A Stable Enzyme Biosensor Using Concanavalin a Complex of Glucose Oxidase for Glucose Determination

Abstract

The thermal stability of an insoluble concanavalin A (ConA) complex of glucose oxidase (GOD) was researched. The thermal deactivation rate constants of the complexes were obtained. It was found that the GOD-ConA complexes were less sensitive to thermal inactivation than the native enzyme GOD. By using the complexes, ferrocene-mediated enzyme electrodes were constructed. The results suggested that the GOD-Con A complex electrodes had good thermal stability at room temperature.     

Thermal Stability of 4-Chloro-3-Nitro- and 5-Chloro-2-Nitrobenzoates of Rare Earth Elements

The physico-chemical properties and thermal stabilities in air of rare earth element 4-chloro-3-nitrobenzoates and 5-chloro-2-nitrobenzoates were compared and the influence of the positions of the Cl and NO₂ substituents on their thermal stabilities was investigated. The complexes of both series are crystalline, hydrated or anhydrous salts with colours typical of Ln³⁺. The carboxylate group in these complexes is a bidentate, chelating ligand. The NO₂ group in the chloronitro complexes does not undergo isomerization. The thermal stabilities of the 4-chloro-3-nitrobenzoates of Y and the lanthanides were studied in the temperature range 273-1173 K, but those of the 5-chloro-2-nitrobenzoates of these elements were studied only at 273-523 K, because they decompose explosively above 523 K. The positions of the Cl and NO₂ substituents on the benzene ring influence the thermal properties of the complexes and their decomposition mechanisms. The different thermal stabilities of the complexes are connected with various inductive and mesomeric effects of the Cl and NO₂ substituents on the electron density in the benzene ring. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal investigation of iron(III) and manganese(II,III) complexes of dianils derived from 6-formylkhellin

Manganese and iron complexes of Schiff bases derived from 6-formylkhellin were prepared and characterized. Complexes of o-phenylenediamine derivative (ligand (I)) are monomeric or dimeric whereas those of p-phenylenediamine derivative (ligand (II)) are polymeric. The complexes obtained are characterized by a lower magnetic moment values. The complexes also have different solvent of crystallization with different nature of interaction. The thermal behaviour of the ligands and their metal complexes was investigated by means of DTA, TG, IR and X-ray diffraction spectroscopy. Ligand (I) shows different thermal behaviour from that of ligands (II) and (III). The complexes of ligand (II) give abnormal oxides as a final product during their thermal decomposition. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermal analysis and spectroscopic studies of some complexes of l,7-diacetoxy-2,4,6-trinitro- 2,4,6-triazaheptane

Complexes of 1 ,7-diacetoxy-2,4,6-triniZro-2.4,6-triazaheptane (BSX) have been prepared with a wide range of organic solvents. The stoichiometrv of the complexes was determined where possible by thermogravimetric analysis, and the mode of thermal decomposition of the complexes was studied by differential scanning calorimetry. The enthalpies of desolvation were evaluated from the thermal about half of the complexes prepared. p]Infrared and Raman spectra were measured on some of the complexes in an attempt to determine the nature of the bonding, if any, taking place between the host BSX molecules and the guest solvent molecules. The spectroscopic results are discussed in terms of similar measurements for other inclusion compounds and also with reference to the detailed crystal structure of some of the BSX complexes.     

Oxidation of Hydrogen by Metal Complexes of Platinum and Palladium Immobilized on Silica

The thermal stability of metal complexes immobilized on the surface of silica and its connection with the catalytic activity in the oxidation of hydrogen were investigated. High catalytic activity was exhibited by heterogenized platinum and palladium acetylacetonate near room temperatures in the initial state and by γ-aminopropylsilicas treated with platinum and palladium complexes. The catalytic activity of the metal complexes correlates with their thermal stability and with the ability to undergo oxidation to a metal state with high valence. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermal Stability of 2,3,4-, 2,4,5- and 3,4,5-tri- Methoxybenzoates of Light Lanthanides

The physico-chemical properties and thermal stability in air of light lanthanide 2,3,4-, 2,4,5- and 3,4,5-trimethoxybenzoates were compared and the influence of the position of –OCH³ substituent on their thermal stability was investigated. The complexes of these series are crystalline, hydrated or anhydrous salts with colours typical of Ln³⁺ ions. The carboxylate group is a bidentate, chelating ligand. The thermal stability of 2,3,4-, 2,4,5- and 3,4,5-trimethoxybenzoates of rare earth elements was studied in the temperature range 273–1173 K. The positions of methoxy groups in benzene ring influence the thermal properties of the complexes and their decomposition mechanism. The different thermal properties of the complexes are connected with various influence of inductive and mesomeric effects of –OCH₃ substituent on the electron density in benzene ring. This revised version was published online in August 2006 with corrections to the Cover Date.     

