Some metrological aspects of the comparison between two ordinal measuring systems

The usage of ordinal scales (sometimes called ‘semi-quantitative’ scales) for performing measurements in the area of applied chemical metrology and quality assurance is widespread. This paper presents a method for handling actions such as calibration, measuring systems’ capabilities comparison and reproducibility evaluation as a comparison between two measuring systems (MSs) referring to a known/unknown reference standard. The strength of the agreement between these MSs is evaluated through two known versions of Cohen’s kappa statistics (the traditional one and the modified one). The effectiveness of these statistics from the metrological point of view is examined, and the preferability of the modified kappa statistics is demonstrated via an example.     

Quantitation of L-arginine and asymmetric dimethylarginine in human plasma by LC-selective ion mode-MS for Type 2 diabetes mellitus study

The article reports a simple, sensitive and fast LC/MS method for the analysis of L-arginine (L-Arg), asymmetric dimethylarginine (ADMA) and symmetric dimethylarginine (SDMA) in human plasma. The homoarginine was used as the internal standard (IS). The chromatographic separation was achieved on C??(150 mm×2.1 mm, 5 μm) column with a mobile phase consisting of ammonium acetate (0.25 mmol/l) and methanol (93 : 7, v/v), at a flow rate of 0.2 ml/min. L-Arg, ADMA and SDMA were well separated by LC/MS with selective ion mode (SIM). The method was successfully applied to type 2 diabetes mellitus (T2DM) study. Twenty-one healthy controls and twenty-two T2DM patients before and after treatment two years were investigated. The results indicated that the level of ADMA in T2DM was significantly higher than that in healthy controls. Furthermore, ADMA has important association with the development of cardiovascular diseases.     

Guidelines for choosing molecular "alligator clip" binding motifs in electron transport devices

We employ a one-electron, tight-binding model of an electrode-molecule-electrode junction to explore the fundamental relationship between adsorption geometry and electron transport, producing exact results (within this model). By varying the chemisorption location (e.g., atop a surface atom or in a hollow site between surface atoms) and the molecule-electrode coupling, we find that the largest currents are realized when the molecule (i) is highly coordinated by the surface and (ii) has favorable overlap with electrode states near the Fermi level. We also show the importance of electrode-induced molecular level shifting for certain adsorption geometries, which can cause molecular levels far from the Fermi level to conduct better than those near the Fermi level. Since all of these factors are greatly influenced by the chemical moiety used to link the molecule to an electrode, these results present a set of guidelines to help choose "alligator clips" for molecular electronic devices.     

A highly selective colorimetric and ratiometric fluorescent chemodosimeter for imaging fluoride ions in living cells

A simple but highly selective colorimetric and ratiometric fluorescent chemodosimeter was designed and synthesized to detect fluoride ions (F(-)) in aqueous solution and living cells by virtue of the strong affinity of F(-) toward silicon.     

Reactions of some new thienothiophene derivatives

Facile and convenient syntheses of bisdimethylthieno[2,3-b]thiophen-2,5-diyl bis(oxazole-2-amine), bis(1H-imidazol-2-amine), bis((3a)-H-indole),[1,2-a]pyrimidine), bis(1H-imidazo[1,2-b][1,2,4]triazole) and bis(9H-benzo[d]imidazo[1,2-a]imidazole) derivatives incorporating a thieno[2,3-b]thiophene moiety from the versatile and readily accessible 1,1'(3,4-dimethylthieno[2,3-b]thiophene-2,5-diyl)-bis(2-bromo-ethanone) (1) are described.     

A study of inclusive Λ polarization from hydrogen and other targets at 28 GeV

We report measurements of inclusive Λ polarization, produced by unpolarized protons incident at several momenta (20, 24, and 28.5 GeV/c) onto hydrogen, deuterium, and beryllium targets. A large polarization from hydrogen, P = ?0.34 ± 0.06 at pP_T = 1.2 GeV/c, establishes the fact that inclusive Λ polarization arises from p-p collisions.     

