Synthesis,characterization and antimicrobial activity of homodinuclear complexes derived from 2,6- bis [3′-methyl- 2′-carboxamidyliminomethyl(6′,7′)benzindole]-4-methylphenol,an end-off compartmental ligand

End-off compartmental pentadentate Schiff base, 2,6-bis[3′-methyl-2′-carboxamidyliminomethyl(6′,7′)benzindole]-4-methylphenol is synthesized and characterized by 2D NMR experiments and mass spectral techniques. The homodinuclear phenalato bridged end-off compartmental Schiff-base complexes Cu(II), Co(II), Ni(II), Mn(II), Fe(III), VO(IV), Zn(II), Cd(II) and Hg(II) have been prepared by the template method using the precursors 2,6-diformyl-4-methylphenol, 3-methyl(6′,7′)-2-benzindolehydrazide and metal chlorides in 1?:?2?:?2 ratio. The complexes are characterized by IR, NMR, UV-vis, FAB-mass, ESR and TGA techniques. Ni(II), Mn(II) and Fe(III) complexes have octahedral geometry, whereas the Cu(II), Co(II), VO(IV), Zn(II), Cd(II) and Hg(II) complexes have square pyramidal geometry. Low magnetic moment values for Cu(II), Co(II), Ni(II), Mn(II), Fe(III) and VO(IV) complexes indicate antiferromagnetic spin-exchange interaction between two metal centers. The metal complexes have been screened for their antibacterial activity against Escherichia coli and Staphyloccocus aureus and antifungal activity against Aspergillus niger and Fusarium oxysporum.     

基于三联吡啶衍生物的Fe~(2+)/Fe~(3+)化学比色敏感器

合成和表征了一种新的化合物(E)-4-′(4-(2-(2-萘)乙烯基)苯基)-2,2′:6′,2″-三联吡啶L.用Fe2+或Fe3+来滴定时,L的溶液(三氯甲烷和乙醇的体积比为1∶20)颜色分别从无色变成洋红色和橙红色,相应的紫外可见吸收光谱都在374和574 nm出现特征吸收峰.此外,即使存在其它过量金属阳离子时,L对Fe2+或Fe3+离子仍然表现出很强的敏感性和选择性.另外,还研究了L对Fe2+或Fe3+离子及两者共同存在时的线性检测浓度范围和最低检测极限(LOD).     

Separation and Recovery of Some Metal Ions Using Pan Sorbed Zinc Silicate as Chelating Ion Exchanger

Abstract

A new inorganic ion exchanger zinc silicate has been synthesized. Its properties such as ion exchange capacity, heat effect and stability etc. have been studied. Sorption of PAN over zinc silicate formed a chelate ion exchanger which showed greater selectivity for some metal ions especially for Cu²⁺, Ni²⁺, Co²⁺, Fe³⁺, Ag⁺, Ag³⁺ and Pt⁴⁺. Selectivity has been determined on the basis of distribution coefficients of these metal ions. Separations of Pt(IV) from Fe(III), Au(III) from Fe(III), Ag(I) from Cu(II) and Au(III) from Cu(II) have been reported. The recovery of Pt(IV) and Au(III) from dilute solutions has also been studied.     

Spectrometric Studies on the Complexation of Pd(II), Fe(III) and Pt(IV) with mandelazo I

Abstract

A spectrometric study of the reaction between Pd(II), Fe(III) and Pt(IV) ions, and Mandelazo I was carried out. The optimum conditions favouring the formation of the complexes are extensively investigated. The stoichiometry of the complexes formed in solution (1:2, 1:1, 1:1), their apparent stability constants (5.45 × 10⁹, 2.39 × 10⁶, 4.12 × 10⁵) and the ranges for obedience to beer's law (0.2 – 6.4, 0.25 – 7.0, 1.5 – 42.0 μg/mL) are reported for Pd(II), Fe(III) and Pt(IV), respectively. The effect of some metal ions including Cu(II), Zn(II), Mn(II), Cd(II), Hg(II), Co(II), Ni(II), Be(II), Al(III), Th(IV) and U(VI), on the maximum absorbance of the formed complexes was also investigated.     

Luminol-K2S2O8体系中金属离子化学发光行为的研究

报导了在自行设计的流动注射式化学发光分析仪上,对Luminal-K2S2O8体系中32种金属离子的化学发光行为的系统研究.确定了对金属离子的最优测定条件以及大多数金属离子的检出极限和线性范围.     