Study of the Thermal Decompositions on N,N-Dialkyl-N'-Benzoylthiourea Complexes of Cu(II), Ni(II), Pd(II), Pt(II), Cd(II), Ru(III) and Fe(III)

The thermal decompositions of the complexes of N,N-dialkyl-N'-benzoylthioureas with Cu(II), Ni(II), Pd(II), Pt(II), Cd(II), Ru(III) and Fe(III) were studied by TG and DTA techniques. These metal complexes decompose in two stages: elimination of dialkylbenzamide, and total decomposition to metal sulphides or metals. The influence of the alkyl substituents in these benzoylthiourea chelates on the thermal behaviour of the metal complexes was investigated.This revised version was published online in November 2005 with corrections to the Cover Date.     

Study on metal complexes of chelating resins bearing iminodiacetate groups

Cu(II), Co(II) and Ni(II) complexes of chelating resins (CR) bearing iminodiacetate (IDA) ligands were prepared. The CR-metal complexes were characterized by FT-IR spectroscopy, X-ray diffraction (XRD), thermal behavior (TG and DTG) under nitrogen atmosphere, and electron paramagnetic resonance (EPR). FT-IR spectra of the CR-metal complexes showed the characteristic bands of CR were still present but red-shifted after the metal complexation, and new bands assigned to Me-N bonds were observed. Thermal behavior of the metal-CR complexes supported the metal complexation, metal complexation leading to the decrease of the thermal stability of the CR, the lowest thermal stability being found when the highest amount of Cu(II) was loaded. Based on the EPR results and the thermal behavior of Cu(II)-CR complexes, the scheme for the complexation of Cu(II) on the CR was suggested.     

Spectrochemical and Thermal Behaviour of the 5-chloro-2-nitrobenzoates of Rare Earth Elements

The conditions of the formation of yttrium and lanthanide 5-chloro-2-nitrobenzoates were studied and their quantitative composition and solubilities in water at 298 K were determined. They are anhydrous or hydrated complexes and their solubilities are of the order of 10-3 mol dm-3. The IR and X-ray spectra for the complexes were recorded. All complexes are crystalline compounds. Their thermal decomposition was studied. It was found that on heating above 523 K the complexes decompose explosively. Therefore their thermal decomposition was carried out in the temperature range 273-523 K. Hydrated complexes lose crystallization water molecules in one step. From the results it appeared that during dehydration process no transformation of nitro group to nitrito took place. Some of physico-chemical properties of rare earth element 5-chloro-2-nitrobenzoates were compared with 2-nitro- and 3-chlorobenzoates of those elements. This revised version was published online in July 2006 with corrections to the Cover Date.     

稀土长链配合物的合成及其性质研究

通过筛选配体、优化合成条件,设计合成了以Tb3 为中心离子,以苯甲酸、水杨酸、对羟基苯甲酸、对甲基苯甲酸、大茴香酸、间氯苯甲酸、对氨基苯甲酸、磺基水杨酸为第一配体,以十一烯酸为第二配体合成8种铽三元荧光配合物。通过红外光谱分析、紫外光谱分析、元素分析、EDTA配位滴定分析以及电导率的测定确定了铽三元荧光配合物的分子结构和组成,采用热分析仪研究了铽三元荧光配合物的热稳定性能,其热稳定性强弱顺序为:Tb(SSA)(UA).3H2O磺基水杨酸>大茴香酸>对氨基苯甲酸>苯甲酸>水杨酸>对羟基苯甲酸>间氯苯甲酸,同时对产生上述现象的原因进行了初步的理论探讨。     

Study of the formation of polyimide from complexes of benzophenonetetracarboxylic acid diester with different diamines. 3. Dielectric study of thermal imidization

Dielectric loss peaks caused by thermal imidization were observed for the three complexes of benzophenonetetracarboxylic acid dimethyl ester (BZPE) with different diamines. The mechanism of the formation of imide rings from complexes with hydrogen bonds and with separated charges was specified. The specific features of thermal imidization of the BZPE·diaminopyridine dimeric complex were confirmed and it was shown that heat treatment of the complex of BZPE with hexamethylenediamine yields a softening polyimide and thermal imidization takes place at lower temperatures.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 534–539, March, 1990.     

