Kink fluctuation asymptotics and zero modes

In this paper we propose a refinement of the heat-kernel/zeta function treatment of kink quantum fluctuations in scalar field theory, further analyzing the existence and implications of a zero-energy fluctuation mode. Improved understanding of the interplay between zero modes and the kink heat-kernel expansion delivers asymptotic estimations of one-loop kink mass shifts with remarkably higher precision than previously obtained by means of the standard Gilkey–DeWitt heat-kernel expansion.     

New Insights into the Diels–Alder Reaction of Graphene Oxide

Graphene oxide is regarded as a major precursor for graphene‐based materials. The development of graphene oxide based derivatives with new functionalities requires a thorough understanding of its chemical reactivity, especially for canonical synthetic methods such as the Diels–Alder cycloaddition. The Diels–Alder reaction has been successfully extended with graphene oxide as a source of diene by using maleic anhydride as a dienophile, thereby outlining the presence of the cis diene present in the graphene oxide framework. This reaction provides fundamental information for understanding the exact structure and chemical nature of graphene oxide. On the basis of high‐resolution ¹³C‐SS NMR spectra, we show evidence for the formation of new sp³ carbon centers covalently bonded to graphene oxide following hydrolysis of the reaction product. DFT calculations are also used to show that the presence of a cis dihydroxyl and C vacancy on the surface of graphene oxide are promoting the reaction with significant negative reaction enthalpies.     

Dielectric relaxation and ac conduction in multiferroic TbMnO3 ceramics: Impedance spectroscopy analysis

Polycrystalline samples of Tb_1−xAl_xMnO₃ (x = 0, 0.1, 0.2) have been synthesized by means of standard high-temperature solid-state reaction technique. Detailed studies on the effect of compositional variation of aluminum (Al) on the electrical behavior (complex impedance Z*, complex modulus M*, and relaxation mechanisms) of the parent TbMnO₃ have been performed by using the nondestructive complex impedance spectroscopy technique at temperatures above room temperature. In the temperature range covered, the impedance plots signalize that the grains are the unique responsible for the conduction mechanism of the concerned material. The impedance spectra are well modeled in terms of electrical equivalent circuit with a grain resistance (R_g) and constant phase element impedance (Z_CPE). The conductivity data of the undoped and Al-doped samples are well fitted by the universal Jonscher's power law. The resulting fitting parameters indicate that for the studied samples, the hopping process occurs between neighboring sites. Activation energy values for dc conductivity are calculated for undoped and Al-doped samples and found to decrease when Al is incorporated. In turn, the emergence of single arc in the complex modulus spectrum for all the compositions of Al suggests that for the studied samples only one type of relaxation behavior is present at the selected temperatures. A non-Debye-type relaxation is clearly verified. The relaxation process in the present samples seems to be composition and temperature dependent, particularly at higher frequencies.     

Synthesis of 4-Octuloses from a Derivative of d-Fructose

Abstract

Reaction of 2,3:4,5-di-O-isopropylidene-β-d-arabino--hexos-2-ulo-2,6-pyranose (1) with (methoxycarbonylmethylene)triphenylphosphorane in either dichloromethane or methanol gave methyl (E)-2,3-dideoxy-4,5:6,7-di-O-isopropylidene-β-d-arabino-oct-2-ene-4-ulo-4,8-pyranosonate (2) or a 1:2.3 mixture of 2 and its Z-isomer (3), respectively. Bishydroxylation of 2 with osmium tetraoxide gave a mixture of methyl 4,5:6,7-di-O-isopropylidene-β-d-glycero-d-galacto- (4) and -d-glycero-d-ido-oct-4-ulo-4,8-pyranosonate (5) which were carefully resolved by column chromatography. Compound 4 was transformed into its 2,3-di-O-methyl derivative (6) which was deacetonated to 7 and subsequently degraded to dimethyl 2,3-di-O-methyl-(+)-L-tartrate (8). On the other hand, acetonation of a mixture of 4 and 5 gave the corresponding tri-O-isopropylidene derivatives (9) and (10). Compounds 4 and 5 were reduced with LiAlH₄ to the related 4,5:6,7-di-O-isopropylidene-β-d-glycero-d-galacto- (11) and β-d-glycero-d-ido-oct-4-ulo-4,8-pyranose (12). Treatment of 11 and 12 with acetone/PTSA/CuSO₄ only produced the acetonation at the C-2,3 positions. Finally, compounds 11 and 12 were deacetonated to the corresponding D-glycero-d-galacto- (15) and D-glycero-d-ido-oct.-4-ulose (16).     

