Chemically controlled pattern formation in phase-separating materials

Summary The role of chemical reactions in the selection of patterns in phase-separating mixtures is presented. Linearized theory and computer simulation show that the initial long-wavelength instability characteristic of spinodal decomposition is suppressed by chemical reactions, which restrict domain growth to intermediate length scales even in the late stages of phase separation. Our findings suggest that chemical reactions may provide a novel way to stabilize and tune the steady-state morphology of phase-separating materials. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Simulations of stochastic sensing of proteins

We have performed Langevin dynamics and Poisson-Nernst-Planck calculations to simulate detection of proteins by genetically engineered alpha-hemolysin channels. In the recent stochastic sensing experiments, one end of a flexible polymer chain is permanently anchored inside the protein channel at a specified location, and the other end undergoes complexation with an analyte. Our simulations, using coarse-grained modeling, reproduce all essential qualitative results of the electrophysiology measurements of stochastic sensing. In addition, the underlying macromolecular mechanisms behind stochastic sensing are revealed in vivid details. The entropic fluctuations of the conformations of the tethered polymer chain dictate crucially the unique signatures of the ionic current trace of the channel and provide design rules for successful stochastic sensing. The origin of strong fluctuations in the ionic current of the channel is found to arise from the obstruction of the entrance at the beta-barrel of the channel by the fluctuating segments of the tether. Silencing of the pore is due to the suppression of conformational fluctuations of the chain, and the permanent blockade of ionic current is due to the threading of the tether through the channel. The onset of silencing and permanent blockade of the channel current cannot necessarily be attributed to the capture of analytes. In order for detection events to be timed accurately, the length and anchoring location of the tether must be tuned appropriately.     

Impact of micelles on the biocidal efficiency in a diesel–water interface

Biodegradation occurs in the diesel/water interface in petroleum product pipelines. The microbial contamination can result in inhibitor/fuel degradation, leading to unacceptable levels of turbidity, filter plugging, storage tank corrosion and stored product souring. Therefore, selection of the biocide/inhibitor plays an important role in the transportation of petroleum products through pipelines. Three biocides (cationic and nonionic) were employed to study the biodegradation in a diesel‐water interface. The biocidal efficiency against degradation of diesel was examined by employing Fourier‐transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy and gas chromatography mass spectrometry (GC‐MS) techniques. Bronopol (2‐bromo‐2‐nitro‐propane‐1, 3‐diol) was found to have higher bactericidal efficiency than N‐cetyl‐N,N, N‐trimethyl ammonium bromide (CTAB) and cetyl pyridinum bromide (CPB). But the cationic biocides (CTAB and CPB) showed good biocidal efficiency at the interface. The data are explained in terms of a model that postulates the formation of a ‘micelle’ at the diesel‐water interface. Copyright © 2007 John Wiley & Sons, Ltd.     

Thiosemicarbazone Complexes of Ruthenium(II) and Rhodium(I) Containing Triphenylphosphine

Several new hexa-coordinated ruthenium(II) and penta-coordinated rhodium(I) complexes of the types [RuCl(CO)(PPh ₃ ) ₂ (TSC)], [RuH(CO)(PPh ₃ ) ₂ (TSC)], and [Rh(PPh ₃ ) ₃ (TSC)] (where TSC = anion of thiosemicarbazone Schiff bases) have been prepared by the reactions of [RuHCl(CO)(PPh ₃ ) ₃ ], [RuH ₂ (CO)(PPh ₃ ) ₃ )], and [RhH(PPh ₃ ) ₄ ] with thiosemicarbazones of 2-furaldehyde (H-FTSC), thiophene-2-carboxaldehyde (H-TCTSC), p-anisaldehyde (H-ATSC), piperonaldehyde (H-PTSC), and cyclohexanone (H-CTSC). All the new complexes obtained have been characterized on the basis of elemental analysis, IR, ¹ H NMR, ³¹ P NMR, and electronic spectral data.     

Heteropoly Acids as Heterogeneous and Reusable Catalyst for α-Thiocyanation of Ketones

Simple, efficient, and mild method for α-thiocyanation of ketones in presence of heteropolyacid has been developed. This methodology offered α-oxothiocyanates in good to excellent yields at room temperature in a highly selective manner. The catalyst could be efficiently recovered from the reaction and reused.     

A Comparative Study of Electrochemical Reduction of 4‐Nitrophenyl Covalently Grafted on Gold and Carbon

4‐Nitrophenyl layers were grafted on gold and glassy carbon surfaces by electrochemical reductive adsorption of the corresponding diazonium salt. Electrochemical conversion efficiencies of 4‐nitrophenyl moieties to 4‐aminophenyl moieties on gold versus on glassy carbon in a protic medium were investigated using X‐ray photoelectron spectroscopy (XPS). In total contrast to all previous comparative studies showing greater electrochemical reactivity of aryl diazonium salt‐derived layers on gold than on glassy carbon, a much lower rate of conversion to 4‐aminophenyl was observed on gold than on glassy carbon by both cyclic voltammetry (CV) and chronoamperometry (CA) methods. The lower electron transfer rate during conversion observed on gold versus glassy carbon was proposed to be due to a mechanism related to the molecular structure rearrangement of 4‐nitrophenyl during the process on glassy carbon. However, whilst complete conversion of 4‐nitrophenyl to 4‐aminophenyl on gold by chronoamperometry was achieved, on glassy carbon complete reduction could not be achieved under the same conditions.     

Effect of environment on the degradation of starch and pro-oxidant blended polyolefins

The aim of this study was to understand the rate of degradation of commercial pro-oxidant blended and starch blended High Density Polyethylene (HDPE), pro-oxidant blended Low Density Polyethylene (LDPE), and starch blended polypropylene in three different environments, namely under direct sunlight, buried in soil and immersed in marine waters for a period of 150 days. The bio-fouling parameters were also monitored in the case of polymers deployed in sea water. Exposure to sunlight showed highest weight loss (>10%) and samples buried in soil showed the lowest (∼1%). Pro-oxidant blended HDPE showed higher weight loss when compared to starch blended (22.7 as against 11%). Scanning electron microscopy revealed surface deterioration and decrease in contact angle indicated reduction in surface hydrophobicity. Increase in the carbonyl and hydroxyl groups in the infra-red spectrum of the exposed samples suggested abiotic degradation. Starch blended PP exposed to sunlight showed the highest thermo gravimetric weight loss (63.8%) followed by the same polymer buried in soil (46.1%).