Multiparametric microsensor chips for screening applications

The identification of drug targets for pharmaceutical screening can be greatly accelerated by gene databases and expression studies. The identification of leading compounds from growing libraries is realized by high throughput screening platforms. Subsequently, for optimization and validation of identified leading compounds studies of their functionality have to be carried out, and just these functionality tests are a limiting factor. A rigorous preselection of identified compounds by in vitro cellular screening is necessary prior to using the drug candidates for the further time consuming and expensive stage, e.g. in animal models. Our efforts are focused to the parallel development, adaptation and integration of different microelectronic sensors into miniaturized biochips for a multiparametric, functional on-line analysis of living cells in physiologically environments. Parallel and on-line acquisition of data related to different cellular targets is required for advanced stages of drug screening and for economizing animal tests.     

CO2 tea laser-induced photochemical enrichment of boron isotopes

Mixtures of BCl₃ and H₂S are irradiated with 10.55 μm radiation (P(16) line of the 001–100 band of CO₂) from a TEA laser. After several hours of irradiation it is found that the maximum ¹⁰B to ¹¹B ratio of recovered gaseous boron containing material (primarily unreacted BCl₃) is 0.413 ± 0.004. The corresponding ratio of the BCl₃ starting material is 0.242 ± 0.002. The ¹⁰B concentration has therefore been increased from 19.5% to 29.2%. Further, by irradiating similar mixtures with 10.18 μm radiation (R(30) line of the same CO₂ vibrational band) this ratio changes to 0.169 ± 0.002, the ¹⁰B concentration being lowered to 14.4%. All experiments are performed in a small static system and chemical procedures for recovering milligram quantities of BCl₃ selectively enriched in either isotope are described.     

Diastereoselective Spirocyclization of C-(Alkyloxycarbonyl)formimines of 2-Substituted 1HIndole-3-ethanamines (= Tryptamines): Basic Studies. 5th Communication on Indoles,Indolenines, and Indolines

C-(Alkoxycarbonyl)formimines of type 15–18 were derived from the 2-substituted tryptamines 2 , 9 , 10 , and 11 and transformed with tosyl chloride into tricyclic 3-spiroindoles of types 19–22 (Scheme 3). The influence of the homochiral alkoxy moieties A–D on the stereochemical outcome of this reaction was studied. Good-to-excellent diastereoselectivities were observed with the (?)-8-(phenylmenth-3-yl)oxy group ( B ) as homochiral auxiliary. The structures of the tricycles 4 , (2′R,3S)- 19B , and (2′S,3R) 20C were established by X-ray analysis, the structures of the others by NOE and CD studies, and by chemical correlation. Possibilities to explain the steric course of the spirocyclizations are discussed.     

In situ studies of methanol decomposition and oxidation on Pd(111) by PM-IRAS and XPS spectroscopy

Methanol decomposition and oxidation on Pd(111) at millibar pressure were studied by in situ polarization-modulation infrared reflection absorption spectroscopy (PM-IRAS), on-line gas chromatography and pre- and postreaction X-ray photoelectron spectroscopy (XPS). Various dehydrogenation products such as methoxy CH3O, formaldehyde CH2O, formyl CHO, and CO could be spectroscopically identified. Methanol oxidation proceeds via dehydrogenation to formaldehyde CH2O, which either desorbs or is further dehydrogenated to CO, which is subsequently oxidized to CO2. Carbonaceous overlayers that are present during the reaction may favorably affect the selectivity toward CH2O. The reaction takes place on metallic Pd, and no indications of an involvement of Pd surface oxide were observed.     

