Kinetics and mechanism of the oxidation of acetaldehyde by chromic acid in perchloric acid

Summary The oxidation of MeCHO by chromium(VI) has been studied in HClO₄ medium over a wide range of experimental conditions and has been found to obey the rate law;v=k[MeCHO][HCrO ₄ ^– ][H⁺]. The calculated H and-S values for the reaction are 30±2kJ mol^–1 and 171±7J mol^–1deg^–1, respectively. The mechanism is discussed in terms of carbon-hydrogen bond cleavage.     

Ternary complexes of substituted catechols and catecholamines

Stability constants of the ternary complexes [CuAL] whereA = 5-Nitro-1,10-phenanthroline, bis(2-pyridyl) ketone (DPK) orbis(2-pyridyl)amine (DPA) andL is the dianion of catechol, tiron, protocatechic acid, pyrogallol, 1,8-dihydroxynaphthalene, catecholaldehyde, 2,3-dihydroxynaphthalene, dopamine or adrenaline have been determined by potentiometric titration in dioxane water (1:1 v/v) medium using a SCOGS computer programme. The observed trend of stability is explained on the basis of the nature of substitution over the ligands, chelate ring size and also the composition of mixed solvent in case of DPK. Structural changes in DPK have also been discussed as a function of pH, composition of medium and coordinating mode of the secondary ligand in the ternary complexes.     

Comment on the CP-violating electric charge of the magnetic monopole

It is shown, using an effective theory, that the electric charge that develops on a magnetic monopole, due to the presence of the CP-violating term \([\theta e^2 /(32\pi ^2 )]F_{\mu v}^a \tilde F^{\mu va} \) , does not vanish for massless fermions.     

Parameterization of peptide 13C carbonyl chemical shielding anisotropy in molecular dynamics simulations.

NMR chemical shielding anisotropy (CSA) relaxation is an important tool in the study of dynamical processes in proteins and nucleic acids in solution. Herein, we investigate how dynamical variations in local geometry affect the chemical shielding anisotropy relaxation of the carbonyl carbon nucleus, using the following protocol: 1) Using density functional theory, the carbonyl (13)C' CSA is computed for 103 conformations of the model peptide group N-methylacetamide (NMA). 2) The variations in computed (13)C' CSA parameters are fitted against quadratic hypersurfaces containing cross terms between the variables. 3) The predictive quality of the CSA hypersurfaces is validated by comparing the predicted and de novo calculated (13)C' CSAs for 20 molecular dynamics snapshots. 4) The CSA fluctuations and their autocorrelation and cross correlation functions due to bond-length and bond-angle distortions are predicted for a chemistry Harvard molecular mechanics (CHARMM) molecular dynamics trajectory of Ca(2+)-saturated calmodulin and GB3 from the hypersurfaces, as well as for a molecular dynamics (MD) simulation of an NMA trimer using a quantum mechanically correct forcefield. We find that the fluctuations can be represented by a 0.93 scaling factor of the CSA tensor for both R(1) and R(2) relaxations for residues in helix, coil, and sheet alike. This result is important, as it establishes that (13)C' relaxation is a valid tool for measurement of interesting dynamical events in proteins.     

Pervaporation from a dense membrane: roles of permeant-membrane interactions, Kelvin effect, and membrane swelling

Dense polymeric membranes with extremely small pores in the form of free volume are used widely in the pervaporative separation of liquid mixtures. The membrane permeation of a component followed by its vaporization on the opposite face is governed by the solubility and downstream pressure. We measured the evaporative flux of pure methanol and 2-propanol using dense membranes with different free volumes and different affinities (wettabilities and solubilities) for the permeant. Interestingly, the evaporative flux for different membranes vanished substantially (10-75%) below the equilibrium vapor pressure in the bulk. The discrepancy was larger for a smaller pore size and for more wettable membranes (higher positive spreading coefficients). This observation, which cannot be explained by the existing (mostly solution-diffusion type) models ofpervaporation, suggests an important role for the membrane-permeant interactions in nanopores that can lower the equilibrium vapor pressure. The pore sizes, as estimated from the positron annihilation, ranged from 0.2 to 0.6 nm for the dry membranes. Solubilities of methanol in different composite membranes were estimated from the Flory-Huggins theory. The interaction parameter was obtained from the surface properties measured by the contact angle goniometry in conjunction with the acid-base theory of polar surface interactions. For the membranes examined, the increase in the "wet" pore volume due to membrane swelling correlates almost linearly with the solubility of methanol in these membranes. Indeed, the observations are found to be consistent with the lowering of the equilibrium vapor pressure on the basis of the Kelvin equation. Thus, a higher solubility or selectivity of a membrane also implies stronger permeant-membrane interactions and a greater retention of the permeant by the membrane, thus decreasing its evaporative flux. This observation has important implications for the interpretation of existing experiments and in the separation of liquid mixtures by pervaporation.     

