Difference spectroscopic studies on binding of Cibacron blue F3GA to ribosome inactivating proteins: effect of beta-mercaptoethanol on the interaction with ricin

The interaction of Cibacron blue F3GA with ribosome inactivating proteins, ricin, ricin A-chain and momordin has been investigated using difference absorption spectroscopy. Ricin was found to bind the dye with a 20- and 2-fold lower affinity than ricin A-chain and momordin, respectively. A time dependent increase in the amplitude of Cibacron blue difference spectrum in the presence of ricin was observed on addition of beta-mercaptoethanol. Analysis of the kinetic profile of this increase showed a biphasic phenomenon and the observed rates were found to be independent of the concentration of beta-mercaptoethanol. Kinetics of reduction of the intersubunit disulphide bond in ricin by beta-mercaptoethanol showed that reduction pet se is a second order reaction. Therefore, the observed changes in the difference spectra of Cibacron blue probably indicate a slow change in the conformation of ricin, triggered by reduction of the intersubunit disulphide bond.

Nanoporous Pt with High Surface Area by Reaction-Limited Aggregation of Nanoparticles

Nanoporous structures with high active surface areas are critical for a variety of applications. Here, we present a general templateless strategy to produce such porous structures by controlled aggregation of nanostructured subunits and apply the principles for synthesizing nanoporous Pt for electrocatalytic oxidation of methanol. The nature of the aggregate produced is controlled by tuning the electrostatic interaction between surfactant-free nanoparticles in the solution phase. When the repulsive force between the particles is very large, the particles are stabilized in the solution while instantaneous aggregation leading to fractal-like structures results when the repulsive force is very low. Controlling the repulsive interaction to an optimum, intermediate value results in the formation of compact structures with very large surface areas. In the case of Pt, nanoporous clusters with an extremely high specific surface area (39 m(2)/g) and high activity for methanol oxidation have been produced. Preliminary investigations indicate that the method is general and can be easily extended to produce nanoporous structures of many inorganic materials.

Enantiospecific approach to the tricyclic core structure of tricycloillicinone, ialibinones, and takaneones via ring-closing metathesis reaction

Enantiospecific synthesis of the tricyclic core structure present in the biologically active natural products tricycloillicinone, ialibinones, and takaneones, starting from the readily available campholenaldehyde employing a transannular RCM reaction as the key step, has been accomplished.

Development of temperature-tolerant strains of Thiobacillus ferrooxidans to improve bioleaching kinetics

An isolate of Thiobacillus ferrooxidans derived from gold mine water samples was repeatedly subcultured at increasing temperatures (from 30 degrees to 42 degrees C) in 9K medium. The temperature-adapted strain was found to be more efficient in the bioleaching of pyrite mineral than the wild type. When temperature-tolerant strains were cultured repeatedly in 9K medium at 30 degrees C, the temperature tolerance was completely lost, These results indicate that the temperature tolerance was stress-dependent and not a permanent trait of the adapted strain, The potential utility of such temperature-tolerant strains of Thiobacillus ferrooxidans in sulphide mineral dissolution is demonstrated.

Metal-free graphitic carbon nitride as mechano-catalyst for hydrogen evolution reaction

Graphitic carbon nitride (g-C3N4), as a promising metal-free catalyst for photo-catalytic and electrochemical water splitting, has recently attracted tremendous research interest. However, the underlying catalytic mechanism for the hydrogen evolution reaction (HER) is not fully understood. By using density functional theory calculations, here we have established that the binding free energy of hydrogen atom (ΔGH∗0) on g-C3N4 is very sensitive to mechanical strain, leading to substantial tuning of the HER performance of g-C3N4 at different coverages. The experimentally-observed high HER activity in N-doped graphene supported g-C3N4 (Zheng et al., 2014) is actually attributed to electron-transfer induced strain. A more practical strategy to induce mechanical strain in g-C3N4 is also proposed by doping a bridge carbon atom in g-C3N4 with an isoelectronic silicon atom. The calculated ΔGH∗0 on the Si-doped g-C3N4 is ideal for HER. Our results indicate that g-C3N4 would be an excellent metal-free mechano-catalyst for HER and this finding is expected to guide future experiments to efficiently split water into hydrogen based on the g-C3N4 materials.

