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451.
Green analytical methods employing flow analysis with simple natural reagent extracts have been exploited. Various formats of flow based analysis systems including a single line FIA, a simple lab on chip with webcam camera detector, and a newly developed simple lab on chip system with reflective absorption detection and the simple extracts from some available local plants including butterfly pea flower, orchid flower, and beet root were investigated and shown to be useful as alternative self indicator reagents for acidity assay. Various tea drinks were explored to be used for chromogenic reagents in iron determination. The benefit of a flow based system, which allows standards and samples to go through the analysis process in exactly the same conditions, makes it possible to employ simple natural extracts with minimal or no pretreatment or purification. The combinations of non-synthetic natural reagents with minimal processed extracts and the low volume requirement flow based systems create some unique green chemical analyses. 相似文献
452.
Pollack SJ Beyer KS Lock C Müller I Sheppard D Lipkin M Hardick D Blurton P Leonard PM Hubbard PA Todd D Richardson CM Ahrens T Baader M Hafenbradl DO Hilyard K Bürli RW 《Journal of computer-aided molecular design》2011,25(7):677-687
The stress-activated kinase p38α was used to evaluate a fragment-based drug discovery approach using the BioFocus fragment library. Compounds were screened by surface plasmon resonance (SPR) on a Biacore(?) T100 against p38α and two selectivity targets. A sub-set of our library was the focus of detailed follow-up analyses that included hit confirmation, affinity determination on 24 confirmed, selective hits and competition assays of these hits with respect to a known ATP binding site inhibitor. In addition, functional activity against p38α was assessed in a biochemical assay using a mobility shift platform (LC3000, Caliper LifeSciences). A selection of fragments was also evaluated using fluorescence lifetime (FLEXYTE(?)) and microscale thermophoresis (Nanotemper) technologies. A good correlation between the data for the different assays was found. Crystal structures were solved for four of the small molecules complexed to p38α. Interestingly, as determined both by X-ray analysis and SPR competition experiments, three of the complexes involved the fragment at the ATP binding site, while the fourth compound bound in a distal site that may offer potential as a novel drug target site. A first round of optimization around the remotely bound fragment has led to the identification of a series of triazole-containing compounds. This approach could form the basis for developing novel and active p38α inhibitors. More broadly, it illustrates the power of combining a range of biophysical and biochemical techniques to the discovery of fragments that facilitate the development of novel modulators of kinase and other drug targets. 相似文献
453.
Current models of the plasma membrane (PM) organization focus on the lateral heterogeneity of the membrane and its relation to the cell function. Increasing evidence in mammals and yeast supports the direct relationship between PM lateral microdomains and specific cell processes and functions (nutrient transport, signaling, protein and lipid sorting, endocytosis, pathogen entry etc.). However, for the present the functional significance of an enrichment of specific proteins and possibly lipids in plant PM domains as well as the underlying molecular mechanism driving the lateral PM segregation remain unaddressed. Here we summarize recent findings on the plant PM organization and its role in signaling pathways, with the special emphasis on auxin transport. 相似文献
454.
Patrick Guidotti Kate Longo 《NoDEA : Nonlinear Differential Equations and Applications》2011,18(4):407-425
A number of image denoising models based on higher order parabolic partial differential equations (PDEs) have been proposed
in an effort to overcome some of the problems attendant to second order methods such as the famous Perona–Malik model. However,
there is little analysis of these equations to be found in the literature. In this paper, methods of maximal regularity are
used to prove the existence of unique local solutions to a class of fourth order PDEs for noise removal. The proof is laid
out explicitly for two newly proposed fourth order models, and an outline is given for how to apply the techniques to other
proposed models. 相似文献
455.
Naive listeners' perceptual assimilations of non-native vowels to first-language (L1) categories can predict difficulties in the acquisition of second-language vowel systems. This study demonstrates that listeners having two slightly different dialects as their L1s can differ in the perception of foreign vowels. Specifically, the study shows that Bohemian Czech and Moravian Czech listeners assimilate Dutch high front vowels differently to L1 categories. Consequently, the listeners are predicted to follow different paths in acquiring these Dutch vowels. These findings underscore the importance of carefully considering the specific dialect background of participants in foreign- and second-language speech perception studies. 相似文献
456.
Interactions Between Alkyl Triphenyl Phosphonium Bromides and Polyvinylpyrrolidones in Aqueous Media
Rebecca Dean Maryjo Doiron Kate Dunlop 《Journal of Dispersion Science and Technology》2013,34(7):1018-1023
The interactions of polyvinylpyrrolidones with alkyl triphenyl phosphonium bromide in aqueous media were investigated with conductometric, fluorimetric and tensiometric techniques. Formation of surfactant-polymer aggregates was detected in the case of C16 and C14 surfactant by these techniques. Tensiometric technique proved to be very sensitive to detect the early stage of association at very low concentrations. The Gibbs free energy of micellization and the dielectric constant values of the micellar interface values were obtained and discussed in terms of strength of interaction between the polymers and surfactants. 相似文献
457.
