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Selected AbstractsHydrophobically Directed Aldol Reactions: Polystyrene-Supported L -Proline as a Recyclable Catalyst for Direct Asymmetric Aldol Reactions in the Presence of Water,EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 28 2007Michelangelo Gruttadauria Abstract A simple synthetic methodology for the preparation of a polystyrene-supported L -proline material is reported, and this material has been used as catalyst in direct asymmetric aldol reactions between several ketones and arylaldehydes to furnish aldol products in high yields and stereoselectivities. Screening of solvents showed that these reactions take place only in the presence of water or methanol, at lower levels of conversion in the latter case. This solvent effect, coupled with the observed high stereoselectivities, has been explained in terms of the formation of a hydrophobic core in the inner surface of the resin, whereas the hydrophilic proline moiety lies at the resin/water interface. Such a microenvironment both promotes the aldol reaction and increases the stereoselectivity. Recycling investigations have shown that this material can be reused, without loss in levels of conversion and stereoselectivity, for at least five cycles. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] On strike-slip faulting in layered mediaGEOPHYSICAL JOURNAL INTERNATIONAL, Issue 3 2002Maurizio Bonafede Summary We study the effects of structural inhomogeneities on the stress and displacement fields induced by strike-slip faults in layered media. An elastic medium is considered, made up of an upper layer bounded by a free surface and welded to a lower half-space characterized by different elastic parameters. Shear cracks with assigned stress drop are employed as mathematical models of strike-slip faults, which are assumed to be vertical and planar. If the crack is entirely embedded within the lower medium (case A), a Cauchy-kernel integral equation is obtained, which is solved by employing an expansion of the dislocation density in Chebyshev polynomials. If the crack is within the lower medium but it terminates at the interface (case B), a generalized Cauchy singularity appears in the integral kernel. This singularity affects the singular behaviour of the dislocation density at the crack tip touching the interface. Finally, the case of a crack crossing the interface is considered (case C). The crack is split into two interacting sections, each placed in a homogeneous medium and both open at the interface. Two coupled generalized Cauchy equations are obtained and solved for the dislocation density distribution of each crack section. An asymptotic study near the intersection between the crack and the interface shows that the dislocation densities for each crack section are bounded at the interface, where a jump discontinuity is present. As a corollary, the stress drop must be discontinuous at the interface, with a jump proportional to the rigidity contrast between the adjoining media. This finding is shown to have important implications for the development of geometrical complexities within transform fault zones: planar strike-slip faults cutting across layer discontinuities with arbitrary stress drop values are shown to be admissible only if the interface between different layers becomes unwelded during the earthquake at the crack/interface junction. Planar strike-slip faulting may take place only in mature transform zones, where a repetitive earthquake cycle has already developed, if the rheology is perfectly elastic. Otherwise, the fault cannot be planar: we infer that strike-slip faulting at depth is plausibly accompanied by en-echelon surface breaks in a shallow sedimentary layer (where the stress drop is lower than prescribed by the discontinuity condition), while ductile deformation (or steady sliding) at depth may be accommodated by multiple fault branching or by antithetic faulting in the upper brittle layer (endowed with lower rigidity but higher stress). [source] Evaluation of the Photodegradation of Crystal Violet upon Light Exposure by Mass Spectrometric and Spectroscopic MethodsJOURNAL OF FORENSIC SCIENCES, Issue 2 2009Céline Weyermann Dr. rer. nat. Abstract:, Crystal violet is a very common dye in ballpoint ink. Recent research suggests that the degradation of triarylmethane dyes gives an indication of the age of a ballpoint pen entry on a document. The main problem for the quantitative evaluation of the degradation is that it is highly dependent on the exposure to light. Moreover additional factors, such as additives and substrate play an important role in this process. The aim of this work is to compare the degradation pathways of the pure dye in water and ethanol upon exposure to xenon light by UV/VIS spectrophotometry and laser desorption ionization. Significant differences have been observed in the products and the kinetics of the degradation. N-demethylation, an expected decomposition process, was found to take place only in aqueous solution and kinetics calculations showed that the degradation occurred 2.5 times faster in ethanol compared to water. The degradation of crystal violet in inks from four ballpoint pens on paper was also studied for entries made over 2,3 years. It