Exercising regiocontrol in palladium-catalyzed asymmetric prenylations and geranylation: unifying strategy toward flustramines A and B

Pd-catalyzed asymmetric prenylation of oxindoles to afford selectively either the prenyl or reverse-prenyl product has been demonstrated. Control of the regioselectivity in this transformation is governed by the choice of ligand, solvent, and halide additive. The resulting prenylated and reverse-prenylated products were transformed into ent-flustramides and ent-flustramines A and B. Additionally, control of the regio- and diastereoselectivity was obtained using π-geranylpalladium complexes.     

Horse radish peroxidase immobilized polyaniline for hydrogen peroxide sensor

Horse radish peroxidase (HRP) has been electrochemically entrapped into perchlorate (ClO) doped polyaniline (PANI) film deposited onto indium‐tin‐oxide (ITO) coated glass plate. This HRP‐PANI‐ClO/ITO bioelectrode characterized using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), UV‐Visible spectroscopy, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) techniques has been utilized for estimation of hydrogen peroxide (H₂O₂). This H₂O₂ sensor exhibits response time of 5 s, linearity from 3 to 136 mM, sensitivity as 0.5638 µA mM^?1 cm^?2 with linear regression of 0.985. The value of the Michaelis–Menten constant (K_m) has been obtained as 1.984 mM. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis of fused bicyclic systems with nitrogen atom at the bridgehead, including indolizidines and quinolizidines

Monocyclic as well as fused bicyclic systems with a nitrogen 10 atom at the bridgehead, including indolizidines and quinolizidines, can be prepared in four steps from N-Boc β-lactams. These easily prepared, highly robust, and flexible building blocks allow the incorporation of chirality and structural diversity, rendering the method feasible for diversity- as well as target-oriented synthesis.     

Surface Coating Rescues Proteins from Magnetite Nanoparticle Induced Damage

The presence of magnetic nanoparticles (NPs) in physiological systems induces toxicity through its effects on mitochondrial function and reactive oxygen species (ROS) imbalance. Magnetic NP induced cytotoxicity has been elaborately evaluated for impending threats, however, a detailed investigation is lacking. It is shown that the interaction of Fe₃O₄ NPs with cytochrome c can lead to different events based on the NPs to protein ratio, the solution conditions, and the type of surface protection. At low NPs concentration, rapid binding and subsequent electron transfer are the preferred events while at higher concentration slow oxidative modification of the protein is initiated. The slow event of protein modification yields conformational disorientation, loss of stability, and formation of amyloid‐like structures with cytochrome c. The possibility that the NP induced oxidative stress and age can work in concert to compromise different aspects of cellular quality control processes is discussed. Suitable surface modifications of the NPs inhibit their direct binding to the protein molecules and minimize NP induced toxicity.     

Mean-velocity distributions of contra-swirling coaxial,confined jets

Conclusions From the study, it is observed that introduction of swirl in the central jet enhances the merger whereas higher swirl in the annulus enhances both mixing and flow development. On qualitative comparison with similar works (Gouldin et al. 1985; Ramos and Sommer 1983) it is seen that imposition of pressure gradient in form of expanded confinement enhances the capability of formation of central recirculation core. Wall static pressure distribution also gives an indication of the wall recirculation size.     

Triphenylmethyl hexafluoroarsinate-initiated polymerization of 1,2-butylene oxide

The polymerization of 1,2-butylene oxide initiated with triphenylmethyl hexafluoroarsinate in the ?20 to +25°C temperature range with 1,2-dichloroethane as solvent is characterized by a rapid nonstationary initial stage. This is followed by a second slower stage, during which the disappearance of monomer is first-order with respect to its concentration. The conversion of monomer at the end of the first stage is related to the initial catalyst concentration but not to the initial monomer concentration. Invoking the hypothesis of an instantaneous initiation reaction, the experimental results lead to the conclusion of the existence of a unimolecular termination step. Propagation-to-termination rate constant ratios yield a propagation–termination activation energy difference of 5.9 kcal/mole. The termination step proposed is thought to involve the formation of stable macrocyclic oxonium ions. These, in turn, can reactivate the polymerization by an intramolecular reaction leading to the formation of new active centers. An energy of activation of 8.7 kcal/mole was calculated for this reactivation. GPC analyses of the reaction products recovered at the end of the first stage revealed the presence of large proportions of oligomers. Based on kinetic data, the formation of oligomers is explained by a backbiting process similar to the reactivation reaction suggested for the initiation of the second stage.     

Thermal studies of N-(p-Hexyloxybenzylidene)-p-Toluidene (HBT)

The effect of quenching on phase transitions in monotropic liquid crystal HBT is investigated using DSC, DTA, X-ray diffraction and microscopic techniques. The phases which are normally seen only during the cooling cycle are observed when the substance is quenched from the isotropic liquid phase at appropriate rate.     

Study of copolymer–copolymer interactions and formation of intermacromolecular complexes

Interpolymer complex formation has been studied between methacrylic acid-methacrylamide copolymer and acrylic acid–acrylamide copolymer. The respective co-monomer units of the two copolymers enter into complex formation through H-bonding and ion dipole interactions. The unreacted units in the copolymer complex also interact with homopolymers such as PEO and PVP to form ternary complex. Formation of complexes and replacement reactions could be shown through several experimental techniques, e.g., viscometry, conductometry, and potentiometry.