Hole Migration in Telomere-Based Oligonucleotide Anions and G-Quadruplexes

Vacuum ultraviolet photoionization of a gas-phase oligonucleotide anion leads to the formation of a valence hole. This hole migrates towards an energetically favorable site where it can weaken bonds and ultimately lead to bond cleavage. We have studied Vacuum UV photoionization of deprotonated oligonucleotides containing the human telomere sequence dTTAGGG and G-quadruplex structures consisting of four dTGGGGT single strands, stabilized by NH₄⁺ counter ions. The oligonucleotide and G-quadruplex anions were confined in a radiofrequency ion trap, interfaced with a synchrotron beamline and the photofragmentation was studied using time-of-flight mass spectrometry. Oligonucleotide 12-mers containing the 5'-TTAGGG sequence were found to predominantly break in the GGG region, whereas no selective bond cleavage region was observed for the reversed 5'-GGGATT sequence. For G-quadruplex structures, fragmentation was quenched and mostly non-dissociative single and double electron removal was observed.     

Fluorescence monitoring of microchip capillary electrophoresis separation with monolithically integrated waveguides

Using femtosecond laser writing, optical waveguides were monolithically integrated into a commercial microfluidic lab-on-a-chip device, with the waveguides intersecting a microfluidic channel. Continuous-wave laser excitation through these optical waveguides confines the excitation window to a width of 12 microm, enabling high-resolution monitoring of the passage of different types of fluorescent analytes when migrating and being separated in the microfluidic channel by microchip capillary electrophoresis. Furthermore, we demonstrate on-chip-integrated waveguide excitation and detection of a biologically relevant species, fluorescently labeled DNA molecules, during microchip capillary electrophoresis. Well-controlled plug formation as required for on-chip integrated capillary electrophoresis separation of DNA molecules, and the combination of waveguide excitation and a low limit of detection, will enable monitoring of extremely small quantities with high spatial resolution.     

Femtosecond laser microstructuring: an enabling tool for optofluidic lab‐on‐chips

This paper provides an overview of the rather new field concerning the applications of femtosecond laser microstructuring of glass to optofluidics. Femtosecond lasers have recently emerged as a powerful microfabrication tool due to their unique characteristics. On the one hand, they enable to induce a permanent refractive index increase, in a micrometer‐sized volume of the material, allowing single‐step, three‐dimensional fabrication of optical waveguides. On the other hand, femtosecond‐laser irradiation of fused silica followed by chemical etching enables the manufacturing of directly buried microfluidic channels. This opens the intriguing possibility of using a single laser system for the fabrication and three‐dimensional integration of optofluidic devices. This paper will review the state of the art of femtosecond laser fabrication of optical waveguides and microfluidic channels, as well as their integration for high sensitivity detection of biomolecules and for cell manipulation.     

Nonlinear analysis of the pharmacological conversion of sustained atrial fibrillation in conscious goats by the class Ic drug cibenzoline

Methods from nonlinear dynamics were applied to test the hypothesis that the dynamics of sustained atrial fibrillation (AF) is modified by the class Ic drug cibenzoline during pharmacological conversion. The experiments were performed in conscious goats in which sustained AF was induced by continuous maintenance of AF via programmed electrical stimulation. Data were collected from electrophysiological experiments in five goats to terminate sustained AF by continuous infusion of cibenzoline. Sets of five unipolar epicardial electrograms of one minute duration were recorded from the left and right atrial free wall during sustained AF (control), and at three episodes during infusion of cibenzoline, when the mean AF interval had been prolonged to 25%, 50% and 85% with respect to control. Ventricular far-field potentials were removed from atrial electrograms by a coherent averaging procedure. Using the Grassberger-Procaccia method, the dynamics of the local atrial electrograms was investigated by estimating the (coarse-grained) correlation dimension and correlation entropy from the correlation integral. The results were related to a recently proposed classification (types I-III) of AF based on the degree of complexity of atrial activation patterns. The coarse-grained correlation dimension D(cg) and entropy K(cg) indicated that sustained AF corresponded to type II. During drug administration the coarse-grained parameters were not significantly different from control. Scaling regions in the correlation integral were observed after infusion of cibenzoline (3 out of 5 goats) suggesting that the drug introduced low-dimensional features (type I) in the dynamics of AF (correlation dimension D ranging from 2.8 to 4.4 and correlation entropy K from 1.6 to 6.2 nats/s). Sinus rhythm recorded shortly after cardioversion was very regular (D<2 and K<3 nats/s). The hypothesis that the electrograms during AF and sinus rhythm were generated by a static transformation of a linear Gaussian random process was rejected using a test for time reversibility. The nonlinear analysis revealed that cibenzoline does not significantly alter the dynamics of sustained AF during pharmacological conversion other than a slowing down of the atrial activation and a somewhat increasing global organization of the atrial activation pattern. The sudden change in the dynamical behavior at cardioversion suggests a mechanism that is reminiscent of a bifurcation. (c) 1997 American Institute of Physics.     

