Conformational analysis of 3‐methyl‐3‐silathiane and 3‐fluoro‐3‐methyl‐3‐silathiane

The conformational equilibria of 3‐methyl‐3‐silathiane 5 , 3‐fluoro‐3‐methyl‐3‐silathiane 6 and 1‐fluoro‐1‐methyl‐1‐silacyclohexane 7 have been studied using low temperature ¹³C NMR spectroscopy and theoretical calculations. The conformer ratio at 103 K was measured to be about 5 _ax: 5 _eq = 15:85, 6 _ax: 6 _eq = 50:50 and 7 _ax: 7 _eq = 25:75. The equatorial preference of the methyl group in 5 (0.35 kcal mol^?1) is much less than in 3‐methylthiane 9 (1.40 kcal mol^?1) but somewhat greater than in 1‐methyl‐1‐silacyclohexane 1 (0.23 kcal mol^?1). Compounds 5–7 have low barriers to ring inversion: 5.65 (ax → eq) and 6.0 (eq → ax) kcal mol^?1 ( 5 ), 4.6 ( 6 ), 5.1 (Me_ax → Me_eq) and 5.4 (Me_eq → Me_ax) kcal mol^?1 ( 7 ). Steric effects cannot explain the observed conformational preferences, like equal population of the two conformers of 6 , or different conformer ratio for 5 and 7 . Actually, by employing the NBO analysis, in particular, considering the second order perturbation energies, vicinal stereoelectronic interactions between the Si–X and adjacent C–H, C–S, and C–C bonds proved responsible. Copyright © 2010 John Wiley & Sons, Ltd.     

CH3NH3PbI3/poly‐3‐hexylthiophen perovskite mesoscopic solar cells: Performance enhancement by Li‐assisted hole conduction

To address if the non‐triphenylamine derivative hole transporting materials such as P3HT (poly‐3‐hexylthiophene) could also exhibit high device efficiency in mesoscopic MAPbI₃ perovskite solar cells, we examined the effect of Li‐TFSI (Li‐bis(trifluoromethanesulfonyl) imide) and t‐BP (4‐tert‐butylpyridine) additives added in P3HT on device performance. Unlike the triphenylamine HTMs, the P3HT thiophene HTM without amine moiety was not doped by the additives but its conductivity was significantly improved by the Li‐TFSI/t‐BP mediated additional hole conduction. By inclusion of Li‐TFSI/t‐BP additive, we could fabricate more efficient mesoscopic MAPbI₃ perovskite solar cells with smaller hysteresis with respect to scan direction due to Li mediated additional hole conduction. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Physicochemical characterization of paramagnetic ionic liquids 1‐vinyl‐3‐alkylimidazolium tetrahalogenidoferrate(III) [VRIM][FeClmBr4 − m]

Using microwave‐assisted synthesis method, a series of paramagnetic ionic liquids comprising 1‐vinyl‐3‐alkylimidazolium VRIM⁺ cation and tetrahalogenidoferrate (III) FeCl_mBr_{4 ? m}^? anion were designed and synthesized. The structure was analyzed using ¹H NMR and Raman spectroscopy. Ultraviolet–visible absorption spectra, thermal stability, magnetic susceptibility, viscosity, ionic conductivity, and solubility were characterized. Results show that elongation of the alkyl chain leads to replacement of bromides with a small amount of chlorides in the anion, shifting of UV maximum absorption peaks to shorter wavelengths, reduction of ionic conductivity, and solubility in polar solvents, as well as increase in fluidity, magnetic susceptibility, and solubility in nonpolar solvents. Copyright © 2014 John Wiley & Sons, Ltd.     

A Novel Penning‐Trap Design for the High‐Precision Measurement of the 3He2 + Nuclear Magnetic Moment

A new experiment is constructed aiming at the first direct high‐precision measurement of the helium‐3 nuclear magnetic moment with a relative precision of parts‐per‐billion or better. Methods similar to those used in proton and antiproton magnetic moment measurements are applied. As those techniques rely on the challenging detection of single spin‐flips, a novel Penning trap design optimized for nuclear spin‐flip detection is developed.     

Bulk superconductivity in single‐phase Bi3O2S3

We report the synthesis of single‐phase Bi₃O₂S₃ sample and confirm the occurrence of bulk superconductivity with transition temperature at 5.8 K. The Bi₃O₂S₃ superconductor is categorized as typical type‐II superconductor based on the results of both temperature and magnetic field dependences of magnetization. Hall coefficient measurements give evidence of a multiband character, with a dominant conduction mainly by electron‐like charge carriers. The charge carrier density is about 1.45 × 10¹⁹ cm^–3, suggesting that the system has very low charge carrier density.

