基于新型可视化学传感阵列的氨基酸快速识别

以卟啉和其衍生物及指示剂为传感元件,构建了一种对氨基酸敏感的可视传感阵列.可视化学传感阵列以交互响应的敏感元件组成阵列,对不同物质产生特异的响应,并通过信号识别处理系统,将检测结果以图谱的方式显示,实现检测的可视化.研究中筛选了对氨基酸敏感的36种化学物质,构建了6×6的传感阵列,使用自主研发的阵列数据采集与处理系统,对10种具有代表性的常见氨基酸进行了检测,氨基酸溶液与阵列的反应时间为5 min.对实验检测结果数据采用主成分分析和判别分析进行了计算和分析.实验结果显示,通过阵列响应的可视差图可以将浓度为375 μmol/L的10种氨基酸明显区分.判别分析结果显示,本可视阵列对氨基酸识别的准确率达到97%.二维主成分散点图和判别分析散点图对10种氨基酸都有显著分辨效果.本可视传感阵列可用于氨基酸的快速识别.     

A Dual Read-out Molecularly Imprinted Composite Membrane Sensor Based on Zinc Porphyrin for the Detection of Dimethyl Methylphosphonate

Molecularly imprinted membrane-zinc porphyrin-mathacrylate(MIM-Zn-MAA), a dual read-out sensor based on a molecularly imprinted membrane, was developed to recognize and detect dimethyl methylphosphonate (DMMP) as an intermediate molecule of organophosphorus pesticides. The membranes were prepared via thermal polymerization of two functional monomers(zinc porphyrin and mathacrylate) on the surface of a glass slide functionalized with ethylene glycol dimethacrylate and azobisisobutyronitrile. The morphology of the as-synthesized MIM-Zn-MAA was determined with scanning electronic microscopy. The composite membranes exhibited macrovoid morphologies, which were affected by the functional monomers. These membranes were selectively adsorbed onto the template molecule and displayed higher adsorbing capacity toward DMMP compared with their structural analogs. Changes in the fluorescent spectra were qualitatively and quantitatively monitored via fluorescence photometry. Difference maps were also obtained using colorimetry before and after the reaction between MIM-Zn-MAA and DMMP at various concentrations. The maps showed a wide linear range varying from 0.1 μmol/L to 10 mmol/L with a low detection limit of 0.1 μmol/L. These preliminary results demonstrate that the as-fabricated dual read-out sensor displays good sensitivity and selectivity toward DMMP, indicating its considerable potential in DMMP detection in practical applications.     

用同步辐射X射线衍射技术分析GaN/Si外延膜的结构与应变

选用有AlN和AlGaN缓冲层的GaN/Si作为测试样品,采用同步辐射X射线衍射(SRXRD)技术对样品外延膜(GaN)的几何结构、晶格常量及其应变进行了分析.结果表明,同步辐射X射线衍射实验可以作为一种有效的技术手段,测试固体结构及应变.     

羟基卟啉化合物的电化学、顺磁共振及时间分辨光电压性质

通过循环伏安法、电子顺磁共振谱和时间分辨电压光谱研究了羟基取代基数目和位置的不同对羟基苯基卟啉化合物的电化学、电子顺磁共振和时间分辨光电压性质的影响. 研究结果表明, 所有氧化还原反应都是在卟啉环上进行的. 卟啉周边取代基数目的增加使得卟啉共轭体系平均电子云密度增大, 导致体系易氧化而难以还原. 对称性增强可能使卟啉化合物的半波电位值向正方向移动, 羟基取代基的给电子效应对于卟啉化合物电化学性质的影响起主导作用. 常态下卟啉分子没有EPR信号, 在光的激发下, 卟啉分子由原来的逆磁性分子变成顺磁性的激发三重态分子, 这种激发三重态分子在分子轨道上具有两个未成对电子, 这两个电子相距很近, 彼此之间发生很强的相互作用而产生电子, 它的g值随卟啉共轭体系平均电子云密度增大而变大. 时间分辨光电压是由分子中的自由光声载流子的存在而产生的, 光电压的衰减与分子结构密切相关, 它们的电荷分离速度基本上随卟啉周边羟基取代基数目的增加而减慢.     

