Determination of the 2,3-pentadienedioic acid enantiomer interconversion energy barrier 1. Classical kinetic approach

A classical kinetic method was used to determine the energy barrier for the inter-conversion of 2,3-pentadienedioic acid enantiomers. Each individual enantiomer was isolated by collecting the appropriate peaks from the HPLC enantiomeric separation, of racemic 2,3-pentadienedioic acid. The isolated enantiomers were racemized at 22 degrees C using various interconversion times. The ratio of enantiomers in each reaction solution was determined by HPLC at 22 degrees C. The corresponding peak areas of the enantiomers and the interconversion times obtained from the HPLC chromatograms were used to calculate both the interconversion rate constants describing (+)--> (-) and (-) --> (+) interconversions as well as the energy barriers. It was confirmed that the interconversion of 2,3-pentadienedioic acid enantiomers is a firstorder kinetic reaction. Both semiempirical and ab initio methods were used to explore the mechanism of the interconversion of 2,3-pentadienedioic acid enantiomers, and to calculate the interconversion energy barrier. Comparison of the interconversion energy barriers found by the ab initio method (deltaG# = 110.7 kJ/mol) and by classical kinetics in the mobile phase solution at 22 degrees C (delta Gapp = 93.9+/-0.2 kJ/mol) shows a difference which may be attributed to the different conditions assumed in the theoretical calculation (i.e., a gaseous state) and the actual experimental conditions (i. e., liquid solution) and a possible catalytic effect of the solution composition.     

Mobile-phase pH influence on the retention of some benzoic acid derivatives in reversed-phase chromatography

Five end-capped octadecyl RP stationary phases, among which one was a polar embedded stationary phase, were tested for the analysis of benzoic acid derivatives using two mobile phases with or without addition of formic acid (water pH was measured by a common approach; pH of water with addition of formic acid was 3.0 and without formic acid 5.8). The influence of mobile-phase pH on the retention of benzoic acid derivatives was under study. Consequently, Purospher-STAR and Alltima columns provided symmetrical peaks for benzoic acid derivatives at pH 3.0 and also at pH 5.8. Reprosil and Symmetry stationary phases showed poor peak shapes at higher pH of the mobile phase. Differences between the tested columns may be caused by surface heterogeneity. Another reason may be the presence of some atoms creating additional adsorption sites on the surface of Reprosil and Symmetry stationary phases. This can lead to enhanced silanol activity resulting in peak tailing. The addition of formic acid into the mobile phase improved peak shapes. The polar embedded C18 stationary-phase Synergi-Fusion-RP appeared as not a suitable column for the analysis of benzoic acid derivatives. Synergi-Fusion-RP provided asymmetrical peaks even if formic acid was added into the mobile phase.     

Novel furanoid alpha-substitued alpha-amino acid as a potent turn mimic in peptide synthesis

A stereoselective approach has been developed to the new sugar amino acid and potential potent turn mimic 5-O-(tert-butyldimethylsilyl)-3-deoxy-1,2-O-isopropylidene-3-methoxycarbonylamino-alpha-D-xylofuranose 3-C-carboxylic acid (12), via the [3,3]-sigmatropic rearrangement of allylic thiocyanates (Z)-6 and (E)-7, prepared from D-xylose. The synthesis of a new dipeptide 13 is also described.     

Computational study of the mechanism of Bcl-2 apoptotic switch

In spite of attention devoted to molecular mechanisms of apoptosis, the details of functioning of one crucial component–the Bcl-2 apoptotic switch–are not completely understood. There are two competing mechanisms of its internal working—the indirect activation and the direct activation. In the absence of conclusive experimental data, we have used computational modeling to assess the properties of both mechanisms and their suitability to act as a biological switch. Since the two mechanisms form opposite poles of continuum of Bcl-2 molecular interaction models, we have constructed more general models including these two models as extreme cases. By studying the relationship between model parameters and the steady-state response we have found optimal interaction patterns which reproduce the behavior of the Bcl-2 apoptotic switch. Our results show, that stimulus–response ultrasensitivity is negatively affected by spontaneous activation of Bcl-2 effectors. We found that ultrasensitivity requires effectors activation, mediated by another subgroup of Bcl-2 proteins—activators. We have shown that the auto-activation of monomeric effector forms provides an ultrasensitivity enhancing feedback loop. Thorough robustness analysis revealed that the interaction pattern postulated in the direct activation hypothesis is able to conserve stimulus–response switching characteristics for wide range changes of its internal parameters. The robustness of the switch against the variation of the reaction parameter is strongly reduced for the intermediate hybrid model and even more for the indirect part of the models. Computer simulations of the more general model presented here suggest, that stimulus–response ultrasensitivity is an emergent property of the direct activation model that is unlikely to occur in the model of indirect activation. Introduction of indirect-model-specific interactions does not provide a better explanation of the Bcl-2 switch functionality compared to the direct model.     

