Study of gas-liquid partitioning of alkane solutes in several organic solvents by using principal component analysis and linear solvation energy relationships

Principal component analysis (PCA) was used to extract the number of factors which can describe the 737 gas-liquid partition coefficients of five linear, four branched, and two cyclic alkanes in 67 common solvents. Based on the reconstruction of partition coefficient data matrix, we concluded that the experimental dataset could readily be reduced to two relevant factors. Using only these two factors, there were no errors larger than 3%, 7 cases had errors larger than 2%, and in 34 cases, errors were between 1 and 2%. n-Hexane and ethylcyclohexane were chosen as the test factors, and all other partition coefficients were expressed in terms of these two test factors. Prediction of the logarithmic partition coefficient of these alkanes in seven chemically different solvents, which were originally excluded from the data matrix, was excellent: the root mean square error was 0.064, only in 11 cases the errors were larger than 1%, and only 3 had errors larger than 4%.Linear solvation energy relationships (LSERs) using both theoretical and empirical solvent parameters were used to explain the molecular interactions responsible for partition. Several combinations of parameters were tried but the standard deviations were not less than 0.31. This could be attributed to the model itself, imprecisions in the data matrix or in some of the LSER parameters. Solvent cohesive parameters and surface tension in combination with polarity-polarizability or dispersion parameters perform the best.Finally, the two principal component factors were rotated onto the most relevant physicochemical parameters that control the gas-liquid partitioning phenomena.     

The Electrochemical Behavior of α‐Ketoglutarate at the Hanging Mercury Drop Electrode in Acidic Aqueous Solution and Its Practical Application in Environmental and Biological Samples

The voltammetric behavior of α‐ketoglutarate (α‐KG) at the hanging mercury drop electrode (HMDE) has been investigated in acetate buffer solution. Under the optimum experimental conditions (pH 4.5, 0.2 M NaAc‐HAc buffer solution), a sensitive reductive wave of α‐KG was obtained by linear scan voltammetry (LSV) and the peak potential was ?1.18 V (vs. SCE), which was an irreversible adsorption wave. The kinetic parameters of the electrode process were α=0.3 and k_s=0.72 1/s. There was a linear relationship between peak current i_{p, α‐KG} and α‐KG concentration in the range of 2×10^?6–8×10^?4 M α‐KG. The detection limit was 8×10^?7 M and the relative standard deviation was 2.0% (C_α‐KG=8×10^?4 M, n=10). Applications of the reductive wave of α‐KG for practical analysis were addressed as follows: (1) It can be used for the quantitative analysis of α‐KG in biological samples and the results agree well with those obtained from the established ultraviolet spectrophotometric method. (2) Utilizing the complexing effect between α‐KG and aluminum, a linear relationship holds between the decrease of peak current of α‐KG Δi_p and the added Al concentration Cequation/tex2gif-inf-5.gif in the range of 5.0×10^?6–2.5×10^?4 M. The detection limit was 2.2×10^?6 M and the relative standard deviation was 3.1% (Cequation/tex2gif-inf-6.gif=4×10^?5 M, n=10). It was successfully applied to the detection of aluminum in water and synthetic biological samples with satisfactory results, which were consistent with those of ICP‐AES. (3) It was also applied to study the effect of Al^III on the glutamate dehydrogenase (GDH) activity in the catalytically reaction of α‐KG+NH +NADH?L ‐glutamate+NAD⁺+H₂O by differential pulse polarography (DPP) technique. By monitoring DPP reductive currents of NAD⁺ and α‐KG, an elementary important result was found that Al could greatly affect the activity of GDH. This study could be attributed to intrinsic understanding of the aluminum's toxicity in enzyme reaction processes.     

Improving constants of strong convexity in linear stochastic programming

We derive formulas for constants of strong convexity (CSCs) of expectation functions encountered in two-stage stochastic programs with linear recourse. One of them yields a CSC as the optimal value of a certain quadratically constrained quadratic program, another one in terms of the thickness of the feasibility polytope of the dual problem associated to the recourse problem. CSCs appear in Hoelder-type estimates relating the distance of optimal solution sets of stochastic programs to a suitable distance of underlying probability distributions.     

New results on multi-dimensional linear discriminant analysis

Fisher linear discriminant analysis is a well-known technique for dimensionality reduction and classification. The method was first formulated in 1936 by Fisher. In this paper we concentrate on three different formulations of the multi-dimensional problem. We provide a mathematical explanation why two of the formulations are equivalent and prove that this equivalency can be extended to a broader class of objective functions. The second contribution is a rate of convergence of a fixed point method for solving the third model.     