     

Catalysis by hydrogen chloride in the gas‐phase elimination kinetics of 2‐phenyl‐2‐propanol and 3‐methyl‐1‐buten‐3‐ol

A homogeneous, molecular, gas‐phase elimination kinetics of 2‐phenyl‐2‐propanol and 3‐methyl‐1‐ buten‐3‐ol catalyzed by hydrogen chloride in the temperature range 325–386 °C and pressure range 34–149 torr are described. The rate coefficients are given by the following Arrhenius equations: for 2‐phenyl‐2‐propanol log k₁ (s^?1) = (11.01 ± 0.31) ? (109.5 ± 2.8) kJ mol^?1 (2.303 RT)^?1 and for 3‐methyl‐1‐buten‐3‐ol log k₁ (s^?1) = (11.50 ± 0.18) ? (116.5 ± 1.4) kJ mol^?1 (2.303 RT)^?1. Electron delocalization of the CH₂?CH and C₆H₅ appears to be an important effect in the rate enhancement of acid catalyzed tertiary alcohols in the gas phase. A concerted six‐member cyclic transition state type of mechanism appears to be, as described before, a rational interpretation for the dehydration process of these substrates. Copyright © 2007 John Wiley & Sons, Ltd.     

Decay Dynamics of 3‐methyl‐3‐pentene‐2‐one from the light absorbing S2(ππ*) state ‐ Resonance Raman Spectroscopy and CASSCF Study

The photophysics of 3‐methyl‐3‐pentene‐2‐one (3M3P2O) after excitation to the S₂(ππ*) electronic state were studied using the resonance Raman spectroscopy and complete active space self‐consistent field (CASSCF) method calculations. The A‐band resonance Raman spectra were obtained in cyclohexane, acetonitrile, and methanol with excitation wavelengths in resonance with the first intense absorption band to probe the structural dynamics of 3M3P2O. The B3LYP‐TD/6‐31++G(d, p) computation was carried out to determine the relative A‐band resonance Raman intensities of the fundamental modes, and the result was used to reproduce the corresponding fundamental band intensities of the 223.1 nm resonance Raman spectrum and thus to examine whether the vibronic‐coupling existed in Franck‐Condon region or not. CASSCF calculations were carried out to determine the minimal singlet excitation energies of S_{1, FC}, S_1,min (nπ*), S_{2, FC}, S_2,min (ππ*), the transition energies of the conical intersection points S_n/S_π, S_n/S₀, and the optimized excited state geometries as well as the geometry structures of the conical intersection points. The A‐band short‐time structural dynamics and the corresponding decay dynamics of 3M3P2O were obtained by the analysis of the resonance Raman intensity pattern and CASSCF computations. It was revealed that the initial structural dynamics of 3M3P2O was towards the simultaneous C₃=C₄ and C₂=O₇ bond elongation, with the C₃=C₄ bond length lengthening greater at the very beginning, whereas the C₂=O₇ bond length changing greater at the later evolution time before reaching the CI(S₂/S₁) conical intersection point. The decay dynamics from S₂(ππ*) to S₁(nπ*) via S₂(ππ*)/S₁(nπ*) in singlet realm and from S₁(nπ*) to T₁(nπ*) via ISC[S₁(nπ*)/T₂(ππ*)/T₁(nπ*)] in triplet realm are proposed. Copyright © 2014 John Wiley & Sons, Ltd.     

Conformational analysis of 3,3‐dimethyl‐3‐silathiane, 2,3,3‐trimethyl‐3‐silathiane and 2‐trimethylsilyl‐3,3‐dimethyl‐3‐silathiane—preferred conformers,barriers to ring inversion and substituent effects

The first conformational analysis of 3‐silathiane and its C‐substituted derivatives, namely, 3,3‐dimethyl‐3‐silathiane 1 , 2,3,3‐trimethyl‐3‐silathiane 2 , and 2‐trimethylsilyl‐3,3‐dimethyl‐3‐silathiane 3 was performed by using dynamic NMR spectroscopy and B3LYP/6‐311G(d,p) quantum chemical calculations. From coalescence temperatures, ring inversion barriers ΔG^≠ for 1 and 2 were estimated to be 6.3 and 6.8 kcal/mol, respectively. These values are considerably lower than that of thiacyclohexane (9.4 kcal/mol) but slightly higher than the one of 1,1‐dimethylsilacyclohexane (5.5 kcal/mol). The conformational free energy for the methyl group in 2 (?ΔG° = 0.35 kcal/mol) derived from low‐temperature ¹³C NMR data is fairly consistent with the calculated value. For compound 2 , theoretical calculations give ΔE value close to zero for the equilibrium between the 2 ‐Me_ax and 2 ‐Me_eq conformers. The calculated equatorial preference of the trimethylsilyl group in 3 is much more pronounced (?ΔG° = 1.8 kcal/mol) and the predominance of the 3 ‐SiMe_{3 eq} conformer at room temperature was confirmed by the simulated ¹H NMR and 2D NOESY spectra. The effect of the 2‐substituent on the structural parameters of 2 and 3 is discussed. Copyright © 2010 John Wiley & Sons, Ltd.     