Trace elemental analysis by laser-induced breakdown spectroscopy—Biological applications

Laser-Induced Breakdown Spectroscopy (LIBS) is a sensitive optical technique capable of fast multi-elemental analysis of solid, gaseous and liquid samples. Since the late 1980s LIBS became visible in the analytical atomic spectroscopy scene; its applications having been developed continuously since then. In this paper, the use of LIBS for trace element determination in different matrices is reviewed. The main emphasis is on spatially resolved analysis of microbiological, plant and animal samples.     

Tail Behavior and Breakdown Properties of Equivariant Estimators of Location

For translation and scale equivariant estimators of location, inequalities connecting tail behavior and the finite-sample breakdown point are proved, analogous to those established by He et al. (1990, Econometrika, 58, 1195–1214) for monotone and translation equivariant estimators. Some other inequalities are given as well, enabling to establish refined bounds and in some cases exact values for the tail behavior under heavy- and light-tailed distributions. The inequalities cover translation and scale equivariant estimators in great generality, and they involve new breakdown-related quantities, whose relations to the breakdown point are discussed. The worth of tail-behavior considerations in robustness theory is demonstrated on examples, showing the impact of the basic two techniques in robust estimation: trimming and averaging. The mathematical language employs notions from regular variation theory.     

Trading crossings for handles and crosscaps

Let c_k = cr_k (G) denote the minimum number of edge crossings when a graph G is drawn on an orientable surface of genus k. The (orientable) crossing sequence c_o, c₁,c₂…encodes the trade‐off between adding handles and decreasing crossings. We focus on sequences of the type c_o > c₁ > c₂ = 0; equivalently, we study the planar and toroidal crossing number of doubly‐toroidal graphs. For every ? > 0 we construct graphs whose orientable crossing sequence satisfies c₁/c_o > 5/6??. In other words, we construct graphs where the addition of one handle can save roughly 1/6th of the crossings, but the addition of a second handle can save five times more crossings. We similarly define the non‐orientable crossing sequence ?₀,?₁,?₂, ··· for drawings on non‐orientable surfaces. We show that for every ?₀ > ?₁ > 0 there exists a graph with non‐orientable crossing sequence ?₀, ?₁, 0. We conjecture that every strictly‐decreasing sequence of non‐negative integers can be both an orientable crossing sequence and a non‐orientable crossing sequence (with different graphs). © 2001 John Wiley & Sons, Inc. J Graph Theory 38: 230–243, 2001     

Calculation of the critical currents of Bi(2223)/Ag tapes and coils with reduced anisotropy in Ic(B) characteristic — effect of different proportional representations of the filaments oriented parallel and perpendicularly to the tape surface

A mathematical model was developed to allow for the prediction of critical currents in Bi(2223)/Ag-sheathed tapes that consist of two groups of filaments, having crystalline texture (c-axis) predominantly in two directions orthogonal to each other and to the length of the conductor (filaments oriented parallel and perpendicular to the tape surface). Using the theory presented, it is possible to estimate the upper limit of critical currents in the tapes prepared with a two-axial rolling technique. Magnetic field and angular dependencies of critical currents were obtained at 77 K measuring tapes with various proportional representations of filaments oriented in both preferred directions, i.e., the parallel and perpendicular directions. The results of calculation indicate that the anisotropy in the I_c(B) characteristic should be reduced considerably using the two-axial rolling. Unfortunately, the effect of anisotropy reduction is accompanied by simultaneous decrease in the current-carrying capacity of the tapes. The data obtained for short tape samples were utilised to estimate the critical currents of the individual turns of a small cylindrical magnet, assembled of eight pancake coils. It is shown that only a slight increase in the critical current of the magnet can be expected if the winding should be made of the tape with reduced anisotropy in the I_c(B) characteristic. The factors that limit the increase of the magnet critical current are discussed in detail.     

The Progress of Ageing of Lignin-containing Paper Induced by Light and its Relation to Chemiluminescence – Temperature Runs

Lignin-containing papers from different sources and of different age were irradiated by the visible light and the progress of the degradation reaction was followed by non-isothermal chemiluminescence method. Kinetic data obtained for papers degraded in oxygen were compared with double fold endurance test and carbonyl groups concentration. The effect of lignin on degradation of cellulose after deacidification treatment of the paper by methoxymagnesium methylcarbonate (MMMC) was ascertained and a mechanism of co-oxidation of lignin and cellulose in originally alkaline conditions was outlined.     

New materials with high π conjugation by reaction of 2-oxazoline containing phenols with polyamidines and inorganic base

The non-covalent interactions between 2-oxazoline containing phenols and an aliphatic polyamidines as well as an inorganic base were studied. The reaction of a weak acid with a strong base results in the formation of the deprotonated species and subsequently in the formation of a new electronic structure. A bathochromic shift of the wavelength of the absorption maxima of the chromophores bounded to polyamidine was observed. Depending on the structure of the chromophore, the shift of the absorption maxima is 40-100 nm. The changes in photochemical behavior can be explained by the higher portion of quinoid structures in the conjugated π-system. The degree of deprotonation is dependent on the molar ratio of the chromophore and the polymeric base. Analogous results were obtained with an inorganic base.