Investigation of Separation and Identification Possibilities of Some Metal-Dithizonate Complexes by Sequential TLC-IR System

The separation and identification possibilities of a number of metal–dithizonate complexes were investigated by means of a TLC-IR sequential system. Dithizonate complexes of some metal cations were pre-pared in a predetermined optimum pH or pH range. Optimum separation conditions of these complexes and the reproducibility of their R _f values were investigated on a series of precoated or laboratory-made TLC plates. R _f values were determined by using the one-dimensional ascending technique. The precision of the procedures was determined for replicates in terms of standard deviation. Detection limits were also determined for each metal complex. The IR spectra were scanned and interpreted for precise identification after preconcentration with the wick-stick procedure for complexes giving overlapped R _f values. The complexes were able to be identified with the aid of IR absorption bands. It has been determined that these IR absorption bands will also be able to be used as reference spectral bands in possible quantitative studies. It has been concluded that an effective and successful qualitative analysis will be executable for incompletely separated complex compounds using an IR spectrophotometer as a TLC detector.     

Investigation of thin-layer chromatography properties of some transition metal complexes based on ditiocarbamates

Sodium diethyldithiocarbamate (DEDTC) and ammonium pyrolidinedithiocarbamate (PyDTC) are prepared as their Co or Cu (M) complexes [M(DEDTC)(2) and M(PyDTC)(2), respectively]. The complexes are prepared by reactions of DEDTC and PyDTC with metal (II) nitrates, and they are examined for chromatographic properties using thin-layer chromatography systems. These complexes and their mixtures are spotted on the activated and non-activated 250-microm thick thin layers of commercial silica gel (Si-60GF(254)). Pure toluene and a toluene-cyclohexane mixture (3:1, v/v) are used as mobile phases for running the complexes. These chromatographic systems are successfully used for the qualitative analysis of the corresponding metal cations and the separation of components in both M(DEDTC)(2) and M(PyDTC)(2) complex mixtures. In addition, non-activated layers are more successful than activated layers. This study may be useful in understanding the effects of stationary and mobile phase properties, retention mechanisms, and the effects of the nature of metal and ligand type on the chromatographic behavior and parameters [e.g., retention factors, theoretical plate numbers, and resolution] of the complexes.     

Studies on some salicylaldehyde Schiff base derivatives and their complexes with Cr(III), Mn(II), Fe(III), Ni(II) and Cu(II)

The formation constants of some transition metal ions Cr(III), Mn(II), Fe(III), Ni(II) and Cu(II) binary complexes containing Schiff bases resulting from condensation of salicylaldehyde with aniline (I), 2-aminopyridine (II), 4-aminopyridine (III) and 2-aminopyrimidine (IV) were determined pH-metrically in ethanolic medium (80%, v/v). The formation constants were determined for all binary complexes. The important infrared (IR) spectral bands corresponding to the active groups in the four ligands and the solid complexes under investigation were studied. The solid complexes have been synthesized and studied by thermogravimetric analysis. The thermal dehydration and decomposition of these complexes were studied kinetically using the integral method applying the Coats-Redfern equation. It was found that the thermal decomposition of the complexes follow second order kinetics. The thermodynamic parameters of the decomposition are also reported. The electronic absorption spectra of the investigated ligands were carried out to determine the pK(a) values spectrophotometrically.     

Mixed-ligand complexes of N-vinylpyrrolidone/N-vinylformamide/N-vinyl iminodiacedic acid copolymers and diethyldithiocarbamate as a co-ligand with indium/indium-111

Mixed-ligand metal-polymer complexes (MPC) of N-vinylpyrrolidone-N-vinylformamide-N-vinyl iminodiacedic acid (VP-VFA-VIDA) copolymers and diethyldithiocarbamate (DEDTC) as a co-ligand with indium were synthesized under mild conditions and pH close to physiological values. Isolated MPC were characterized by UV, IR, ¹H NMR, atomic absorption spectrophotometry, and HPLC. The obtained data implied that the MPC contain 8–10?wt% of (IDA)In(DEDTC) fragments. The optimal conditions for radiochemical synthesis of VP-VFA-VIDA-¹¹¹In-(DEDTC) metal-polymer complex with mixed ligands were defined. The closest coordination environment of ¹¹¹In was studied by perturbed angular correlation technique. The obtained data are in good agreement with the information about weight amounts of the corresponding indium MPC.     

