Unsteady motion in single-line flow-injection systems

Unsteady motion in single-line flow-injection systems consisting of n tubular elements with valve or hydrodynamic injection is studied theoretically. A formula for the duration of the initial period of unsteady flow is derived. This initial period is much shorter than the mean residence time of the analyte in practical systems. It can therefore be neglected in mathematical modelling of such systems. Experimental data obtained with single-line systems with valve and hydrodynamic injection confirmed the validity of the theoretical equations.     

Potential for micromachined actuation of ultra-wide continuously tunable optoelectronic devices

Tailored scaling represents a principle of success that, both in nature and in technology, allows the effectiveness of physical effects to be enhanced. Mutation and selection in nature are imitated in technology, e.g. by model calculation and design. Proper scaling of dimensions in natural photonic crystals and our fabricated artificial 1D photonic crystals (DBRs, distributed Bragg reflectors) enable efficient diffractive interaction in a specific spectral range. For our optical microsystems we illustrate that tailored miniaturization may also increase the mechanical stability and the effectiveness of spectral tuning by thermal and electrostatic actuation, since the relative significance of the fundamental physical forces involved considerably changes with scaling. These basic physical principles are rigorously applied in micromachined 1.55-μm vertical-resonator-based devices. We modeled, implemented and characterized 1.55-μm micromachined optical filters and vertical-cavity surface-emitting laser devices capable of wide, monotonic and kink-free tuning by a single control parameter. Tuning is achieved by mechanical actuation of one or several air-gaps that are part of the vertical resonator including two ultra-highly reflective DBR mirrors of strong refractive index contrast: (i) Δn=2.17 for InP/air-gap DBRs (3.5 periods) using GaInAs sacrificial layers and (ii) Δn=0.5 for Si₃N₄/SiO₂ DBRs (12 periods) with a polymer sacrificial layer to implement the air-cavity. In semiconductor multiple air-gap filters, a continuous tuning of >8% of the absolute wavelength is obtained. Varying the reverse voltage (U=0–5 V) between the membranes (electrostatic actuation), a tuning range of >110 nm was obtained for a large number of devices. The correlation of the wavelength and the applied voltage is accurately reproducible without any hysteresis. In two filters, tuning of 127 and 130 nm was observed for about ΔU=7 V. The extremely wide tuning range and the very small voltage required are record values to the best of our knowledge. For thermally actuated dielectric filters based on polymer sacrificial layers, Δλ/ΔU=-7 nm/V is found. Received: 10 May 2002 / Published online: 8 August 2002     

Analysis of Decomposition Algorithms with Benders Cuts for p-Median Problem

In this paper the algorithms for solving the p-median problem based on the Benders decomposition are investigated. A family of problems hard for solving with such algorithms is constructed and then generalized to a special NP-hard case of the p-median problem. It is shown that the effectiveness of the considered algorithms depends on the choice of the optimal values of the dual variables used in Benders cuts. In particular, the depth of the cuts can be equal to one.     

Solving Linear Systems Whose Elements Are Nonlinear Functions of Intervals

The paper addresses the problem of solving linear algebraic systems the elements of which are, in the general case, nonlinear functions of a given set of independent parameters taking on their values within prescribed intervals. Three kinds of solutions are considered: (i) outer solution, (ii) interval hull solution, and (iii) inner solution. A simple direct method for computing a tight outer solution to such systems is suggested. It reduces, essentially, to inverting a real matrix and solving a system of real linear equations whose size n is the size of the original system. The interval hull solution (which is a NP-hard problem) can be easily determined if certain monotonicity conditions are fulfilled. The resulting method involves solving n+1 interval outer solution problems as well as 2n real linear systems of size n. A simple iterative method for computing an inner solution is also given. A numerical example illustrating the applicability of the methods suggested is solved.     

Rational incorporation of defects within metal–organic frameworks generates highly active electrocatalytic sites

The allure of metal–organic frameworks (MOFs) in heterogeneous electrocatalysis is that catalytically active sites may be designed a priori with an unparalleled degree of control. An emerging strategy to generate coordinatively-unsaturated active sites is through the use of organic linkers that lack a functional group that would usually bind with the metal nodes. To execute this strategy, we synthesize a model MOF, Ni-MOF-74 and incorporate a fraction of 2-hydroxyterephthalic acid in place of 2,5-dihydroxyterephthalic acid. The defective MOF, Ni-MOF-74D, is evaluated vs. the nominally defect-free Ni-MOF-74 with a host of ex situ and in situ spectroscopic and electroanalytical techniques, using the oxidation of hydroxymethylfurtural (HMF) as a model reaction. The data indicates that Ni-MOF-74D features a set of 4-coordinate Ni–O₄ sites that exhibit unique vibrational signatures, redox potentials, binding motifs to HMF, and consequently superior electrocatalytic activity relative to the original Ni-MOF-74 MOF, being able to convert HMF to the desired 2,5-furandicarboxylic acid at 95% yield and 80% faradaic efficiency. Furthermore, having such rationally well-defined catalytic sites coupled with in situ Raman and infrared spectroelectrochemical measurements enabled the deduction of the reaction mechanism in which co-adsorbed *OH functions as a proton acceptor in the alcohol oxidation step and carries implications for catalyst design for heterogeneous electrosynthetic reactions en route to the electrification of the chemical industry.

The allure of metal–organic frameworks (MOFs) in heterogeneous electrocatalysis is that catalytically active sites may be designed a priori with an unparalleled degree of control.     

Die multikomponenten Formen von Cellulase (EC 3.2.1.4) ausAspergillus oryzae

The enzyme cellulase fromAspergillus oryzae was resolved into four multiple forms, using anion exchange chromatography on DEAE Sephadex A-50 and gel filtration on Sephadex G-75. The stages of fractionation were followed by electrophoresis on cellulose acetate strips. These enzyme forms are characterized by different enzyme activities and isoelectric points.

Herrn Univ.-Prof. Dr.Hans Tuppy zum 65. Geburtstag herzlichst gewidmet.     

Experimental and computational studies of the structure and vibrational spectra of pyridinium-betaine of squaric acid

The FTIR spectra of pyridinium-betaine of squaric acid in 4000-100 cm(-1) frequency region in solid state were measured. In addition, the structure and harmonic vibrational frequencies of this molecule were theoretically evaluated using restricted Hartree-Fock and B3LYP density functional methods. The computed vibrational frequencies are used to determine the types of molecular motions associated with each of the experimental bands observed. Comparison with the experimental spectra provides important information about the ability of these computational methods to describe the vibrational modes in these highly polar strained ring compounds.     

Matrices with Heterogeneous Distribution of the Binding Sites for Immobilization of Biomacromolecules

The coupling of photosensitive reagents has been carried out with the goal of obtaining the predetermined distribution of binding sites either for “surface” or “spacial” immobilization of biomacromolecules. The correlation holds between light intensity and the number of readant groups emerged in a matrix.     

Ligand-protein docking using a quantum stochastic tunneling optimization method

A novel hybrid optimization method called quantum stochastic tunneling has been recently introduced. Here, we report its implementation within a new docking program called EasyDock and a validation with the CCDC/Astex data set of ligand-protein complexes using the PLP score to represent the ligand-protein potential energy surface and ScreenScore to score the ligand-protein binding energies. When taking the top energy-ranked ligand binding mode pose, we were able to predict the correct crystallographic ligand binding mode in up to 75% of the cases. By using this novel optimization method run times for typical docking simulations are significantly shortened.