Amphiphilic silica nanoparticles as pseudostationary phase for capillary electrophoresis separation

Amphiphilic silica nanoparticles surface-functionalized by 3-aminopropyltriethoxysilane (APTES) and octyltriethoxylsilane (OTES) were successfully prepared and characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectrometry (FT-IR) and thermogravimetry (TG) techniques. The potential use of these bifunctionalized nanoparticles as pseudostationary phases (PSPs) in capillary electrophoresis (CE) for the separation of charged and neutral compounds was evaluated in terms of their suitability. As expected, fast separation of representative aromatic acids was fulfilled with high separation efficiency, because they migrate in the same direction with the electroosmotic flow (EOF) under optimum experimental conditions. Using a buffer solution of 30mmol/L phosphate (pH 3.0) in the presence of 0.5mg/mL of the synthesized bifunctionalized nanoparticles, the investigated basic compounds were baseline-resolved with symmetrical peaks. Due to the existence of amino groups on the surface of nanoparticles, "silanol effect" that occurs between positively charged basic analytes and the silanols on the inner surface of capillary was greatly suppressed. Furthermore, the separation systems also exhibited reversed-phase (RP) behavior when neutral analytes were tested.     

Simultaneous direct analysis of benzimidazole fungicides and relevant metabolites in agricultural products based on multifunction dispersive solid-phase extraction and liquid chromatography–mass spectrometry

A fast and flexible multi-residue procedure for effective extraction of benzimidazole fungicides and the related transformation products in various raw agricultural commodities is developed for direct and simultaneous analysis by liquid chromatography–tandem mass spectrometry (LC–MS/MS). The new sample preparation method, introduced to allow direct extraction of the labile fungicides as the intact forms in complex matrices, is achieved using a conservative homogenizing extraction and multifunction adsorption cleanup (CHEMAC), which basically involves salting-out partitioning/extraction with acetate-buffered acetonitrile at low-temperature and sequential rapid solid-phase dispersive cleanup with a ternary sorbent mixture. The CHEMAC procedure was optimized and further modified by incorporating several pretreatment variables influencing sample stability and process efficiency, such as pH, temperature, salt and sorbent utilized. By using CHEMAC, a noteworthy improvement in extraction recoveries was obtained for the problematic fungicides, while no significant differential matrix effects were detected on the LC–MS/MS analysis in all 9 matrices. The in-source fragmentation of benomyl occurred but caused no cross-talk interference in multi-component analysis. Thus the CHEMAC-based LC–MS/MS strategy can serve as an attractive approach to satisfactory overall process efficiencies (70–92%) with acceptable repeatability (relative standard deviations below 16%) for all the analyte–matrix combinations. Mean accuracies were obtained within the range of 70–110% at fortified levels of 1–500 ng/g, with intra-day and inter-day variations less than 15 and 20%, respectively. The successful practical application of the proposed method to real samples has also been demonstrated.     

荧光偏振技术分析全血XPD基因单核苷酸多态性的研究

将荧光偏振与非对称基因扩增技术联用,建立了可用于检测全血XPD基因单核苷酸多态性的新方法。用不等量(1∶5)的XPD基因上、下游引物对含单核苷酸多态性位点的目的片段进行非对称扩增,再用两种单核苷酸多态性序列特异的荧光标记探针对扩增产物进行检测。由于扩增得到的单链片段能够与各自不同的荧光标记探针特异结合,使荧光标记分子的分子量增加,偏振值(FP)增高。通过检测增高的FP值,可确定目的片段单核苷酸多态性。采用本方法对98例全血的XPD基因第751位密码子进行了单核苷酸多态性分析,并与传统的荧光偏振检测方法进行了比较,取得满意结果。     

室温下钯-金属酞菁/分子筛复合催化剂催化甲烷选择氧化制甲醇

 在交换了 Fe2+, Co2+或 Cu2+的 Y 型分子筛上, 采用苯酐-尿素固相合成法制备了组装在 Y 型分子筛超笼中的金属酞菁类催化剂. 以 H2O2 为氧化剂, 考察了该金属酞菁/分子筛复合物上甲烷选择氧化制甲醇反应的性能, 并优化了反应条件. 结果表明, 在室温下, 金属酞菁/分子筛复合催化剂 FePc/Y, CoPc/Y 和 CuPc/Y 对 H2O2 氧化甲烷反应均有催化作用. 在这些复合物上进一步担载可催化 H2O2 原位生成的 Pd, Au 或 PdAu 贵金属, 并考察了其催化分子氧选择氧化甲烷反应的性能. 贵金属与金属酞菁/分子筛复合催化剂的偶合实现了室温下分子氧对甲烷的活化. 其中, Pd 与 CuPc/Y 间的协同效应使得室温下甲烷选择氧化反应活性有了较大提高.     

