Catalytic Effect of Electric Fields on the Kemp Elimination Reactions with Neutral Bases

The effect of solvent reaction fields and oriented electric fields on the Kemp elimination reaction between methylamine or imidazole and 5-nitrobenzisoxazole has been theoretically studied. The Kemp reaction is the most widely used for the design of new enzymes. Our results, using the SMD continuous model for solvents, are in quite good agreement with the experimental fact that the rate of the analogous reaction with butylamine is one order of magnitude smaller in water than in acetonitrile. In the case of external electric fields, our results show that they can increase or decrease the energy barrier depending on the magnitude and orientation of the field. A duly oriented electric field may have a notable catalytic effect on the reaction. So, external electric fields and reaction fields due to the medium can contribute to the design of new enzymes. Several factors that must be taken into account to increase the catalytic effect are discussed.     

Coal analysis by diffuse reflectance near-infrared spectroscopy: Hierarchical cluster and linear discriminant analysis

An extensive study was carried out in coal samples coming from several origins trying to establish a relationship between nine coal properties (moisture (%), ash (%), volatile matter (%), fixed carbon (%), heating value (kcal/kg), carbon (%), hydrogen (%), nitrogen (%) and sulphur (%)) and the corresponding near-infrared spectral data. This research was developed by applying both quantitative (partial least squares regression, PLS) and qualitative multivariate analysis techniques (hierarchical cluster analysis, HCA; linear discriminant analysis, LDA), to determine a methodology able to estimate property values for a new coal sample. For that, it was necessary to define homogeneous clusters, whose calibration equations could be obtained with accuracy and precision levels comparable to those provided by commercial online analysers and, study the discrimination level between these groups of samples attending only to the instrumental variables. These two steps were performed in three different situations depending on the variables used for the pattern recognition: property values, spectral data (principal component analysis, PCA) or a combination of both. The results indicated that it was the last situation what offered the best results in both two steps previously described, with the added benefit of outlier detection and removal.     

Quantification of the effect of nonphotochemical quenching on the determination of in vivo chl a from phytoplankton along the water column of a freshwater reservoir

Nonphotochemical quenching (NPQ) is a well-known collection of different photoprotective mechanisms of plants and algae to avoid photodamage under an excess of light energy. In order to evaluate the overall effect of NPQ processes on the fluorometric determination of in vivo Chl a from a phytoplankton community dominated by diatoms, we compared the results obtained by two different fluorometric field devices with the total concentration of extracted Chl a measured by HPLC ( in vitro Chl a ). A different set of measurements were made to assess the performance of these fluorometers at high, moderate and low irradiance conditions. The Fbbe fluorometer, which is capable of distinguishing different algal groups according to their pigment content, allowed a better determination of in vivo Chl a under high irradiance conditions, with only a 10% mean difference from the in vitro Chl a concentration. In turn, the FMII fluorometer underestimated by as much as 50% the in vitro Chl a concentration under the same light conditions. As data from both fluorometers were in accordance with the in vitro Chl a values at moderate irradiance levels, the differences observed at high irradiances were attributed to the decrease in the yield of Chl a fluorescence caused by photoprotective NPQ processes. Accordingly, we estimated the effect of NPQ processes on the in vivo Chl a determination and the results allow us to provide an equation to correct this effect when in situ fluorometric measurements are carried out under high irradiance regimes. Our results demonstrate that under certain circumstances NPQ seriously compromises the results obtained by in situ fluorometric probes and highlight the need for a cautious interpretation of field data under such environmental conditions.     

Secret Sharing Schemes with Detection of Cheaters for a General Access Structure

In a secret sharing scheme, some participants can lie about the value of their shares when reconstructing the secret in order to obtain some illicit benefit. We present in this paper two methods to modify any linear secret sharing scheme in order to obtain schemes that are unconditionally secure against that kind of attack. The schemes obtained by the first method are robust, that is, cheaters are detected with high probability even if they know the value of the secret. The second method provides secure schemes, in which cheaters that do not know the secret are detected with high probability. When applied to ideal linear secret sharing schemes, our methods provide robust and secure schemes whose relation between the probability of cheating and the information rate is almost optimal. Besides, those methods make it possible to construct robust and secure schemes for any access structure.     

Current trends in the computational modelling of polyoxometalates

Computational chemistry applied to the study of polyoxometalates has achieved its maturity in the last years. During two decades, important advances have been made using theoretical tools in the comprehension and interpretation of many relevant issues. In the present mini-review, we want to stress that different techniques have been incorporated to the routine of computation: from the very first Hartree?CFock LCAO-SCF calculation on the decavanadate anion, followed by numerous density functional theory?Cbased studies on increasingly complex systems, also applying correlated ab initio techniques for magnetism and, more recently, using molecular dynamics to analyse properties in liquid media, the information provided by computational chemistry gets more and more relevant.     