Thermal Studies on Solid Complexes of Uracil With Some Divalent Transition Metal Ions

The thermal behaviour of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pd(II) complexes of uracil was studied by TG, DTG and DTA in a dynamic nitrogen atmosphere. Two processes occur in the isolated uracil complexes: dehydration and pyrolytic decomposition. In the hydrated complexes, the first stage observed was the loss of water molecules, which was followed by decomposition of the uracil. The thermal dehydration of the complexes occurred in from one to three steps. The final decomposition products were found to be the respective metal oxides, except in the cases of the Co(II) and Pd(II) complexes, which produced metallic cobalt and palladium, respectively. The order of reaction and energy of activation for the dehydration stage were evaluated.This revised version was published online in November 2005 with corrections to the Cover Date.     

Co(II)Schiff碱配合物的合成、氧合反应热力学及热分解动力学的研究

合成了两种新的钴(II)schiff碱配合物水杨醛L-甲硫氨酸-水合钴(II)(1), 邻香兰素L-甲硫氨酸-水合钴(II)(2)。通过元素分析、红外光谱、热分析等测试手段研究了配合物的性质, 并确定了配合物的组成。用气体吸收装置测定配合物在乙腈溶液中不同温度下的饱和吸氧量, 求得氧合反应的平衡常数及热力学参数, 同时探讨了温度和配体结构对配合物氧合性能的影响。用TG-DTG法研究了配合物的热稳定性及非等温热分解动力学, 并采用积分法和微分法相结合的方法,推断了两种配合物的第一步热分解反应机理, 得到了热分解反应动力学参数及其动力学方程。     

Thermal Degradation Studies of Complexes of a Derivative of Phenhomazine (Dibenzo[b,f][1:5]diazocine‐6:12‐Dione (PHZD)) by Thermoanalytical Techniques

Some of the bis‐complexes of a derivative of phenhomazine (dibenzo[b,f][1:5]diazocine‐6:12‐dione; PHZD) with Ni(II), Cu(II), Co(II), Cd(II), Zn(II) and Hg(II) of the general formula M(PHZD)₂X₂ [where X = C1, Br and I], were prepared and identified. These complexes have been characterised on the basis of elemental analysis, and spectroscopic, magnetic and conductance data. The thermal mode of decomposition and thermal stability of these complexes was investigated on the basis of the respective thermal curves in a static air atmosphere. The thermoanalytical investigations indicate that these complexes undergo two‐step changes as temperature is raised, except for Cd(II) and Hg(II) complexes, with the formation of metal oxides as end product. The degradation mechanism of the complexes has also been proposed.     

Thermal, spectral and magnetic studies of some first row transition metal complexes of 2-(p-tolyl) pyridine

Some chloro complexes of cobalt, nickel and copper with 2-(p-tolyl) pyridine have been prepared. The stereochemical configurations of the complexes were deduced using spectral and magnetic properties. The decomposition of the complexes was studied by thermogravimetry and differential thermal analysis.     

New metal(II) complexes with ceftazidime Schiff base

Complexes of Co(II), Ni(II) and Cu(II) with the Schiff base (LH) derived from ceftazidime and salicylaldehyde were synthesized. The proposed structures of the new metal complexes based on the results of elemental analyses, molar conductivity, IR, DRUV and ¹H NMR spectra, effective magnetic moment and thermal analysis were discussed. The surface morphology of Schiff base and metal complexes was studied by SEM. The composition of the metal complexes was ML₂, where L is the deprotonated Schiff base ligand and M = Co(II), Ni(II) and Cu(II). IR spectral data indicated the Schiff base ligand being bidentately coordinated to the metallic ions with N and O atoms from azomethine and phenolic groups. All the complexes have square-planar geometry and are nonelectrolytes. The thermal analysis recorded that TG, DTG, DTA and DSC experiments confirmed the assigned composition and gave information about the thermal stability of complexes in dynamic air atmosphere. Theoretical investigation of the molecular structure of Schiff base ligand and its complexes was studied using programs dedicated to chemical modeling and quantomolecular calculation of chemical properties. The newly synthesized complexes were tested for in vitro antibacterial activity against selected Gram-negative and Gram-positive bacterial strains, and they exhibited an antibacterial activity superior to that of the Schiff base ligand.     