was observed that degradation reactions were quenched by the presence of another dye due to competitive absorption. It was also observed that the thickness of a stroke (concentration of ink) influenced the degradation process. In the absence of light only one ballpoint pen showed slight degradation. A better understanding of the influence of the paper, ink composition, and storage conditions is necessary to interpret correctly the age of an ink based on the degradation of dyes. [source] Prediction of two-phase flow distribution in parallel pipes using stability analysisAICHE JOURNAL, Issue 10 2006L. Pustylnik Abstract Two-phase gas liquid flow in pipes is a complex process. One of the problems that is hardly understood is how the two phases are distributed among two or more parallel lines with a common inlet manifold. Steady-state analysis yields multiple steady-state solutions. Linear and nonlinear (simulation) stability analyses are performed in order to determine the actual distribution of the flow that will take place in a real system. The analysis shows that when there are four parallel pipes, for example, the two-phase flow mixture from the common inlet manifold can choose to flow in one, two, three, or in all four pipes, depending on the flow rates of the liquid, and the gas and on the pipes inclination. For low-flow rates of gas and liquid, the flow tends to take place only in one line, while stagnant liquid columns are present in the other three pipes. As the flow rate increases the flow will take place in 2, 3 and finally in 4 pipes. Experimental data confirm the analysis although matching is only approximate. © 2006 American Institute of Chemical Engineers AIChE J, 2006 [source] Radical copolymerization of vinylidene cyanide with 2,2,2-trifluoroethyl methacrylate: Structure and characterization,JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 21 2010Mustapha Raihane Abstract A novel copolymer of vinylidene cyanide (VCN) and 2,2,2-trifluoroethyl methacrylate (MATRIF) was synthesized by bulk free radical process in a 52% yield from an equimolar comonomer feed. The copolymer's composition and microstructure were analyzed by FTIR, 1H- and 13C-NMR spectroscopy, SEC, and elemental analysis. The reactivity ratios calculated from both the Q-e Alfrey-Price parameters and the Jenkins' Patterns Scheme indicate a tendency to alternation in the copolymerization, the latter method suggesting that MATRIF homopropagation be slightly favoured (rV = r12 = 0.1, rM = r21 = 0.3). The molar incorporation of VCN in the copolymer was only 42 mol % according to the 9.0 wt % nitrogen content determined by elemental analysis, in good agreement with the value obtained by 1H-NMR. High-resolution 1H and 13C-NMR spectra were used to study the microstructure of the copolymer. As an example, the three well-resolved carbonyl resonances in the 13C-NMR spectrum were assigned to the MATRIF-centered triads VMV, VMM, and MMM, respectively, (V and M stand for VCN and MATRIF, respectively). The presence of VCN dyads (e.g., in VVM and VVV sequences) was shown to be marginal or absent altogether. Thermogravimetric analysis of poly(VCN- co -MATRIF) copolymer showed good thermal stability, and its main pyrolytic degradation taking place only above 368 °C. A 4% weight loss at about 222 °C suggested the presence of a few VCN homodyads, possibly inducing thermal depolymerization. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 [source] AN EVALUATION OF THE 1997 EDWARDS AQUIFER IRRIGATION SUSPENSION,JOURNAL OF THE AMERICAN WATER RESOURCES ASSOCIATION, Issue 4 2000Keith O. Keplinger ABSTRACT: In early 1997, the Texas Edwards Aquifer Authority implemented a pilot Irrigation Suspension Program with the objectives of increasing springflow and providing relief to municipalities during drought. Irrigators were paid an average of $234 per acre to suspend water use, a price higher than regional land rental rates. Auction theory and program implementation details suggest that the program implementation partially caused inflated bids. The Irrigation Suspension Program is also compared to two alternative programs: (1) subsidizing more efficient irrigation technology and (2) buying land. The irrigation suspension is found to be more cost-effective relative to subsidizing improved irrigation efficiency because it can be put in place only when aquifer levels are low. Land purchase is a cheaper alternative if the bid levels remain at the levels observed. [source] The giant kelp Macrocystis pyrifera presents a different nonphotochemical quenching control than higher plantsNEW PHYTOLOGIST, Issue 3 2007Ernesto García-Mendoza Summary ,,Here the mechanisms involved in excitation energy dissipation of Macrocystis pyrifera were characterized to explain the high nonphotochemical quenching of chlorophyll a (Chla) fluorescence (NPQ) capacity of this alga. ,,We performed a comparative analysis of NPQ and xanthophyll cycle (XC) activity in blades collected at different depths. The responses of the blades to dithiothreitol (DTT) and to the uncoupler NH4Cl were also assayed. ,,The degree of NPQ induction was related to the amount of zeaxanthin synthesized in high light. The inhibition of zeaxanthin synthesis with DTT blocked NPQ induction. A slow NPQ relaxation