Accurate estimation of solvation free energy using polynomial fitting techniques

This report details an approach to improve the accuracy of free energy difference estimates using thermodynamic integration data (slope of the free energy with respect to the switching variable λ) and its application to calculating solvation free energy. The central idea is to utilize polynomial fitting schemes to approximate the thermodynamic integration data to improve the accuracy of the free energy difference estimates. Previously, we introduced the use of polynomial regression technique to fit thermodynamic integration data (Shyu and Ytreberg, J Comput Chem, 2009, 30, 2297). In this report we introduce polynomial and spline interpolation techniques. Two systems with analytically solvable relative free energies are used to test the accuracy of the interpolation approach. We also use both interpolation and regression methods to determine a small molecule solvation free energy. Our simulations show that, using such polynomial techniques and nonequidistant λ values, the solvation free energy can be estimated with high accuracy without using soft‐core scaling and separate simulations for Lennard‐Jones and partial charges. The results from our study suggest that these polynomial techniques, especially with use of nonequidistant λ values, improve the accuracy for ΔF estimates without demanding additional simulations. We also provide general guidelines for use of polynomial fitting to estimate free energy. To allow researchers to immediately utilize these methods, free software and documentation is provided via http://www.phys.uidaho.edu/ytreberg/software . © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010     

Development of an efficient protein phosphatase-based colorimetric test for okadaic acid detection

Okadaic acid (OA), responsible for gastrointestinal problems, inhibits protein phosphatase 2A (PP2A). Therefore, the inhibition exerted by the toxin on PP2A could be used to detect the presence of OA in aqueous solution and in shellfish sample.In this work, two commercial PP2As (from ZEU Immunotec and Millipore) and one produced by molecular engineering (from GTP Technology) were tested. Enzymes were used in solution and also immobilized within a polymeric gel. In solution, best performances were obtained using PP2A purchased from ZEU Immunotec (Spain). OA was detected in aqueous solution in concentration as low as 0.0124 μg L⁻¹ using the enzyme from ZEU Immunotec whereas the detection limits were 0.47 μg L⁻¹ and 0.123 μg L⁻¹ with PP2As from Millipore and GTP Technology, respectively. Considering that the immobilization step contributes to stabilize the PP2A activity, enzymes were entrapped within a photopolymer and an agarose gel. These different polymeric matrices were optimized, tested and compared. Agarose gel seems to be a good alternative to the photopolymer largely used in our group. For instance, the IC₅₀ value obtained with the test based on PP2A from ZEU Immunotec immobilized within an agarose gel was 1.98 μg L⁻¹. This value was 1.8-fold lower than those obtained with the photopolymer test using the same enzyme. The proposed test is sensitive, fast and does not require expensive equipment. To evaluate the efficiency of the assay, PP inhibition tests based on PP2A from ZEU Immunotec in solution or immobilized within a gel were used for OA detection in contaminated shellfish.     

Silica sputtering as a novel collective stationary phase deposition for microelectromechanical system gas chromatography column: feasibility and first separations

Since the late 1970s, approaches have been proposed to replace conventional gas chromatography apparatus with silicon-based microfabricated separation systems. Performances are expected to be improved with miniaturization owing to the reduction of diffusion distances and better thermal management. However, one of the main challenges consists in the collective and reproducible fabrication of efficient microelectromechanical system (MEMS) gas chromatography (GC) columns. Indeed, usual coating processes or classical packing with particulate matters are not compatible with the requirements of collective MEMS production in clean room facilities. A new strategy based on the rerouting of conventional microfabrication techniques and widely used in electronics for metals and dielectrics deposition is presented. The originality lies in the sputtering techniques employed for the deposition of the stationary phase. The potential of these novel sputtered stationary phases is demonstrated with silica sputtering applied to the separation of light hydrocarbons and natural gases. If kinetic characteristics of the sputtered open tubular columns were acceptable with 2500 theoretical plates per meter, the limited retention and resolution of light hydrocarbons led us to consider semipacked sputtered columns with rectangular pillars allowing also significant reduction of typical diffusion distances. In that case separations were greatly improved because retention increased and efficiency was close to 5000 theoretical plates per meter.     

