The effect of interlayer coupling on critical current density in Bi2212 system

The dependences of critical current density J _c on the interlayer coupling strength and magnetic field in Bi2212 crystals were obtained by measuring the magnetic loop of the crystals with different interlayer coupling strengths. It was revealed that J _c decreases with the decrease in the interlayer coupling of the crystals. The relation of J _{c ∞ exp} (−H ^β) was also found in the crystals, and further analysis indicated that it was the result of Zeldov pinning potential model. __________ Translated from Chinese Journal of Low Temperature Physics, 2005, 27(1) (in Chinese)     

A new method for functionalizing α,γ‐dinitro compounds at the β‐position: application to the cyclization of β‐alkoxy‐α,γ‐dinitro compounds

Treatment of 2,4‐dinitropentane with bromine and sodium methoxide in methanol, affords formation of an ether product, 2,4‐dibromo‐3‐methoxy‐2,4‐dinitropentane, in 59% yield as a mixture of three diastereomers. This observation has led to a general synthesis of 3‐alkoxy‐2,4‐dibromo‐2,4‐dinitropentanes, obtained in 75‐86% yield from 2,4‐dibromo‐2,4‐dinitropentane as the preferred reactant. 4‐Bromo‐2,4‐dinitro‐2‐pentene has been identified as an intermediate in these reactions. The nitroalkene has been isolated and undergoes conjugate addition with alkoxides to afford the same ether products after brominative work‐up. The nitroalkene undergoes conjugate addition with sodium azide to give 3‐azido‐2,4‐dibromo‐2,4‐dinitropentane in 38% yield as a mixture of two isomers in which the (R*,R*) isomer predominates. Sequential treatment of 2,4‐dibromo‐2,4‐dinitropentane with sodium methoxide followed by sodium iodide and acetic acid gives 3‐methoxy‐2,4‐dinitropentane in 63% yield, the overall product of simple methoxylation of 2,4‐dinitropentane. However, attempted complete debromination of 2,4‐dibromo‐3‐methoxy‐2,4‐dinitropentane with excess sodium iodide and acetic acid results only in monodebromination to give 2‐bromo‐3‐methoxy‐2,4‐dinitropentane in 86% yield. Likewise, 2‐bromo‐3‐ethoxy‐2,4‐dinitropentane is formed in 93% yield from the ethoxy analog. A mechanistic rationale is offered for condition‐specific removal of the second Br atom in these reactions. Treatment of 3‐methoxy‐2,4‐dinitropentane with potassium acetate/iodine in dimethyl sulfoxide affords formation of 4,5‐dihydro‐3,4‐dimethyl‐3‐methoxy‐4‐nitroisoxazole 2‐oxide in 30% yield as a single diastereomer. Conversion of 2‐bromo‐3‐methoxy‐2,4‐dinitropentane in 15% yield to 4,5‐dihydro‐3,4‐dimethyl‐3‐methoxy‐4‐nitroisoxazole 2‐oxide is also possible by using potassium acetate in dimethyl sulfoxide. The mechanistic pathways for formation of 4,5‐dihydro‐3,4‐dimethyl‐3‐methoxy‐4‐nitroisoxazole 2‐oxide apparently involve unstable 3‐methoxy‐1,2‐dimethyl‐1,2‐dinitrocyclopropane as the common intermediate. Similarly, 2‐bromo‐3‐ethoxy‐2,4‐dinitropentane affords 4,5‐dihydro‐3‐ethoxy‐3,4‐dimethyl‐4‐nitroisoxazole 2‐oxide in 13% yield. Copyright © 2013 John Wiley & Sons, Ltd.     