Tuning the selectivity/specificity of fluorescent metal ion sensors based on N2S2 pyridine-containing macrocyclic ligands by changing the fluorogenic subunit: spectrofluorimetric and metal ion binding studies

Two new fluorescent chemosensors for metal ions have been synthesized and characterized, and their photophysical properties have been explored; they are the macrocycles 5-(2-quinolinylmethyl)-2,8-dithia-5-aza-2,6-pyridinophane (L5) and 5-(5-chloro-8-hydroxyquinolinylmethyl)-2,8-dithia-5-aza-2,6-pyridinophane (L6). Both systems have a pyridyl-thioether-containing 12-membered macrocycle as a binding site. The coordination properties of these two ligands toward CuII, ZnII, CdII, HgII, and PbII have been studied in MeCN/H2O (1:1 v/v) and MeCN solutions and in the solid state. The stoichiometry of the species formed at 25 degrees C have been determined from absorption, fluorescence, and potentiometric titrations. The complexes [CuL5](ClO4)(2).1/2MeCN, [ZnL5(H2O)](ClO4)2, [HgL5(MeCN)](ClO4)2, [PbL5(ClO4)2], [Cu3(5-Cl-8-HDQH-1)(L6H-1)2](ClO4)(3).7.5H2O (HDQ=hydroxyquinoline), and [Cu(L6)2](BF4)(2).2MeNO2 have also been characterized by X-ray crystallography. A specific CHEF-type response of L5 and L6 to the presence of ZnII and CdII, respectively, has been observed at about pH 7.0 in MeCN/H2O (1:1 v/v) solutions.     

一种可视化液体传感阵列农药检测新方法

以筛选出的7种染料与合成的纳米金共同构建了液体传感器阵列,每个敏感点对不同农药样品产生不同的响应光谱,通过酶标仪采集光谱数据,结合主成分分析(PCA)、分层聚类分析(HCA)、判别分析(LDA)等模式识别方法建立了一种快速检测有机磷、氨基甲酸酯、有机氯、拟除虫菊酯类农药残留的新方法。PCA结果表明,前三个主成分反映了总信息量的92.69%,且能够对5种农药进行区分;HCA结果表明,对25个样品能够正确的归类;LDA结果表明,对5种农药识别的准确率达100%。表明这种可视化的液体阵列可为农药残留检测提供一个可靠平台,在农药残留检测中具有潜在的应用价值。     

单质碘掺杂纳米TiO2光催化剂的制备及性能

以钛酸四异丙酯和单质碘为起始原料,用改进的溶胶-凝胶法制备了掺碘的纳米TiO2的前驱体,经500 ℃煅烧得到棕黄色TiO2/I2纳米粉末.采用X射线衍射(XRD),紫外-可见(UV-Vis)漫反射光谱,透射电镜(TEM)等手段对TiO2/I2粉末进行了表征,并研究了其光催化性能.结果表明,掺杂的碘存在于TiO2内部纳米孔洞中,不会因为高温而被氧化;光催化降解甲基橙反应是一级反应;TiO2掺杂碘单质后对光响应波长拓展至可见光范围,对甲基橙的降解效率可提高15%以上.     

N,N′-disubstituted imidazolidine-2-thiones as ligands in cobalt(ii) complexes

Summary By treating COX₂ (X = Cl, Br, I or BF₄) withN,Ndimethyl-andN,N-diethylimidazolidine-2-thione, CoL₂ X₂ (X = Cl, Br or I) and CoL₄ (BF₄)₂ complexes have been obtained. The i.r. spectra show all of them to be S-bonded to the metal atom; the cobalt-halogen vibrational frequencies fall in the expected range, while thev(CoS)'s fall at lower wavenumbers than those found for the N-monosubstituted-imidazolidine-2-thione derivatives. Colours, magnetism and electronic spectra support a tetrahedral stereochemistry around Co^II. From the electronic spectra the crystal field parameters have been evaluated. The Dq values for [CoL₄]²⁺ seem to depend on the steric effect of the two alkyl groups of the ligands.This work was supported by the National Research Council (C.N.R.) of Rome.     

Hydrogen bonding abilities and self-association of thiazolidin-and imidazolidin-2-ones and 2-selenones

The hydrogen bonding abilities of iV-methylimidazolidin-2-one and -2-selone and thiazolidin-2-one and -2-selenone have been studied by ir spectroscopy at 25° in carbon tetrachloride solutions, using dimethyl sulphoxide and 4-chlorophenol as proton acceptor (K_A) and proton donor (K_B), respectively. The results are compared with those previously reported for N-methylimidazolidine-2-thione and thiazolidine-2-thione. The K_A values increase in each series in the order O < S < Se and Kg in the reverse order. The and K_B values are discussed in terms of the substituent in ring. The self-association constants (K_D) are dependent on both K_A and K_B, although K_A seems to be much more important.