Layer-by-layer assembly of Ag2S quantum dots-sensitized ZnO/SnO2 core-shell nanowire arrays for enhanced photocatalytic activity

Ag₂S quantum dots-sensitized ZnO/SnO₂ core-shell nanowire arrays were successfully synthesized layer by layer through hydrothermal growth, atomic layer deposition, and successive ionic layer adsorption and reaction process. By introducing the two-layer semiconductors, the bandgap of ZnO component in the arrays was slightly modulated, while the light absorption was obviously improved with an absorptivity higher than 95% in visible and ultraviolet range. In contrast to the ZnO NW arrays, the photocurrent response of the ZnO/SnO₂/Ag₂S NW arrays for the visible light was improved from 0.42 μA to 22.5 μA, and the photodegradation efficiency of methylene blue was increased from 45.24% to 71.61%, and 42.61% to 57.58%, respectively in visible light and ultraviolet light. Band structure analysis indicated that the coating layer brought different staggered gaps and suitable band alignment for efficient photocatalytic performance, which could be extended to design heterogeneous semiconductor nanomaterials for their potential applications.     

Enantioselective epoxidation by the chiral auxiliary approach: Asymmetric total synthesis of (+)-Ambrisentan

Enantioselective and a highly concise total synthesis of Ambrisentan are described. The chiral auxiliary controlled enantioselective epoxidation (Azerad protocol), photochemical regioselective epoxide opening, and base mediated ester hydrolysis reactions are the key reactions.     

Spatial Dynamics of a Diffusive Prey-predator Model with Stage Structure and Fear Effect

To understand the influence of fear effect on population dynamics, especially for the populations with obvious stage structure characteristics, we propose and investigate a diffusive prey-predator model with stage structure in predators. First, we discuss the existence and stability of equilibrium of the model in the absence of diffusion. Then, we obtain the critical conditions for Hopf and Turing bifurcations. Some numerical simulations are also carried out to verify our theoretical results, which indicate that the fear can induce the prey population to show five pattern structures: cold-spot pattern, mixed pattern with cold spots and stripes, stripes pattern, hot-spot pattern, mixed pattern with hot spots and stripes. These findings imply that the fear effect induced by the mature predators plays an important role in the spatial distribution of species.     

A Fully Conjugated Porphyrin-[36]Octaphyrin-Porphyrin Hybrid Tape Exhibiting Möbius Aromaticity

Directly meso-meso linked porphyrin-tetrabromo[36]octaphyrin-porphyrin hybrid trimer 10 was successfully synthesized via acid-catalyzed condensation reaction and subsequent oxidation. Zn^II-metalation of 10 induced transannular meso-meso bond formation to give Möbius aromatic bis-Zn^II octaphyrin 11 , which was oxidized by DDQ/Sc(OTf)₃ to provide fully conjugated porphyrin-[36]octaphyrin-porphyrin hybrid tape 12 as the first example of porphyrin tape exhibiting Möbius aromaticity. Hybrid tape 12 displays significantly red-shifted absorption and small electrochemical HOMO-LUMO gap, indicating the effective conjugation through the whole chromophores.     

Photoinduced DNA Interstrand Cross-Linking by 1,1′-Biphenyl Analogues: Substituents and Leaving Groups Combine to Determine the Efficiency of Cross-Linker

Two series of 1,1′-biphenyl analogues with various leaving groups (L=OAc, OCH₃, OCHCH=CH₂, OCH₂Ph, SPh, SePh, and Ph₃P⁺) were synthesized. Their reactivity towards DNA and the reaction mechanism were investigated by determining DNA interstrand cross-link (ICL) efficiency, radical and carbocation formation, and the cross-linking reaction sites. All compounds induced DNA ICL formation upon 350 nm irradiation via a carbocation that was generated from oxidation of the corresponding free radicals. The ICL efficiency and the reaction rate strongly depended on the combined effect of the leaving group and the substituent. Among all compounds tested, the high ICL efficiency (30–43 %) and fast reaction rate were observed with compounds carrying a nitrophenyl group and acetate ( 2 a ), ether ( 2 b and 2 c) , or triphenylphosphonium salt ( 2 g ) as leaving groups. Most compounds with a 4-methoxybenzene group showed similar DNA ICL efficiency (≈30 %) with a slow DNA cross-linking reaction rate. Both cation trapping and free radical trapping adducts were detected in the photo activation process of these compounds, which provided direct evidence for the proposed mechanism. Heat stability study in combination with sequence study suggested that these photo-generated benzyl cations alkylate DNA at dG, dA, and dC sites.     