Ca‐doped Ba2Cu3O7–δ bicrystal junctions fabricated on asymmetric SrTiO3 substrates

Bicrystal grain–boundary Josephson junctions of Ca–doped YBa₂Cu₃O_7–δ that is Y_0.7Ca_0.3Ba₂Cu₃O_7–δ were fabricated on three bicrystal SrTiO₃ (001) substrates with asymmetric 30°, 40° and 45° orientations. An enhancement of the critical current density in these Ca–doped junctions was observed when compared with normal YBCO grain–boundary junctions with similar angular orientations. The observed increase in the critical current density is large for the junctions fabricated on the asymmetric 30° bicrystal substrate and small or negligible, for those on the asymmetric 45° bicrystal substrate. The critical current was modulated by a magnetic field applied in the plane of the junctions. However, the Fraunhofer pattern observed due to the applied magnetic field deviates from the ideal one.     

Spectroscopic and structural investigations of α‐, β‐, and γ‐AlH3 phases

With its reputation as a high‐energy density fuel, aluminum hydride (AlH₃) has received renewed attention as a material that is particularly suitable, not only for hydrogen storage but also for rocket propulsion. While the various phases of AlH₃ have been investigated theoretically, there is a shortage of experimental studies corroborating the theoretical findings. In response to this, we present here an investigation of these compounds based primarily on two research areas in which there is the greatest scarcity of information in the literature, namely Raman and infrared (IR) absorption analysis. To the authors' knowledge, this is the first report of experimental far‐IR absorption results on these compounds. Two different samples prepared by broadly similar ethereal reactions of AlCl₃ with LiAlH₄ were analyzed. Both Raman and IR absorption measurements indicate that one sample is purely γ‐AlH₃ and that the other is a mixture of α‐, β‐, and γ‐AlH₃ phases. X‐ray diffraction confirms the spectroscopic findings, most notably for the β‐AlH₃ phase, for which optical spectroscopic data are reported here for the first time. Copyright © 2010 John Wiley & Sons, Ltd.     

Organocatalysis: quantum chemical modeling of nucleophilic addition to α,β‐unsaturated carbonyl compounds

One of the successful transformations within the field of organocatalysis, the organocatalytic asymmetric addition of nitromethane to α,β‐unsaturated aldehydes and ketones, has been studied by quantum chemical modeling. The level of accuracy of the hybrid density functional theory method B3LYP/6‐31G(d) was compared to a high level ab initio benchmark for this reaction. It is concluded that B3LYP/6‐31G(d) performs very well for this reaction type, giving good estimates of critical energies. The reaction between acrolein and nitromethane was studied in detail. The reaction mechanism revealed an intermediate oxazolidin structure, which is currently unknown. Alkyl substitution in various positions on the amine catalyst or α,β‐unsaturated carbonyl compound influences the reactivity in a predictive fashion. The iminium ion, prop‐2‐en‐iminium, is less activated towards nucleophilic attack compared to protonated acrolein. Copyright © 2007 John Wiley & Sons, Ltd.     

Critical current densities of high pressure oxygen sputtered thin films of YBa2Cu3O7−x by non-resonant rf absorption method

The critical current densities (J _c) have been measured at 77K in high pressure oxygen sputtered thin films of YBa₂Cu₃O_7−x superconductor using the non-resonant rf absorption technique. High values ofJ _c (∼ 10⁵ A/cm²) are observed in these relatively large area (∼ 1·2 cm²) films.     

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.     

Thermodynamic Parameters of Single‐ or Multi‐Band Superconductors Derived from Self‐Field Critical Currents

Key questions for any superconductor include: what is its maximum dissipation‐free electrical current (its ‘critical current') and can this be used to extract fundamental thermodynamic parameters? Present models focus on depinning of magnetic vortices and implicate materials engineering to maximise pinning performance. But recently we showed that the self‐field critical current for thin films is a universal property, independent of microstructure, controlled only by the penetration depth. Here, using an extended BCS‐like model, we calculate the penetration depth from the temperature dependence of the superconducting energy gap thus allowing us to fit self‐field critical current data. In this way we extract from the T ‐dependent gap a set of key thermodynamic parameters, the ground‐state penetration depth, energy gap and jump in electronic specific heat. Our fits to 79 available data sets, from zinc nanowires to compressed sulphur hydride with critical temperatures of 0.65 to 203 K, respectively, are excellent and the extracted parameters agree well with reported bulk values. Samples include thin films, wires or nanowires of single‐ or multi‐band s ‐wave and d ‐wave superconductors of either type I or type II. For multiband or multiphase samples we accurately recover individual band contributions and phase fractions.     