On the separation of initial and final state effects in photoelectron spectroscopy using an extension of the auger-parameter concept

First, we show that the quantity Δβ(i) = ΔE_A(kii) + 2ΔE_B(i) — ΔE_B(k) is directly related to the final state relaxation contribution ΔE_R(i) of the binding energy shift ΔE_B(i). ΔE_A(kii) is the kinetic energy shift of the Auger transition which corresponds to the decay of a hole state with a hole in level k into a final state with two holes in level i. The shift parameter Δβ(i), which is based on information on two binding energies, is conceptually similar to Wagner's Auger parameter. To establish the relation between Δβ(i) and ΔR(i) one needs, however, less drastic approximations than in the case of Auger parameter shifts. The only approximation necessary is the assumption that ΔR(i) is determined by coulomb contributions.Secondly, we use Δβ (i) to analyse the experimental data of eighteen gaseous phosphorus-containing compounds obtained by Sodhi and Cavell¹. It is shown that ΔR(P_2p) is strongly related to changes in the polarizability of the ligands. The initial state effects derived from our study deviate from those expected on the basis of simple electronegativity considerations.     

Influence of substrate morphology on organic layer growth: PTCDA on Ag(1 1 1)

By UV-excited photoelectron emission microscopy (UV-PEEM) we investigated the microscopic growth behavior of organic thin films using 3,4,9,10-perylene-tetracarboxylicacid dianhydride (PTCDA) on a Ag(1 1 1) single crystal substrate as example. Direct, real time observation allows to correlate the initial growth modes and the related kinetic parameters with substrate properties like terrace width, step density, and step bunches from the submonolayer range up to 5 layers or more. Above room temperature PTCDA grows in a Stranski–Krastanov fashion: after completion of the first two stable layers three-dimensional islands are formed. The nucleation density strongly depends on the temperature and the substrate morphology thus affecting the properties of the organic film.     

A potential-function reduction algorithm for solving a linear program directly from an infeasible “warm start”

This paper develops an algorithm for solving a standard-form linear program directly from an infeasible “warm start”, i.e., directly from a given infeasible solution \(\hat x\) that satisfies \(A\hat x = b\) but \(\hat x \ngeqslant 0\) . The algorithm is a potential function reduction algorithm, but the potential function is somewhat different than other interior-point method potential functions, and is given by $$F(x,B) = q\ln (c^T x - B) - \sum\limits_{j = 1}^n {\ln (x_j + h_j (c^T x - B))}$$ where \(q = n + \sqrt n\) is a given constant,h is a given strictly positive shift vector used to shift the nonnegativity constaints, andB is a lower bound on the optimal value of the linear program. The duality gapc ^T x ? B is used both in the leading term as well as in the barrier term to help shift the nonnegativity constraints. The algorithm is shown under suitable conditions to achieve a constant decrease in the potential function and so achieves a constant decrease in the duality gap (and hence also in the infeasibility) in O(n) iterations. Under more restrictive assumptions regarding the dual feasible region, this algorithm is modified by the addition of a dual barrier term, and will achieve a constant decrease in the duality gap (and in the infeasibility) in \(O(\sqrt n )\) iterations.     

Polynomial-time algorithms for linear programming based only on primal scaling and projected gradients of a potential function

This paper presents extensions and further analytical properties of algorithms for linear programming based only on primal scaling and projected gradients of a potential function. The paper contains extensions and analysis of two polynomial-time algorithms for linear programming. We first present an extension of Gonzaga's O(nL) iteration algorithm, that computes dual variables and does not assume a known optimal objective function value. This algorithm uses only affine scaling, and is based on computing the projected gradient of the potential function $$q\ln (x^T s) - \sum\limits_{j = 1}^n {\ln (x_j )} $$ wherex is the vector of primal variables ands is the vector of dual slack variables, and q = n + \(\sqrt n \) . The algorithm takes either a primal step or recomputes dual variables at each iteration. We next present an alternate form of Ye's O( \(\sqrt n \) L) iteration algorithm, that is an extension of the first algorithm of the paper, but uses the potential function $$q\ln (x^T s) - \sum\limits_{j = 1}^n {\ln (x_j ) - \sum\limits_{j - 1}^n {\ln (s_j )} } $$ where q = n + \(\sqrt n \) . We use this alternate form of Ye's algorithm to show that Ye's algorithm is optimal with respect to the choice of the parameterq in the following sense. Suppose thatq = n + n ^t wheret?0. Then the algorithm will solve the linear program in O(n ^r L) iterations, wherer = max{t, 1 ? t}. Thus the value oft that minimizes the complexity bound ist = 1/2, yielding Ye's O( \(\sqrt n \) L) iteration bound.