Bead injection for surface enhanced Raman spectroscopy: automated on-line monitoring of substrate generation and application in quantitative analysis

The technique of bead injection has been adapted for surface enhanced Raman scattering (SERS) to substantially improve precision, long term stability and sensitivity of SERS detection in analytical chemistry. For this purpose a fully automated flow system comprising a dedicated flow-cell has been developed and tested. With the developed flow-cell, which contains two inlet and two outlet channels, it is possible to retain, perfuse and discharge minute amounts of polymer beads while monitoring all steps by Raman spectroscopy. First, beads carrying cation exchanger moieties were retained in the flow-cell and subsequently perfused with a silver nitrate and a hydroxylamine solution using one inlet of the flow cell. By this sequence homogeneous SERS active silver layers were formed on the beads. The uniformity of the achieved silver layer was studied by secondary electron microscopy. For measurement, the analyte was then introduced from the second inlet channel such that the interaction between the activated SERS beads and analyte occurred in close proximity and within the focus of the laser excitation beam. Due to the complete computer control of all experimental steps, including bead entrapment, SERS layer generation, sample introduction and final bead removal, highly reproducible conditions for SERS were achieved. The method was developed using 9-aminoacridine as a test molecule. Quantitative studies were carried out for 9-aminoacridine and acridine showing linear calibrations from 1-100 nmol l(-1) and 50-1,000 nmol l(-1), respectively, using a sample volume of 200 microl each. Typical relative standard deviations were 4.7% for 9-aminoacrine and 5.8% for acridine.     

Six-dimensional vibrational analysis of coupled intermolecular vibrations in a binary cluster

We report on full- (six-) dimensional calculations of the intermolecular vibrations of a binary aromatic-solvent cluster. An exact Hamiltonian for this kind of interaction is modified in a general manner in order to perform calculations of molecules without symmetry. The binary cluster phenol(H2O)1 is used as a test case since its intermolecular vibrations are anharmonic and highly coupled. The formulation of the Schrodinger equation leads to a complex-valued eigenvalue problem with a dimension larger than two million, which is solved by filter diagonalization to obtain both eigenvalues and eigenvectors. With the knowledge of the eigenvectors, an interpretation of all eigenvalues is possible by a characterization with pseudoquantum numbers that are related to the widely used nomenclature of intermolecular normal motions in aromatic(solvent) clusters.     

\mathcal{O}(\alpha ^2 L^2 ) radiative corrections to deep inelasticep scattering for different kinematical variables

The QED radiative corrections are calculated in the leading log approximation up to $\mathcal{O}(\alpha ^2 )$ for different definitions of the kinematical variables using jet measurement, the ‘mixed’ variables, the double angle method, and a measurement based onθ _e andy _JB . Higher order contributions due to exponentiation of soft radiation are included.     

Constructing nonresidues in finite fields and the extended Riemann hypothesis

We present a new deterministic algorithm for the problem of constructing th power nonresidues in finite fields , where is prime and is a prime divisor of . We prove under the assumption of the Extended Riemann Hypothesis (ERH), that for fixed and , our algorithm runs in polynomial time. Unlike other deterministic algorithms for this problem, this polynomial-time bound holds even if is exponentially large. More generally, assuming the ERH, in time we can construct a set of elements that generates the multiplicative group . An extended abstract of this paper appeared in Proc. 23rd Ann. ACM Symp. on Theory of Computing, 1991.

     

Flow-through microdispenser for interfacing micro-HPLC to Raman and mid-IR spectroscopic detection

A flow-through microdispenser has been coupled to a micro HPLC separation system and used as a solvent elimination interface for Fourier transform infrared (FTIR) and Raman spectroscopic detection of the separated compounds. Using the microdispenser picoliter sized droplets can be generated and deposited on an appropriate target placed on a computerized x, y-stage. Evaporation of volatile solvent and buffer is rapid and allows analysis of the obtained dry deposits by various techniques. Due to the destruction free character of Raman and FTIR spectroscopy they can be applied sequentially to interrogate the same deposit. In the reported application five phenolic acids typically present in wine have been separated on a C-18 column technique using a mixture of water, methanol and acetic acid as mobile phase. For spectrum acquisition infrared and Raman microscopes have been used. The spectra recorded from the dried deposits of the separated compounds agreed well with the reference spectra of corresponding components.     

A unified and quantitative receptor model for the microtubule binding of paclitaxel and epothilone

[formula: see text] Paclitaxel and epothilone represent the two major classes of antimicrotubule agents that promote tubulin polymerization and, presumably, mitotic arrest during cell division. A common minireceptor binding site model at beta-tubulin has been constructed for these structurally divergent compounds. Utilizing 20 amino acids identified in photoaffinity labeling experiments, the 3-D model correlates measured and predicted Ki's with r = 0.99 and rms(delta Gcalc-delta Gexp) = 0.2 kcal/mol. In addition, the model predicts the affinity of compounds not used in the training set and explains much of the SAR for the paclitaxel and epothilone families.