Defining the Scope of the Acid-Catalyzed Glycosidation of Glycosyl Bromides

Following the recent discovery that traditional silver(I) oxide-promoted glycosidations of glycosyl bromides (Koenigs–Knorr reaction) can be greatly accelerated in the presence of catalytic TMSOTf, reported herein is a dedicated study of all major aspects of this reaction. A thorough investigation of numerous silver salts and careful refinement of the reaction conditions led to an improved mechanistic understanding. This, in turn, led to a significant reduction in the amount of silver salt required for these glycosylations. The progress of this reaction can be monitored by naked eye, and the completion of the reaction can be judged by the disappearance of characteristic dark color of Ag₂O. Further evidence on higher reactivity of benzoylated α-bromides in comparison to that of their benzylated counterparts has been acquired.     

奖惩机制下闭环供应链非正规渠道社会效应研究

针对闭环供应链非正规渠道在促进资源回收再利用的同时又对环境造成二次污染的情况,给出资源回收当量指标以综合考量渠道资源回收和再造污染效应,利用数学优化和数值仿真方法对比分析存在政府奖惩机制下非正规渠道的经济效应和资源回收效应,获得了非正规渠道积极社会效应的通用定理以及不同再造回收率和奖惩强度下非正规渠道社会效应的特点,给出了政府治理非正规渠道的参考建议和分析方法。     

吡喃木糖热裂解机理的密度泛函理论研究

采用密度泛函理论理论方法M062X/6-311++G(d,p),对吡喃木糖的热解反应机理进行了理论计算分析。针对吡喃木糖热解可能发生的化学反应共设计了九条可能的热解路径,并对各路径中的反应物、中间体和过渡态的几何结构进行了能量梯度全优化,并在梯度全优化的基础上计算了各热解反应路径的热力学和动力学参数。文中以两大类方式来设计反应路径：1）木糖首先经过过渡态TS1发生开环反应生成链状中间体2,该步的反应能垒为188.7 kJ/mol,对于中间体2共设计了五种可能的热解反应路径;2）考虑双键同时断裂的情况,木糖先发生脱水反应,接着按C-C和C-O键同时断裂的情况发生开环反应,针于这种情况共设计了四条可能的热解路径。计算结果表明,吡喃木糖热解的主要反应产物有乙醇、乙醛、糠醛、丙酮、酸类、CO2和CO等小分子化合物。     

New Insight into the EC’ Mechanism of Uric Acid Regeneration in the Presence of Ascorbic Acid on a Poly(3,4‐ethylenedioxithiophene) Modified Gold Electrode

A gold electrode surface was functionalized by means of an electropolymerized conductive poly(3,4‐ethylenedioxythiophene) (PEDOT) organic layer. This modified electrode was used for the electrochemical detection of ascorbic (AA) and uric (UA) acids in an aqueous mixture with a selectivity around 340 mV. The electrochemical reactions kinetics were limited by AA diffusion and UA adsorption at the electrode surface, respectively. Following a previous study ([Electrochem Comm. 2011 , 13, 423–425]) cyclic voltammetry was used to provide a better understanding of the EC’ mechanism of regeneration of UA by AA. Experiments particularly showed that allantoin (i. e. the final product of UA oxidation) is not actually involved in the synergic mechanism but rather the oxidized UA product diimine which is adsorbed at the electrode surface.     

Results from solvophobic theory applied to methylene selectivity in reversed-phase HPLC

A significant amount of work has been previously dedicated to the understanding of methylene selectivity parameter. The conventional theory applied for this understanding was mostly based on the assumption that the difference in the Gibbs free energy of transfer from the mobile phase to the stationary phase is a constant for any two compounds in a homologous series that differ by a CH₂ group. In the present study, it is shown based on solvophobic theory that this assumption is indeed correct, but it provides a theoretical justification for it. Exemplification of the results of theory was obtained using the values for methylene selectivity (α(CH₂)) measured experimentally for seven different C18 chromatographic columns including two core–shell columns and using water and either methanol or acetonitrile as an organic component. Four different homologous series of compounds were used for evaluation. The study proved the theoretical prediction that the values for α(CH₂) obtained using different homologous series of compounds are only slightly different from those obtained using the toluene–butylbenzene series. Even using different homologous series, the same type of information regarding the columns comparison, and the changes in log α(CH₂) with the solvent composition was obtained.     