Liquid extraction of noble metal ions with bis(α-aminophosphonates)

Extraction of Au(III), Pt(IV), and Pd(II) ions from hydrochloric acid media with solutions of two bis(aminophosphonates), such as N,N-bis(dipentoxyphosphorylmethyl)octylamine and N,N′-bis[[(dioctyloxyphosphoryl)methyl]butylamine], in chloroform and xylene was investigated. Both these extractants proved to be highly effective for Au(III) ions in a wide acidity range, which allows these ions to be separated from other noble metal ions with a high degree of selectivity. At the same time, Pt(IV) and Pd(II) ions cannot be separated from one another with the extractants studied. The selectivity of their separation from Fe(III), Cu(II), Co(II), and Ni(II) metal ions is, too, not high. The reasons for these results lie in the specific structural features of the extractants, which predetermine the extraction mechanism.     

Further Determination of Cadmium Ions in Water by an Electrochemiluminescence Method

ABSTRACT

Two new electrochemiluminescence (ECL) reactions in aqueous solution involving cadmium(II) ions are reported. The ECL reaction occurs in the presence of a common co-reactant, tripropylamine (TPA), and either of two organic ligands, 2,2′:6′,2″-terpyridine or 2,2′-bipyridine. The reaction is presumed to arise from the metal-ligand complex and the co-reactant. Conditions for ECL emission were optimised and a calibration graph constructed. Emission was linear over the range 10-1 000 ppb. The calculated limits of detection (LOD) were 8 and 50 ppb using terpyridine and bipyridine, respectively. Comparison with a previously reported reaction involving cadmium(II) ions and 1, 10-phenathroline is made.     

Synthesis and efficiency of poly(acrylamidrazonehydrazide) chelating fiber for preconcentrating and separating trace gold and palladium from solution

A new poly(acrylamidrazone-hydrazide) chelating fiber has been synthesized using polyacrylonitrile fiber as a starting material. An ICP-OES method for applying the fiber to preconcentrate and separate trace Au(III) and Pd(IV) ions in solution has been established. The experiments show that 8 ng/ml Au(III) and 6 ng/ml Pd(IV) in 1000 ml of solution can be enriched quantitatively by the fiber column at a flow rate of 12 ml/min at pH 2. These ions can be desorbed quantitatively with 10 ml of 2.5% CS(NH₂)₂ + 6% H₂SO₄ containing 0.2% Fe(II) from the column at an elution rate of 6 ml/min. A fiber treated with 12M HCl or 15M HNO₃ can be re-used 10 times with above 95% recoveries of Au(III) and Pd(IV), and 120–800-fold excesses of Cu(II), Mn(II), Fe(III), Al(III), Ni(II), Mg(II) and Ca(II) ions cause little interference. The RSDs are 2.0% for 8 ng/ml Au and 3.5% for 6 ng/ml Pd. The recovery of added standard in a solution sample from a metal smelter is 96.2% for Au and 100% for Pd, and the content of each ion in the sample determined by the method is in agreement with the analysed value from the smelter laboratory.     

Kinetics of Free Radical Polymerization. XXXVIII. Solvent Effect on the Degree of Polymerization of Poly(ethyl Acrylates) and Poly(methyl Acrylates)

Abstract

Polychelates of VO(II), Mn(II), Zn(II), Cr(III), and Fe(III) with the bis-oxime of 5, 5′-methylene-bis-salicylaldehyde have been prepared and are characterized on the basis of their elemental analyses, IR, diffuse reflectance spectra, magnetic moments, and thermogravimetric analyses. Except for VO(II), the other metal ions form octahedral polychelates. VO(II) forms a square-pyramidal coordination polymer. The Zn(II) poly-chelate has the highest thermal stability.     

Separation and determination of trace amounts of beryllium(II), aluminium(III) and chromium(III) with chromotrope 2C chelates by RP-HPLC

A reversed-phase high-performance liquid chromatographic separation and determination of beryllium(II), aluminium(III) and chromium(III) with chromotrope 2C chelates on a C18-bonded stationary phase is reported. Methanol-water (45:55 v/v) containing 6 x 10(-3)M tetra-n-butylammonium bromide (TBAB) and 2 x 10(-2)M acetate buffer solution (pH 6.0) as mobile phase and with spectrophotometric detection at 530 nm was applied. The method has high sensitivity, the detection limits being 0.2 ppb for beryllium(I), 1 ppb for aluminium(III) and 2 ppb for chromium(III). Under the optimum conditions, most other metal ions did not interfere, e.g. up to 2 mg of Hg(II), Sn(II, IV), Pb(II), Bi(III), Ag(I), Zn(II), Cd(II), Cu(II), 1.5 mg of Fe(II), Co(II), Ni(II), 1.2 mg of Ca(II), Mg(II), Sr(II), Ba(II), 1 mg of Ga(III), In(III), 0.5 mg of Fe(III), 1 mg of Ga(III), In(III), 0.5 mg of Fe(III), 0.4 mg of Th(IV), Zr(IV). The method can be applied to the simultaneous determination of trace amounts of beryllium(II), aluminium(III) and chromium(III), in water, rice, flour and human hair samples.     