Raman spectroscopic study of serum albumins: an effect of proton‐ and γ‐irradiation

Raman spectroscopy was applied to analyse structural changes in serum albumins (bovine serum albumin, BSA; human serum albumin, HSA) following proton and γ‐irradiation (0.5, 5 and 50 Gy). Characteristic Raman bands of both polypeptide backbone and amino acid residues were sensitive to irradiation. Significant damage of HSA/BSA was observed only at the highest dose (50 Gy). Raman spectra confirmed radiation‐induced denaturation, destruction of helical structures and aggregation of serum albumins. The differences in the dose‐dependent effects of proton and γ‐radiation on studied proteins are discussed. Copyright © 2007 John Wiley & Sons, Ltd.     

Gate‐controlled metal–insulator transition in the LaAlO3/SrTiO3 system with sub‐critical LaAlO3 thickness

We studied the electrical conduction in the LaAlO₃/SrTiO₃ (LAO/STO) interface electron system with a sub‐critical LAO layer thickness of ～3.5 unit cells (uc). It was found that the true dividing point between metallic and insulating behaviour without gating lies near the LAO thickness of 3.5 uc. Our marginally metallic 3.5 uc sample showed a sharp transition to insulating state at temperatures which strongly depended on the applied negative back‐gate voltage. The superior gate‐controllability of the sample was attributed to its sheet carrier density which was an order of magnitude lower than those of conducting LAO/STO samples with 4 uc or more of LAO layers. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Relative stabilities and molecular structures of the isomeric enol ethers and carboxylic esters derived from α‐acetyl‐γ‐butyrolactone and α‐acetyl‐δ‐valerolactone

Recently recorded ¹⁷O NMR spectra of compounds studied in a previous work (Taskinen E. Acta Chem. Scand. 1985; B39 : 489–494) dealing with the thermodynamics of isomerization of the enol ethers of α‐acetyl‐γ‐butyrolactone reveal an error in compound identification, caused by an unexpected isomerization reaction during the synthetic procedure. Thus, acid‐catalyzed treatment of the lactone with HC(OR)₃ in the respective alcohol ROH is shown to lead initially to the desired enol ethers which, however, are gradually isomerized to a mixture of the enol ethers and an ester of 2‐methyl‐4,5‐dihydrofuran‐3‐carboxylic acid. As a result, only one of the two isomeric compounds detected in the previous equilibration study was the expected enol ether (the thermodynamically more stable E isomer) of α‐acetyl‐γ‐butyrolactone, while the other, dominating species was the respective carboxylic ester. In the present work, the evidence provided by the ¹⁷O NMR spectra is presented, and the relative stabilities of the isomeric compounds are discussed on the basis of computational enthalpy data. The treatment is also extended to the respective isomeric compounds derived from α‐acetyl‐δ‐valerolactone. Copyright © 2007 John Wiley & Sons, Ltd.     

Raman spectroscopic study of calf thymus DNA: an effect of proton‐ and γ‐irradiation

Raman spectroscopy was applied to analyse structural changes in calf thymus double‐stranded deoxyribonucleic acid (dsDNA) after proton‐ and γ‐irradiation (0.5, 5 and 50 Gy). Characteristic Raman bands of phosphodiester linkages, nucleic bases and deoxyribose moieties were sensitive to irradiation. A significant damage of the macromolecules was observed only at the highest dose (50 Gy) of both types of radiations. Spectral changes confirmed a radiation‐induced alteration of the native structure of dsDNA. Nucleic bases, especially pyrimidines, were the most sensitive to radiation, while some alterations in the sugar–phosphate backbone were also detected. The differences in the dose‐dependent effects of proton vs γ‐irradiation on studied biomolecule are discussed. Copyright © 2007 John Wiley & Sons, Ltd.     

Equivalent magnetic noise in magnetoelectric Metglas/Pb(Mg1/3Nb2/3)O3‐PbTiO3 laminate composites

We have experimentally and theoretically investigated the equivalent magnetic noise in a magnetoelectric Metglas/ 0.7Pb(Mg_1/3Nb_2/3)O₃‐0.3PbTiO₃ laminate sensor unit by considering the constituent noise sources of dielectric loss (N_DE) and DC leakage resistance (N_R). In the low frequency range (f = 1 Hz), theory predicts that N_R dominates the noise charge (1.6 times larger than N_DE), with a 1 Hz noise of 9.1\;{\rm pt}/\sqrt {\rm Hz}. The experimental equivalent magnetic noise was 10.8\;{\rm pt}/\sqrt {\rm Hz}. This observed value is slightly higher than the predicted one, which might be due to an oversimplification of the theoretical model in terms of electrical charge amplifier and external vibration noise sources. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Layer‐by‐layer AuCl3 doping of stacked graphene films