Gas‐phase elimination kinetics of selected aliphatic α,β‐unsaturated aldehydes catalyzed by hydrogen chloride

The gas‐phase elimination of 2‐methyl‐2‐propenal catalyzed by HCl yields propene and CO gas, while E‐2‐pentenal with the same catalyst gives butene and CO gas. The kinetics determinations were carried out in a static system with the reaction vessels deactivated with allyl bromide and the presence of the free radical inhibitor toluene. Temperature and pressure ranges were 350.0–410.0 °C and 34–76 Torr. The elimination reactions are homogeneous and unimolecular, and follow a first‐order rate law. The rate coefficients for the reactions are expressible by the following Arrhenius equations: Data from the kinetic and thermodynamic parameters of these catalyzed elimination reactions implies a mechanism of a concerted five‐membered cyclic transition state structure for the formation of the corresponding olefin and carbon monoxide. Copyright © 2015 John Wiley & Sons, Ltd.     

A comparative study on the gas‐phase and liquid‐phase thermal isomerization reaction of α‐pinene

In this paper, a method of preparation of ocimene is investigated, which is obtained from isomerization reaction of α‐pinene. Two kinds of experimental apparatus are established for the investigation of the thermal isomerization reaction of α‐pinene. The behavior of thermal isomerization reaction of α‐pinene is respectively discussed in the gas phase and in the liquid phase. Under gas phase conditions, the conversion of α‐pinene is 80% and the selectivity of ocimene is 30%–33%. Under liquid phase conditions, the conversion of α‐pinene is 60% and the selectivity of ocimene is 50%–54%. According to the kinetic‐molecular theory of ideal gases, two kinds of reaction models are proposed to visualize the reaction process. In addition, the mechanism and kinetics of thermal isomerization reaction of α‐pinene are respectively discussed. The conclusion is that the gas phase reaction temperature is calculated to be 390–450 °C and the liquid phase reaction temperature is calculated to be 450–550 °C. From a bond dissociation energy point of view, results support the hypothesis that the reaction involves biradical intermediates. Copyright © 2012 John Wiley & Sons, Ltd.     

Prediction of γ‐B28 ELNES with comparison to α‐B12

Using ab initio techniques we have calculated the electron energy loss near edge structure (ELNES) of a new high pressure phase of boron (γ‐B₂₈) and the structurally similar allotrope, α‐B₁₂. The total ELNES spectra are presented as weighted sums of the site specific spectra of the constituent non‐equivalent B atoms. The five different non‐equivalent B sites in γ‐B₂₈ all show rich ELNES spectra and their similarities and differences to the simpler α‐B₁₂ case are detailed. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Raman spectroscopy of the transition of α‐gallium oxyhydroxide to β‐gallium oxide nanorods

The thermo‐Raman spectra of synthesised α‐gallium oxyhydroxide nanorod prove that the transition of α‐gallium oxyhydroxide to β‐gallium oxide nanorods occurs above 350 °C but below 400 °C. Scanning electron microscopy proves that the morphology of the α‐gallium oxyhydroxide nanorods is retained upon calcination to β‐gallium oxide. X‐ray diffraction patterns show that the nanorods are α‐gallium oxyhydroxide converting upon calcination to β‐gallium oxide. Intense Raman bands are observed at 190, 262, 275, 430, 520, 605, and 695 cm⁻¹, which undergo a red shift of ∼5 cm⁻¹ upon heating to 350 °C. Upon thermal treatment above 350 °C, the Raman spectrum shows a significantly different pattern. Raman bands are observed at 155, 212, 280, 430, 570, and 685 cm⁻¹. The thermo‐Raman spectra are in harmony with the TG and DTG patterns, which show that the reaction of α‐gallium oxyhydroxide to β‐gallium oxide occurs at 365 °C. Copyright © 2008 John Wiley & Sons, Ltd.     