Sulfonylcalix[4]arenetetrasulfonate as pre-column chelating reagent for selective determination of aluminum(III), iron(III), and titanium(IV) by ion-pair reversed-phase high-performance liquid chromatography with spectrophotometric detection

Sulfonylcalix[4]arenetetrasulfonate (SO₂CAS) has been examined as a pre-column chelating reagent for ultratrace determination of metal ions by ion-pair reversed-phase high-performance liquid chromatography with spectrophotometric detection. Metal ions were converted into the SO₂CAS chelates in an acetic buffer solution (pH 4.7). The chelates were injected onto a n-octadecylsilanized silica-type Chromolith™ Performance RP-18e column and were eluted using a methanol (50 wt.%)-water eluent (pH 5.6) containing tetra-n-butylammonium bromide (7.0 mmol kg⁻¹), acetate buffer (5.0 mmol kg⁻¹), and disodium ethylendiamine-N,N,N′,N′-tetraacetate (0.10 mmol kg⁻¹). Under the conditions used, Al(III), Fe(III), and Ti(IV) were selectively detected among 21 kinds of metal ions [Al(III), Ba(II), Be(II), Ca(II), Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Ga(III), Hf(IV), In(III), Mg(II), Mn(II), Mo(VI), Ni(II), Pb(II), Ti(IV), V(V), Zn(II), and Zr(IV)]. The detection limits on a 3σ blank basis were 8.8 nmol dm⁻³ (0.24 ng cm⁻³) for Al(III), 7.6 nmol dm⁻³ (0.42 ng cm⁻³) for Fe(III), and 17 nmol dm⁻³ (0.80 ng cm⁻³) for Ti(IV). The practical applicability of the proposed method was checked using river and tap water samples.     

Hg(II), Tl(III), Cu(I), and Pd(II) Complexes with 2,2'-Diphenyl-4,4'-Bithiazole (DPBTZ), Syntheses and X-Ray Crystal Structure of [Hg(DPBTZ)(SCN)2]

Reaction of the ligand 2,2′-diphenyl-4,4′-bithiazole (DPBTZ) with Hg(SCN)₂, Tl(NO₃)₃, CuCl, and PdCl₂ gives complexes with stoichiometry [Hg(DPBTZ)(SCN)₂], [Tl(DPBTZ)(NO₃)₃], [Cu(DPBTZ)(H₂O)Cl]_, and [Pd(DPBTZ)Cl₂]. The new complexes were characterized by elemental analyses and infrared spectroscopy. The crystal structure of [Hg(DPBTZ)(SCN)₂] determined by X-ray crystallography. The Hg atom in the title monomeric complex, (2,2′-diphenyl-4,4′-bithiazole)mercury(II)bisthiocyanate, [Hg(C₁₈H₁₂N₂S₂)(SCN)₂], is four-coordinate having an irregular tetrahedral geometry composed of two S atoms of thiocyanate ions [Hg-S 2.4025(15) and 2.4073(15) Å] and two N atoms of 2,2′-diphenyl-4,4′-bithiazole ligand [Hg-N 2.411(4) and 2.459(4) Å]. The bond angle S(3)-Hg(1)-S(4) of 147.46(5)° has the greatest derivation from ideal tetrahedral geometry. Intermolecular interaction between Hg(1) and two S atoms of two neighboring molecules, 3.9318(15) and 3.9640(18) Å, make the Hg(1) distort from a tetrahedron to a disordered octahedron. The attempts for preparation complexes of Tl(I), Pb(II), Bi(III), Cd(II) ions with 2,2′-diphenyl-4,4′-bithiazole ligand were not successful and also the attempts for preparation complexes of 4,4′,5,5′-tetraphenyl-2,2′-bithizole ligand with Cu(II), Ni(II), Co(II), Co(III), Mn(II), Mn(III), Fe(II), Fe(III), Cr(III), Zn(II), Tl(III), Pb(II), Hg(II), Cu(I), Pd(II) were not successful. This point can be regarded as the initial electron withdrawing of phenyl rings and also their spatial steric effects.     

