Electroreduction of a series of alkylcobalamins: mechanism of stepwise reductive cleavage of the Co-C bond

The electrochemical (EC) reduction mechanism of methylcobalamin (Me-Cbl) in a mixed DMF/MeOH solvent in 0.2 M tetrabutylammonium fluoroborate electrolyte was studied as a function of temperature and solvent ratio vs a nonaqueous Ag/AgCl/Cl(-) reference electrode. Double-potential-step chronoamperometry allowed the rate constant of the subsequent homogeneous reaction to be measured over the temperature range from 0 to -80 degrees C in 40:60 and 50:50 DMF:MeOH ratios. Activation enthalpies are 5.8 +/- 0.5 and 7.6 +/- 0.3 kcal/mol in the 40:60 and 50:50 mixtures of DMF/MeOH, respectively. Digital simulation and curve-fitting for an EC mechanism using a predetermined homogeneous rate constant of 5.5 x 10(3) s(-1) give E degrees' = -1.466 V, k degrees = 0.016 cm/s, and alpha = 0.77 at 20 degrees C for a quasi-reversible electrode process. Digital simulation of the results of Lexa and Savéant (J. Am. Chem. Soc. 1978, 100, 3220-3222) shows that the mechanism is a series of stepwise homogeneous equilibrium processes with an irreversible step following the initial electron transfer (ET) and allows estimation of the equilibrium and rate constants of these reactions. An electron coupling matrix element of H(kA) = (4.7 +/- 1.1) x 10(-4) eV ( approximately 46 J/mol) is calculated for the nonadiabatic ET step for reduction to the radical anion. A reversible bond dissociation enthalpy for homolytic cleavage of Me-Cbl is calculated as 31 +/- 2 kcal/mol. The voltammetry of the ethyl-, n-propyl-, n-butyl-, isobutyl-, and adenosyl-substituted cobalamin was studied, and estimated reversible redox potentials were correlated with Co-C bond distances as determined by DFT (B3LYP/ LANL2DZ) calculations.     

基于激光雷达的移动机器人避障控制研究

以VFH算法思想为基础,提出适用于激光雷达的数据处理算法,将其作为避障算法用于移动机器人的室内自主行进过程中。根据室内避障问题的特点,通过仿真研究设计了适用于室内避障的障碍物阈值规则。在移动机器人实验中发现,受室内地面环境影响,直接将仿真程序应用到移动机器人实际操作中,会出现打滑偏航乃至不能顺利到达目标点的严重后果。为此,根据航向角变化率提出了分段降速方法,应用该方法移动机器人在起始点与目标点可以自主移动,验证了算法的有效性与实用性。     

Highly soluble heteroheptacene: a new building block for p-type semiconducting polymers

A facial synthetic route to a new heteroheptacene with the inclusion of carbazole and thiophene units is described. The synthesis of two new semiconducting copolymers with use of the heteroheptacene unit is also reported. The introduction of heteroatoms (sulfur, nitrogen) in the fused-ring system leads to small optical band-gaps of these polymers. The charge carrier mobilities for these polymers are measured in ambient conditions which are sufficient for photovoltaic applications.     

A minimal core based fluorophore for selective detection of Zn(II) ions in aqueous solution and living cells

A minimal core based fluorophore was introduced as a selectively fluorescent "turn on" sensor for Zn(2+) ions in aqueous solution. Addition of Zn(2+) ions to the fluorophore generates a significant emission through a 1:1 ligand-to-metal complex. The fluorescence titration experiment of the minimal core based fluorophore with various metal ions shows that the pyromellitic diimide derivative also has the advantage of a high selectivity to Zn(2+) ions over other metals such as Ni(2+), or Co(2+), Cu(2+), Fe(3+), Fe(2+). More than 8 fold increase in the intensity of fluorescence was observed for the Zn(2+)-bound fluorophore compared to Zn-free fluorophore. Due to its small molecular size, the fluorophore was cell-permeable and successfully applied to the detection of Zn(2+) in living cells. With its relatively high sensitivity to Zn(2+) in living cells, the synthesized new fluorophore will be very useful in the studies on various biological functions of Zn(2+).     