Design and interaction mechanism of ligand targeted with folate receptor α and β

Four compounds 1 to 4 (folic acid, methotrexate and 2 dyes) were used to interact with folate receptor (FR)α and FRβ. The interaction structures and binding energies of the bound complexes were investigated. In order to analyze the differences between FRα and FRβ complexes, the details of the weak intermolecular interactions were analyzed, and the frontier orbital properties of the FR complexes were studied by a dispersion complemented density functional tight‐binding method. By comparing the different interaction properties of the 4 compounds with FRα and FRβ, the basic strategies for design of novel compound targeted with FR subtype were suggested. Further, a novel compound with high selectively with FRα based on compound 3 was designed to illustrate our conclusion. These data should be helpful for the design of novel molecules with extreme discerningly with FRα and FRβ.     

Raman spectroscopy and characterisation of α‐gallium oxyhydroxide and β‐gallium oxide nanorods

Raman spectroscopy complemented by infrared spectroscopy was used to characterise both gallium oxyhydroxide (α‐GaO(OH)) and gallium oxide (β‐Ga₂O₃) nanorods synthesised with and without the surfactants using a soft chemical methodology at low temperatures. Nano‐ to micro‐sized gallium oxyhydroxide and gallium oxide materials were characterised and analysed by both X‐ray diffraction and Raman spectroscopy. Rod‐like GaO(OH) crystals with average length of ∼2.5 µm and width of 1.5 µm were obtained. Upon thermally treating gallium oxyhydroxide GaO(OH) to 900 °C, β‐Ga₂O₃ was synthesised retaining the initial GaO(OH) morphology. Raman spectroscopy has been used to study the structure of nanorods of GaO(OH) and Ga₂O₃ crystals. Raman spectroscopy shows bands characteristic of GaO(OH) at 950 and ∼1000 cm⁻¹ attributed to Ga OH deformation modes. Bands at 261, 275, 433 and 522 cm⁻¹ are assigned to vibrational modes involving Ga OH units. Bands observed at 320, 346, 418 and 472 cm⁻¹ are assigned to the deformation modes of Ga₂O₆ octahedra. Two sharp infrared bands at 2948 and 2916 cm⁻¹ are attributed to the GaO(OH) symmetric stretching vibrations. Raman spectroscopy of Ga₂O₃ provides bands at 630, 656 and 767 cm⁻¹ which are assigned to the bending and stretching of GaO₄ units. Raman bands at 417 and 475 cm⁻¹ are attributed to the symmetric stretching modes of GaO₂ units. The Raman bands at 319 and 347 cm⁻¹ are assigned to the bending modes of GaO₂ units. Copyright © 2008 John Wiley & Sons, Ltd.     

Field induced flux pinning in Nd1+xBa2−xCu3O7−δ single crystal

The flux pinning behavior of a Nd_1+xBa_2−xCu₃O_7−δ (Nd123) single crystal, which exhibited a peak effect, has been studied by monitoring the time decay of the magnetic moment. The apparent pinning energy (U₀^*) was deduced from flux creep data on the basis of the Anderson-Kim model. The magnetic field dependence of U₀^* showed maxima at peak fields which depended on the temperatures, in a similar manner to those of critical current densities. In addition, the temperature dependence of U₀^* showed several features. To explain the increase in U₀^* with the field as well as its temperature and field dependence, we made a numerical calculation by introducing an additional pinning energy which increased with increasing field. The results are in good agreement with the experimental data, especially at temperatures above 60 K, where the contribution of field induced pinning centers is believed to be dominant.     

Magnetic hysteresis of the magnetoresistance and the critical current density in polycrystalline YBa2Cu3O7−δ–Ag superconductors

A systematic study of the magnetic hysteresis in transport properties of polycrystalline YBa₂Cu₃O_7−δ–Ag compounds has been made based on two kinds of measurements at 77 K and under applied magnetic fields up to 30 mT: critical current density J_c(B_a) and magnetoresistance R(B_a). The R(B_a) curves show a minimum in their decreasing branch occurring at B=B_min which was found to be both the excitation current I_ex and the maximum applied magnetic field B_am dependent. In addition, for a certain value of B_am>5 mT, we have observed that B_min increases with increasing I_ex and reaches a saturation value. The J_c(B_a) curves show a maximum in decreasing applied magnetic fields occurring at B=B_max. We have also found that B_max increases with increasing B_am and reaches a saturation value. The minimum in the R(B_a) and the maximum in J_c(B_a) curves were found to be related to the trapped flux within the grains. All the experimental results are discussed within the context of the flux dynamics and transport mechanisms in these high-T_c materials.     

