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131.
Berríos C Marco JF Gutiérrez C Ureta-Zañartu MS 《The journal of physical chemistry. B》2008,112(40):12644-12649
Films of nickel tetrasulfophthalocyanine and - p-phenylporphyrin (NiTSPc and NiTSPP, respectively) were obtained by repetitive cyclic voltammetry (RCV) of the 1 mM complex in aqueous solution, while films of the water-insoluble nickel tetraaminophthalocyanine and - p-phenylporphyrin (NiTAPc and NiTAPP, respectively) had to be obtained by RCV of the 1 mM complex in organic solvents. Glassy carbon (GC), ITO, or platinum electrodes were used as substrates. The modified electrodes were characterized by cyclic voltammetry (CV) and UV-visible, infrared, and X-ray photoelectron spectroscopies. The CVs of the sulfo films showed the characteristic peaks of the Ni(II)/Ni(III) process, whereas the CVs of the amino films did not, very small Ni(II)/Ni(III) peaks appearing only after activation by RCV. Upon oxidation to Ni(III) both sulfo films changed from transparent to dark violet. The IR spectra of the polyNiTSPP and the polyNiTSPc films showed bands at 3628 cm (-1) and 3500 cm (-1), respectively, which could be due to interstitial water molecules occluded during the polymerization. The Ni 2p XP spectra indicate that the magnetic character of the Ni(II) ions in NiTSPP is dramatically changed by the polymerization, from diamagnetic in the monomer to paramagnetic in the polymeric film, indicating the formation of Ni-O-Ni bridges or of clusters of Ni(OH) 2. On the contrary, the Ni 2p XP spectra of the unactivated NiTAPP film, in which the Ni(II)/Ni(III) process was absent, showed only diamagnetic Ni(II). Therefore, it is concluded that only paramagnetic Ni(II) ions can be electrooxidized to Ni(III). 相似文献
132.
Colombres M Garate JA Lagos CF Araya-Secchi R Norambuena P Quiroz S Larrondo L Pérez-Acle T Eyzaguirre J 《Journal of computer-aided molecular design》2008,22(1):19-28
The soft-rot fungus Penicillium purpurogenum secretes to the culture medium a variety of enzymes related to xylan biodegradation, among them three acetyl xylan esterases (AXE I, II and III). AXE II has 207 amino acids; it belongs to family 5 of the carbohydrate esterases and its structure has been determined by X-ray crystallography at 0.9 A resolution (PDB 1G66). The enzyme possesses the alpha/beta hydrolase fold and the catalytic triad typical of serine esterases (Ser90, His187 and Asp175). AXE II can hydrolyze esters of a large variety of alcohols, but it is restricted to short chain fatty acids. An analysis of its three-dimensional structure shows that a loop that covers the active site may be responsible for this strict specificity. Cutinase, an enzyme that hydrolyzes esters of long chain fatty acids and shows a structure similar to AXE II, lacks this loop. In order to generate an AXE II with this broader specificity, the preparation of a mutant lacking residues involving this loop (Gly104 to Ala114) was proposed. A set of molecular simulation experiments based on a comparative model of the mutant enzyme predicted a stable structure. Using site-directed mutagenesis, the loop's residues have been eliminated from the AXE II cDNA. The mutant protein has been expressed in Aspergillus nidulans A722 and Pichia pastoris, and it is active towards a range of fatty acid esters of up to at least 14 carbons. The availability of an esterase with broader specificity may have biotechnological applications for the synthesis of sugar esters. 相似文献
133.
Decanoic acid reverse micelle-based coacervates for the microextraction of bisphenol A from canned vegetables and fruits 总被引:1,自引:0,他引:1
Decanoic acid reverse micelle-based coacervates were proposed for the extraction of bisphenol A (BPA) from canned vegetables and fruits prior to its determination by liquid chromatography and fluorescence detection at lambda(exc) = 276 nm and lambda(em) = 306 nm. The procedure involved the extraction of minute quantities (300-700 mg) of homogenized food sample with an aqueous solution containing 10% of THF and 0.5% of decanoic acid, conditions under which the coacervate (around 340 microL) formed in situ and instantaneously. The overall sample treatment, which included extraction and centrifugation, took about 25-30 min, and several samples could be simultaneously treated using conventional lab equipment. No clean-up or solvent evaporation were required. Extraction efficiencies mainly depended on the decanoic acid and THF concentration in the aqueous solution and were not affected by the pH or the temperature in the ranges studied (1-4 and 20-60 degrees C, respectively). Recoveries in samples ranged between about 81 and 96%. The precision of the method, expressed as relative standard deviation, was about 3% and the quantitation limit was around 9 ng g(-1), which was far below the current specific migration limit (SML) set for BPA by the EU Commission (600 ng g(-1)). The method was successfully applied to the determination of BPA in the solid content of canned fruit salad, peaches in syrup, mango slices, red peppers, sweetcorn, green beans and peas. BPA was present at concentrations in the range from 7.8 to 24.4 ng g(-1) in canned fruits and from 55 to 103 ng g(-1) in canned vegetables. 相似文献
134.
