A theoretical study of the [4 + 4] dimerization of thioformylketene

[reaction and structure: see text] A theoretical study (B3LYP and G3MP2B3) of the dimerization of thioformylketene (1) was performed. Four pathways-two [4 + 2] pathways with thioformylketene (1), one [4 + 4] pathway with 1, and one [4 + 2] pathway involving 1 and thietone (11)-were considered. Interestingly, the [4 + 4] pathway with 1 had the lowest barrier (3.8 kcal/mol). The geometry of the transition state TS14 is unusual, with the forming bonds in the plane of the ketene. This suggests that the reaction is pseudopericyclic.     

Stopped-flow kinetics of tetrazine cycloadditions; experimental and computational studies toward sequential transition states

The Diels-Alder cycloadditions of tetrazines (1) with alkynes (2) are expected to give bicyclic adducts (3). Kinetic measurements of the cycloadditions of 1a and 1b with 2a give DeltaG(++) = 19.2 +/- 1.0 and 11.5 +/- 1.2 kcal/mol, respectively. Stopped-flow UV studies on the reaction of 1b with 2a show an isosbestic point at 428 nm; this places an upper limit of 11.6 +/- 2.6 kcal/mol on DeltaG(++) for loss of N(2) from the putative bicyclic intermediate 3b. Calculations (B3LYP/6-31G(d,p) + ZPVE) of transition structures for the reaction of tetrazinediacid 1d with propynylamine 2c are consistent with the experimental results for the reaction of 1b with 2a. This and several related model systems reveal two interesting features of the calculated energy surfaces. First, there may be no barrier for the loss of nitrogen from structures 3 and thus there may be two sequential transition states. This also extends Berson's correlation of activation energy with reaction energy in pericyclic reactions to significantly lower barriers. Second, for the cycloaddition of 4e and 2c, there is neither an intermediate nor a transition state between TS3e and the final product 6e. It appears that the energy surface "turns a corner" in the vicinity of a structure resembling 5e. This is not a mathematically well-defined point but has chemical consequences in that the overall exothermicity of the reaction from 4e to 6e is not felt in TS3e.     

Improved Modification of the Closed-Loop-Controlled AC-AC Resonant Converter for Induction Heating

A single-switch parallel resonant converter for induction heating is implemented. The circuit consists of an input LC-filter, a bridge rectifier, and a controlled power switch. The switch operates in soft commutation mode and serves as a high frequency generator. The output power is controlled via the switching frequency. A steady state analysis of the converter operation is presented. A closed-loop circuit model is also presented, and the experimental results are compared with the simulation results.     

An evolutionary approach for personalization of content delivery in e-learning systems based on learner behavior forcing compatibility of learning materials

This paper presents an evolutionary approach for personalizing learning content for individual learners from a very large database in an e-learning system. The proposed work improves the quality of the self-learning process in an adaptive e-learning system by providing the most suitable content for individual learners. The paper depicts the results of personalizing the learning process by tuning the compatibility level of the learning objects with respect to the learning style of the learner, the complexity level of the learning objects with respect to the knowledge level of the learner and the interactivity level of the learner based on the satisfaction level of the learner during the learning process using a modified form of genetic algorithm named as Compatible Genetic Algorithm (CGA). The proposed work improves the efficiency of the genetic algorithms by forcing compatibility in the learning objects which has not been implemented so far in existing systems. Forcing compatibility into the search space not only helps to reduce the search space but also fills the search space with better chromosomes. The results show improvement in scores of the learners and also in their satisfaction levels. A comparison with the standard algorithms shows improvement in execution time, number of executing generations and fitness values. The results indicate that personalization of content delivery based on behavioral traits of learners leads to better learning.     

Synthesis,crystal growth and characterisation of 2-aminomethylpyridinium picrate (2-ampp)-a charge transfer molecular complex and organic nonlinear optical material

Single crystals of 2-aminomethylpyridinium picrate (2-AMPP) were grown by slow evaporation-solution growth technique at room temperature. The cell and structural parameters of the grown crystal were determined by single crystal X-ray diffraction analysis. The characteristic functional groups in the compound were identified from Fourier transform infrared spectroscopy. The transmission and absorption spectra of this crystal show that the lower cut-off wavelength lies at 360 nm. Thermal analysis was performed to study the thermal stability of the grown crystal. The powder second harmonic generation efficiency of the grown crystal measured by Kurtz technique is 2 times efficient than potassium dihydrogen orthophosphate (KDP). Vicker's microhardness test showed that the hardness value increases with increasing the applied load up to 50 g. The dielectric measurements of the compound in the frequency region from 50 Hz to 5 MHz showed that the material has lesser defects and can be used for optical application.     

