Selectivity in Garratt-Braverman Cyclization: An Experimental and Computational Study

Bispropargyl sulfones equipped with aromatic rings of dissimilar nature were synthesized. Under basic conditions, these sulfones isomerized to the bisallenic sulfones, creating a competitive scenario between two alternate Garratt-Braverman (GB) cyclization pathways. The observed product distribution ruled out the involvement of any ionic intermediate and supported the diradical mechanism with greater involvement of the electron-rich aromatic ring via the more nucleophilic radical. DFT-based calculations supported the diradical mechanism along with the observed selectivity.

Growing pseudo-eigenmodes and positive logarithmic norms in rotating shear flows

Rotating shear flows, when angular momentum increases and angular velocity decreases as functions of radiation coordinate, are hydrodynamically stable under linear perturbation. The Keplerian flow is an example of such a system, which appears in an astrophysical context. Although decaying eigenmodes exhibit large transient energy growth of perturbation which could govern nonlinearity in the system, the feedback of inherent instability to generate turbulence seems questionable. We show that such systems exhibiting growing pseudo-eigenmodes easily reach an upper bound of growth rate in terms of the logarithmic norm of the involved non-normal operators, thus exhibiting feedback of inherent instability. This supports the existence of turbulence of hydrodynamic origin in the Keplerian accretion disc in astrophysics. Hence, this answers the question of the mismatch between the linear theory and experimental/observed data and helps in resolving the outstanding question of the origin of turbulence therein.

Diastereospecific Coupling of Imines by Low-Valent Titanium: An Experimental and Computational Study

The reaction of phenylsilane (PhSiH3) and titanium(IV) isopropoxide Ti(OiPr)(4)] generates low-valent titanium alkoxides that reduce and reductively couple imines. The C-C coupling reaction is diastereospecific, with exclusive formation of the (+/-)-isomer. The yield is dependent on the concentration of titanium(IV) isopropoxide used. Using imines with varying electronic demand revealed that the coupling is most efficient for unsubstituted imines. The involvement of a trimeric titanium biradical species is invoked to explain the observed concentration dependence and diastereospecificity in the reaction. Multilayer ONIOM (''our own n-layered integrated molecular orbital and molecular mechanics'') calculations were carried out on the plausible intermediates involved by using the Guassian 09 suite of programs. Formation of the trimeric biradical species leading to the formation of the (+/-)-isomer is more favored than formation of the trimeric biradical species, which leads to the meso-isomer. Similar calculations with dimeric intermediates do not predict the (+/-)-selectivity. Mass spectral analysis of the reaction mixture indicates the presence of a trimeric titanium alkoxide species.

Particle filters for structural system identification using multiple test and sensor data: A combined computational and experimental study

The problem of structural system identification when measurements originate from multiple tests and multiple sensors is considered. An offline solution to this problem using bootstrap particle filtering is proposed. The central idea of the proposed method is the introduction of a dummy independent variable that allows for simultaneous assimilation of multiple measurements in a sequential manner. The method can treat linear/nonlinear structural models and allows for measurements on strains and displacements under static/dynamic loads. Illustrative examples consider measurement data from numerical models and also from laboratory experiments. The results from the proposed method are compared with those from a Kalman filter-based approach and the superior performance of the proposed method is demonstrated. Copyright (C) 2009 John Wiley & Sons, Ltd.

Nanoscale ZnO/CdS heterostructures with engineered interfaces for high photocatalytic activity under solar radiation

Semiconductor based nanoscale heterostructures are promising candidates for photocatalytic and photovoltaic applications with the sensitization of a wide bandgap semiconductor with a narrow bandgap material being the most viable strategy to maximize the utilization of the solar spectrum. Here, we present a simple wet chemical route to obtain nanoscale heterostructures of ZnO/CdS without using any molecular linker. Our method involves the nucleation of a Cd-precursor on ZnO nanorods with a subsequent sulfidation step leading to the formation of the ZnO/CdS nanoscale heterostructures. Excellent control over the loading of CdS and the microstructure is realized by merely changing the initial concentration of the sulfiding agent. We show that the heterostructures with the lowest CdS loading exhibit an exceptionally high activity for the degradation of methylene blue (MB) under solar irradiation conditions; microstructural and surface analysis reveals that the higher activity in this case is related to the dispersion of the CdS nanoparticles on the ZnO nanorod surface and to the higher concentration of surface hydroxyl species. Detailed analysis of the mechanism of formation of the nanoscale heterostructures reveals that it is possible to obtain deterministic control over the nature of the interfaces. Our synthesis method is general and applicable for other heterostructures where the interfaces need to be engineered for optimal properties. In particular, the absence of any molecular linker at the interface makes our method appealing for photovoltaic applications where faster rates of electron transfer at the heterojunctions are highly desirable.