Pentagalloyl Glucose (PGG) Partially Prevents Arterial Mechanical Changes Due to Elastin Degradation

Experimental Mechanics - Elastic fibers are composed primarily of the protein elastin and they provide reversible elasticity to the large arteries. Degradation of elastic fibers is a common...     

On the Properties of Convex Multilayered Cyclofusene

Cyclofusene is a corona-condensed benzenoid whose graph-theoretic representation consists of hexacycles each having exactly two non-adjacent shared edges. Multilayered cyclofusene is a fused hexacylic system which can be partitioned into successive layers of cyclofusene. In such systems, an edge shared by two consecutive hexacycles in the same layer is termed radial. We present upper bounds for the number of radial π-bonds in a convex k-layered cyclofusene.     

Modulation de phase controlée dans les fibres optiques monomodales

Résumé La propagation d'une impulsion laser de profil énergétique temporel P(t) dans une fibre optique monomodale s'accompagne, par effet Kerr optique, d'une modulation de phase qui s'accumule tout au long de la fibre. Sous certaines conditions particulières, ce déphasage est proportionnel áP(t): la loi de modulation de fréquences que présente l'impulsion à l'extrémité de la fibre est alors proportionnelle à la dérivée par rapport au temps du profil énergétique temporel de l'impulsion injectée à l'entrée de la fibre. Dans cet article, nous décrivons des expériences d'automodulation de fréquences d'impulsions présentant des profils temporels énergétiques variés et contrôlés. Les résultats expérimentaux obtenus sont en bon accord avec les prévisions analytiques formulés par Stolen et Chinlon Lin; ici, nous les expliquons dans le cadre d'une interprétation inédite de quelques propriétés des spectres d'impulsions peu modulées en amplitude, largement modulées en phase.

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In single-mode fibres, the propagation of laser pulses with temporal energy profile P(t) induces a self-phase modulation (due to the optical Kerr effect) which increases along the fibre. Under particular conditions this phase shift is proportional to the derivative of the temporal energy pulse profile at the fibre input. In this paper we describe experiments on self-frequency modulation with laser pulses which exhibit various controlled temporal energy profiles. The experimental results agree quite well with analytic calculations previously given by Stolen and Chinlon Lin; here, they are explained within the framework of a new geometrical interpretation of various properties of pulse spectra which exhibit smooth amplitude modulation and large phase modulation.

     

Polychloroformiate de vinyle: Support inerte de principes actifs,fixation et hydrolyse in vitro de sympathomimétiques

The chemical modification of poly(vinyl chloroformate) with sympathomimetics (phenyl ethylamine, ephedrine, p-hydroxyephedrine and p-hydroxymorephedrine) has been investigated. We have found convenient conditions to obtain soluble modified polymers with nearly quantitative substitution. The use of labelled compounds has shown that the rate and the yield of fixation on the polymer are independent of the nature of the amine. Kinetics in vitro of cleavage has shown that the rates of hydrolysis in stomacal, intestinal and enzymatic media are very low and similar; the observed variations seem to result from differences in solubility of the various modified polymers.     

Sequential closure in product spaces

Let X denote the product of m-many second countable Hausdorff spaces. Main theorems: (1) If S?X is invariant under compositions, m is weakly accessible (resp., nonmeasurable), and F?S is sequentially closed and a sequential G_σ-set which is invariant under projections for finite sets (resp., F?S is sequentially open and sequentially closed), then F is closed. (2) If S?X is invariant under projections and m is nonmeasurable, then every sequentially continuous {0, 1} valued function on S is continuous. (3) A sequentially continuous {0, 1}-valued function on an m-adic space of nonmeasurable weight is continuous. Now let X denote the product of arbitrarily many W-spaces and S?X be invariant under compositions. (4) Then in S, the closure of any Q-open subset coincides with its sequential closure.