Synthesis,spectral and thermal characterization of Bis(diethylammonium) tetrachloromercurate(II)-An nonlinear optical material

A new semiorganic compound, bis(diethylammonium) tetrachloromercurate(II) was grown by slow evaporation solution growth technique at ambient temperature from its aqueous solution. The crystal system and the cell parameters have been identified from the powder X-ray diffraction pattern. The UV–visible absorption of the compound shows absorption at 246 nm and there is absorption observed in the entire visible region indicates that the compound can be used as a nonlinear optical material. The UV–visible transmittance spectrum of grown crystal shows a lower cut-off wavelength at 275 nm and it was found that the crystal is suitable for optoelectronic applications. Thermal studies were carried out to find out the thermal stability and confirm the stoichiometric ratio of the compound. The thermal anomalies in DSC study indicate the occurrence of first order transition in the compound at low temperatures. The FTIR spectrum of the compound characterizes various functional groups. The various kinds of protons and carbons were assigned through NMR (¹H and ¹³C) spectroscopic techniques. The SHG efficiency of the compound was studied by Kurtz-Perry power technique and observed that it has SHG efficiency 1.5 times greater than that of potassium dihydrogen phosphate (KDP). The dielectric constant and dielectric loss of the compound decreases with increase in frequency.     

Mechanistic Study of the Titanocene(III)‐Catalyzed Radical Arylation of Epoxides

An atom‐economical and catalytic arylation of epoxide‐derived radicals is described. The key step of the catalytic system is a sequential electron and proton transfer for the rearomatization of the radical σ‐complex and catalyst regeneration. Kinetic, computational, spectroscopic, and cyclovoltammetric investigations highlight the key issues of the reaction mechanism and catalyst stabilization by collidine hydrochloride. Studies employing radicophiles rule out the participation of cations as reactive intermediates.     

Strategies for controlling the active layer morphologies in OPVs

This review focuses on the recent developments in our understanding of active layer morphologies for organic photovoltaic cells and approaches to obtain active layer morphologies for high power conversion efficiencies. The evolution of active layer morphologies, as studied by high resolution electron microscopy, X-ray and neutron scattering, and dynamic secondary ion mass spectrometry, is covered, along with strategies including the use of small molecule additives, polymer nanowires and polymer nanoparticles to realize active layer morphologies. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Mechanistic study of samarium diiodide-HMPA initiated 5-exo-trig Ketyl-Olefin coupling: the role of HMPA in post-electron transfer steps

The mechanistic importance of HMPA and proton donors (methanol, 2-methyl-2-propanol, and 2,2,2-trifluoroethanol) on SmI2-initiated 5-exo-trig ketyl-olefin cyclizations has been examined using stopped-flow spectrophotometric studies. In the presence of HMPA, the rate order of proton donors was zero and product studies showed that they had no impact on the diastereoselectivity of the reaction. Conversely, reactions were first-order in HMPA, and the additive displayed saturation kinetics at high concentrations. These results were consistent with HMPA being involved in a rate-limiting step before cyclization, where coordination of the intermediate ketyl to the sterically congested Sm(III)HMPA both stabilizes the intermediate and inhibits cyclization. Liberation of the contact ion pair through displacement by an equivalent of HMPA provides a solvent-separated ion pair releasing the steric constraint to ketyl-olefin cyclization. The mechanism derived from rate studies shows that HMPA is important not only in increasing the reduction potential of Sm(II) but also in enhancing the inherent reactivity of the radical anion intermediate formed after electron transfer through conversion of a sterically congested contact ion pair to a solvent-separated ion pair. The mechanistic complexity of the SmI2-HMPA-initiated ketyl-olefin cyclization is driven by the high affinity of HMPA for Sm(III), and these results suggest that simple empirical models describing the role of HMPA in more complex systems are likely to be fraught with a high degree of uncertainty.