Lipase-catalyzed solvent-free transesterification of wood sterols

Eighteen commercial lipase preparations, either immobilized or crude enzyme powders, were screened for the transesterification of wood sterols. The reactions were carried out in a solvent-free system, at the optimum temperature of the enzyme preparations as reported by the manufacturer and at the pressure of 2 mbar, with 5 or 10% in weight of the enzyme relative to the wood sterol content of the reacting mixture. Methyl esters of sunflower fatty acids were used as transesterifying agent. Of all the enzymes assayed, only Lipase TL from Pseudomonas stutzeri PL-836 (Meito Sangyo) exhibited any significant transesterifying capacity, 85 and 95% of conversion after 2 and 8 h of reaction, respectively, when 10% in weight of enzyme was used.     

Pore formation by 6-ketocholestanol in phospholipid monolayers and its interpretation by a general nucleation-and-growth model accounting for the sigmoidal shape of voltage-clamp curves of ion channels

6-Ketocholestanol (KC), a steroid that differs from cholesterol mainly by the presence of a carbonyl group, forms pores inside a dioleoylphosphatidylcholine monolayer self-assembled on mercury by a mechanism similar to that of channel-forming peptides and proteins. The potential steps responsible for pore formation by KC molecules give rise to potentiostatic charge vs time curves whose sigmoidal shape and potential dependence can be quantitatively interpreted on the basis of a mechanism of nucleation and growth of KC clusters. Pore formation by KC allows the penetration of thallous ions across the otherwise impermeable phosphatidylcholine monolayer, while pore disruption taking place at more negative potentials causes a drop in thallous ion permeation. Pore disruption is also accounted for by a mechanism of nucleation and growth of holes inside the KC clusters. The kinetic model of nucleation and growth is general, and accounts quantitatively for the sigmoidal shape and potential dependence of the classical Hodgkin-Huxley voltage-clamp curves of potassium channels in squid giant axon,(1) using a minimum number of free parameters.     

Polygonal heat conductors with a stationary hot spot

We consider a convex polygonal heat conductor whose inscribed circle touches every side of the conductor. Initially, the conductor has constant temperature and, at every time, the temperature of its boundary is kept at zero. The hot spot is the point at which temperature attains its maximum at each given time. It is proved that, if the hot spot is stationary, then the conductor must satisfy two geometric conditions. In particular, we prove that these geometric conditions yield some symmetries provided the conductor is either pentagonal or hexagonal. This research was partially supported by Grants-in-Aid for Scientific Research (B) (# 12440042) and (B) (# 15340047) of Japan Society for the Promotion of Science, and by a Grant of the Italian MURST.     

Displacement measurements in structural elements by optical techniques

Speckle metrology and holographic interferometry (HI) have been used in several civil engineering applications. We present the results obtained by applying speckle photography (SP) to the study of two quadratic shearwalls with different boundary conditions, and the potential of the technique in the study of this kind of structures is described. The analysis of Young's fringes obtained with this technique at certain points on each shearwall provides the whole field of displacement measurements. HI has been used to measure the three components of absolute displacement, verifying that the bulging phenomenon does not affect the in-plane components when the applied load remains on the same plane as the shearwall. A qualitative analysis is carried out following an electronic speckle pattern interferometry (ESPI) technique. The results obtained by optical techniques are compared to the numerical results obtained by the finite element method (FEM), finding good correlation between them in all the cases.     

Photophysics and Photochemistry of z‐Chlorprothixene in Acetonitrile†

Chlorprothixene (CPTX, Taractan^®) is a low potency antipsychotic mainly used for the treatment of psychotic disorders (e.g. schizophrenia) and acute mania occurring as part of bipolar disorders. As in the case of other numerous drugs used in the treatment of psychiatric disorders, CPTX presents geometric isomerism. Therefore, in vitro irradiation induces a rapid Z/E isomerization, which can affect its pharmacokinetic properties. This photoisomerization is not dependent on the oxygen concentration. The Z/E quantum yields determined for zCPTX in acetonitrile are 0.22 and 0.21 in anaerobic and aerobic environments, respectively. In the presence of water, both isomers decompose to produce 2‐chlorothioxanthone (CTX) after prolonged irradiation. This process strongly depends on the water concentration and the irradiation time, i.e. it is autocatalyzed by the CTX through a triplet‐energy transfer mechanism. The protonation state of the terminal amino group, on the other hand, has no effect on the isomerization process, but inhibits the formation of CTX. These results indicate that the phototoxicity of zCPTX is somehow affected by the formation of CTX.     

A Counterexample on Sample-Path Optimality in Stable Markov Decision Chains with the Average Reward Criterion

This note deals with Markov decision chains evolving on a denumerable state space. Under standard continuity-compactness requirements, an explicit example is provided to show that, with respect to a strong sample-path average reward criterion, the Lyapunov function condition does not ensure the existence of an optimal stationary policy.     

Denumerable controlled Markov chains with average reward criterion: Sample path optimality

We consider discrete-time nonlinear controlled stochastic systems, modeled by controlled Makov chains with denumerable state space and compact action space. The corresponding stochastic control problem of maximizing average rewards in the long-run is studied. Departing from the most common position which usesexpected values of rewards, we focus on a sample path analysis of the stream of states/rewards. Under a Lyapunov function condition, we show that stationary policies obtained from the average reward optimality equation are not only average reward optimal, but indeed sample path average reward optimal, for almost all sample paths.Research supported by a U.S.-México Collaborative Research Program funded by the National Science Foundation under grant NSF-INT 9201430, and by CONACyT-MEXICO.Partially supported by the MAXTOR Foundation for applied Probability and Statistics, under grant No. 01-01-56/04-93.Research partially supported by the Engineering Foundation under grant RI-A-93-10, and by a grant from the AT&T Foundation.     

Proximal methods in reflexive Banach spaces without monotonicity

We introduce the concept of hypomonotone point-to-set operators in Banach spaces, with respect to a regularizing function. This notion coincides with the one given by Rockafellar and Wets in Hilbertian spaces, when the regularizing function is the square of the norm. We study the associated proximal mapping, which leads to a hybrid proximal-extragradient and proximal-projection methods for nonmonotone operators in reflexive Banach spaces. These methods allow for inexact solution of the proximal subproblems with relative error criteria. We then consider the notion of local hypomonotonicity and propose localized versions of the algorithms, which are locally convergent.     

Direct and indirect electrochemical oxidation of Indigo Carmine using PbO2 and TiRuSnO2

Journal of Solid State Electrochemistry - In this paper, the electrocatalytic properties of PbO2 and TiRuSnO2 anodes for direct and indirect electrochemical oxidation of a synthetic solution...