微乳液中球形及棒状SrTiO3纳米粒子的控制合成

以氢氧化锶和钛酸四丁酯为原料, 在水溶液/Triton X-100/环己烷/正己醇反相微乳液体系中制备了直径约为20～80 nm的钛酸锶球形纳米粒子和长约300～1200 nm、直径约为30～150 nm的钛酸锶纳米棒. 用XRD, ICP, TEM, SAED和SEM对样品的结构、成分和形貌进行了表征; 用DLS分析了样品的粒度分布. 结果显示, 水与表面活性剂的物质的量比(ω₀)、反应物浓度、陈化时间等因素都能影响钛酸锶纳米粒子的形貌和尺寸. 所得钛酸锶的锶钛物质的量比约为1.0, 粒度分布较窄, 为立方相单晶结构.     

环境水样中百菌清残留的单滴微萃取-反相液相色谱测定

应用单滴微萃取(SDME)-反相液相色谱(RPLC)检测了环境水样中的百菌清残留.优化了单滴微萃取条件:环己烷萃取剂6 μL、单滴体积2 μL、搅拌速率350 r/min、萃取时间40 min、水溶液温度35 ℃、无盐度.水样经单滴微萃取后,使用Hypersil C18柱反相液相色谱分离测定百菌清.反相液相色谱条件:100%甲醇流动相、流速1.0 mL/min、柱温25 ℃、224 nm检测.方法的线性范围、检出限、相对标准偏差和富集倍数分别为1.0 ～50 μg/L、0.02 μg/L、6.1%和427倍.采用该法对环境水样中的百菌清残留进行了测定,环境水样的加标回收率为98% ～106%.     

气相中W~+活化CO_2分解的自旋禁阻反应机理

用密度泛函理论中的UB3LYP方法,对W采用相对论校正赝势基组(SDD),对C、O采用6-311+G(3d)基组,研究了气相中不同自旋态W+活化CO2分解的反应机理.计算结果表明,W+活化CO2分解反应以六重态进入反应通道,经过六重态势能面到四重态势能面的系间窜越(ISC),最后产物WO+和CO以四重态离开反应通道.运用Harvey方法优化出最低能量交叉点(MECP),并计算了MECP处的自旋-轨道耦合(SOC)常数(494.95cm-1),势能面的交叉和在MECP处较强的自旋-轨道耦合作用降低了自旋禁阻反应能垒,为反应提供了一条低能反应路径,反应总放热量为122.33kJ.mol-1.     

硝酸铈对Calpain基因表达的影响

运用逆转录聚合酶链式反应研究了硝酸铈对大白鼠肝脏Calpain Ⅰ、Calpain Ⅱ基因表达的影响。腹腔注射高浓度硝酸铈可引起Calpain基因表达的变化，提示硝酸铈对肝细胞的损伤可能是因为细胞内钙超负荷所致。     

Long‐Lived Charge‐Transfer State Induced by Spin‐Orbit Charge Transfer Intersystem Crossing (SOCT‐ISC) in a Compact Spiro Electron Donor/Acceptor Dyad

We prepared conceptually novel, fully rigid, spiro compact electron donor (Rhodamine B, lactam form, RB)/acceptor (naphthalimide; NI) orthogonal dyad to attain the long‐lived triplet charge‐transfer (³CT) state, based on the electron spin control using spin‐orbit charge transfer intersystem crossing (SOCT‐ISC). Transient absorption (TA) spectra indicate the first charge separation (CS) takes place within 2.5 ps, subsequent SOCT‐ISC takes 8 ns to produce the ³NI* state. Then the slow secondary CS (125 ns) gives the long‐lived ³CT state (0.94 μs in deaerated n‐hexane) with high energy level (ca. 2.12 eV). The cascade photophysical processes of the dyad upon photoexcitation are summarized as ¹NI*→¹CT→³NI*→³CT. With time‐resolved electron paramagnetic resonance (TREPR) spectra, an EEEAAA electron‐spin polarization pattern was observed for the naphthalimide‐localized triplet state. Our spiro compact dyad structure and the electron spin‐control approach is different to previous methods for which invoking transition‐metal coordination or chromophores with intrinsic ISC ability is mandatory.     