氮氧自由基研究:XXI,水溶液中哌啶氮氧自由基单电子还原反应机理的极谱研究

本文采用取样直流极谱, 常规脉冲极谱, 微分脉冲极谱和交流极谱考察了,2,2,6,6-四甲基-4-羟基哌啶 -1-氧和2,2,6,6-四甲基-4-氧哌啶 -1-氧由基及2,2,6,6-四甲基哌啶 -1-氧自由基在水溶液中的还原反应, 并研究了它们的还原经历电化学过程 。     

Hydrogenated carbon clusters produced by highly charged ion impact on solid

The emission of small (hydrogenated) carbon cluster ions C_nHm ⁺ (n =2-22) upon highly charged Xe^q+ (q =20-44) impact on C₈₄ surfaces is studied by means of time-of-flight secondary ion mass spectrometry. The respective stage of hydrogenation/protonation of a certain carbon cluster ion Cn ⁺ is a strong indication for its geometrical structure. From the cluster ion yield as a function of cluster size it can be concluded, that the hydrogenation takes place after the initial carbon cluster formation. The carbon clusters seem to be emitted as an entity in agreement with “equilibrium” and “shock wave” models. Received 4 February 2000     

Optical sensing in microfluidic lab-on-a-chip by femtosecond-laser-written waveguides

We use direct femtosecond laser writing to integrate optical waveguides into a commercial fused silica capillary electrophoresis chip. High-quality waveguides crossing the microfluidic channels are fabricated and used to optically address, with high spatial selectivity, their content. Fluorescence from the optically excited volume is efficiently collected at a 90° angle by a high numerical aperture fiber, resulting in a highly compact and portable device. To test the platform we performed electrophoresis and detection of a 23-mer oligonucleotide plug. Our approach is quite powerful because it allows the integration of photonic functionalities, by simple post-processing, into commercial LOCs fabricated with standard techniques. Figure Femtosecond laser written waveguides can selectively excite fluorescence in a microfluidic channel of a commercial lab-on-a-chip. A compact scheme for on-chip detection by laser induced fluorescence is applied to capillary electrophoresis of a 23-mer Cy3-labeled oligonucleotide     

一类单完备李代数

确定了代数Va,b.c的导子代数,其中Va.b.c是由非交换代数Ca,b,c[X±1,Y±1,Z±1]的所有内导子所张成的李代数,证明了导子代数数Va.b,c是由所有内导子和3个外导子D1,0,0,DO,1,0,D0,0,1张成的,同时还给出了一类无限维的单完备李代数.     

基于金属卟啉的甲基磷酸二甲酯分子印迹聚合物微球的合成及性能

合成了分别以5-(4-甲基丙烯酰氧苯基)-10,15,20-三苯基锌卟啉(ZnMOTPP)和5-(4-甲基丙烯酰氧苯基)-10,15,20-三苯基钆卟啉(GdMOTPP)为功能单体, 甲基丙烯酸(MAA)为辅助功能单体的甲基磷酸二甲酯(DMMP)分子印迹聚合物微球. 扫描电子显微镜(SEM)表征结果表明, 微球平均粒径为50～100 μm, 粒度均匀. 与甲基丙烯酸作为功能单体的分子印迹聚合物微球的吸附性能和特异性进行对比发现, ZnMOTPP分子印迹微球的吸附性能优于 GdMOTPP分子印迹微球, 金属卟啉分子印迹微球的吸附性能优于仅以甲基丙烯酸作为功能单体的分子印迹微球, 并且微球对其印迹分子DMMP具有特异性吸附. Scatchard分析表明, DMMP分子印迹空穴中只存在一类结合位点, MIPMs-Zn+MAA的最大吸附量Q_max=148 μmol/g, MIPMs-Gd+MAA的Q_max=78.9 μmol/g, MIPMs-MAA的Q_max=13.57 μmol/g.     

可视交叉传感阵列对蛋白质及其热变性过程的快速识别

以卟啉及其衍生物和特异性染料为敏感化学元件, 基于交叉响应原理构建了识别蛋白质的可视6×6阵列. 该阵列以颜色差谱图显示其与蛋白质作用呈现的特异性光谱反应, 采用聚类分析、 主成分分析和欧氏距离对图谱进行了分析. 结果表明, 该阵列可以鉴别模式蛋白牛血清白蛋白(BSA)、 牛血红蛋白(BHb)和卵清白蛋白(Ova)及其混合物, 且有望实现定量分析. 此外, 阵列的高敏感性使其不仅能识别天然蛋白质和不同变性程度的蛋白质, 还能对其热变性过程进行可视化实时监控. 该阵列产生的特殊颜色变化与蛋白质的空间构型、 微环境pH值的差异及溶解度有关. 因此, 该方法不仅能实现对蛋白质的快速识别, 为蛋白质热变性机理的研究提供新途径, 而且在临床医学和食品安全等的实时快速检测方面有潜在的应用价值.