Structure of the products of condensation of hydroxylamine with trifluoromethyl-beta-diketones: assignments of the diastereotopic protons of the 4-methylene group in 5-hydroxy-5-trifluoromethyl-delta2-isoxazolines

The combined use of 1H NMR spectroscopy with theoretical calculations of chemical shifts (GIAO) and coupling constants (B3LYP/6-311 ++G**) of a 5-hydroxy-5-trifluoromethyl-Delta2-isoxazoline has enabled solving the problem of the assignments of the diastereotopic protons in this compound. This result has been extended to 5-hydroxy-5-trifluoromethyl-Delta2-pyrazolines and the corresponding 5-trichloromethyl derivatives.     

Abiotic metallofoldamers as electrochemically responsive molecules

Described are the design, synthesis, and study of nonbiological molecules based on salophen and salen ligands that fold into single-stranded helices in the presence of either Ni(II) or Cu(II). X-ray diffraction studies show that the materials fold into helical structures in the solid state, and a series of NMR studies provide strong evidence that the folded structures are conserved in solution. Metal coordination is required for folding, as NMR and X-ray show that the free ligands do not adopt helical structures. Two of the racemic metallofoldamers spontaneously resolve during crystallization from CHCl3/acetonitrile, and CD spectroscopy and optical rotation show that the resolved, crystalline materials racemize quickly when dissolved at 5 degrees C. This shows that the secondary structures can reorganize easily and can, therefore, provide the basis for responsive materials. By comparison, an analogue from enantiomerically pure (R,R)-(-)-trans-cyclohexanediamine showed a strong CD signal and a large specific rotation. Electrochemical experiments show that a structural reorganization occurs upon metal-centered reduction of a Cu(II)-containing foldamer. When the reduction is carried out in the presence of coordinating ligands, it is proposed that apical binding of those ligands gives square pyramidal complexes. Semiempirical (AM1) calculations support that the helical structure would be disrupted by the reduction to Cu(I) with concomitant reorganization to a square pyramidal complex.     

Acid catalyzed condensation of isoprene with orcinol: Synthesis of 2,2-dimethylchromans and 5-methylxanthyletin derivatives

Condensation of orcinol with 2-methylbuta-1,3-diene (isoprene) has been achieved in the presence of orthophosphoric acid as catalyst leading to the exclusive formation of 2,2-dimethylchromans in one step. A novel route for the synthesis of 5-methylxanthyletin derivatives is described.     

Ultrasonic degradation of poly(methyl methacrylate-co-alkyl acrylate) copolymers

The copolymers, poly(methyl methacrylate-co-methyl acrylate) (PMMAMA), poly(methyl methacrylate-co-ethyl acrylate) (PMMAEA) and poly(methyl methacrylate-co-butyl acrylate) (PMMABA), of different compositions were synthesized and characterized. The effect of alkyl acrylate content, alkyl group substituents and solvents on the ultrasonic degradation of these copolymers was studied. A model based on continuous distribution kinetics was used to study the kinetics of degradation. The rate coefficients were obtained by fitting the experimental data with the model. The linear dependence of the rate coefficients on the logarithm of the vapor pressure of the solvent indicated that vapor pressure is the crucial parameter that controls the degradation process. The rate of degradation increases with an increase in the alkyl acrylate content. At any particular copolymer composition, the rate of degradation follows the order: PMMAMA > PMMAEA > PMMABA. It was observed that the degradation rate coefficient varies linearly with the mole percentage of the alkyl acrylate in the copolymer.     

Finite size effect on Gd doped CoGdxFe2−xO4 (0.0≤x≤0.5) particles

Nanoparticles of CoGd_xFe_2−xO₄ (where x=0.0, 0.1, 0.3, 0.5) series have been prepared by chemical co-precipitation. The effect of Gd³⁺ ion concentration on crystalline phase, crystallinity, crystallite size, molecular vibrations and magnetic resonance has been investigated in detail. The crystallinity decreases with an increase in Gd³⁺ ion concentration and changes the structural parameters. The spin lattice relaxation has been correlated with the doping ion concentration. Similarly, the superparamagnetic behavior of these particles has been observed with EPR spectroscopy.     

Topological Dyons

Using a two potential approach, dyon solutions have been found in the temporal and non-temporal gauges for a non-Abelian theory. Both the charges, electric and magnetic, of the temporal dyon solution are topological, while for the non-temporal case both charges are partially topological.     

Synthesis, Photo-physical and DFT Studies of ESIPT Inspired Novel 2-(2′,4′-Dihydroxyphenyl) Benzimidazole, Benzoxazole and Benzothiazole

Novel ESIPT inspired benzimidazole, benzoxazole and benzothiazole were synthesized from 2,4-dihydroxy benzoic acid and 1,2-phenelenediamine, 2-aminophenol, and 2-aminothiophenol respectively. The synthesized 2-(2′,4′-dihydroxyphenyl) benzimidazole, benzoxazole and benzothiazole are fluorescent and the emission characteristic are very sensitive to the micro-environment. They show a single absorption and dual emission with large Stokes shift originating from excited state intramolecular proton transfer. The absorption-emission characteristics of all these compounds are studied as a function of pH. The change in the electronic transition, energy levels, and orbital diagrams of synthesized compounds were investigated by the molecular orbital calculation and were correlated with the experimental spectral emission. Experimental absorption and emission wavelengths are in good agreement with those predicted using the Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) [B3LYP/6-31G(d)].

Spin waves transport across a ferrimagnetically ordered nanojunction of cobalt-gadolinium alloy between cobalt leads

A model calculation is presented for the spin wave scattering and coherent transport at the ferrimagnetically ordered cobalt-gadolinium alloy nanojunction between cobalt leads. The structural model for the amorphous alloy nanojunction [Co_1/2Gd_1/2]₃ is considered as an ordered alloy hcp structure of three (0001) atomic planes between the leads. To analyze the spin dynamics and spin wave scattering at the nanojunction boundary, the phase field matching method (PFMT) is implemented over the ground state of the system, in the Heisenberg Hamiltonian representation. The coherent reflection and transmission probabilities of spin waves from the cobalt leads incident onto the nanojunction boundary are calculated, and numerical results are presented for the coherent SW transport across the nanojunction over the entire range of their frequencies. The results are especially valid in the interval between nanometric SW wavelengths greater than the nanojunction width and macroscopic wavelengths. They demonstrate in particular, the possibility of the resonance assisted maxima for the SW transmission spectra owing to the interactions between the incident spin waves and the localized spin resonances on the nanojunction. This effect is general and may be observed at different characteristic frequencies and corresponding incident angles.     

Intra‐laser‐cavity microparticle sensing with a dual‐wavelength distributed‐feedback laser

An integrated intra‐laser‐cavity microparticle sensor based on a dual‐wavelength distributed‐feedback channel waveguide laser in ytterbium‐doped amorphous aluminum oxide on a silicon substrate is demonstrated. Real‐time detection and accurate size measurement of single micro‐particles with diameters ranging between 1 µm and 20 µm are achieved, which represent the typical sizes of many fungal and bacterial pathogens as well as a large variety of human cells. A limit of detection of ∼500 nm is deduced. The sensing principle relies on measuring changes in the frequency difference between the two longitudinal laser modes as the evanescent field of the dual‐wavelength laser interacts with micro‐sized particles on the surface of the waveguide. Improvement in sensitivity far down to the nanometer range can be expected upon stabilizing the pump power, minimizing back reflections, and optimizing the grating geometry to increase the evanescent fraction of the guided modes.