Principal component analysis combined with truncated-Newton minimization for dimensionality reduction of chemical databases

 The similarity and diversity sampling problems are two challenging optimization tasks that arise in the analysis of chemical databases. As a first step to their solution, we propose an efficient projection/ refinement protocol based on the principal component analysis (PCA) and the truncated-Newton minimization method implemented by our package TNPACK (PCA/TNPACK). We show that PCA can provide the same initial guess as the singular value decomposition (SVD) for the optimization task of solving the distance-geometry optimization problem if each column of a database matrix has a mean of zero. Hence, our PCA/TNPACK approach is analogous to the SVD/TNPACK projection/refinement protocol that we developed recently for visualizing large chemical databases. Using PCA/TNPACK and the Merck MDDR database (MDL Drug Data Report), we further investigate the projection/refinement procedure with regards to the preservation of the original clusters of chemical compounds, the accuracy of similarity and diversity sampling of chemical compounds, and the potential application in the study of structure activity relationships. We also explore by simple experiments accuracy and efficiency aspects of the PCA/TNPACK procedure compared to those of a global optimization algorithm (simulated annealing, as implemented by the program package SIMANN) in terms of producing the projection mapping of a database. Numerical results show that the 2D PCA/TNPACK mapping can preserve the distance relationships of the original database and is thus valuable as a first step in similarity and diversity applications. Of course, the generation of a global rather than local minimizer and its interpretation in terms of pharameceutical applications remains a challenge. Since all numerical tests are performed on the Merck MDDR database, results are representative of realistic cases encountered in the field of drug design, and may help analyze properties of medicinal compounds. Received: December 21, 2000 / Accepted: August 19, 2002 Published online: September 27, 2002 Mathematics Subject Classification (2000): 65K10, 62H25, 92C50     

Molecular dynamics by the Backward-Euler method

This paper introduces a new computational method for molecular dynamics. The method combines the Backward-Euler scheme for the solution of stiff differential equations with a Langevin-equation approach to the establishment of thermal equilibrium. The method allows the user to choose a cutoff frequency ω_c. Vibrational modes with frequencies below ω_c will be fully excited (receive a mean energy of kT per mode), while modes with frequencies greater than ω_c will be effectively frozen by the method. By setting ω_c = kT/h, one can obtain reasonable agreement with the quantum-mechanical energy distribution among the various modes, despite the classical character of the computation.     

Two point problems and analyticity of solutions of abstract parabolic equations

Fort ∈ [a, b], letA(t) be the unbounded operator inH ^0,p (G) associated with an elliptic-boundary value problem that satisfies Agmon’s conditions on the rays λ=±iτ, τ ≥0. Existence and uniqueness results are obtained for weak and strict solutions of two-point problems of the type (du/dt)−A(t) u(t) =f(t),E ₁(α)u (α)=u _α,E ₂ (β)u (β)=u _β. Here [α, β) χ- [a, b],E ₁ (α) andE ₂ (β) are spectral projections associated withA(α) andA(β) respectively, andA(α)E ₁ (α) and =A (β)E ₂ (β) are infinitesimal generators of analytic semigroups. WhenA(t) andf(t) are analytic in a convex, complex neighborhoodO of [a, b] we show that for someθ _i ,i=1,2, any solution ofdu/dt =A(t)u (t)=f(t) in [a, b] is analytic and satisfies the above equation in the setO∩{t; t ≠ a, t ≠ b, | arg (t −a) | <θ ₁, | arg (b −t) |θ ₂}. Research partially supported by N. N. F. grant at Brandeis University.     

Topology and measure in logics for region-based theories of space

Space, as we typically represent it in mathematics and physics, is composed of dimensionless, indivisible points. On an alternative, region-based approach to space, extended regions together with the relations of ‘parthood’ and ‘contact’ are taken as primitive; points are represented as mathematical abstractions from regions.Region-based theories of space have been traditionally modeled in regular closed (or regular open) algebras, in work that goes back to [5] and [21]. Recently, logics for region-based theories of space were developed in [3] and [19]. It was shown that these logics have both a nice topological and relational semantics, and that the minimal logic for contact algebras, ${\mathbb{L}}_{min}^{cont}$ (defined below), is complete for both.The present paper explores the question of completeness of ${\mathbb{L}}_{min}^{cont}$ and its extensions for individual topological spaces of interest: the real line, Cantor space, the rationals, and the infinite binary tree. A second aim is to study a different, algebraic model of logics for region-based theories of space, based on the Lebesgue measure algebra (or algebra of Borel subsets of the real line modulo sets of Lebesgue measure zero). As a model for point-free space, the algebra was first discussed in [2]. The main results of the paper are that ${\mathbb{L}}_{min}^{cont}$ is weakly complete for any zero-dimensional, dense-in-itself metric space (including, e.g., Cantor space and the rationals); the extension ${\mathbb{L}}_{min}^{cont}+(Con)$ is weakly complete for the real line and the Lebesgue measure contact algebra. We also prove that the logic ${\mathbb{L}}_{min}^{cont}+(Univ)$ is weakly complete for the infinite binary tree.