Qualitative analysis of Cu2+, Co2+, and Ni2+ cations using thin-layer chromatography

The M(DEDTC)2 (M = Cu, Co, or Ni) and M(PyDTC)2 (M = Cu or Co) complexes prepared by reactions of sodium diethyldithiocarbamate and ammonium pyrollidinedithiocarbamate with metal (II) nitrates are examined for qualitative analysis and separation using thin-layer chromatography systems. These complexes and their mixtures are spotted to the activated thin layers of silica gel 60GF254 (Si-60GF254) with a 250-microm thickness. Pure toluene and a toluene-cyclohexane mixture (3:1, v/v) are used as mobile phases for running of the complexes. These chromatographic systems are successfully used for qualitative analysis of corresponding metal cations and separation of components in both M(DEDTC)2 and M(PyDTC)2 complex mixtures.     

Acid modified diatomaceous earth--a sorbent material for thin layer chromatography

Natural diatomaceous earth (DE) is modified by flux calcination and refluxing with acid. To characterize natural DE, modified DE's [flux calcinated (FC)DE and FCDE-I] and silica gel 60GF(254) (Si-60GF(254)) are analyzed microscopically, physically, and chemically by various techniques. FCDE-I and Si-60GF(254) are investigated for their usefulness in the stationary phase of thin layer chromatography (TLC) both individually and in composition. Sodium diethyldithiocarbamate (DEDTC) and ammonium pyrrolidinedithiocarbamate (PyDTC) are prepared as Co or Cu (M) complexes [M(DEDTC)(2) and M(PyDTC)(2), respectively]. These complexes and their mixtures are run on thin layers of Si-60GF(254) and FCDE-I individually, and on various FCDE-I and Si-60GF(254) mixtures. Pure toluene and various toluene-cyclohexane mixtures (3:1, 1:1, 1:2, 1:3, v/v) are used as mobile phases for the running the complexes. The best analytical separations of both M(DEDTC)(2) and M(PyDTC)(2) complexes are obtained when using pure toluene and toluene-cyclohexane (3:1, 1:1, v/v) as mobile phases on FCDE-I-Si-60GF(254) (1:3, 1:1, w/w) layers as stationary phases. This study shows that it is possible to qualitatively analyze and to satisfactorily separate a mixture Cu(2+) and Co(2+) cations on cited chromatographic systems.     

苯酚和苯胺类衍生物的结构与薄层色谱保留值关系的研究

以不同比例的己烷－乙酸乙酯二元体系作为展开剂,在硅胶板上测定了２４种苯酚和苯胺类衍生物的比移值Ｒｆ。用斜交因子分析方法将这２４种化合物分为具有不同特征的两大类：第一类的苯环上均不含甲基,而第二类的苯环上均含甲基。第一类化合物的比移值均比第二类要小;苯环上取代基团使Ｒｆ值增大的顺序为ＣＨ３＞ＯＨ＞ＮＨ２;邻位取代的化合物,由于分子内形成氢键,极性减弱,因而比移值增大。分别对两类化合物的保留值与其拓扑指数进行多元回归分析的结果表明,它们的色谱保留行为与其分子结构之间存在着较好的相关性。     

锰、铑原卟啉IX-二甲酯配合物共振拉曼光谱研究

合成了MnPPCl,RhPPCl,RhPPN3,RhPP(CO)Cl四种配合物 (PP =ProtophyrinIXDimethy1Ester) ,用元素分析、红外吸收光谱及紫外吸收光谱确定了配合物的组成 ,测定了它们的共振拉曼光谱 ,对特征谱带进行了归属。分析了拉曼谱带和电子吸收谱带变化的原因 ,提出了谱带频率的变化受金属离子外层d电子和轴配体的影响。     

