Search for pi(0)-->nu(mu)nu(mu) decays in the LSND detector

We observe a net beam excess of 8.7+/-6.3(stat)+/-2.4(syst) events, above 160 MeV, resulting from the charged-current reaction of nu(micro) and/or nu;(mu) on C and H in the LSND detector. No beam-related muon background is expected in this energy regime. Within an analysis framework of pi(0)-->nu(mu)nu;(mu), we set a direct upper limit for this branching ratio of Gamma(pi(0)-->nu(mu)nu;(mu))/Gamma(pi(0)-->all)<1.6 x 10(-6) at 90% confidence level.     

Experimental study of the time-dependent rate of K → πππ

The time-dependence of the decay rate of initially pure K⁰ into the final state (π⁺π⁻π⁰) has been studied in search for the decay k_S⁰→π⁺π⁻π⁰. No evidence is found in a sample of 384 observed events. The ratio of the CP -violating K_S⁰ amplitude and the K_L⁰ amplitude is η₊₋₀ = (0.13_−0.20^+0.17) + i(0.17_−0.26^+0.27); the ratio of the CP-conserving K_S⁰ amplitude and the K_L⁰ amplitude is < 0.4. The energy dependence of the K⁰→π⁺π⁻π⁰ matrix element is found to be a₊₋₀ = −0.31 ± 0.03.     

The photochemical rearrangement of a steroidal dienol triflate

Photolysis of the steroidal dienol triflate in pyridine solution using a medium pressure mercury lamp leads to the formation of 6β-trifluoromethyl enone in 78% yield. The structure of compound was confirmed by x-ray analysis.     

镁掺杂氧化铈整体式催化剂催化CO2和CH3OH直接合成碳酸二甲酯

采用共沉淀法成功地合成了不同Mg掺杂量的Ce_1-xMg_xO₂(x=0.05、0.10、0.15、0.20)固溶体催化材料,并运用透射电子显微镜(TEM)、X射线衍射(XRD)、氮气吸附-脱附测试、拉曼光谱、X射线光电子能谱(XPS)、CO₂程序升温脱附(CO₂-TPD)等技术对这些材料进行了表征。结果发现,通过调控CeO₂晶格中Mg的含量,可以调控所制备的Ce_1-xMg_xO₂催化材料的粒径、比表面积、表面缺陷等。其中Ce_0.90Mg_0.10O₂展现了最佳的表面性质,具有最小的平均粒径(约5.8 nm),最大的比表面积(约136 m2·g^-1)以及最高的表面氧含量(31.98%)。将Ce_1-xMg_xO₂催化材料涂覆在堇青石蜂窝陶瓷上制成整体催化剂,考察其对CO₂和CH₃OH直接合成碳酸二甲酯的催化性能。在140℃、2.4 MPa、反应2 h的条件下,Ce_0.90Mg_0.10O₂整体催化剂上碳酸二甲酯的收率高达20.21%,催化效果明显优于CeO₂和其余的Ce_1-xMg_xO₂(x=0.05、0.15、0.20)催化材料。     

Rearrangement of 5-trimethylsilylthebaine on treatment with L-selectride: an efficient synthesis of (+)-bractazonine

Treatment of 5-trimethylsilylthebaine with L-Selectride gave rise to a rearrangement to 10-trimethylsilylbractazonine through migration of the phenyl group, whereas treatment of thebaine with strong Lewis acids is known to lead to a similar rearrangement through migration of the alkyl bridge to give, after reduction, (+)-neodihydrothebaine. It is suggested that the rearrangement of the alkyl group of thebaine is favored due to the formation of a tertiary benzylic cation. However, for 5-trimethylsilylthebaine, the lithium ion of L-Selectride acts as the Lewis acid and the beta-silyl effect dominates in the stabilization of any positive charge. This rearrangement provides a clear example of the greater relative migratory aptitude of phenyl groups over alkyl groups, and provides an efficient synthesis of (+)-bractazonine from thebaine.     

Rationalizing the generation of broad spectrum antibiotics with the addition of a positive charge

Antibiotic resistance of Gram-negative bacteria is largely attributed to the low permeability of their outer membrane (OM). Recently, we disclosed the eNTRy rules, a key lesson of which is that the introduction of a primary amine enhances OM permeation in certain contexts. To understand the molecular basis for this finding, we perform an extensive set of molecular dynamics (MD) simulations and free energy calculations comparing the permeation of aminated and amine-free antibiotic derivatives through the most abundant OM porin of E. coli, OmpF. To improve sampling of conformationally flexible drugs in MD simulations, we developed a novel, Monte Carlo and graph theory based algorithm to probe more efficiently the rotational and translational degrees of freedom visited during the permeation of the antibiotic molecule through OmpF. The resulting pathways were then used for free-energy calculations, revealing a lower barrier against the permeation of the aminated compound, substantiating its greater OM permeability. Further analysis revealed that the amine facilitates permeation by enabling the antibiotic to align its dipole to the luminal electric field of the porin and form favorable electrostatic interactions with specific, highly-conserved charged residues. The importance of these interactions in permeation was further validated with experimental mutagenesis and whole cell accumulation assays. Overall, this study provides insights on the importance of the primary amine for antibiotic permeation into Gram-negative pathogens that could help the design of future antibiotics. We also offer a new computational approach for calculating free-energy of processes where relevant molecular conformations cannot be efficiently captured.

A rapid pathway sampling method combining Monte Carlo and graph theory, developed to describe permeation pathways through outer membrane porins, can distinguish between structurally similar analogs with different permeabilities.     

4-氨基-7-硝基苯并-2-氧杂-1,3-二唑类衍生物的合成及其对汞离子的识别研究

以4-氯-7-硝基苯并-2-氧杂-1,3-二唑、乙二胺和溴乙酸乙酯等为原料,合成4-氨基-7-硝基苯并-2-氧杂-1,3-二唑类衍生物(NBD-OEt),通过IR、NMR和MS对其进行结构表征。研究NBD-OEt的吸收光谱和荧光光谱性质,探讨其在H2O/EtOH(60/40, V/V) pH 7.40的HEPES缓冲体系中对Hg₂ 的响应,以及NBD-OEt与Hg₂ 的结合模式。结果表明, 随Hg₂ 的不断加入可诱使NBD-OEt在476nm的吸收峰红移至514nm,并有两个等吸收点(347nm、482nm);其荧光发射峰由536nm红移至559nm,且在525nm出现等发射点;通过Job plot法测定NBD-OEt与Hg₂ 以1:1的计量比结合。