A pilot study in different unstable designs on the biomechanical effect of gait characteristics

The purpose of this study was to compare kinematics and kinetics during walking for healthy subjects using unstable shoes with different designs. Ten subjects participated in this study, and foot biomechanical data during walking were quantified using motion analysis system and a force plate. Data were collected for unstable shoes condition after accommodation period of one week. With soft material added in the heel region, the peak impact force was effectively reduced when compared among similar shapes. In addition, the soft material added in the rocker bottom showed more to be in dorsiflexed position during the initial stance. The shoe with three rocker curves design reduced the contact area in the heel strike, which may result in increasing human body forward speed. Further studies shall be carried out after adapting to long periods of wearing unstable shoes.

Acid-catalysed cyclisations: structures of novel products isolated in the reaction of 2-[3-(2,6-dimethoxyphenyl)but-2-enyl]-2-methylcyclopentane-1,3-dione with MeOH-HCl

Reaction of the title compound (1a) with anhydrous MeOH-HCl gave 2-endo-(2,6-dimethoxyphenyl)-2-exo-methyl-5-methylbicyclo[3.2.1]octane-6,8-dione (3a), 1,5,14-timethoxy-5,8-seco-6,7-dinorestra-1,3,5(10),9(11)-tetraen-17-one (4), 1,5-dimethoxy-5,8-seco-6,7-dinorestra-1,3,5(10),8,14-pentaen-17-one (5), and 3,4,5,6-tetrahydro-2,7-dimethoxy-3,6-dimethyl-3,2,6-(13-oxopropan[1]yI[3]ylidene)-2H-1-benzoxocin (6). Structures assigned to compounds (3a), (4), and (6) are based on spectral data. The exo-tricyclic acetal structure (6) was further confirmed by the analysis of the 1H n.m.r. spectra of the isomeric alcohols (11) and (12), obtained by sodium borohydride reduction of (6).

Vilsmeier reaction on some 6- and 7-methoxy-1- and 2-tetralones.

Vilsmeier reaction on a few representative 6- and 7-methoxy-1- and 2-tetralones has been investigated. While 1-tetralones give the corresponding 1-chloro-2-formyl3, 4-dihydronaphthalenes, the 2-tetralones afford 1,3-bisformyl-2-chloronaphthalenes. Spectral characteristics of all the products obtained are given and a mechanistic proposal has been made to explain the observed chlorobisformylation.

The carbon dioxide hydration activity of the sulfonamide-resistant carbonic anhydrase from the liver of male rat: pH independence of the steady-state kinetics

The steady-state kinetic constants for the catalysis of CO2 hydration by the sulfonamide-resistant and testosterone-induced carbonic anhydrase from the liver of the male rat has been determined by stopped-flow spectrophotometry. The turnover number was 2.6 ± 0.6 × 103 s− at 25 °C, and was invariant with pH ranging from 6.2 to 8.2 within experimental error. The Km at 25 °C was 5 ± 1 mImage , and was also pH independent. These data are in quantitative agreement with earlier findings of pH-independent CO2 hydration activity for the mammalian skeletal muscle carbonic anhydrase isozyme III. The turnover numbers for higher-activity isozymes I and II are strongly pH dependent in this pH range. Thus, the kinetic status of the male rat liver enzyme is that of carbonic anhydrase III. This finding is consistent with preliminary structural and immunologic data from other laboratories.