1:1- und 1:2-Metallchelate unsulfierter o,o′-Dihydroxyazoverbindungen. Eine dünnschicht-chromatographische Untersuchung

In an earlier publication [4] the possibility of the Chromatographic separation of structurally isomeric metal chelates was mentioned; this is dealt with here in more detail. Further the separation of 1:2 mixed complexes from azo dyes and 1:2 metal-complex mixtures by thin-layer chromatography (TLC) on polyamide is described. In certain circumstances it is possible to distinguish between 1:2 metal-complex dyes with sulphonamide or alkylsulphonyl groups and those without these substituents by TLC on silica gel. The TCL methods described allow-when correctly interpreted-an unambiguous distinction between structurally isomeric metal complexes of the 1:1 and 1:2 series, and mixed complexes and mixtures of complexes of the 1:2 metal-chelate type of unsulphonated o,o′-dihydroxyazo compounds. Symmetrical o,o′-dihydroxyazo compounds, such as 2,2′-dihydroxy-5,5′-dimethylazobenzene(7), are suitable as complex-formers for heavy-metal ions, allowing the separation of the latter as their coloured chelates with aid of TLC. Structural isomers are excluded because of the molecular symmetry, so that the results are unambiguous.     

Chromatographic determination of metal chelates of 2,6-diacetylpyridine bis(N-methylenepyridiniohydrazone)

Metal ions were determined chromatographically as their metal chelates after complexation with 2,6-diacetylpyridine bis(N-methylenepyridiniohydrazone). At a pH of 7 it was possible to separate and determine eight metal complexes, in a single run, under gradient conditions on a polyestyrene-divinylbenzene polymer-based column. Possible separation of rare earth complexes and ion-pairing behavior were also investigated. Linear calibration ranges and detection limits are presented for the metal complexes of Sn(II), Ti(IV), Mn(II), Co(II), Cd(II), Sb(III), Cu(II), Ni(II) and U(VI). Interferences due to the presence of other metal ions in solution were also investigated.     

Spectrophotometric, conductometric and thermal studies of Co(II), Ni(II) and Cu(II) complexes with 2-(2-hydroxynaphthylazo)-4-hydroxy-6-methyl-1,3-pyrimidine

The electronic absorption spectra of 2-(2-hydroxynaphthylazo)-4-hydroxy-6-methyl-1,3-pyrimidine in pure organic solvents of different polarities and in buffer solutions of varying pH are studied. The important bands in the IR and the main signals in the (1)H NMR spectra are assigned. The observed UV-vis absorption bands are assigned to the corresponding electronic transitions. The molecular stoichiometry, stability constant, absorption maximum, molar absorptivity and Sandell's sensitivity of the complexes are calculated. Obeyence to Beer's law and Ringbom optimum concentration ranges are also determined. The ability of using the titled azodye as metalochromic indicator in complexometric titrations was also studied. The effect of Co(II), Ni(II) and Cu(II) ions on the fluorescence of the azodye is also considered. The solid Cu(II) complexes of the titled azodye have been prepared and characterized by elemental, IR, UV-vis spectra as well as by conductometric and magnetic measurements. The data suggest square planar geometry for 1:1 and 1:2 (M:L) complexes. The thermal behaviour of the complexes has been studied. The kinetic parameters (n, E, A, deltaH, DeltaS and deltaG) of the thermal decomposition steps are computed using Coats-Redfern equations.     

Effects of amine-pretreatment of silica gel on the TLC behaviour of rare earths

The TLC behaviour of all the rare earths except Pm has been examined on silica gel pretreated with aqueous solutions of four different amines [iminodi-2-ethanol, tris(hydroxymethyl)aminomethane, nitrilotri-2-ethanol, and 1,3-diazole] in a 1 mol/l NH₄Cl solution. The Rf value of each metal decreased with increasing pKa value of the amines and also with increasing concentration and pH of the amine solution used for the pretreatment. The technique is simple and reproducible, and makes it possible to arbitrarily regulate the adsorbability of silica gel. Thus, the use of the amine-treated silica gels serves to develop many solvent systems for the separation of the rare earths.     

