂](NO₃)₂(cf. Fig. 2), was recognized to be a binuclear complex in which each copper(II) ion has a five-coordinated environment. The data from analyses, IR and electronic spectra, magnetic susceptibility measurements, and conductivity measurements were used to establish the structures.     

双核Cu(II)-牛磺酸缩水杨醛席夫碱配合物的合成、晶体结构及生物活性

合成了双核铜配合物 [Cu(TSSB) (H2 O) ] 2 ·2H2 O (TSSB =牛磺酸缩水杨醛席夫碱 ) ,通过元素分析、红外光谱对配合物进行了表征 ,并利用X射线法测定其结构 .晶体属三斜晶系 ,空间群P1- ,其晶胞参数为 :a =0 .69613 ( 19)nm ,b =0 .93 0 7( 3 )nm ,c=1.0 43 9( 3 )nm ;α =10 8.796( 5 )° ,β =10 1.2 71( 5 )° ,γ =10 5 .617( 5 )° ,V =0 .5 869( 3 )nm3 ,Z =1,Dcald=1.849g/cm3 ,μ =2 .0 5 8mm-1,F( 0 0 0 ) =3 3 4,Gof =1.0 79,Δρ =3 79～ -4 0 6e·nm-3 .两个铜原子配位数各为五 ,处于变形四方锥的配位环境中 .并对配合物进行了的生物活性试验 ,结果表明 ,配合物抗菌活性与青霉素接近 ,肿瘤抑制率达 63 .5 % .半数致死量为 10 0 0mg/kg .有可能成为一种新的抗菌、抗肿瘤药物     

Neutral Nickel(II) and Copper(II) Tetraazamacrocyclic Complexes as Molecular Rods Attached to Gold Electrodes

New dithiolated derivatives of neutral Cu^II and Ni^II tetraazamacrocyclic complexes have been synthesized and characterized by spectroscopic and diffractional methods. These rod‐shaped molecules were assembled in monocomponent and mixed monolayers on gold electrodes. In the mixed monolayers, the active molecules were embedded in a hexanethiol matrix. The dithiolated complexes are oriented perpendicularly to the electrode, and reveal faster kinetics of electron transfer than those assembled in a single‐component monolayer. They appear as protrusions, which are easily addressed by using the STM method. In the presence of a suitable electron acceptor in the solution, the donor properties of the anchored Cu complex were weakened, which revealed donor–acceptor interactions with the monolayer. The peak position in the voltammogram indicates a stronger interaction of the solution‐based acceptor with the reduced Cu^II form than with the Cu^III complex. This suggests the possibility of switching the association on or off by applying an appropriate potential.     

双核Cu(Ⅱ)—牛磺酸缩水杨醛席夫碱配合物的合成、晶体结构及生物活性

合成了双核铜配合物[Cu(TSSB)(H2O)]2.2H2O(TSSB=牛磺酸缩水杨醛席夫碱） ，通过元素分析，红外光谱对配合物进行了表征，并利用X射线法测定其结果，晶 体属三斜晶系，空间群P1，其晶胞参数为：a=0.69613(19)nm,b=0.9307(3)nm,c=1. 0439(3)nm;a=108.796(5)°,β=101.271(5)°,γ=105.617(5)°,V=0.5869(3) nm^3,Z=1,Dcald=1.849g/cm^3,μ=2.058nm^-1,F(000)=334，Gof=1.079,Δρ=379- 406e.nm^-3，两个铜原子配位数各为五，处于变形四方锥的配位环境中，并对配合 物进行了的生物活性试验，结果表明，配合物抗菌活性与青霉素接近，肿瘤抑制率 达63、5，半数臻死量为1000mg/kg,有可能成为一种新的抗菌、抗肿瘤药物。     

A Substituted Tetraazaporphyrinogen as an Electroactive Component for a Polymeric Membrane Anion-Selective Electrode