A laser flash photolysis study of pivalothiophenone triplets: steric and electronic effects in thione photoreaction kinetics

Upon laser pulse excitation (Aex = 532 nm) into the lowest-lying '(n,a*) band system, pivalothiophenones in benzene solutions give rise to short-lived triplets (Ama: = 325-335 nm, em: = (1 1-15) X lo3 M-' cm-I) with quantitative intersystem crossing efficiencies. The triplet yields decrease slightly (by 10-30%) upon changing A, to 308 nm (Le., upon excitation into S2). Kinetic data are presented for intrinsic triplet lifetimes, self-quenching, and quenching by oxygen, di-tert-butylnitroxy radical, and various reagents capable of interacting with the triplets via energy, electron, or hydrogen-atom transfer and by biradical formation (possibly leading to cycloaddition). The mechanisms of the quenching processes are discussed. Relative to rigid aromatic thiones, namely, xanthione and thiocoumarin, the interaction of pivalothiophenone triplets with most of the quenchers are kinetically inefficient. This is interpreted primarily as a manifestation of the steric crowding at positions a to the thiocarbonyl group.

Kinetics of thermal decomposition of strontium zirconyl carbonate, Sr2Zr2O5CO3

The kinetics of decomposition of the carbonate Sr2Zr2O5CO3, are greatly influenced by the thermal effects during its formation. (α−t) curves are found to be sigmoidal and they could be analysed based on power law equations followed by first-order decay. The presence of carbon in the vacuum-prepared sample of carbonate has a strong deactivating effect. The carbonate is fairly crystalline and its decomposition leads to the formation of crystalline strontium zirconate.

Simplified Mathematical Model for Effects of Freezing on the Low-Temperature Performance of the Lead-Acid Battery

Discharge periods of lead-acid batteries are significantly reduced at subzero centigrade temperatures. The reduction is more than what can he expected due to decreased rates of various processes caused by a lowering of temperature and occurs despite the fact that active materials are available for discharge. It is proposed that the major cause for this is the freezing of the electrolyte. The concentration of acid decreases during battery discharge with a consequent increase in the freezing temperature. A battery freezes when the discharge temperature falls below the freezing temperature. A mathematical model is developed for conditions where charge-transfer reaction is the rate-limiting step. and Tafel kinetics are applicable. It is argued that freezing begins from the midplanes of electrodes and proceeds toward the reservoir in-between. Ionic conduction stops when one of the electrodes freezes fully and the time taken to reach that point, namely the discharge period, is calculated. The predictions of the model compare well to observations made at low current density (C/5) and at -20 and -40 degrees C. At higher current densities, however, diffusional resistances become important and a more complicated moving boundary problem needs to be solved to predict the discharge periods. (C) 2009 The Electrochemical Society.

Ultrafast and reversible multiblock formation by the SET-Nitroxide radical coupling reaction

The single electron transfer-nitroxide radical coupling (SET-NRC) reaction has been used to produce multiblock polymers with high molecular weights in under 3 min at 50◦C by coupling a difunctional telechelic polystyrene (Br-PSTY-Br)with a dinitroxide. The well known combination of dimethyl sulfoxide as solvent and Me6TREN as ligand facilitated the in situ disproportionation of CuIBr to the highly active nascent Cu0 species. This SET reaction allowed polymeric radicals to be rapidly formed from their corresponding halide end-groups. Trapping of these carbon-centred radicals at close to diffusion controlled rates by dinitroxides resulted in high-molecular-weight multiblock polymers. Our results showed that the disproportionation of CuI was critical in obtaining these ultrafast reactions, and confirmed that activation was primarily through Cu0. We took advantage of the reversibility of the NRC reaction at elevated temperatures to decouple the multiblock back to the original PSTY building block through capping the chain-ends with mono-functional nitroxides. These alkoxyamine end-groups were further exchanged with an alkyne mono-functional nitroxide (TEMPO–≡) and ‘clicked’ by a CuI-catalyzed azide/alkyne cycloaddition (CuAAC) reaction with N3–PSTY–N3 to reform the multiblocks. This final ‘click’ reaction, even after the consecutive decoupling and nitroxide-exchange reactions, still produced high molecular-weight multiblocks efficiently. These SET-NRC reactions would have ideal applications in re-usable plastics and possibly as self-healing materials.