Cocaine detection by structure-switch aptamer-based capillary zone electrophoresis

Aptamers, which are nucleic acid oligonucleotides that can bind targets with high affinity and specificity, have been widely applied as affinity probes in capillary electrophoresis (CE). Due to relative weak interaction between aptamers and small molecules, the application of aptamer-based CE is still limited in certain compounds. A new strategy that is based on the aptamer structure-switch concept was designed for small molecule detection by a novel CE method. A carboxyfluorescein (fluorescein amidite, FAM) label DNA aptamer was first incubated with partial complementary strand (CS), and then the free aptamer and the aptamer-CS duplex were well separated and determined by metal cation mediated CE/laser-induced fluorescence. When the target was introduced into the incubated sample, the hybridized form was destabilized, resulting in the changes of the fluorescence intensities of the free aptamer and the aptamer-CS duplex. The length of CS was investigated and 12 mer CS showed the best sensitivity for the detection of cocaine. The presented CE-LIF method, which combines the separation power of CE with the specificity of interactions occurring between target, aptamer, and CS, could be a universal detection strategy for other aptamer-specified small molecules.     

Synthesis,crystal structure and nonlinear optical properties of a new cluster complex: WCu3OS3(PPh3)3{S2P(OPr i 2)2}

A new cluster compound WCu₃OS₃(PPh₃)₃{S₂P(OPr ⁱ ₂)₂}, prepared by reacting (NH₄)₂WOS₃ with PPh₃ and [CuS₂P(OPr ⁱ ₂)₂], was characterized by elemental analysis, i.r. spectroscopy and X-ray crystallography. The structure consists of a tetra-nuclear distorted tetragonal core with one W atom coordinated by one O atom, three ₃-S and three Cu atoms. Anisotropic refinement for all nonhydrogen atoms yielded the value R = 0.0718. Investigation of third-order optical nonlinearity using the Z-scan technique shows that the cluster compound exhibits good nonlinear properties with ₂ values of 1.23 × 10^–10 m w^–1 and n ₂ values of –9.3 × 10^–18 m² w^–1 respectively.     

四叔丁基四氮杂卟啉配合物的合成、热稳定性及光限幅特性研究

采用无金属四氮杂卟啉与金属盐回流的方法合成了2种四叔丁基四氮杂卟啉配合物，其中四叔丁基四氮杂卟啉铅(II)配合物未见文献报道。研究了该2种配合物及其配体的电子吸收光谱行为、热稳定性及在532 nm对8 ns激光的光限幅特性。结果表明：该类配合物的Q带的最大吸收峰值λ_max在570~630 nm之间，B带的最大吸收峰值λ_max在330~350 nm之间，随中心金属离子不同，Q带吸收峰位置有明显差异；配合物在氮气气氛中的起始分解温度大于250 ℃，其在热重图上的失重过程对应着4个取代基(-C(CH₃)₃)的脱去，共轭大环在500 ℃以下没有分解；它们的光限幅机制属于激发三重态的反饱和吸收(RSA)，其中四氮杂卟啉铅配合物具有更强的光限幅效应，这与铅的重原子效应有关。     

三维超分子配合物[MoO_2(OCH_2C_5H_4N)_2]制备、晶体结构及三阶非线性光学性质

Na_2MoO_4·2H_2O和2-氯甲基吡啶在水中反应得到了超分子化合物：[MoO_2 (OCH_2C_5H_4N)_2]。其单晶结构测试表明：该化合物含有两种均为6配位的但化学 环境不同的Mo(1)和Mo(2)原子;由此两种钼原子构成的中性配合物[Mo(1)O_2 (OCH_2C_5H_4N_2)]和[Mo(2)O_2(OCH_2C_5H_4N)_2]分别通过氢键O…H-C及吡啶环 间的π-π堆积作用形成了二维的A层和B层,A层与B层之间又在层间氢键的作用下 交错形成了三维的网状固态结构。用Z-scan法在DMF溶液中测试了该化合物的三阶 非线性光学性能,发现它有强的非线性吸收(α_2 = 1.92 * 10~(-9) m·W~(-1)) ,非线性极化率X~((3)) = 1.21 * 10~(-12) esu。     

Transformation of Sign of Nonlinear Refraction between Mo（W）/S/Cu Planar Metal Clusters

Optical nonlinear refractive properties of a series of Mo（W）/S/Cu planar square clusters are investigated using the Z-scan technique with the ns laser pulses at the wavelength of 532 nm. The result shows that the planar metal clusters containing the halogen ligands demonstrate the self-focusing effect, and the other planar metal dusters demonstrate the self-defocusing effect. These facts indicate that the halogen ligands can act as crucial factors in determining the sign of the nonlinear refraction of the Mo（W）/S/Cu planar metal clusters. The analysis of the experimental data shows that the planar clusters with halogen ligands possess greater refraction volume of the excited state than that of the ground state, while the other planar clusters possess the smaller refraction volume of the excited state than that of the ground state.     