Preparation and characterization of a new series of solid solutions of Bi1−xYxFeO3 (0 < x < 1) from the thermal decomposition of hexacyanoferrates doped with yttrium

Solid solutions of Bi_1?xY_x[Fe(CN)₆]·4H₂O (0?<?x?<?1) complexes were synthesized and characterized. The crystal structures were refined by Rietveld analysis using X-ray powder diffraction data. The complexes of the series crystallized in the orthorhombic system, space group Cmcm. The gradual decrease in cell volume indicates that the substitution of Bi³⁺ by Y³⁺ was appropriately materialized. The thermal behavior was studied by thermogravimetric and differential thermal analysis. A single phase of perovskite-type Bi_1?xY_xFeO₃ powders was obtained by thermal decomposition of the complexes at about 600 °C. The obtained products were identified and characterized by energy-dispersive spectroscopy, Raman and Fourier transform infrared spectroscopy and powder X-ray diffraction. The size and morphology of the complexes and their thermal decomposition products were evaluated by scanning electron microscopy. Thermal analysis showed that the complexes were good intermediaries for the synthesis of high-purity mixed oxides with a uniform particle size of the order of nanometers. To evaluate the effect of doping with yttrium, electrical transport measurements were performed.

     

Spectral and thermal studies of new Co(II) and Ni(II) hexaaza and octaaza macrocyclic complexes

The macrocyclic complexes of Co(II) and Ni(II) having chloride or thiocyanate ions in the axial position have been synthesized and characterized. These complexes are synthesised by the template condensation of o-phenylenediamine or 2,3-butanedionedihydrazone with the appropriate aldehydes in NH₄OH solution in the presence of the metal ions, Co(II) and Ni(II). The complexes were characterized by spectroscopic methods (IR, UV-Vis and ESR) and magnetic measurements as well as thermal analysis (TG and DTA). The results obtained are commensurate with the proposed formulae. Spectral studies indicate that these complexes have an octahedral structure. From conductivity measurements the complexes are non-electrolytes. The kinetic of the thermal decomposition of the complexes was studied and the thermodynamic parameters are reported.     

Synthesis and thermal study of rhenium(V) coordination compounds with pyroracemic acid and phenylglyoxylic acid thiosemicarbazones

Rhenium(V) coordination compounds with pyroracemic acid and phenylglyoxylic acid thiosemicarbazones were synthesized for various metal-to-ligand ratios in 1–7 M hydrohalic acids. The composition and structure of the complexes were characterized using a set of physicochemical methods. The thermal stability of rhenium(V) complexes with pyroracemic acid and phenylglyoxylic acid thiosemicarbazones and rhenium(V) solvato complexes with pyroracemic acid thiosemicarbazone was studied thermogravimetrically. The thermolysis mechanism for the complexes was determined as follows: elimination of outer-sphere water, decarboxylation, and dehalogenation.     

Induced crystal G phase through intermolecular hydrogen bonding II. Influence of alkyl chain length of n-alkyl p-hydroxybenzoates on thermal and phase behaviour

A new series of intermolecular hydrogen-bonded complexes have been synthesized using p-n-alkoxybenzoic acid (alkyl chain length varies from propyl- to decyl- and dodecyl-) and methyl p-hydroxybenzoate moieties. The thermal and phase behaviour of these complexes were studied by thermal microscopy and differential scanning calorimetry. Further, the stabilization of intermolecular hydrogen bonding in solution was studied by IR spectroscopy. A detailed IR spectral investigation in the solid and dissolved states suggests that the acid and phenol groups act as proton donor and proton acceptor, respectively. The thermal studies also reveal the inducement of a crystal G phase in the complexes.