Synthesis of submicron CaZrO<Subscript>3</Subscript> in combustion reactions

Submicron CaZrO₃ powder is obtained in combustion reactions (solution combustion synthesis—SCS) with glycine. It is found that SCS reduces the sintering temperature of CaZrO₃ powders. The dielectric properties of calcium zirconate ceramics are studied by the electrochemical impedance method. It is shown that a ceramics of powders obtained by the SCS method has high dielectric characteristics.     

C- and N-Amidotrichloroethylation of Azoles

1H-Pyrazoles, triazoles, and imidazoles in reaction with ethoxycarbonylimine and arylsulfonylimines of chloral yield addition products, corresponding 1-(1-amidotrichloroethyl)azoles. Derivatives of 1-alkylpyrazoles and pyrazolones react with chloral 4-chlorophenylsulfonylimine to furnish products of C-amidotrichloroethylation into position 4 of the azole ring.     

Computational analysis of native and modified oligofructosides

This paper presents a quantum chemical calculation of native (2–7 fructoside residues) and chemically modified (2–4 fructoside residues) levan molecule models. A levan modification was carried out by oxidation and the following reduction or hyrdazonation of the fructoside rings. The conformational particularity and reaction ability was studied for the native and for the modified levan molecules.     

Synthesis and Properties of Carbocyclic Schiff Bases

New Schiff bases containing both adamantyl and phenyl fragments in a single molecule were synthesized by condensation of appropriate diamines with aromatic aldehydes. The condensation products were brought into reduction and nucleophilic addition reactions.     

Copolymerization of N‐vinylcaprolactam and glycidyl methacrylate: Reactivity ratio and composition control

Free‐radical copolymerizations of N‐vinylcaprolactam (VCL) and glycidyl methacrylate (GMA) were investigated to synthesize temperature‐responsive reactive copolymers with minimized compositional heterogeneity. The average copolymer composition was determined by Fourier transform infrared and nuclear magnetic resonance techniques. The reactivity ratios for VCL and GMA were found to be 0.0365 ± 0.0009 and 6.44 ± 0.36 by the Fineman–Ross method and 0.039 ± 0.006 and 6.75 ± 0.29 by the Kelen–Tudos method, respectively. When prepared by batch polymerization, VCL–GMA copolymers had a highly heterogeneous composition and fractions of different solubilities in water. The use of a gradual feeding technique, which included the sequential addition of more reactive GMA monomer into the reaction, yielded copolymers with much more homogeneous composition. The produced copolymers with 0.9 and 0.11 fractional GMA contents preserved their temperature‐responsive properties and precipitated from aqueous solutions when the temperature exceeded 31 °C. The GMA units in the VCL–GMA copolymers were capable of reacting with amino end‐functionalized poly(ethylene oxide) at room temperature to produce poly(N‐vinylcaprolactam)–poly(ethylene oxide) graft copolymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 183–191, 2006     

V4S9Br4: a novel high-spin vanadium cluster thiobromide with square-planar metal core

The novel vanadium thiobromide, V4S9Br4, with a square-planar metal cluster core was synthesized and characterized by single-crystal X-ray diffraction, measurements of magnetic properties and the heat capacity, and DFT calculations of the electronic structure. At the room temperature, the compound displays paramagnetic properties with an independent spin on each V atom and with a weak exchange constant (J approximately 10 cm(-1)). The paramagnetic state is transformed into a low-spin state (AF-type ordering) at low temperatures. This change is accompanied by a heat-capacity anomaly. The observed magnetic and heat-capacity anomalies can be explained by the thermal excitation of electrons on the closely spaced molecular energy levels in the presence of the Jahn-Teller effect.     

Mild template synthesis of a copper(II)-containing macrocyclic compound with 4,4,6-trimethyl-2,3,7,8-tetraazanonen-6-dithiohydrazide-1,9 in a gelatin-immobilized matrix

The complexing processes in the triple copper(II)–thiocarbohydrazide–propanone system taking place in a copper(II) hexacyanoferrate(II) gelatin-immobilized matrix in contact with aqueous-alkaline solutions (pH12), containing thiocarbohydrazide and propanone, have been studied. Template synthesis leading to a macrocyclic coordination compound with the tetradentate N,N,S,S-donor ligand, (4,4,6-trimethyl-2,3,7,8-tetraazanonen-6-dithiohydrazide-1,9), occurs under these specific conditions when thiocarbohydrazide and propanone are the ligand synthons.     

Platinum metallodrug-protein binding studies by capillary electrophoresis-inductively coupled plasma-mass spectrometry: characterization of interactions between Pt(II) complexes and human serum albumin

Characterizing how platinum metallocomplexes bind to human serum albumin (HSA) is essential in evaluating anticancer drug candidates. Using cisplatin as a reference complex, the application of capillary electrophoresis (CE) to reliably assess drug/HSA interactions was validated. Since this complex is small compared to the size of the protein, the binding response could only be recognized when applying CE coupled to a (platinum) metal-specific mode of detection, namely inductively coupled plasma-mass spectrometry (ICP-MS). This coupling allowed for confirmation of a specific affinity of cisplatin and novel Pt complexes to HSA, measurement of the kinetics of binding reactions, and determination of the number of drug molecules attached to the protein. As the cisplatin/HSA molar ratio increased, the reaction rate became faster with a maximum on the kinetic curve appearing at about 50 h of incubation at 20 times excess of cisplatin. The reaction was characterized as a pseudo-first order reaction with the rate constant k = 0.003 min(-1) at 37 degrees C. When incubated with a 20-fold excess of cisplatin, HSA bound up to 10 mol of Pt per mol of the protein. This is indicative for a strong metal-protein coordination occurring at several HSA sites other than the only protein cysteine residue. Structural analogs of cisplatin, bearing aminoalcohol ligands, showed comparable protein binding reactivity and stoichiometry but a common equilibrium was not reached even after one week of incubation. Also apparent was a two-step mechanism of the binding reaction. Results demonstrated the suitability of CE-ICP-MS as a rapid assay for high-throughput studying of drug/HSA interactions.