Self‐Assembly of Uranyl–Peroxide Nanocapsules in Basic Peroxidic Environments

A wide range of uranyl–peroxide nanocapsules have been synthesized using very simple reactants in basic media; however, little is known about the process to form these species. We have performed a density functional theory study of the speciation of the uranyl ions under different experimental conditions and explored the formation of dimeric species via a ligand exchange mechanism. We shed some light onto the importance of the excess of peroxide and alkali counterions as a thermodynamic driving force towards the formation of larger uranyl–peroxide species.     

Implicational (semilinear) logics I: a new hierarchy

In abstract algebraic logic, the general study of propositional non-classical logics has been traditionally based on the abstraction of the Lindenbaum-Tarski process. In this process one considers the Leibniz relation of indiscernible formulae. Such approach has resulted in a classification of logics partly based on generalizations of equivalence connectives: the Leibniz hierarchy. This paper performs an analogous abstract study of non-classical logics based on the kind of generalized implication connectives they possess. It yields a new classification of logics expanding Leibniz hierarchy: the hierarchy of implicational logics. In this framework the notion of implicational semilinear logic can be naturally introduced as a property of the implication, namely a logic L is an implicational semilinear logic iff it has an implication such that L is complete w.r.t. the matrices where the implication induces a linear order, a property which is typically satisfied by well-known systems of fuzzy logic. The hierarchy of implicational logics is then restricted to the semilinear case obtaining a classification of implicational semilinear logics that encompasses almost all the known examples of fuzzy logics and suggests new directions for research in the field.     

A non-homogeneous boundary-value problem for the Korteweg-de Vries equation in a quarter plane

The Korteweg-de Vries equation was first derived by Boussinesq and Korteweg and de Vries as a model for long-crested small-amplitude long waves propagating on the surface of water. The same partial differential equation has since arisen as a model for unidirectional propagation of waves in a variety of physical systems. In mathematical studies, consideration has been given principally to pure initial-value problems where the wave profile is imagined to be determined everywhere at a given instant of time and the corresponding solution models the further wave motion. The practical, quantitative use of the Korteweg-de Vries equation and its relatives does not always involve the pure initial-value problem. Instead, initial-boundary-value problems often come to the fore. A natural example arises when modeling the effect in a channel of a wave maker mounted at one end, or in modeling near-shore zone motions generated by waves propagating from deep water. Indeed, the initial-boundary-value problem

studied here arises naturally as a model whenever waves determined at an entry point propagate into a patch of a medium for which disturbances are governed approximately by the Korteweg-de Vries equation. The present essay improves upon earlier work on (0.1) by making use of modern methods for the study of nonlinear dispersive wave equations. Speaking technically, local well-posedness is obtained for initial data in the class for \frac34$"> and boundary data in , whereas global well-posedness is shown to hold for when , and for when . In addition, it is shown that the correspondence that associates to initial data and boundary data the unique solution of (0.1) is analytic. This implies, for example, that solutions may be approximated arbitrarily well by solving a finite number of linear problems.

     

2-pyridones from cyanoacetamides and enecarbonyl compounds: application to the synthesis of nothapodytine B

The condensation of an enone or enal with cyanoacetamide derivatives and t-BuOK furnishes either 3-cyano-2-pyridones or 3-unsubstituted-2-pyridones, depending on whether the reaction is carried out in the presence or in the absence of O(2). In the first case, in situ oxidation of Michael-type intermediates takes place; in the second case, the products result from "decyanidative aromatization" of such intermediates. A one-step synthesis of 3-alkyl-2-pyridones has been devised on the basis of decyanative union of an enone/enal and a 2-alkylcyanoacetamide. The new reaction forms the centerpiece of an unusually concise synthesis of nothapodytine B (mappicine ketone).     

Buyer-seller exactness in the assignment game

In the assignment game framework, we try to identify those assignment matrices in which no entry can be increased without changing the core of the game. These games will be called buyer-seller exact games and satisfy the condition that each mixed-pair coalition attains the corresponding matrix entry in the core of the game. For a given assignment game, a unique buyer-seller exact assignment game with the same core is proved to exist. In order to identify this matrix and to provide a characterization of those assignment games which are buyer-seller exact in terms of the assignment matrix, attainable upper and lower core bounds for the mixed-pair coalitions are found. As a consequence, an open question posed in Quint (1991) regarding a canonical representation of a “45^o-lattice” by means of the core of an assignment game can now be answered. Received: March 2002/Revised version: January 2003 RID="*" ID="*"  Institutional support from research grants BEC 2002-00642 and SGR2001-0029 is gratefully acknowledged RID="**" ID="**"  The authors thank the referees for their comments