TATB生成焓的量子力学计算

采用Hartree-Fock方法和密度泛函 BPW91方法,对TATB分子的几何结构进行了优化,计算了其电子能量和热运动的能量.计算并讨论了TATB的生成焓.结果表明,TATB分子中的苯环离域电子结构引起TATB生成焓计算的较大的系统偏差;利用具有相似离域电子结构的苯和NO的生成焓进行修正,计算得到的TATB生成热与实验结果符合较好.?     

Electrical pumping of a third-order mode semiconductor laser

AlGaAs-based quantum well laser structures with third-order waveguide mode emission at 775 nm are a promising route toward compact twin-photon sources at 1.55 μm based on the principle of modal phase matching between the pumping frequency and fundamental modes at half frequency in III–V semiconductor waveguides. Following the demonstration and characterization of an optically pumped third-order mode semiconductor laser, in this paper we present data of the corresponding structure under conditions of electrical pumping. By pumping electrically and optically the same sample made for current injection, identical transverse far-field angular laser mode profiles are measured and with very low parasitic losses. Although they do not follow the third-order mode emission pattern as it is expected, however this means that the different way of pumping, that of the electrical one as compared to optical pumping is not responsible for the absence of third-order mode emission. Furthermore, since the undoped optically pumped laser sample correctly emits on the third-order mode, it is concluded that the cladding layers of the structure still need to be optimized in doping and thickness, in order to reduce the internal losses for the third-order mode.     

Two-dimensional cellular automata

A largely phenomenological study of two-dimensional cellular automata is reported. Qualitative classes of behavior similar to those in one-dimensional cellular automata are found. Growth from simple seeds in two-dimensiona! cellular automata can produce patterns with complicated boundaries, characterized by a variety of growth dimensions. Evolution from disordered states can give domains with boundaries that execute effectively continuous motions. Some global properties of cellular automata can be described by entropies and Lyapunov exponents. Others are undecidable.This work was supported in part by the U.S. Office of Naval Research under Contract No. N00014-80-C-0657.     

Production of hypernuclei with the reaction

We present results on the production of bound states of Θ⁺ in nuclei using the (K⁺,π⁺) reaction. By taking into account the states obtained within a wide range of strength of the Θ⁺ nucleus optical potential, plus the possibility to replace different nucleons of the nucleus, we obtain an excitation spectra with clearly differentiated peaks. The magnitude of the calculated cross sections is well within reachable range.     

Carbon dioxide activation and alkali compound formation. I. Vibrational characterization of oxalate intermediates

The activation of CO₂ in thin potassium layers adsorbed on Cu(1 1 1) has been studied with time-evolved Fourier transform-infrared reflection absorption spectroscopy. The growth of thin layers by reactive evaporation of potassium in a CO₂ atmosphere permits control of the K:CO₂ stoichiometry, which strongly affects the selectivity in the formation of intermediates and the decomposition pathways of the layer. Layers grown in a CO₂ rich atmosphere exhibit the preferential growth of stoichiometric potassium oxalate K₂C₂O₄ (D_2h). The molecular identity of oxalate with D_2h symmetry is confirmed by vibrational spectra utilizing isotopic substitution methods (¹³CO₂ and C¹⁸O₂) and by the use of isotopic mixtures of CO₂/C¹⁸O₂ and CO₂/¹³CO₂. A comparison of the isotope data with theoretical calculations gives an estimated OCO bond angle in oxalate of 132°. Far-IR spectra obtained with synchrotron radiation indicate the equivalent interaction of all oxygen atoms with the potassium. A comparison of the vibrational data with theoretical ab initio calculations confirms the structural model of an oxalate species that is bulk coordinated with no strong directional bonding and all oxygen atoms equally interacting with potassium.At medium and low CO₂:K ratios, very complex vibrational spectra are observed, indicating the formation of an oxalate surface species with C_2v symmetry in addition to D_2h⁻ oxalate, CO₂⁻ and CO₂²⁻ species.