Electrocatalytic activity of binary Palladium Ruthenium anode catalyst on Ni-support for ethanol alkaline fuel cells

In search for a cheaper anode catalyst for the oxidation of ethanol for development of direct alcohol fuel cells, Pd has been considered here as an interesting substitute for Pt in Pt Ru binary electrodeposite. The binary catalyst when co-deposited on nickel support has been found to increase the current density and decrease the anodic overvoltage significantly with respect to pure Pt, Pd and Ni. Its electrocatalytic capability is also comparable with that of the Pt-Ru binary electrocatalyst on Ni-support, when studied in 1 M EtOH containing 1 M NaOH solution. The effect of loading of Pd Ru electrocatalyst on Ni support has also been tested. The electrocatalytic activity of the electrodes for oxidation of ethanol has been explained by studies of cyclic voltammetry, chronopotentiometry, steady-state polarization, and conjugated scanning electron microscopy–energy dispersion X-ray spectroscopy. It has been found that electrode containing the higher amount of deposit are less affected by carbonaceous poisons.     

Biyclo[2.2.1]heptane as cyclopentane precursor. Part 4 Stereocontrolled syhthesis of a potential intermediate to chromophycane dolastane and clavularane

The regio– and stereoselective synthesis of the keto-esters 20 and 22 are described, the latter being a potential intermediate to several diterpenes. The key steps involve the Diels-Alder cycloaddition between the benzocycloheptenone 5 and cyclopentadiene followed by a regioselective functionalisation of the adduct 6. A remarkable reversal of regioselectivity was observed during oxymercuration of the unsymmetric double bond in 6 and its reduced product 11 leading to 8 and 12 which were subsequently transformed to 20 and 22 respectively.     

Biotechnological storage and utilization of entrapped solar energy

Our laboratory has recently developed a device employing immobilized F₀F₁ adenosine triphosphatase (ATPase) that allows synthesis of adenosine triphosphate (ATP) from adenosine 5′-diphosphate and inorganic phosphate using solar energy. We present estimates of total solar energy received by Earth’s land area and demonstrate that its efficient capture may allow conversion of solar energy and storage into bonds of biochemicals using devices harboring either immobilized ATPase or NADH dehydrogenase. Capture and storage of solar energy into biochemicals may also enable fixation of CO₂ emanating from polluting units. The cofactors ATP and NADH synthesized using solar energy could be used for regeneration of acceptor d-ribulose-1,5-bisphosphate from 3-phosphoglycerate formed during CO₂ fixation.     

2-(2-Selenocyanic acid ethyl ester)-1H-benz[de] isoquinoline-1,3-(2H)-dione, synthesis photophysics and interaction with bovine serum albumin: a spectroscopic approach

The compound 2-(2-selenocyanic acid ethyl ester)-1H-benz[de] isoquinoline-1,3-(2H)-dione (SEBID), a ubiquitous, bioactive naphthalimide derivative is expected to possess an anticancer, anti-tumor and other important therapeutic activities of significant potency with low systematic toxicity. In this paper, the synthesis of the compound, photophysics of the newly prepared naphthalimide derivative and its interaction with model transport protein Bovine serum albumin (BSA) have been reported using the absorption and steady state fluorescence spectroscopic techniques exploiting the intrinsic fluorescence emission properties of BSA as a probe. Interaction of this organoselenium compound in different dioxane-water mixtures with increase in the polarity of the medium has been studied spectroscopically. Interaction of SEBID with BSA leads to a dramatic decrease in the fluorescence intensity of BSA, which suggests the binding of SEBID with the tryptophan residue of BSA. Furthermore, different thermodynamic parameters for SEBID-BSA interaction have been calculated. Rationalization of the data has been attempted, particularly in relation to prospective applications in the biomedical research.     

An interesting ring contraction of a class of bromohydrins and trans-dibromides

An efficient ring contraction of stereoisomeric 1,2-benzo-4-bromo-3-hydroxycyclohept-1-ene and their derivatives (1a-e) to (2a-c) is reported, and a probable mechanism for this ring contraction has been suggested.