Kinetics and mechanism of oxidation of methanol by acid bromate

The kinetics of oxidation of methanol by bromate ion in hydrochloric acid medium has been investigated. A mechanism consistent with the experimental observations is suggested.

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Spectroscopic and computational studies on the adenosylcobalamin-dependent methylmalonyl-CoA mutase: evaluation of enzymatic contributions to Co-C bond activation in the Co3+ ground state

Methylmalonyl-CoA mutase (MMCM) is an enzyme that utilizes the adenosylcobalamin (AdoCbl) cofactor to catalyze the rearrangement of methylmalonyl-CoA to succinyl-CoA. Despite many years of dedicated research, the mechanism by which MMCM and related AdoCbl-dependent enzymes accelerate the rate for homolytic cleavage of the cofactor's Co-C bond by approximately 12 orders of magnitude while avoiding potentially harmful side reactions remains one of the greatest subjects of debate among B(12) researchers. In this study, we have employed electronic absorption (Abs) and magnetic circular dichroism (MCD) spectroscopic techniques to probe cofactor/enzyme active site interactions in the Co(3+)Cbl "ground" state for MMCM reconstituted with both the native cofactor AdoCbl and its derivative methylcobalamin (MeCbl). In both cases, Abs and MCD spectra of the free and enzyme-bound cofactor are very similar, indicating that replacement of the intramolecular base 5,6-dimethylbenzimidazole (DMB) by a histidine residue from the enzyme active site has insignificant effects on the cofactor's electronic properties. Likewise, spectral perturbations associated with substrate (analogue) binding to holo-MMCM are minor, arguing against substrate-induced enzymatic Co-C bond activation. As compared to the AdoCbl data, however, Abs and MCD spectral changes for the sterically less constrained MeCbl cofactor upon binding to MMCM and treatment of holoenzyme with substrate (analogues) are much more substantial. Analysis of these changes within the framework of time-dependent density functional theory calculations provides uniquely detailed insight into the structural distortions imposed on the cofactor as the enzyme progresses through the reaction cycle. Together, our results indicate that, although the enzyme may serve to activate the cofactor in its Co(3+)Cbl ground state to a small degree, the dominant contribution to the enzymatic Co-C bond activation presumably comes through stabilization of the Co(2+)Cbl/Ado. post-homolysis products.     

Study of formation of nano-quasicrystals and crystallization kinetics of Zr-Al-Ni-Cu metallic glass

The formation of nano-quasicrystals on isothermal annealing of melt-spun ribbons of Zr_69.5Al_7.5Ni₁₁Cu₁₂ metallic glass has been investigated using transmission electron microscopy (TEM). The crystallization study of this metallic glass has been carried out using differential scanning calorimetry (DSC) in non-isothermal (linear heating) mode. It exhibits two-stage crystallization where the first stage corresponds to the precipitation of icosohedral nano-quasicrystalline phase. This has been confirmed with the help of TEM investigations. The crystallization parameters like the activation energy (E _c) and frequency factor (k ₀) have been derived using the Kissinger peak shift analysis. The activation energies for the first and second crystallization peak are found to be 278 and 295 kJ mol^–1, respectively. The frequency factors obtained for the two peaks are respectively 7.16·10¹⁹ and 1.42·10²⁰ s^–1. E _c, k ₀ and the Avrami exponent (n) have also been derived by fitting the Johnson-Mehl-Avrami-Kolmogorov (JMAK) equation for the transformed volume fraction (x) to the crystallization data. JMAK results of E _c for the first and second crystallization peak turn out to be 270 and 290 kJ mol^–1 respectively. However, k ₀ and n are found to be heating rate dependent as reported in similar studies. The values of n for the first crystallization stage ranges between 1.66 and 2.57 indicating diffusion-controlled transformation in agreement with earlier reports.     