Complexes of 2,2′,2″-Nirtilotriphenol. Part IV. Cage Compounds with Phosphorus(III) and Phosphorus(V)

The ligand 2,2′,2″-nitrilotriphenol reacts with P(III) and P(V) compounds to form corresponding phosphorus complexes. Syntheses and NMR data of 2,2′,2″-nitrilotriphenyl phosphite ( II ), 2,2′,2″-nitrilotriphenyl phosphate ( III ) and of a hydrolysis product of II , 2,2′-[N-(2-hydroxyphenyl)imino]diphenly phosphonate ( IV ), are reported, as well as crystal structures of II and IV . Phosphite II shows a bicycloundecane framework; no N?Pinteraction is present. The phosphonate IV shows two coordinated and one dangling phenol group; the N-atom does not interact with the P-atom. Strong acids protonate II as well as III to form cations: in these, NMR evidence indicates coordination of the N-atom to the P-atom.     

Complexation and Thermal Studies of Uric Acid with Some Divalent and Trivalent Metal Ions of Biological Interest in the Solid State

Nine new [metal uric acid] complexes [M(Ua) n ]°·XH 2 O have been synthesized. These complexes have been characterized by elemental analysis, X-ray diffraction (XRD), magnetic susceptibility ( w eff. ), FTIR spectra, thermal analysis (TG & DTA), and electronic spectra (UV/visible). Uric acid (HUa) coordinates as a bidentate ligand to Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Al(III), Cr(III) and Fe(III) through the protonated N-7 within the imidazole ring and O-6 within the pyrimidine ring. Uric acid forms neutral metal urate complexes with all the above metal ions. The quantitative compositions were determined as [M(Ua) 2 ·(H 2 O) 2 ]°·XH 2 O where M(II)=Mn, Fe, Co, Ni, Cu, Zn and X=2, 4, 2, 4, 2, 2, respectively. The M(II) complexes exhibit an isostructural octahedral coordination with N-7, O-6 of two uric acid ligand molecules, and O of two water molecules. Compositions were also determined as [M(Ua) 3 ]°·YH 2 O where M(III)=Al, Cr, Fe and Y=6, 3, 3 respectively. All the M(III) complexes form an isostructural octahedral coordination with N-7 and O-6 of three uric acid ligand molecules. Iron(III) complexes prepared with N 1 , N 3 and N 9 -methyl uric acid yielded brown complexes with a metal ligand ratio of 1 3, while N 7 -methyl uric acid did not yield a complex due to blockage of N-7 with a methyl group.     

Mandelazo I As A Reagent For Zr(IV) Determination

Abstract

A spectromeric study of the reaction of the Zr(IV) ions with Mandelazo I was carried out. Absorption spectra revealed that the maximum absorption of the zirconium compound appears at a wavelength (316 nm) different from the maxima of the reagent (253 and 390 nm). Beer-Lambert law is followed for zirconium concentrations of the order of 8.8x 10^?5 M (i.e. 8 μg Zr (IV)/mL). Possible interferences of ions such as Be(II), Cu(II), Zn(II), Al(III), Th(IV), U(VI), Mn(II), Fe(III), Co(II) and Ni(II) were investigated in connection with some masking agents such as SO₄ ^2- and C₂O₄ ^2-. Also, the solid state Zr(IV)-Mandelazo I compound was prepared and characterized by nitrogen and thermogravimetric analyses.     

Coordination modes of multidentate azodye ligand derived from 4,4′‐methylenedianiline towards some transition metal ions: Synthesis,spectral characterization,thermal investigation and biological activity

Nine new azodye metal complexes of Mn(II), Co(II), Ni(II), Cu(II), Cr(III), Fe(III), Ru(III), Hf(IV) and Zr(IV) ions have been prepared via the reaction of 5,5′‐((1E,1′E)‐(methylenebis(1,4‐phenylene))bis(diazene‐2,1‐diyl))bis(6‐hydroxy‐2‐thioxo‐2,3‐dihydropyrimidin‐4(5H)‐one) (H₄L) with the corresponding metal salts affording sandwich (1 L:1 M), mononuclear (2 L:1 M), binuclear (1 L,2 M) and tetranuclear (1 L,4 M) complexes. Elemental analyses, spectral methods, magnetic moment measurements and thermal studies were utilized to confirm the mode of bonding and geometrical structure for the ligand and its metal complexes. Infrared spectral data show that the H₄L ligand chelates with some metal ions in keto–enol–thione or keto–thione manner. It behaves in a neutral/dibasic tetradentate fashion in sandwich and binuclear complexes. Also, it acts as a neutral bidentate moiety in the Cr(III) complex. The spectra reveal that azo group participates in chelation in all complexes. Octahedral geometry was suggested for all chelates but the Cu(II) complex with square planar geometry. The thermal stability and decomposition of the compounds were studied, the data showing that the thermal decomposition ended with metal or metal oxide mixed with carbon as final product. The electron spin resonance spectrum of the Cu(II) complex demonstrates that the free electron is located in the ( ) orbital. Measurements of biological activity against human cell lines Hep‐G₂ and MCF‐7 reveal that the Cu(II) complex has a higher cytotoxicity in comparison to the free ligand and other metal complexes, with IC₅₀ values of 6.10 and 5.2 μg ml^?1, respectively, while the ligand has anti‐tumour activity relative to some of the investigated metal complexes.     

