Magnetic properties of single crystal alpha-benzoin oxime: An EPR study

The electron paramagnetic resonance (EPR) spectra of gamma irradiated single crystals of alpha-benzoinoxime (ABO) have been examined between 120 and 440 K. Considering the dependence on temperature and the orientation of the spectra of single crystals in the magnetic field, we identified two different radicals formed in irradiated ABO single crystals. To theoretically determine the types of radicals, the most stable structure of ABO was obtained by molecular mechanic and B3LYP/6-31G(d,p) calculations. Four possible radicals were modeled and EPR parameters were calculated for the modeled radicals using the B3LYP method and the TZVP basis set. Calculated values of two modeled radicals were in strong agreement with experimental EPR parameters determined from the spectra. Additional simulated spectra of the modeled radicals, where calculated hyperfine coupling constants were used as starting points for simulations, were well matched with experimental spectra.     

Role of copper species in the oxidative dimerization of arylboronic acids: synthesis of symmetrical biaryls

Certain Cu(I) and Cu(II) salts are able to mediate the dimerization of arylboronic acids in DMF. They provide the corresponding symmetrical biaryls in moderate to very good yields. It is possible to run the reaction catalytically under an oxygen atmosphere without a significant loss of yields.     

Linear and Nonlinear Optical Properties in Spherical Quantum Dots

We calculate the energy eigenvalues and the sate functions of one-electron Quantum Dot （QD） by using a combination of Quantum Genetic Algorithm （QGA） and Hartre-Fock-Roothaan （HFR） method. The linear and the third-order nonlinear optical absorption coefficients for the 1s-1p, 1p-1d, and 1d-1f transitions are examined as a function of the incident photon energy for three different values of the stoichiometric ratio. The results show that the stoichiometric ratio, impurity, relaxation time, and dot size have great influence on the optical absorption coefficients of QDs.     

The third order nonlinear optical characteristics of amorphous vanadium oxide thin film

We studied the nonlinear absorptive characteristics (saturation intensity threshold and effective nonlinear absorption coefficients) and nonlinear refraction in a 50-nm-thick VO _x thin amorphous film prepared by pulsed DC magnetron reactive sputtering. The absorptive and refractive nonlinearities were investigated by pump–probe and Z-scan techniques. The closed-aperture Z-scan results reveal self-defocussing characteristics of the amorphous VO _x thin film for both nanosecond and picosecond pulse durations. Experimental results show that a phase transition does not occur in the range of intensities used for the experiments and the investigated sample can be treated as an amorphous semiconductor structure. The open-aperture Z-scan curves with nanosecond pulses exhibit saturable absorption for all input intensities. On the other hand, the open-aperture Z-scan curves with picosecond pulses exhibit nonlinear absorption/saturable absorption for low/high input intensities, respectively. Saturation intensity thresholds were found to be 15.3 MW/cm² for 4-ns pulse duration and 586 MW/cm² for 65-ps pulse duration.     

Commutators of sublinear operators generated by Calderón-Zygmund operator on generalized weighted Morrey spaces

In this paper, the boundedness of a large class of sublinear commutator operators T _b generated by a Calderón-Zygmund type operator on a generalized weighted Morrey spaces \({M_{p,\varphi }}(w)\) with the weight function w belonging to Muckenhoupt’s class A _p is studied. When 1 < p < ∞ and b ∈ BMO, sufficient conditions on the pair (φ ₁, φ ₂) which ensure the boundedness of the operator T _b from \({M_{p,\varphi 1}}(w)\) to \({M_{p,\varphi 2}}(w)\) are found. In all cases the conditions for the boundedness of T _b are given in terms of Zygmund-type integral inequalities on (φ ₁, φ ₂), which do not require any assumption on monotonicity of φ ₁(x, r), φ ₂(x, r) in r. Then these results are applied to several particular operators such as the pseudo-differential operators, Littlewood-Paley operator, Marcinkiewicz operator and Bochner-Riesz operator.     

Identification of radiation‐induced radical structure in azocalix[4]arene: an EPR study

A macrocyclic azocalix[4]arene (1) based ester derivative was synthesized. The single crystals of azocalix[4]arene were produced by slow evaporation of concentrated ethyl acetate solutions. These single crystals were exposed to ⁶⁰Co gamma rays with a dose rate of 0.980 kGy h^‐1 for 48 and 72 h to produce a stable free radical. Electron paramagnetic resonance (EPR) measurements were performed in three mutually perpendicular planes of the single crystal in the magnetic field, in addition, temperature dependence of the EPR signal was studied between 120 K and 450 K. The spectra were found to be temperature and angular dependent. Analysis based on the spectra recorded showed that a free radical was formed by fission of a C–H bond. This radical is described as ^?C_aHC_bH₃ The averages of the principal values of the hyperfine parameters and g‐factor are: g = 2.0034, A_Ha = 1.28 mT, A_H1=H2 = 1.00 mT, and A_H3 = 0.49 mT. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis and proton conductivity studies of polystyrene‐based triazole functional polymer membranes

In this study, poly(vinylbenzylchloride) (PVBC) was produced by free‐radical polymerization of 4‐vinylbenzylchloride, and then it was functionalized with 3‐amino‐1,2,4‐triazole (ATri) and 1H‐1,2,4‐triazole (Tri). The composition of the polymers was verified by elemental analysis, and the structure was characterized by Fourier transform infrared and ¹³C‐nuclear magnetic resonance spectra. PVBC was modified by ATri with 68% and Tri with 50% yield. The polymers were doped with trifluoromethanesulfonic acid (TA) at various molar ratios, X = 0.5, 1, 2, and 3 with respect to aminotriazole and triazole units. Proton transfer from TA to the triazole rings was proved with Fourier transform infrared spectroscopy. Thermogravimetric analysis showed that the samples are thermally stable up to approximately 200 °C. Differential scanning calorimetry results illustrated the homogeneity of the materials. Under anhydrous conditions, PVBCATri3TA and PVBCTri3TA showed highest proton conductivity of 0.086 and 0.042 S/cm, respectively. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Asymmetric benzoin reaction catalyzed by benzoylformate decarboxylase

Aromatic aldehydes are converted into benzoins by benzoylformate decarboxylase catalyzed C–C bond formation. The reaction affords (R)-benzoins with high enantiomeric excess and in good chemical yields. A broad range of aromatic aldehydes can be used as substrates in aqueous buffer or buffer/DMSO-solutions.     

Poly(cyclohexene oxide)/clay nanocomposites by photoinitiated cationic polymerization via activated monomer mechanism

Poly(cyclohexene oxide) (PCHO)/clay nanocomposites were prepared by in situ photoinitiated activated monomer cationic polymerization. The polymerization of cyclohexene oxide through the interlayer galleries of the clay can provide distribution of the clay layers in the polymer matrix homogenously and results in the formation of PCHO/clay nanocomposites. The exfoliated structures were characterized by X‐ray diffraction spectroscopy, thermogravimetric analysis, transmission electron microscopy, and atomic force microscopy. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5328–5335, 2009