NaOH对苯胺气液两相介质阻挡放电特性的影响

研究气液两相介质阻挡放电(DBD)的特性,对于深入理解其放电机理、促进其在环保等工业领域中应用具有重要意义。通过电压电流波形和Lissajous图形等电气特性诊断及发射光谱和发光图像等光学特性诊断,研究了液体成分对大气压气液两相DBD放电特性的影响。比较了苯胺和苯胺加NaOH溶液中气液两相DBD放电特性,利用实验结果计算得到放电功率和传输电荷,并结合放电理论对放电机制进行了分析。结果表明,苯胺加NaOH溶液中气液两相DBD,其放电特性与纯苯胺溶液有明显不同,相同电压下其放电电流约为纯苯胺溶液的两倍,其发光强度更强,放电功率和传输电荷更大,且在光谱特性图波长589nm处出现Na原子谱线,NaOH的加入增加了溶液的电导率,同时促进了气相放电强度,使得放电增强。     

Proton conductivity of phosphoric acid derivative of fullerene

The proton conductive property of methano [60] fullerene diphosphoric acid has been investigated under various humidity conditions at the temperature range between 15 and 45 °C. It shows proton conductivity as high as 10⁻² S cm⁻¹ at 25 °C under relative humidity of 95%. Thermal analyses including TG–DTA and thermal desorption mass spectroscopy (TDS) confirm that the compound is thermally stable up to 200 °C. Proton conduction of the compound depends very much on humidity or water content. The logarithmic conductivity at 25 °C is increased linearly with increasing relative humidity. The activation energy (E_a) estimated from the slope of log(σT) vs. 1/T is decreased from 1.08 to 0.52 eV, as the relative humidity is increased from 40% to 75%. The humidity dependence of conductivity is discussed in the light of the observed hydration isotherm.     

紫外Sc_2O_3薄膜的光学和结构性能表征及其激光作用下的损伤机理

利用电子束蒸发方法,在不同沉积温度(50~350℃)下制备了Sc2O3薄膜。分别用分光光度计,小角掠入射X射线衍射仪和轮廓仪测试了薄膜样品的光谱、微结构和表面粗糙度信息,并用薄膜分析软件Essential Macleod计算了Sc2O3薄膜的折射率和消光系数。结果表明:随着沉积温度升高,Sc2O3薄膜结晶程度增强,晶粒尺寸增大,且较高的沉积温度有利于获得较高的折射率。最后用355 nm,8 ns的三倍频Nd:YAG激光器测试了其激光损伤阈值(LIDT),最大值为2.6 J/cm2,且阈值与薄膜的消光系数、表面粗糙度、光学损耗均呈现相反的变化趋势。用光学显微镜和扫描电子显微镜表征了该薄膜的破坏形貌,详细分析了薄膜在不同激光能量作用下破坏的发展过程,以及Sc2O3薄膜在355 nm紫外激光作用下LIDT与制备工艺的关系,重点分析了355 nm激光作用下薄膜的破坏机理。     

应用PDF方法对甲烷射流火焰组分浓度分布的数值研究

本文用k-ε模型和PDF方程相结合的方法对甲烷湍流射流扩散火焰进行了求解，发现Peters等提出的四步反应模型在径向分布预示性能不好，本文对甲烷射流扩散火焰的实际工况进行了分析，提出反应模型的改进方案。改进后的模型所给出的组分浓度分布比原四步反应模型更符合实验结果。验证了修正模型所依据的思想．     

Coordinating a decentralized supply chain with customer returns and price-dependent stochastic demand using a buyback policy

We investigate a decentralized supply chain that consists of a manufacturer and a retailer where the retailer simultaneously determines the retail price and order quantity while experiencing customer returns and price dependent stochastic demand. We propose an agreement between the manufacturer and the retailer that includes two buyback prices, one for unsold inventory and a second for customer returns, and show that this type of easy-to-implement agreement can achieve perfect supply chain coordination and be a win-win for both manufacturer and retailer when a complementary profit-sharing agreement is included.