Hydrogen chemical ionization mass spectrometry of metalloporphyrins

The hydrogen chemical ionization (H₂ CI) mass spectra of a range of metal(II) (Ni, Cu, Co, Pt), metal (III) (Al, Mn, Ga, Fe (bearing a single axial ligand)) and metal(IV) (Si, Ge, Sn (bearing two axial ligands) and V (as V?O²⁺)) porphyrins have been determined, The spectra are highly dependent on the coordinated metal, rather than the axial ligand(s) (where present). Ni(II), Cu(II), Mn(II or III), Ga(III), Ge(IV), Fe(III) and Sn(IV) porphyrins fragment via hydrogenation and demetallation, followed by cleavage of the resulting porphyrinogens at the meso(bridge) positions to give mono- and di-pyrrolic fragments. Tripyrrolic fragments are also observed in the case of Ni(II), Cu(II) and Sn(IV). Fragmentations of this type are similar to those observed for free-base porphyrins. In the case of Pt(II), Co(II), Al(III), Si(IV) and V(IV) (as vanadyl), the dipyrrolic fragment ions are either very weak or completely absent; hence their H₂CI spectra contain limited structural information. This variable CI behaviour may be related to the relative stabilities of the metalloporphyrins together with the multiple stable valency states exhibited by several metals.     

Thin-Layer Chromatographic Separation of Some Allied Metal Ions and Their Determination by Ring Colorimetry

Abstract

Suitable methods have been worked out for the separation and determination of various groups of similar metal ions in mixtures, employing a combination of thin-layer chromatography and ring colorimetry. Solvent mixtures employed were: n-butanol + 12N HCl + dioxan (5:1:4); n-butanol + 6N HCl + dioxan (5:1:4); hexanol + dioxan + acetic acid + water (160:10:2:40); methanol + water (9:1 and 7:3). The following mixtures of cations were separated by TLC and the separated constituents were subsequently determined by ring colorimetry: Fe(III)- Co(II)- Cu(II)- Pb(II)- Ni(II); Pt(IV)- Co(II)- Cu(II)- Pd(II)- Ni(II); Ag(I)- Ni(II)- Co(II)- Fe(III); Cu(II)- Ni(II)- Bi(III); Cu(II)- Bi(III)- Hg(II).     

Effects of nonmesomorphic substituted benzonitriles on the dielectric properties of cyanobiphenyl liquid crystals

The effects of the cyano-substituted aromatic nonmesomorphic additives N-(3,4-dicyanophenyl)-4′-nonyloxybenzamide (I), 3,4-dicyanophenyl-4′-nonyloxybenzoate (II), 3,4-dicyanophenyl-3′,4′,5′-tris-(4″-undecyloxyphenylbenzoate)benzoate (III), and 4-(6-hydroxyhexyloxy)benzonitrile (IV) on the dielectric properties of 4-hexyloxy-4′-cyanobiphenyl and a liquid-crystal mixture E3 were studied. Dielectric anisotropy, birefringence, and orientational ordering were studied to show that monocyano derivative IV most strongly increased the dielectric anisotropy of mesomorphic compositions because of its effective incorporation into the liquid crystal matrix.     

Determination of Metal Ions by High Performance Liquid Chromatography

The mixture of metal ions [Bi(III), Fe(III), Fe(II), Cu(II), Zn(II), Ni(II), Co(II), Pb(II), Cd(II), Mn(II)] were separated in the bonded-phase strong cation exchange column (Vydac-401 SA) and monitored at 540 nm after a postcolumn reaction with 4-(2-pyridylazo)-resorcinol (PAR). Citrate, tartrate, lactate and α-hydroxyisobutyrate buffer were used as eluent and it has been found that the elution order of some metal ions were changed with different eluents. The detection limits and the calibration curves of metal ions were also studied.