Infrared two-photon-excited visible lasing from a DNA-surfactant-chromophore complex

Infrared two-photon-pumped and cavity-enhanced frequency upconversion lasing has been achieved in a novel DNA-surfactant-chromophore complex (DSCC) gel system, which is a new step toward producing a biological laser. Once the focused intensity of the 150 fs and approximately 775 nm pump laser beam is higher than a certain threshold level, highly directional stimulated emission at approximately 582 nm wavelength can be observed from a 1 cm long DSCC complex gel cell. With cavity feedback provided by the two optical windows, the pump threshold can be further reduced, the highly directional output lasing can be greatly enhanced, and the output spectral linewidth can be reduced to less than 1/5 of the spontaneous fluorescence spectral bandwidth.     

大学物理实验教学改革的实践与探索

对我校大学物理实验教学存在的弊端进行了分析,指出了大学物理实验教学改革的思路、内容和方法,并付诸实践,取得了较好的效果.     

理性调控聚合物给体-非富勒烯受体的混溶性制备高效率有机太阳能电池※

除了非富勒烯受体的设计与合成, 聚合物给体的选择对非富勒烯太阳能电池的光伏性能同样重要. 本工作设计并合成一种共轭骨架无sp³杂化碳原子的新型非富勒受体(命名为MDB), 并将其作为模型化合物研究给受体混溶性和分子有序堆积对太阳能电池性能的影响. 本工作选择三种宽带隙聚合物给体(PM6、J71和P3HT)与MDB共混来制备太阳能电池. 得益于MDB和PM6之间适度的混溶性, 由二者组成的混合膜表现出合适的相分离, “face-on”的分子取向和更紧密有序的分子堆积, 从而促进了载流子传输, 并抑制了电荷复合. 因此基于PM6:MDB的器件实现了13.26%的优异光电转换效率, 远高于基于J71:MDB (8.16%)和P3HT:MDB (0.45%)的器件. 该工作证明了给体-受体之间合适的混溶性是实现高效率有机太阳能电池的关键因素之一, 这对有机光伏材料的设计与合成具有重要指导意义.     

内部爆轰加载下的钢管膨胀断裂研究

采用一种改进后的前照明分幅摄影技术,研究了45号钢管在三种不同猛度炸药加载下的膨胀断裂行为,得到了与材料动态断裂行为有关的一些参数值。还结合壳体材料性质及载荷强度,对破片的断裂特征及尺度分布进行了讨论。     

锰叶绿素的形成和伏安行为

锰叶绿素的形成和伏安行为乔庆东（抚顺石油学院应用化学系,抚顺１１３００１）叶绿素广泛存在于绿色植物中,在光合作用中发挥着重要的生理功能￣［１］．锰离子是植物生长中必需的金属离子之一,与植物的光化学析氧反应有密切关系￣［２］。系统地研究叶绿素和金属叶绿...     

鱼洗内颗粒流动的数值模拟

实验表明,鱼洗内的流动存在高度非线性的相互作用,并最终导致表面连续性的破坏. 在数值模拟中,这类问题是非常难处理的. 该文从离散的观点出发,直接考虑容器内部粒子的运动. 即采用分子动力学方法,模拟鱼洗内的流动. 该方法所考虑的实质是颗粒流动,不要求介质是连续的,从统计物理的观点看,当所模拟的粒子数非常大时,在统计上和连续介质相当. 该文首先发展了基于消息传递(MPI)的并行计算程序,可以用来做大规模的颗粒流动模拟. 对鱼洗内的颗粒流动模拟结果表明,在外界激励下,鱼洗内的颗粒流动表现出的现象和液体流动类似,边界的能量以波的形式向内部传播,并很快耗散掉,在边界激励点附近,颗粒因为受到边界和内部粒子的挤压作用而跳起,从直观现象上看, 和鱼洗的流动实验一致. 在能量的概率密度分布函数中,可以观察到两个明显的指数区.