Kinetics and mechanism of formation and dissociation of copper(II) and nickel(II) complexes of the Schiff base bis(acetylacetone)ethylenediimine in aqueous-organic solvent media

Summary In NH₄NO₃+NH₄OH buffered 10% (v/v) dioxan-water media (pH 7.0–8.5), thePseudo-first-order rate constant for the formation of the title complexes M(baen),i.e. ML, conforms to the equation 1/k_obs=1/k+1/(kK_o.s · T_L), where T_L stands for the total ligand concentration in the solution, K_o.s is the equilibrium constant for the formation of an intermediate outer sphere complex and k is the rate constant for the formation of the complex ML from the intermediate. Under the experimental conditions the free ligand (pK_a>14) exists virtually exclusively in the undissociated form (baenH₂ or LH₂) which is present mostly as a keto-amine in the internally hydrogen-bonded state. Although the observed formation-rate ratio k^Cu/k^Ni is of the order of 10⁵, as expected for systems having normal behaviour, the individual rate constants are very low (at 25°C, k^Cu=50 s^–1 and k^Ni=4.7×10^–4s^–1) due to the highly negative S values (–84.2±3.3 JK^–1M^–1 for CuL and –105.8±4.1 JK^–1M^–1 for NiL); the much slower rate of formation of the nickel(II) complex is due to higher H value (41.2±1.0 kJM^–1 for CuL and 78.2±1.2 kJM^–1 for NiL) and more negative S value compared to that of CuL. The K_o.s values are much higher than expected for simple outer-sphere association between [M(H₂O)₆] and LH₂ and may be due to hydrogen bonding interaction.In acid media ([H⁺], 0.01–0.04 M) these complexes M(baen) dissociate very rapidly into the [M(H₂O)₆]²⁺ species and baenH₂, followed by a much slower hydrolytic cleavage of the ligand into its components,viz. acetylacetone and ethylenediamine (protonated). For the dissociation of the complexes k_obs=k₁[H⁺]+k₂[H⁺]². The reactions have been studied in 10% (v/v) dioxan-water media and also ethanolwater media of varying ethanol content (10–25% v/v) and the results are in conformity with a solvent-assisted dissociativeinterchange mechanism involving the protonated complexes.     

Toward the development of new photolabile protecting groups that can rapidly release bioactive compounds upon photolysis with visible light

The synthesis and characterization of a new photolabile protecting group (caging group) for carboxylic acids, the 2-(dimethylamino)-5-nitrophenyl (DANP) group, is described. This compound has a major absorption band in the visible wavelength region with a maximum near 400 nm (epsilon400 = 9077 M(-1) cm(-1) at pH 7.4 and 21 degrees C). The caging group is attached through an ester linkage to the carboxyl functionality of beta-alanine, which activates the inhibitory glycine receptor in the mammalian central nervous system. Such caged compounds play an important role in transient kinetic investigations of fast cellular processes. Upon photolysis of DANP-caged beta-alanine, the caging group is released within 5 micros. Quantum yields of 0.03 and 0.002 were obtained in the UV region (308 and 360 nm) and the visible region (450 nm), respectively. Laser-pulse photolysis experiments, using 337 or 360 nm light, were performed with the caged compound equilibrated with HEK 293 cells transiently transfected with cDNA encoding the alpha1 homomeric, wild-type glycine receptor. The experiments demonstrated that neither DANP-caged beta-alanine nor its byproducts inhibit or activate the glycine receptors on the cell surface. Under physiological conditions, the DANP-caged beta-alanine is water-soluble and stable and can be used for transient kinetic measurements.     

Polyether azomethines. I. Synthesis and characterization

Six new polyether azomethines were synthesized by melt and solution polycondensation of six different diamines with 4,4′-[1,4-phenylene bis(oxy)] bisbenzaldehyde. The polymers synthesized by solution method are yellow to white in color and had inherent viscosities up to 0.59 dL/g in concentrated H₂SO₄. The polymers obtained by melt condensation show higher viscosity. Except polymer IV , others are insoluble in common organic solvents. The polymers were characterized by IR, x-ray, elemental analysis, and DSC study. The thermal stability of the polymers was evaluated by TGA and IGA study. Polymers I-III are highly thermally and thermooxidatively stable and exhibit no appreciable decomposition up to 420°C both in air and nitrogen atmosphere. It was shown that the curing of the polyazo-methines takes place by opening up of the ? CH?N? linkages at higher temperature. The electrical conductivities of the virgin and iodine doped polymers were as high as 10^?11?10^?16 and 10^?6?10^?8S cm^?1, respectively, at 30°C. Electronic spectra of the undoped polymers ( I-III ) indicated a large bathochromic shift of the ? – ?^* absorptions band (376 nm) due to ? C?N? bonds of the model compound. This can be attributed to extensive delocalization of the electrons along the polymer chain. © 1995 John Wiley & Sons, Inc.     