upon the addition of NH4Cl, which disrupts the transthylakoid proton gradient, was detected. The slow NPQ relaxation took place only in the presence of de-epoxidated XC pigments and was related to the epoxidation of zeaxanthin. ,,These results indicate that in M. pyrifera, in contrast to higher plants, the transthylakoid proton gradient alone does not induce NPQ. The role of this gradient seems to be related only to the activation of the violaxanthin de-epoxidase enzyme. [source] Implications of Genotypic Diversity and Phenotypic Plasticity in the Ecophysiological Success of CAM Plants, Examined by Studies on the Vegetation of Madagascar,PLANT BIOLOGY, Issue 3 2001M. Kluge Abstract: On the basis of ,13C-values, genotypic diversity and phenotypic plasticity of CAM behaviour in plants of the Malagasy vegetation is surveyed. The study compares CAM patterns performed in the wild on the levels of genera (Kalanchoë [Crassulaceae], Angraecum [Orchidaceae], Lissochilus [Orchidaceae] and Rhipsalis [Cactaceae]), on the level of a family (Didiereaceae) and finally on the level of a common growth form, namely in leafless orchids. For Rhipsalis, also non-Malagasy species were included in the comparison. The genus Kalanchoë was found to be dominated by species representing the CAM-physiotype with CO2 fixation taking place only during the night, whereas the CAM/C3- and the C3-physiotypes (with limited intrinsic CAM potential) were less frequent. The opposite holds true for Angraecum. In the genus Rhipsalis, in the Didiereacean family and in the leafless orchids only the CAM-physiotype is represented. The photosynthetic physiotypes of CAM plants were found to be related to the environmental conditions of the habitat. That is, strong CAM performers are typically abundant in the dry climatic zones or at otherwise dry niches, species of the C3-physiotype (possibly with weak intrinsic capability of CAM performance) are distributed at humid sites and those of the CAM/C3-physiotype occupy sites with medium and changing exposure to stress. Phenotypic plasticity of CAM, as indicated by the intraspecific variability of the ,13C-values, was lower in the CAM-physiotype compared with the CAM/C3-physiotype. Our data support the view that strong stress leads to the dominance of highly adapted specialists among the CAM plants, with low phenotypic plasticity of the photosynthetic behaviour, whereas medium stress advances the unfolding of plastic CAM behaviour. Moreover, the data suggest that genera comprising all three physiotypes (Kalanchoë, Angraecum) are dispersed all over Madagascar, whilst groups comprising only strong CAM performers are restricted to limited areas or special types of habitats. This suggests that both genotypic diversity and phenotypic plasticity are important factors for the ecophysiological success of CAM. [source] Unconventional method based on circular dichroism to detect peanut DNA in food by means of a PNA probe and a cyanine dyeCHIRALITY, Issue 9 2005Stefano Sforza Abstract In this paper we report an innovative and unconventional method based on circular dichroism for the identification of peanut DNA in food, which can be detected after PCR amplification at the nanomolar level by using an achiral PNA probe complementary to a tract of the peanut Ara h 2 gene and an achiral 3,3,-diethylthiadicarbocyanine dye [DiSC2(5)]. Peanuts are one of the most common causes of severe allergic reactions to foods and are particularly dangerous when they are "hidden" (undeclared) in food. For better protection of consumers, detection methods are required to specifically detect the presence of hidden allergens in a wide variety of food items. Alternative to the detection of the proteins is the determination of species-specific DNA, which is more resistant to technological treatments. PNAs are very specific probes able to recognize DNA sequences with high affinity and evidence for the binding can be obtained by using the DiSC2(5) dye, which aggregates onto the PNA,DNA duplex giving rise to a characteristic visibile band at 540 nm. Because the PNA,DNA duplex is in a right-handed helical conformation, the aggregation of the dye to the duplex gives also rise to a strong CD signal in the 500,600 nm region with a strong exciton coupling due to the formation of multimeric species, since the handedness of the helix is transferred to the dye aggregate. The dye does not interact with the free single-stranded DNA and although aggregating on the achiral PNA, this interaction is obviously not detectable by circular dichroism. Thus, only the formation of the PNA,DNA duplex, which takes place only upon specific Watson,Crick hydrogen binding between the PNA and the DNA bases, is detected, ensuring a very high specificity and sensitivity. The method has been optimized in a model system by using a synthetic oligonucleotide complementary to the PNA probe, showing that the intensity of the signal is linearly related to the amount of the DNA. The optimized method has been applied to the identification and quantitation of DNA extracted and amplified by PCR from peanuts and from peanut-containing foods, allowing for a very sensitive detection at a very low level (few pmol). © 2005 Wiley-Liss, Inc. Chirality 17:515,521, 2005. [source] | |||||||||||||