We investigated the effect of layer‐by‐layer AuCl₃ doping on the electrical and optical properties of stacked graphene films. Graphene grown by the chemical‐vapor deposition method on a Cu‐foil was chemically doped by AuCl₃ solution with a concentration of 20 mM. Eight different configurations were prepared and analyzed by using four‐point probe measurements, optical transmittance measurements, scanning electron microscopy, and micro‐Raman spectroscopy to compare the optical and electrical characteristics of the different graphene samples. In our study, the top‐layer doping method was very effective because better performances considering both sheet resistance and optical transmittance were observed from the configurations with the top‐layer doped. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Characterization of high‐density bit‐patterned media using ultra‐high resolution magnetic force microscopy

Bit‐patterned media at one terabit‐per‐square‐inch (Tb/in²) recording density require a feature size of about 12 nm. The fabrication and characterization of such magnetic nanostructures is still a challenge. In this Letter, we show that magnetic dots can be resolved at 10 nm spacing using magnetic force microscopy (MFM) tips coated with a magnetic film possessing a perpendicular magnetic anisotropy (PMA). Compared to MFM tips with no special magnetic anisotropy, MFM tips with PMA can resolve the bits clearly, because of a smaller magnetic interaction volume, enabling a simple technique for characterizing fine magnetic nanostructures. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Yolk–Shell‐Structured Cu/Fe@γ‐Fe2O3 Nanoparticles Loaded Graphitic Porous Carbon for the Oxygen Reduction Reaction

Core–shell Cu/γ‐Fe₂O₃@C and yolk–shell‐structured Cu/Fe@γ‐Fe₂O₃@C particles are prepared by a facile synthesis method using copper oxide as template particles, resorcinol‐formaldehyde as the carbon precursor, and iron nitrate solution as the iron source via pyrolysis. With increasing carbonization temperature and time, solid γ‐Fe₂O₃ cores are formed and then transformed into Fe@γ‐Fe₂O₃ yolk–shell‐structured particles via Ostwald ripening under nitrogen gas flow. The composition variations are studied, and the formation mechanism is proposed for the generation of the hollow and yolk–shell‐structured metal and metal oxides. Moreover, highly graphitic carbons can be obtained by etching the metal and metal oxide nanoparticles through an acid treatment. The electrocatalytic activity for oxygen reduction reaction is investigated on Cu/γ‐Fe₂O₃@C, Cu/Fe@γ‐Fe₂O₃@C, and graphitic carbons, indicating comparable or even superior performance to other Fe‐based nanocatalysts.     

Single‐crystal X‐ray diffraction and resonant X‐ray magnetic scattering at helium‐3 temperatures in high magnetic fields at beamline P09 at PETRA III

The resonant scattering and diffraction beamline P09 at PETRA III at DESY is equipped with a 14 T vertical field split‐pair magnet. A helium‐3 refrigerator is available that can be fitted inside the magnet's variable‐temperature insert. Here the results of a series of experiments aimed at determining the beam conditions permitting operations with the He‐3 insert are presented. By measuring the tetragonal‐to‐orthorhombic phase transition occurring at 2.1 K in the Jahn–Teller compound TmVO₄, it is found that the photon flux at P09 must be attenuated down to 1.5 × 10⁹ photons s^?1 for the sample to remain at temperatures below 800 mK. Despite such a reduction of the incident flux and the subsequent use of a Cu(111) analyzer, the resonant X‐ray magnetic scattering signal at the Tm L_III absorption edge associated with the spin‐density wave in TmNi₂B₂C below 1.5 K is intense enough to permit a complete study in magnetic field and at sub‐Kelvin temperatures to be carried out.     

Investigation of a CPG‐array CdZnTe γ‐ray imaging detector with single collecting electrodes readout

The single‐electrode readout method has been applied to a coplanar grid (CPG) array CdZnTe detector in order to halve the number of preamplifiers previously needed and to facilitate imaging applications of CPG detectors. A method of predetermining the width of the optimum collecting electrodes has also been proposed, using the calculated optimum relative gain factor G. Meanwhile, a detailed process for calculating the charge induction efficiency (CIE) is presented. To simplify the calculation process, the computational formula of the CIE was deduced through the integration of the weighting potential. For performance evaluation, a 2 × 2 CPG‐array CdZnTe detector was elaborately designed and tested with ¹³⁷Cs at 662 keV. Experimental results showed the capability of using the CPG‐array CdZnTe detector with single collecting electrode readout for γ‐ray imaging applications, with the same complexity of associated readout electronics as that of the pixelated CdZnTe detectors.