An orthotropic plate model for decks of suspension bridges

The main purpose of the present paper is to compare two different kinds of approaches in modeling the deck of a suspension bridge: in the first approach we look at the deck as a rectangular plate and in the second one we look at the deck as a beam for vertical deflections and as a rod for torsional deformations. Throughout this paper we will refer to the model corresponding to the second approach as the beam-rod model. In our discussion, we observe that the beam-rod model contains a larger number of elastic parameters if compared with the isotropic plate model. For this reason the beam-rod model is supposed to be more appropriate to describe the behavior of the deck of a real suspension bridge. A possible strategy to make the plate model more efficient could be to relax the isotropy condition with a more general condition of orthotropy, which is expected to increase the number of elastic parameters. In this new setting, a comparison between the two approaches becomes now possible.Basic results are proved for the suggested problem, from existence and uniqueness of solutions to spectral properties. We suggest realistic values for the elastic parameters thus obtaining with both approaches similar responses in the static and dynamic behavior of the deck. This can be considered as a preliminary article since many work has still to be done with the perspective of formulating models for a complete suspension bridge which take into account not only the deck but also the action on it of cables and hangers. With this perspective, a section is devoted to possible future developments.     

Some problems of linear differential equations on abstract spaces and unbounded perturbations of linear operator semigroup

This paper is a survey for development of linear distributed parameter system. At first we point out some questions existing in current study of control theory for the L^p linear system with an unbounded control operator and an unbounded observation operator, such as stabilization problem and observer theory that are closely relevant to state feedback operator. After then we survey briefly some results on relevant problems that are related to solvability of linear differential equations in general Banach space and semigroup perturbations. As a principle, we propose a concept of admissible state feedback operator for system (A, B). Finally we give an existence result of admissible state feedback operators, including semigroup generation and the equivalent conditions of admissibility of state feedback operators, for an L^p well-posed system.     

Smoothing methods for convex inequalities and linear complementarity problems

A smooth approximationp (x, ) to the plus function max{x, 0} is obtained by integrating the sigmoid function 1/(1 + e^–x ), commonly used in neural networks. By means of this approximation, linear and convex inequalities are converted into smooth, convex unconstrained minimization problems, the solution of which approximates the solution of the original problem to a high degree of accuracy for sufficiently large. In the special case when a Slater constraint qualification is satisfied, an exact solution can be obtained for finite. Speedup over MINOS 5.4 was as high as 1142 times for linear inequalities of size 2000 × 1000, and 580 times for convex inequalities with 400 variables. Linear complementarity problems are converted into a system of smooth nonlinear equations and are solved by a quadratically convergent Newton method. For monotone LCPs with as many as 10 000 variables, the proposed approach was as much as 63 times faster than Lemke's method.This material is based on research supported by Air Force Office of Scientific Research Grant F49620-94-1-0036 and National Science Foundation Grants CCR-9101801 and CCR-9322479.     

Precise bounds for the petersen time-varying real parameter uncertainty system stabilized via linear static controllers

Using a class of linear static controllers, we stabilize the Petersen open-loop two-dimensional linear system (Ref. 1), which consists of one time-varying uncertainty in the state matrixA and one timevarying uncertainty in the input matrixB. We show that the worst-case uncertainty strategy for the closed-loop system is a piecewise constant strategy of the angular state with three switches on the half-turn, –/2/2; it is unique with respect to a set of measure zero. Formulas are derived for the worst-case half-turn radius gainr _HT as a function of the parameters of the class of stabilizing linear static controllers. Using the class of scalar-quadratic Lyapunov functions, we show that a necessary and sufficient condition for the closed-loop system to be robustly stable against all time-varying admissible uncertainties is thatr _HT be less than unity. The bound on the time-varying real parameter uncertainties for the closed-loop system to be robustly stable is derived for the class of linear static feedback controllers. We obtain stabilizing linear static controllers such that the bound is as close to infinity as desired. The derived results are compared with numerical results obtained using commerical robust-control software.     

A new pivoting algorithm for the linear complementarity problem allowing for an arbitrary starting point

The linear complementarity problem is to find nonnegative vectors which are affinely related and complementary. In this paper we propose a new complementary pivoting algorithm for solving the linear complementarity problem as a more efficient alternative to the algorithms proposed by Lemke and by Talman and Van der Heyden. The algorithm can start at an arbitrary nonnegative vector and converges under the same conditions as Lemke's algorithm.This research is part of the VF-program Competition and Cooperation.     

Misclassification minimization

The problem of minimizing the number of misclassified points by a plane, attempting to separate two point sets with intersecting convex hulls inn-dimensional real space, is formulated as a linear program with equilibrium constraints (LPEC). This general LPEC can be converted to an exact penalty problem with a quadratic objective and linear constraints. A Frank-Wolfe-type algorithm is proposed for the penalty problem that terminates at a stationary point or a global solution. Novel aspects of the approach include: (i) A linear complementarity formulation of the step function that counts misclassifications, (ii) Exact penalty formulation without boundedness, nondegeneracy or constraint qualification assumptions, (iii) An exact solution extraction from the sequence of minimizers of the penalty function for a finite value of the penalty parameter for the general LPEC and an explicitly exact solution for the LPEC with uncoupled constraints, and (iv) A parametric quadratic programming formulation of the LPEC associated with the misclassification minimization problem.This material is based on research supported by Air Force Office of Scientific Research Grant F49620-94-1-0036 and National Science Foundation Grants CCR-9101801 and CDA-9024618.