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61.
Crisma M De Borggraeve WM Peggion C Formaggio F Royo S Jiménez AI Cativiela C Toniolo C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,12(1):251-260
Terminally blocked, homo-peptide amides of (R,R)-1-amino-2,3-diphenylcyclopropane-1-carboxylic acid (c3diPhe), a chiral member of the family of Calpha-tetrasubstituted alpha-amino acids, from the dimer to the tetramer, and diastereomeric co-oligopeptides of (R,R)- or (S,S)-c3diPhe with (S)-alanine residues to the trimer level were prepared in solution and fully characterized. The synthetic effort was extended to terminally protected co-oligopeptide esters to the hexamer, where c3diPhe residues are combined with achiral alpha-aminoisobutyric acid residues. The preferred conformations of the peptides were assessed in solution by FT-IR absorption, NMR, and CD techniques, and for seven oligomers in the crystal state (by X-ray diffraction) as well. This study clearly indicates that c3diPhe, a sterically demanding cyclopropane analogue of phenylalanine, tends to fold peptides into beta-turn and 3(10)-helix conformations. However, when c3diPhe is in combination with other chiral residues, the conformation preferred by the resulting peptides is also dictated by the chiral sequence of the amino acid building blocks. The (S,S)-enantiomer of this alpha-amino acid, unusually lacking asymmetry in the main chain, strongly favors the left-handedness of the turn/helical peptides formed. 相似文献
62.
An aggregation parameter-based analytical approach, the surfactant-dye binding degree (SDBD) method, was used, for the first time, to determine aromatic hydrotropic compounds. The anionic dye Coomassie Brilliant Blue G (CBBG) was used as inductor of didodecyldimethylammonium bromide (DDABr) aggregates, whose formation was monitored from changes in the spectral features of the dye. Interactions between hydrotrope and DDABr molecules resulted in a decrease of the degree of binding of the cationic surfactant to CBBG, which was proportional to the concentration of hydrotrope in the aqueous solution. The CBBG-DDABr-hydrotrope chemical system was found to fit to the mathematical expression previously derived for the determination of amphiphilic compounds. The hydrotrope-surfactant bond strength determined the sensitivity achieved for the determination of hydrotropic compounds, which was highly dependent on the molecular structure of the analyte. The high precision (the relative standard deviation for 7 mg l(-1) of salicylic acid was 0.8%), rapidity (measurements were performed in a few minutes) and low cost (in both instrumentation and reactants) of the proposed method, made it especially suitable for quality control. The practical analytical applicability of the SDBD method for the control of hydrotropic drugs in pharmaceutical preparations was demonstrated by quantifying salicylic acid and acetyl salicylic acid in liquid (solutions) and solid (tablets, granulates, unguents, gels and creams) samples, which were directly analyzed after dissolution of the samples. 相似文献
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64.
Soledad García Fontn Elvira Lamas Castro Pilar Rodríguez Seoane Ezequiel M. Vzquez‐Lpez 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(5):532-533
The title compound consists of [Re(C12H10PS2)(CO)4] molecules in which the Re atom is octahedrally coordinated by four carbonyl groups and two dithiophosphinate S atoms. The main coordination distortion is imposed by the ligand bite angle of 78.29 (4)°. The bidentate coordination of the dithiophosphinate ligand involves almost equal Re—S [2.5366 (15) and 2.5535 (14) Å] and P—S distances [2.0100 (19) and 2.0212 (19) Å]. 相似文献
65.
66.