One-step synthesis and characterization of difunctionalized N-confused tetraphenylporphyrins

Three disubstituted N-confused porphyrins (2-4) were prepared in ca. 4% yield using a one-pot synthesis. These porphyrins bear 3,5-di-tert-butylphenyl groups substituted at the C(5) and C(20) meso positions and para-substituted (Br, NO(2), ethynyl) phenyl groups at the C(10) and C(15) meso positions. The specific orientation of the aryl rings around the macrocycle in porphyrin 2 was definitively determined using a combination of 1D ((1)H and (13)C) and 2D (gHMQC and gHMBC) NMR spectroscopy. The absorption spectra of 2-4 in CH(2)Cl(2) and dimethylacetamide are similar to those of N-confused tetraphenylporphyrin in the same solvents but have Soret and Q-bands that are shifted to lower energies. Steady-state fluorescence measurements revealed Q(x)(0,0) and Q(x)(0,1) bands similar in energy to the unsubstituted NCPs 1i and 1e. The fluorescence quantum yield results for two of these NCPs (2, 4) are atypical of porphyrin behavior and are being further investigated by time-resolved spectroscopy.     

Studies of solvation of ketocyanine dyes in homogeneous and heterogeneous media by UV/Vis spectroscopic method

Solvation characteristics of ketocyanine dyes (I-VI) have been investigated in pure solvents and heterogeneous media by absorption and fluorescence studies. The dyes are good reporters of solvent polarity. In protic solvents they exist as equilibrium mixtures of bare and hydrogen-bonded form in the ground state (S0), the latter being the emitting species. In aprotic solvents of low polarity association of the S1 state of the dye takes place. In aqueous micellar media the dye resides at the micelle water interface. The binding constant for dye-micelle interaction has been determined. Fluorescence data in beta-cyclodextrine solution resemble that for that neutral micellar solution indicating that the interaction between the -OH group of the heterogeneous part (micelle/cyclodextrine cavity) and the carbonyl oxygen of the dye is important in both the cases.     

Novel feature extraction technique for fuzzy relational clustering of a flexible dopamine reuptake inhibitor

This paper describes a novel clustering methodology for classifying over 700 conformations of a flexible analogue of GBR 12909, a dopamine reuptake inhibitor that has completed phase I clinical trials as a treatment for cocaine abuse. The major aspect of the clustering methodology includes an efficient data-conditioning scheme where a systematic feature extraction procedure based on the structural properties of the molecule was used to reduce the associated feature space. This allowed region-specific clustering that focused on individual pharmacophore elements of the molecule. For clustering of the reduced feature set, the fuzzy clustering partitional method was utilized. Due to the relational nature of the feature data, fuzzy relational clustering was employed, and it successfully detected natural groups defined by rotational minima around N(sp(3))-C(sp(3)), O(sp(3))-C(sp(3)), and C(sp(3))-C(sp(2)) bonds. The proposed clustering methodology also employed several cluster validity measures, which corroborated the partitions produced by the clustering technique and agreed with the results of hierarchical clustering using the XCluster program. Representative structures which exhibited a reasonable spread of energies and showed good spatial coverage of the conformational space were identified for use as putative bioactive conformations in a future Comparative Molecular Field Analysis of GBR 12909 analogues. The clustering methodology developed here is capable of handling other computational chemistry problems, and the feature extraction technique can be easily generalized to other molecules.     

Heterometallic Ln/Hg compounds with fluorinated thiolate ligands

The early lanthanide benzenefluorothiolates (Ln(SC(6)F(5))(3); Ln = La, Ce, Pr, Nd, Sm, Gd) react with Hg(SC(6)F(5))(2) in DME to form ionic heterometallic compounds with Ln cations and Hg anions. X-ray diffraction analyses of all compounds reveal an isostructural series with the general formula [(DME)(3)Ln(SC(6)F(5))(2)](2)[Hg(2)(SC(6)F(5))(6)]. In the structures, a fluorothiolate ligand has been extracted from the Ln coordination sphere that is saturated with three neutral DME donor ligands and a dative interaction between one ortho fluorine and the Ln. Distances between Ln and F do not vary simply with Ln ionic radius. There are two Ln cations with charge balanced by a Hg(2)(SC(6)F(5))(6) dianion composed of two distinctly nonideal Hg(II) tetrahedra, all connected through a series of pi-pi interactions that link cations with anions in a one-dimensional array and anions to anions in a more complex 2D network.