跨断层埋地管线-土接触非连续变形分析

跨断层埋地管线系统主要由管线及其周围土体两种不同介质组成,具有分析介质不连续性特性.为实现对管-土接触介质的不连续性分析,采用非连续变形分析与有限元分析相结合的方法,将跨逆断层埋地管线系统从实际工作状态中取出一部分作为分析对象.利用有限元分析方法对管线及其周围土体进行网格划分;而管-土之间的相互作用,利用非连续变形分析中的不连续介质接触处理方法实现模拟.通过模型的数值分析,研究了逆断层作用下管-土之间的非连续变形相互作用状态,验证了利用非连续变形分析与有限元方法相结合解决埋地管线-土接触的可行性和有效性,为管-土相互作用分析提供了新的研究思路和研究方法.     

用反向渐进结构优化方法研究洞室支护优化

洞室开挖支护的优化是在铁路隧道、矿山开挖、水电站建设中经常面对的课题,特别是研究洞室开挖支护拓扑优化有着重要的意义。本文利用近年来发展的渐进优化方法(ESO)的概念,提出了反向ESO方法的迭代格式,建立了洞室开挖支护优化的准则及其敏感度,研究了均匀地基不同地应力条件使得开挖卸荷产生的总应变能最小的最优支护拓扑。结果证明了反向ESO方法的适用性,最优支护拓扑大致成椭圆或者圆形,其主轴方向与最大主应力主轴方向相同。     

Multivariate Liouville distributions

A random vector (X₁, …, X_n), with positive components, has a Liouville distribution if its joint probability density function is of the formf(x₁ + … + x_n)x₁^a₁.1 … x_n^a_n.1 with thea_i all positive. Examples of these are the Dirichlet and inverted Dirichlet distributions. In this paper, a comprehensive treatment of the Liouville distributions is provided. The results pertain to stochastic representations, transformation properties, complete neutrality, marginal and conditional distributions, regression functions, and total positivity and reverse rule properties. Further, these topics are utilized in various characterizations of the Dirichlet and inverted Dirichlet distributions. Matrix analogs of the Liouville distributions are also treated, and many of the results obtained in the vector setting are extended appropriately.     

考虑车辆随机停放的停车楼减震设计与可靠度分析

在停车楼的设计中通常将车辆荷载以活荷载的方式均匀分布到结构上,实际上受车辆随机停放的影响,停车楼结构整体质量中心偏移,一旦结构遭遇罕遇地震时,车辆的随机停放可能造成停车楼结构发生扭转破坏.本文在传统减震设计方法的基础上考虑车辆活荷载的随机性,并从可靠度的角度验算减震结构在大震作用下的倒塌概率.结果表明,相同的减震设计布...     

Optimization of Biocompatibility for a Hydrophilic Biological Molecule Encapsulation System

Despite considerable advances in recent years, challenges in delivery and storage of biological drugs persist and may delay or prohibit their clinical application. Though nanoparticle-based approaches for small molecule drug encapsulation are mature, encapsulation of proteins remains problematic due to destabilization of the protein. Reverse micelles composed of decylmonoacyl glycerol (10MAG) and lauryldimethylamino-N-oxide (LDAO) in low-viscosity alkanes have been shown to preserve the structure and stability of a wide range of biological macromolecules. Here, we present a first step on developing this system as a future platform for storage and delivery of biological drugs by replacing the non-biocompatible alkane solvent with solvents currently used in small molecule delivery systems. Using a novel screening approach, we performed a comprehensive evaluation of the 10MAG/LDAO system using two preparation methods across seven biocompatible solvents with analysis of toxicity and encapsulation efficiency for each solvent. By using an inexpensive hydrophilic small molecule to test a wide range of conditions, we identify optimal solvent properties for further development. We validate the predictions from this screen with preliminary protein encapsulation tests. The insight provided lays the foundation for further development of this system toward long-term room-temperature storage of biologics or toward water-in-oil-in-water biologic delivery systems.