Noelia Luque Ana Ballesteros-Gómez Stefan van Leeuwen Soledad Rubio 《Journal of chromatography. A》2010,1217(24):3774-3782
An analytical method combining both a simple, fast and efficient solvent microextraction and a sensitive and selective monitoring mode, based on ion isolation ion-trap mass spectrometry (MS), was developed for analysis of perfluorinated compounds (PFCs) in biota. The method involved the vortex-shaking of 0.2 g of tissue sample and 800 μL of tetrahydrofuran (THF):water (75:25, v/v) for 7 min, subsequent centrifugation for 13 min and direct quantitation of PFCs in the extract against solvent-based calibration curves. Selection of solvent composition was based on Hildebrand solubility parameters and their components (i.e. dispersion, dipole–dipole and hydrogen bonding forces). Recoveries in samples for PFCs with hydrocarbon chain lengths between C4 and C14 ranged from 85 to 111%, with relative standard deviations between 1 and 11%. The ion isolation monitoring mode, proposed for the first time for ion-trap-MS quantitation, proved to be effective in avoiding space-charge effects caused by co-eluting matrix components while keeping the sensitivity of full scan MS operation. Detection limits of the method were in the range 0.8−6 ng g−1 for perfluoroalkyl carboxylates (PFACs) and 0.4–0.8 ng g−1 for perfluoroalkyl sulfonates (PFASs) in wet weight samples. The method was validated using a reference material made up of flounder muscle and by comparison with triple quadrupole MS measurements and it was applied to the determination of PFCs in liver and muscle samples from sea birds and fishes. Only PFASs were found in samples at quantifiable levels (2.9 and 13.1 ng g−1) while PFACs were below the respective quantitation limits. This method allows quick and simple microextraction of PFCs with minimal solvent consumption, while delivering accurate and precise data. 相似文献
67.
Jaime Millán-Santiago Rafael Lucena Soledad Cárdenas 《Journal of separation science》2022,45(1):223-232
Lignocellulosic materials have arisen as a sustainable alternative in microextraction techniques during the last 10 years. As they are natural materials, their use fits into some of the principles of Green Analytical Chemistry. Their inherent porosity, narrow shape, and rigidity permit their use in ambient ionization mass spectrometry techniques. In particular, the combination of wooden-based materials and direct analysis gives birth to the so-called wooden-tip electrospray ionization mass spectrometry technique. This approach has been used for the direct analysis of complex samples, and as a streamlined tool for fingerprint quality analysis. Also, wooden-based materials can be superficially modified to boost the interaction with target compounds, allowing their isolation from complex samples. This review describes the potential and applicability of direct analysis using lignocellulosic materials, as well as other alternatives related to their use in microextraction. 相似文献
68.
César Zúñiga Loyola Soledad Ureta-Zañartu José H. Zagal F. Tasca 《Current Opinion in Electrochemistry》2022
Electrochemistry and electrochemical experiments are powerful tools for obtaining information about the thermodynamics and kinetics of electrochemical reactions. In electrocatalysis, these two parameters are often framed together to improve the understanding of the interactions of a catalyst and a reactant. Generally, “volcano-type” correlations are composed to compare similar catalysts. In this type of correlation, kinetic versus thermodynamic parameters are juxtapose to identify the most active catalyst positioned at the top of the volcano trend. In this work, we delve into the obtaining of this type of correlations to clarify the significance and utility. In particular, the study of the oxygen reduction reaction (ORR) has been selected due to its importance in energy conversion devices such as fuel cells and metal-air batteries. 相似文献
69.
Fernández-González V Concha-Graña E Muniategui-Lorenzo S López-Mahía P Fernández-Fernández E Prada-Rodríguez D 《Journal of separation science》2010,33(23-24):3741-3750
A simultaneous matrix solid-phase dispersion extraction-gel permeation chromatography cleanup with programmed temperature vaporisation GC-MS determination is proposed for the analysis of parent and alkylated polycyclic aromatic hydrocarbons (PAHs) in mussel samples. The parameters affecting the extraction and elution efficiency were studied. Final conditions were: 0.5?g of mussel sample, 0.5?g diatomaceous earth as dispersant; and 4?g of Bio-Beads S-X3 for the gel permeation chromatography. Ethyl acetate/hexane (1:1, v/v) was selected for the elimination of the lipid fraction and the elution of PAHs. The detection and quantification limits achieved with this procedure were between 0.01?μg/kg and 0.67?μg/kg and 0.02?μg/kg and 1.93?μg/kg, respectively. The linearity of the method ranged between 5?μg/kg and 1000?μg/kg for most of the studied PAHs. The method was validated by the analysis of mussel tissue reference material (SRM 2977). The repeatability, intermediate precision and accuracy of the method obtained are in excellent agreement with the certified values. The proposed method is simple, precise and robust; no special instruments or costly equipment are required, and a reduction in the total time of analysis, sample handling and solvent consumption is achieved in comparison with classic procedures. 相似文献
70.