二茂铁亚甲基三氮唑配合物的合成、晶体结构及性能研究

以二茂铁亚甲基三氮唑为配体,通过与金属离子的自组装得到了两个新的二茂铁基功能配合物：[Cd(tmf)2(SCN)2]n (1) 和 [Ni(tmf)4(SCN)2] (2) (tmf =二茂铁亚甲基三氮唑)。其中,配合物1呈一维链状结构;配合物2是一个通过氢键作用而形成的二维超分子。三阶非线性光学性质测试结果表明,配合物1（n2 = 2.11 × 10-11 esu）和2（n2 = 1.92 × 10-11 esu）的三阶非线性光学折射效应与配体tmf（n2 = 2.49 ×10-11 esu）接近,说明配合物1和2的三阶非线性光学性质主要受配体控制。循环伏安法(CV)测试结果显示,这两个配合物在电极上的氧化还原过程是受扩散控制的。计时电流法(CA)和计时电量法(CC)测得配合物1的扩散系数比配合物2的扩散系数小。     

三-α-(2,4-二甲基-3-戊氧基)溴硼亚酞菁的三阶非线性光学性质研究

应用Z扫描技术，在波长为532nm、脉宽为8ns条件下，对一种新型亚酞菁配合物三-α-(2,4-二甲基-3-戊氧基)溴硼亚酞菁的三阶非线性光学特性进行了研究，结果发现，该新化合物有较强的反饱和吸收(β=3.7×10^-10 m/W)效应和非线性自聚焦折射效应(n₂=7.2×10^-11esu)，其三阶非线性极化率χ⁽³⁾=1.1×10^-11esu.分析了溴硼亚酞菁配合物特殊的锥形分子结构和重原子溴的轴向配位等因素对其三阶非线性光学性质的重要影响. 关键词： 亚酞菁 Z扫描 三阶光学非线性     

Nonlinear optical properties in double-sided nonlinear media with Z-scan technique based on the Huygens——Fresnel principle

We present a theoretical model to analyse the propagation of a Gaussian laser beam through double-sided nonlinear media. This model is based on the Huygens--Fresnel diffraction integral method. This theoretical model is not only consistent with the cascade structure model for a small nonlinear phase-shift but also can be used for a large nonlinear phase-shift. It has been verified that it is suitable to characterize the double-sided nonlinear media compared with the cascade structure model. A good agreement between the experimental data and the results from the theoretical model is obtained. It will be useful for the design of multi-sided nonlinear materials.     

辐射对称金字塔型剪纸的力学行为

通过在弹性薄板上引入切口,构建了多边形辐射对称金字塔型剪纸结构.利用伽辽金法求解的悬臂梁形变公式和悬臂梁组合的方法,创建了用于解释形变过程的"梁模型",得到n个模块的正N边形金字塔结构的弹性系数与结构参数的关系公式,并求出弹性系数线性阈值的表达式,解释了该结构产生平面外扭曲的原因.利用推导的"梁模型"公式,并通过有限元仿真和实验的方法,系统研究了辐射对称金字塔型剪纸结构的力学响应特征,验证模型的准确性,并用于已有报道的石墨烯剪纸结构的力学特征分析.这项工作系统解释了竖直拉伸的金字塔型剪纸结构的力学响应.     

基于咪唑基配体的Mn(Ⅱ)配合物的水热合成及结构、理论计算和三阶非线性光学性质

在水热条件下用氯化锰和咪唑基配体合成了配合物Mn[（IPB）₂Cl₂]·4H₂O （IPB=4-（1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl） benzaldehyde）,并通过元素分析、红外光谱、紫外衍射、X射线单晶衍射法和Z-扫描技术对其结构和性质进行了表征。X射线单晶衍射结果表明,该化合物晶体属正交晶系,空间群Pnna。采用Z-扫描技术测量了该化合物的非线性光学特性,结果显示,以45 μJ的脉冲能量,在焦点处的透光率为93%,非线性吸收系数为-4.5×10^-11 m·W^-1,非线性折射率为1.0×10^-19 m²·W^-1。该化合物显示了自聚焦的性质。在紫外-可见光谱区,该化合物的最大吸收波长为282nm。