Dr. Pavel Jiroš Dr. Blanka Kalinová Dr. Anna Jirošová Dr. Jakub Straka Kateřina Černá Dr. Jan Šobotník Dr. Josef Cvačka Dr. Ullrich Jahn 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(26):8515-8524
The asymmetric total synthesis of the diastereomers of stylopsal establishes the absolute configuration of the first reported sex pheromone of the twisted‐wing parasite Stylops muelleri as (3R,5R,9R)‐trimethyldodecanal. The key steps for the diastereo‐ and enantiodivergent introduction of the methyl groups are two different types of asymmetric conjugate addition reactions of organocopper reagents to α,β‐unsaturated esters, whereas the dodecanal skeleton is assembled by Wittig reactions. The structure of the natural product was confirmed by chiral gas chromatography (GC) techniques, GC/MS and GC/electroantennography (EAD) as well as field tests. An investigation into the biosynthesis of the pheromone revealed that it is likely to be produced by decarboxylation of a 4,6,10‐trimethyltridecanoic acid derivative, which was found in substantial amounts in the fat body of the female, but not in the host bee Andrena vaga. This triple‐branched fatty acid precursor thus seems to be biosynthesized de novo through a polyketide pathway with two consecutive propionate‐propionate‐acetate assemblies to form the complete skeleton. The simplified, motionless and fully host‐dependent female exploits a remarkable strategy to maximize its reproductive success by employing a relatively complex and potent sex pheromone. 相似文献
458.
Kateřina Nováková Tomáš Navrátil Jana Jaklová Dytrtová Jaromíra Chýlková 《Journal of Solid State Electrochemistry》2013,17(6):1517-1528
The complexes formed between copper and thiram and between mercury and thiram have been electrochemically (voltammetrically) investigated in the present work. Their structure was confirmed using electrospray ionization mass spectrometry. Due to formation of the complex between copper (from copper solid amalgam electrode) and thiram, the concentration of this pesticide can be determined. The voltammetric behavior of thiram was investigated at polished (p-CuSAE) and mercury meniscus modified (m-CuSAE) copper solid amalgam electrodes (inner diameter 1.5 mm) by differential pulse voltammetry (DPV) and by direct current voltammetry (DCV). Optimum conditions for DPV determination of thiram were found in Britton–Robinson buffer. The reaction mechanism was investigated using DCV and elimination voltammetry with linear scan. DPV with optimized parameters was applied for determination of thiram in analyzed solutions. The limits of detection were calculated as 16 nmol?L?1 (t acc?=?100 s) for m-CuSAE and 23 nmol?L?1 (t acc?=?60 s) for p-CuSAE. The proposed method was successfully applied for thiram determination in real sample solutions. 相似文献
459.
Kate J. Akerman Orde Q. Munro 《Acta Crystallographica. Section C, Structural Chemistry》2013,69(3):258-262
The Schiff base enaminones (3Z)‐4‐(5‐ethylsulfonyl‐2‐hydroxyanilino)pent‐3‐en‐2‐one, C13H17NO4S, (I), and (3Z)‐4‐(5‐tert‐butyl‐2‐hydroxyanilino)pent‐3‐en‐2‐one, C15H21NO2, (II), were studied by X‐ray crystallography and density functional theory (DFT). Although the keto tautomer of these compounds is dominant, the O=C—C=C—N bond lengths are consistent with some electron delocalization and partial enol character. Both (I) and (II) are nonplanar, with the amino–phenol group canted relative to the rest of the molecule; the twist about the N(enamine)—C(aryl) bond leads to dihedral angles of 40.5 (2) and −116.7 (1)° for (I) and (II), respectively. Compound (I) has a bifurcated intramolecular hydrogen bond between the N—H group and the flanking carbonyl and hydroxy O atoms, as well as an intermolecular hydrogen bond, leading to an infinite one‐dimensional hydrogen‐bonded chain. Compound (II) has one intramolecular hydrogen bond and one intermolecular C=O...H—O hydrogen bond, and consequently also forms a one‐dimensional hydrogen‐bonded chain. The DFT‐calculated structures [in vacuo, B3LYP/6‐311G(d,p) level] for the keto tautomers compare favourably with the X‐ray crystal structures of (I) and (II), confirming the dominance of the keto tautomer. The simulations indicate that the keto tautomers are 20.55 and 18.86 kJ mol−1 lower in energy than the enol tautomers for (I) and (II), respectively. 相似文献
460.
Synchrotron far‐infrared spectroscopy of corroded steel surfaces using a variable angle of incidence
Kateřina Lepková Wilhelm van Bronswijk Vedapriya Pandarinathan Rolf Gubner 《Journal of synchrotron radiation》2014,21(3):580-585
Far‐infrared spectroscopy, using a synchrotron source, has been used to study carbon steel corroded in CO2‐saturated brine in the presence and absence of the corrosion inhibitor 2‐mercaptopyrimidine (MPY), which allowed the steel surface roughness to be modified. The effect of the angle of incidence (θi, 30–80°) on the band intensity and observed bands of the spectra from these surfaces has been determined. For the MPY‐treated steel (low surface roughness) the highest band intensity is observed at high θi (80°) and different bands were observed at different θi. In contrast, for the MPY‐free steel (high surface roughness) the highest band intensity is observed at low θi (30°) and spectral content changes were not observed. The results are explained in terms of the roughness of the MPY‐treated and MPY‐free steels, and their effect on the level of diffusely reflected light of the incident infrared beam. 相似文献