A novel anion-selective electrode has been prepared by usingtetraazaporphyrinogen as the electroactive component and o-nitrophenyloctylether as the plasticizer. The electrode exhibits almost Nernstian responsecharacteristics for Pic^-, ReO ₄ ^- ,SCN^-, ClO ₄ ^- and TPB^-. The linearresponse ranges towards the above-mentioned anions are 10^-6 10^-2, 10^-5 10^-2,10^-5 10^-2, 10^-5 10^-1, and 10^-5 10^-2mol/Land the corresponding slopes are -56.8, -57.1, -56.3, -56.1, and -59.9mV/decade with correlation coefficients of -0.99978, -0.99987, -0.99999,-0.99998, and -0.99998, respectively. The electrode shows an anti-Hofmeisterselectivity sequence: Pic^- > SCN^- >ReO ₄ ^- > ClO ₄ ^- > I^- >Br^- > BF ₄ ^- > Sal^->NO ₃ ^- > Cl^-. The unusual responsemechanism of the novel anion-selective electrode was investigated byexperimental observations and calculation with the MNDO method. Theelectrode was used as a TPB^- and a Pic^-sensitiveelectrode, respectively, and applied to the assay of levamisolehydrochloride tablets by potentiometric titration and Gran's methods. Theresults obtained are in excellent agreement with that determined by thestandard pharmacopoeia method based on nonaqueous titration.     

Endo and Exo Coordination to Cofacial Binuclear Copper(II) Complexes

A structural study of internal (endo) and external (exo) coordination to cofacial binuclear complexes is reported.Cu₂(NBA)₂(NBAH₂=3,3'-[2,7-naphthalenediylbis(methylene)]-bis(2,4-pentanedione)) is large enough to accommodate 2-methylpyrazine as an intramolecularly coordinated guest molecule Cu₂(NBA)₂((2Mepyz))4CH₂Cl₂Cu₂C₅₃H₅₈N₂O₈Cl₈, orthorhombic, space group Pnma (No. 62); a = 22.4674(11); b = 22.230(2); c = 11.4520(6) Å V = 5719.6(6) ų (at 100 K); Z = 4; R = 0.058; R _w = 0.167 for 344 parameters and 5339 reflections with I > 2(I). The Cu₂(NBA)₂(-(2-Mepyz)) molecules possess crystallographic m symmetry, with the CuCu vector (CuCu' 7.4801(8) Å) perpendicular to the mirror plane; this requires disorder in the 2-Mepyz guests. The two ``Cu(acac)₂' moieties (acacH = 2,4-pentanedione) are not quite parallel (dihedral angle between (acac)₂ planes = 3.93(7)^circ), forming a slightly wider opening on the side of the methyl group in the 2-Mepyz guest. On the other hand, the cavity in Cu₂(XBA)₂ (XBAH₂ = 3,3'-[1,3-phenylenebis(methylene)]-bis(2,4-pentanedione)) is smaller, so that CH₃CN must bind externally.Cu₂(XBA)₂(CH₃CN)₂1.5CH₃CNH₂O,Cu₂C₄₃H_52.5N_3.5O₉, monoclinic, space group P2₁/c (No. 14); a = 11.7361(16); b = 14.197(3); c = 13.299(3) Å; = 92.22(2)^{^}; V = 2214.3(7) ų (at 100 K); Z = 2; R = 0.044; R _w = 0.124 for 275 parameters and 4983 reflections with I > 2 (I). This structure contains centrosymmetric Cu₂(XBA)₂ units (CuCu' 4.8302(12) Å) with externally coordinated CH₃CN ligands. The crystal packing in Cu₂(NBA)₂((2Mepyz))4CH₂Cl₂,which contains close contacts between layers of Cu₂(NBA)₂(-(2-Mepyz)) moieties, is also similar to that in three other crystalline host–guest adducts M₂(NBA)₂(-G). Cu₂(XBA)₂(CH₃CN)₂1.5CH₃-CNH₂O does not contain similar layers of molecules, presumably because the adduct molecules do not have the same type of exposed flat surfaces.     

Synthesis, Structure and Spectral Characterization of a Discrete Binuclear Copper (II) Complex

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