Terahertz absorption spectra of some saccharides and their metal complexes

In this work, THz absorption spectra of some saccharides and their metal complexes were measured. The main purpose of this work is to investigate the M-O vibrations, intermolecular and intramolecular hydrogen bonds and other vibrations in the FIR region using powerful spectroscopic techniques adopting the metal-sugar complexes prepared in our laboratory. The M-O vibrations in the FIR spectra of metal-sugar complexes indicate the formation of metal complexes. The THz spectrum of glucose below 100cm(-1) was measured at first to confirm the THz experimental method. Characteristic absorption bands in the spectra of various samples are observed. THz spectra of saccharides below 100cm(-1) often have several absorption bands, and different saccharides have various absorption peaks in the THz region, which may be used to distinguish different saccharides. The differences in the number of bands observed are related to different structures of the samples, and these absorption bands are related to the collective motion of molecules. But the THz spectra of their metal complexes are different from the ligands, and no band appears in the region below 50cm(-1) at the present experimental condition, which indicates that THz spectroscopy may also be helpful to identify the formation of metal-sugar complexes, and the changes after complexation in the THz spectra below 100cm(-1) may be related to different metal ions. The metal-sugar complexes with similar crystal structures resemble mid-IR spectra, but their THz spectra may have some differences.     

Studying the interaction between silica nanoparticles and metals by spectrophotometry

The optical absorption spectra of water silica sols containing nanoparticles (NPs) of metals (Ag, Pd, Fe, and Pt) are investigated. Silica sols are obtained from natural hydrothermal solutions via membrane concentration (ultrafiltration). Water sols of silica with specific sizes, pH values, ζ potentials of SiO₂ NP surfaces, and low concentrations of SiO₂ NPs are used. Plasmon resonance in optical absorption spectra is used to study the interaction between silica and metal NPs. Parameters of plasmon resonance (position, height, and half-width of optical absorption bands), from which the degree of interaction is assessed, are determined. Relationships between the optical properties of the surfaces of nanoparticle-size silica particles, the method of their production, and the effect of adsorbed metal particles on these properties are established.     

Tautomeric structures, electronic spectra, acid-base properties of some 7-aryl-2,5-diamino-3(4-hydroxyphenyazo)pyrazolo[1,5-a]pyrimidine-6-carbonitriles, and effect of their copper(II) complex solutions on some bacteria and fungi

Infrared and electronic spectra were used to investigate the tautomerism of some azo compounds, in both the solid and solution states. It was found that the compounds exist in azo<==>hydrazone tautomeric equilibrium in solid and in solutions. The different bands displayed in the electronic spectra of the compounds in various organic solvents are assigned to the suitable electronic transitions. The solvatochromic behavior of the compounds was investigated by studying their visible spectra in pure and mixed organic solvents. DeltaG and formation constant, Kf, values of the molecular complexes formed in solution have been determined. Effect of concentration of the compounds in DMF and EtOH solutions has been investigated. The basicity and acidity constants of the different compounds were determined from the spectra of these compounds in aqueous-ethanolic solutions of varying pH values. Some complexes of copper(II) with these compounds in solution were tested as for their antibacterial and antifungal activity.     

Spectrophotometric Studies on Some Arylazo Barbituric Acids and Arylazo Pyrimidine in Organic Solvents and in Buffer Solutions

The UV and visible spectra of some arylazo barbituric acids and arylazo pyrimidine in pure and mixed organic solvents of varying polarities have been studied. The different absorption bands displayed in the electronic spectra of these compounds are assigned and the possibility of the existence of these compounds in tautomeric equilibrium as well as in intra‐ and intermolecular H‐bonding were examined. The solute‐solvents molecular complexes liable to exist in polar‐nonpolar mixed solvents are investigated. The structure of the azo compounds were confirmed by ¹H NMR and IR spectroscopy. The ionization processes of the compounds were investigated and the possible ionization constants were determined and discussed in terms of molecular structure of the azo compounds.     