Spectroscopic and thermal studies on the inclusion of trans‐cinnamic acid and a number of its hydroxyl‐derivatives with α, β and γ‐cyclodextrins molecules

The inclusion compounds of α‐, β‐ and γ‐cyclodextrins (α‐CD, β‐CD and γ‐CD) with trans‐cinnamic acid (t‐CIA), 3‐hydroxy‐trans‐cinnamic acid (t‐3OHCIA), 4‐hydroxy‐trans‐cinnamic acid (t‐4OHCIA) and 3,4‐dihydroxy‐trans‐cinnamic acid (t‐3,4OHCIA) were prepared and characterized, in the solid state, by means of thermogravimetry and Raman spectroscopy. The effects of the inclusion process on the guest molecules and on the hydrogen bond interactions of the guest were studied by monitoring sensitive vibrational modes, such as CO, CC and ring C H stretching modes. By combining Raman and TG data with ab initio calculations and information from CSD database on similar compounds, inclusion geometries for the different compounds are proposed. The size of the host cavity and the maximization of host/guest hydrogen‐bonding contacts appear to be the main factors determining the inclusion geometries. Copyright © 2009 John Wiley & Sons, Ltd.     

High‐pressure Raman spectroscopy study of α and γ polymorphs of AlH3

For the first time, Raman spectroscopy of α and γ polymorphs of AlH₃ has been performed in the pressure range from ambient up to 16.9 and 32.7 GPa, respectively using the diamond anvil cell (DAC) technique. An analysis of pressure response wavenumbers (ν) for α‐AlH₃ showed a change of dν_i/dP at a pressure of about 8 GPa and may indicate a monoclinic distortion from the initially hexagonal α‐AlH₃. The distortion is stable at least up to 16.9 GPa. The γ form exhibited more complex behavior transforming to the α form at a pressure of about 12 GPa. The structural phase transition was shown to be an irreversible and kinetically slow process that required at least 5 h to complete. Copyright © 2008 John Wiley & Sons, Ltd.     

Substituent effects on conformational preference in α‐substituted α‐fluorophenylacetic acid methyl ester model systems for chiral derivatizing agents

In connection with study of chiral derivatizing agents (CDAs) for NMR determination of absolute configuration of organic compounds, factors controlling the conformational preference between syn‐ and anti‐forms in α‐substituted α‐fluorophenylacetic acid methyl ester (FC(X)(Ph)COOMe) model systems were theoretically investigated. Substituents X at the stereogenic carbon atom were X = H, C?CH and CH₃, the electronic and steric properties of which were significantly different from each other. The model system with X = C?CH and that with X = CH₃ were found to be possible candidates for fluorine‐containing CDAs. The syn conformation is stable compared with the anti one by 0.7 kcal mol^?1 for the ester with X = C?CH. On the other hand, the anti conformation is stable compared with the syn one by 0.5 kcal mol^?1 for the ester with X = CH₃. Both natural bond orbital (NBO) analysis and deletion of selected orbitals based on the donor–acceptor NBO scheme were adopted for semi‐quantitative estimation of factors responsible for the conformational preference as well as a qualitative inspection of occupied canonical molecular orbitals (MOs). It was shown that [σ–(σ* + π*)(C?O)] and [σ–σ*(Ph) and π(Ph)–σ*] hyperconjugations are the main factors controlling the conformational preferences between the syn and anti conformations. Other types of effects such as electrostatic effects were also investigated. The role of the fluorine atom was also clarified. Copyright © 2009 John Wiley & Sons, Ltd.