铜催化的乙酰苯胺间位碳氢芳基化反应机理的理论研究

通过系统的理论计算研究了Gaunt报道的一个新颖的间位选择性C-H键芳基化反应的机理. Oxycupration机理含有一个关键的Cu(III)基团和酰胺氧原子对苯环C2=C3键的反式加成步. 但是计算结果表明这个反应路径的活化能太高(>175.56 kJ/mol),所以是动力学禁阻的. 提出了一个含有关键的酰胺导向的Cu(III)-Aryl对底物C2=C3键的顺式加成步的机理,这一步是反应的决速步,也是决定产物区域选择性的一步. 这个机理的活化能与实验条件是符合的,而且这个机理预测的产物区域选择性与实验     

An exact algorithm for minimum CDS with shortest path constraint in wireless networks

In this paper, we study a minimum connected dominating set problem (CDS) in wireless networks, which selects a minimum CDS with property that all intermediate nodes inside every pairwise shortest path should be included. Such a minimum CDS (we name this problem as SPCDS) is an important tache of some other algorithms for constructing a minimum CDS. We prove that finding such a minimum SPCDS can be achieved in polynomial time and design an exact algorithm with time complexity O(δ ² n), where δ is the maximum node degree in communication graph.     

Near-infrared emission bands of Er-doped YAP and LSO crystals

The ground state absorption (GSA), photoluminescence (PL) and photoluminescence excitation (PLE) spectra for Er(1.0 at%):YAP and Er(0.5 at%):LSO were measured at room temperature. Based on the GSA spectra, the radiative transition rates and luminescence branch ratios of erbium ions were determined by the Judd-Ofelt (J-O) method. In the range of 1400-1700 nm Er(1.0 at%):YAP has intense absorption at 1509 nm (0.96×10⁻²⁰ cm²), which is almost two times larger than the peak absorption of Er(0.5 at%):LSO. From the PL and PLE spectra, four intense emission bands around 850 nm (⁴S_3/2→⁴I_13/2), 980 nm (⁴I_11/2→⁴I_15/2), 1230 nm (⁴S_3/2→⁴I_11/2) and 1520 nm (⁴I_13/2→⁴I_15/2) were observed. The stimulated emission cross-sections of the four bands were calculated by the Fuchtbauer-Ladenberg (F-L) equation. The results suggest that Er(1.0 at%):YAP has potential to realize laser oscillation at 858 nm because of the relatively large simulated emission cross-section (1.76×10⁻²⁰ cm²). The temperature dependences of the PL spectra for the two crystals were also investigated in the range of 290-12 K. The ∼1520 nm emission presents continuous increase with temperature, while the emissions around 850, 1230 and 980 nm firstly increase with temperature, then reach their own largest values at the transition temperatures (about 100 K), and finally decrease with temperature. These results were well interpreted by the temperature dependence of multi-phonon process.     

Effects of nanostructure on optoelectronic properties of β phase polyoctylfluorene thin film

β phase polyoctylfluorene thin films were obtained by exposure to toluene vapor for various annealing times or dipping into a THF/methanol mixture. The photoluminescence and electroluminescence of PFO thin films decrease with increasing annealing time. Grazing incident X-ray diffraction of the thin films indicates that more and larger β phase crystallites will be generated in thin film exposed for longer time, which will lead to more defects that reduce photoluminescence and electroluminescence. By analyzing the mechanism of formation of β phase, we assume that the defects mainly come from the formation of out-of-plane crystalline structure. The assumption is confirmed by higher photoluminescence of β phase polyoctylfluorene thin film achieved by dipping into a THF/methanol mixture that has less out-of-plane crystalline structure.     

Propagation of the degree of cross-polarization of stochastic electromagnetic pulsed beams in free space

The concept of the degree of cross-polarization is extended from stochastic electromagnetic stationary beams to stochastic electromagnetic pulsed beams, and the propagation properties of the degree of cross-polarization of stochastic spatially and spectrally partially coherent electromagnetic pulsed beams is studied. The influence of pulse duration and temporal coherence length on the degree of cross-polarization P is emphasized. It is shown that P exhibits an oscillatory behavior in free-space propagation. An increase in the pulse duration or a decrease in the temporal coherence length can weaken the oscillation of P. The validity of the results is interpreted physically.     

Squeezing and entanglement of a two-mode field in a four-level tripod atomic system

The interaction of a collection of N four-level tripod configuration atoms with two orthogonally polarized probe fields is investigated. Under the condition of electromagnetically induced transparency (EIT), we calculate the squeezing and entanglement spectra of the output probe fields. By analyzing the output spectrum, we find that the squeezing and entanglement of the probe fields can be well-preserved after passing through the optically thick medium. Additionally, the effects of the ground state dephasing rates of the atoms on the entanglement and squeezing of the output two-mode squeezed fields are investigated. It is shown that the dephasing rates will degrade the entanglement and squeezing, and these quantum properties can be lost when the dephasing rates increase up to a certain value. This will be useful in the quantum computation and quantum communication.