Electrophoretic techniques in element species analysis. Comparison between flow-through and flat-bed techniques

A comparison of electrophoretic techniques for the separation of metal-protein complexes from food extracts is described. A preparative flow-through electrophoresis system with continuous elution of the fractionated substances and an analytical flat-bed gel electrophoresis technique with off-line electro-elution are optimized with regard to this separation problem. The metal-protein complexes are extracted from four flour samples using Tris-glycine buffer (pH 8.3). For the separation, polyacrylamide gels of 14% T and 3% C are prepared and Tris-HCl (pH 8.9) is used as an electrophoresis buffer. For a soy bean flour, not only the separation of protein fractions is achieved but also the metal distribution patterns that are determined by flame atomic absorption spectrometry are given. The results show that the use of the flow-through technique is limited to special fields of application, whereas the flat-bed electrophoresis with subsequent electro-elution of metal-protein complexes is a useful technique in element species analysis.     

Synthesis of New Reagent 2‐Acetylthiophenethiocynate and its Use in Extraction of Pt(IV) Spectrophotometrically

2‐Acetyl thiophenethiocynate (ATT) was synthesized and its characterization study was carried out using elemental analysis, IR and NMR techniques. The new reagent was proposed as an extractant for the development of the extractive spectrophotometric method for determination of Pt(IV) metal. The reagent complexes with the metal to produce a yellow colored complex which was then extracted into ethyl acetate at pH 11.2–11.6 having an absorption maxima at 400 nm. The thermal study showed that the extraction reactions are exothermic in nature with the reagent, and the stoichiometric ratio of Pt(IV) to 2‐acetyl thiophenethiocynate in the organic phase was 1:2. The method permits separation and determination of platinum from real and binary mixtures. The separation of Pt(IV) from bivalent metal ions has been also studied.     

UV/Vis,IR and 1H NMR spectroscopic studies of bisazo-dianil compounds based on 5-(2-carboxyphenyl azo)-salicylaldehyde and primary diamines

The electronic absorption and emission spectra of the titled biazo-dianils are studied in organic solvents of different polarity as well as in aqueous buffer solutions of varying pH. The important bands in the IR spectra as well as the main signals of the 1H NMR spectra are assigned. The observed UV/Vis absorption bands are assigned to the corresponding electronic transitions. The fluorescence quantum yield and pK(a)(-) values in the ground and excited states are determined.     

Synthesis, spectroscopic characterization and DNA nuclease activity of Cu(II) complexes derived from pyrazolone based NSO-donor Schiff base ligands

Two neutral mononuclear Cu(II) complexes have been prepared in EtOH using Schiff bases derived from 4-toluoyl pyrazolone and thiosemicarbazide. Both the ligands have been characterized on the basis of elemental analysis, IR, (1)H NMR, (13)C NMR and mass spectral data. The molecular geometry of one of these ligands has been determined by single crystal X-ray study. It reveals that these ligands exist in amine-one tautomeric form in the solid state. Microanalytical data, Cu-estimation, molar conductivity, magnetic measurements, IR, UV-Visible, FAB-Mass, TG-DTA data and ESR spectral studies were used to confirm the structures of the complexes. Electronic absorption and IR spectra of the complexes suggest a square-planar geometry around the central metal ion. The interaction of complexes with pET30a plasmid DNA was investigated by spectroscopic measurements. Results suggest that the copper complexes bind to DNA via an intercalative mode and can quench the fluorescence intensity of EB bound to DNA. The interaction between the complexes and DNA has also been investigated by agarose gel electrophoresis, interestingly, we found that the copper(II) complexes can cleave circular plasmid DNA to nicked and linear forms.