Synthetic Application of Partially Protected Fructopyranoses

Partial deacetonation of 1-O-benzoyl-2,3:4,5-di-O-isopropylidene-β-D-fructopyranose (2) yielded the related 2,3-O-isopropylidene derivative (3) that was subsequently transformed into the corresponding 1-O-benzoyl-4,5-O-dibutylstannylene-2,3-O-isopropylidene-β-D-fructopyranose (4). Reaction of 4 with benzyl bromide proceeded with high regioselectivity to afford 1-O-benzoyl-5-O-benzyl-2/3-O-isopropylidene-β-D-fruc-topyranose (5) together with a small quantity of the 4-O-benzyl derivative (6). Oxidation of 5 gave the 4-oxo derivative (10) which was reduced to yield a mixture of 5 and its 4-epimer (11). Debenzylation of 11, followed by a debenzoylation reaction produced 2,3-O-isopropylidene-β-O-tagatopyranose (13). Aceto-nation of 13 yielded 1,2:3,4-di-O-isopropylidene-α-D-tagatofuranose (14). Structures and configurations of the above compounds were established on the basis of their analytical and spectroscopic data.     

Action of Base on Methyl 6-Thio- (and 6-Deoxy-) 2-O-Methanesulfonyl-α-d-Glucopyranoside Derivatives1

Abstract

Treatment of methyl 4-O-benzoyl-3-O-tert-butyldiphenylsilyl-2-O-methanesulfonyl-6-thio-α-d-glucopyranoside (8) and its 6-deoxy analogue (11) with methanolic sodium methoxide, afforded methyl 2,3-anhydro-mannopyranoside derivatives as a consequence of an O₃ → O₄ TBDPS rearrangement. When the protecting group at C-3 was 2-methoxyethoxy methyl ether only deacylation and methanolysis of the methanesulfonyl group occurred.     

Single‐Step Sulfo‐Selenization Method to Synthesize Cu2ZnSn(SySe1−y)4 Absorbers from Metallic Stack Precursors

Pentenary Cu₂ZnSn(S_ySe_1?y)₄ (kesterite) photovoltaic absorbers are synthesized by a one‐step annealing process from copper‐poor and zinc‐rich precursor metallic stacks prepared by direct‐current magnetron sputtering deposition. Depending on the chalcogen source—mixtures of sulfur and selenium powders, or selenium disulfide—as well as the annealing temperature and pressure, this simple methodology permits the tuning of the absorber composition from sulfur‐rich to selenium‐rich in one single annealing process. The impact of the thermal treatment variables on chalcogenide incorporation is investigated. The effect of the S/(S+Se) compositional ratio on the structural and morphological properties of the as‐grown films, and the optoelectronic parameters of solar cells fabricated using these absorber films is studied. Using this single‐step sulfo‐selenization method, pentenary kesterite‐based devices with conversion efficiencies up to 4.4 % are obtained.     

Al2O3基Ni-Cu双金属催化剂上乙酰丙酸氢解（英）

Inexpensive γ-alumina-based nickel-copper bimetallic catalysts were studied for the hydrogenolysis of levulinic acid,a key platform molecule for biomass conversion to biofuels and other valued chemicals,into γ-valerolactone as a first step towards the production of 2-methyltetrahydrofurane.The activities of both monometallic and bimetallic catalysts were tested.Their textural and chemical characteristics were determined by nitrogen physisorption,elemental analysis,temperature-programmed ammonia desorption,and temperature-programmed reduction.The monometallic nickel catalyst showed high activity but the highest bγ-product production and significant amounts of carbon deposited on the catalyst surface.The copper monometallic catalyst showed the lowest activity but the lowest carbon deposition.The incorporation of the two metals generated a bimetallic catalyst that displayed a similar activity to that of the Ni monometallic catalyst and significantly low bγ-product and carbon contents,indicating the occurrence of important synergetic effects.The influence of the preparation method was also examined by studying impregnated- and sol-gel-derived bimetallic catalysts.A strong dependency on the preparation procedure and calcination temperature was observed.The highest activity per metal atom was achieved using the sol-gel-derived catalyst that was calcined at 450 ℃.High reaction rates were achieved;the total levulinic acid conversion was obtained in less than 2 h of reaction time,yielding up to 96%γ-valerolactone,at operating temperature and pressure of 250 ℃ and 6.5 MPa hydrogen,respectively.     

On Riemann surfaces with non-unique cyclic trigonal morphism

A closed Riemann surface which can be realized as a 3-sheeted covering of the Riemann sphere is called trigonal, and such a covering will be called a trigonal morphism. If the trigonal morphism is a cyclic regular covering, the Riemann surface is called cyclic trigonal Riemann surface. Accola showed that the trigonal morphism is unique for Riemann surfaces of genus greater or equal to 5. Using the characterization of cyclic trigonality by Fuchsian groups given in [3], we obtain the Riemann surfaces of low genus with non-unique trigonal morphisms. Partially supported by BFM2002-4801. Partially supported by the Swedish Research Council (VR)