Aguilera-Herrador E Lucena R Cárdenas S Valcárcel M 《Journal of chromatography. A》2008,1201(1):106-111
The direct coupling between ionic liquid-based single-drop microextraction and gas chromatography/mass spectrometry is proposed for the rapid and simple determination of benzene, toluene, ethylbenzene and xylenes isomers (BTEX) in water samples. The extraction procedure exploits not only the high affinity of the selected ionic liquid (1-methyl-3-octyl-imidazolium hexaflourophosphate) to these aromatic compounds but also its special properties like viscosity, low vapour pressure and immiscibility with water. All the variables involved in the extraction process have been studied in depth. The developed method allows the determination of these single-ring compounds in water under the reference concentration level fixed by the international legislation. In this case, limits of detection were in the range 20 ng L(-1) (obtained for benzene) and 91 ng L(-1) (for o-xylene). The repeatability of the proposed method, expressed as RSD (n=5), varied between 3.0% (o-xylene) and 5.2% (toluene). 相似文献
135.
Optimal control of infinite dimensional bilinear systems: application to the heat and wave equations
Mathematical Programming - In this paper we consider second order optimality conditions for a bilinear optimal control problem governed by a strongly continuous semigroup operator, the control... 相似文献
136.
Solvents used in microextraction require high solubilising capability to efficiently extract the target compounds. In this article, nanostructured solvents made up of alkyl carboxylic acids (ACAs) aggregate are proposed for the efficient microextraction of acidic pesticides from natural waters. The target compounds were chlorophenoxy acid herbicides (CPAHs) widely used in agriculture, forestry and gardening (viz. 2,4-D, MCPA, MCPP, 2,4,5-T and MCPB). The supramolecular solvents (SUPRASs) tested were generated from solutions of reverse micelles of octanoic (OcA), decanoic (DeA) and dodecanoic (DoA) acid in THF by the addition of water, which acted as the coacervating agent. The DeA-based SUPRAS was the most efficient extractant for CPAHs; actual concentration factors (ACFs) of 260 for 2,4-D, 290 for MCPA, and 400 for MCPP, 2,4,5-T and MCPB were obtained. The explanation for so high ACFs can be found in the extremely efficient retention mechanisms that the DeA-based SUPRAS provides for CPAHs (i.e. formation of hydrogen bonds and hydrophobic interactions), and the high number of binding sites that it contains (i.e. the concentration of biosurfactant in the SUPRAS was 0.56 mg μL−1). Both characteristics permitted to effectively extract the target analytes in a low volume of solvent (about 2 μL of solvent per mL of sample). Others assets of the proposed supramolecular solvent-based microextraction (SUSME) approach included recoveries no dependent on matrix composition, rapidity (sample treatment spent about 15 min), use of low volume of sample (63 mL per analysis) and simplicity (no special lab equipments was needed). Combination with liquid chromatography/ion–trap mass spectrometry [LC–(IT)MS] afforded method quantitation limits for CPAHs within the interval 22–30 ng L−1. The precision of the method, expressed as relative standard deviation (n = 11, [CPAH] = 200 ng L−1), was in the range 2.9–5.8%. The applicability of the method to the analysis of natural waters was assessed by determining the target analytes in fortified river and underground water samples. 相似文献
137.
138.
Noe Oña Antonio Romero-Carrasco M. Soledad Pino-González 《Tetrahedron: Asymmetry》2013,24(2-3):156-163
Epoxyamides obtained from d-glucose have been evaluated as tools to obtain polyhydroxyazepanes. The stereoselectivity in formation of the epoxyamides was proven to be dependent of the protecting group. The conversion of epoxyamides into epoxyalcohols was necessary to obtain polyhydroxyazepanes, because the direct cyclization of 2-N-amides to azepanecarboxamides was unsuccessful from derivatives obtained from d-glucose. Epoxyamides and epoxyalcohols were regioselectively (alpha) opened by nitrogen nucleophiles. Reduction of diethyl epoxyamide by catalytic transfer hydrogenation gave the alpha deoxy product. 相似文献
139.
Encarnación Borrego Dolores Sicilia Soledad Rubio Dolores Pérez-Bendito 《International journal of environmental analytical chemistry》2013,93(1-2):181-200
Abstract The determination of dialkyldimethylammonium surfactants (DDAS) based on the measurement of the critical micelle concentration (CMC) of mixed sodium dodecylsulphate (SDS)-DDAS aggregates in a basic medium ([NaOH]=4.8 × 10?3 M) is proposed. The dye Coomassie Brilliant Blue G (CBBG) was used as a photometric probe for the rapid determination of CMCs. Formation of CBBG-DDAS and DDAS-SDS premicellar aggregates of well-defined stoichiometrics at cationic and anionic surfactant concentrations far below their CMCs is demonstrated. Increased SDS concentration in the titration medium results in the formation of DDAS-SDS mixed micelles. The strong interaction between the opposite charged head group of DDAS and SDS permits these cationic surfactants to be determined at the ng ml?1 level with a nearly uniform response for all the DDAS tested (12–18 alkyl carbons). The relative standard deviation for 1.10 μg ml?1 ditetradecyldimethylammonium bromide (DTDAB) was 1.5%. The mixed-micelle based methodology was applied to the determination of DDAS in softeners and aqueous environmental samples (river water and laundry effluents) with average recoveries ranged from 87.1 to 100.6 and from 96.3 to 104.0, respectively. 相似文献
140.