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41.
An intercalated nanocomposite of the organically modified montmorillonite Cloisite C25A and a degradable poly(ester amide) based on glycolic acid and 6-aminohexanoic acid units (poly(glc-alt-amh)) was prepared using a twin-screw co-rotating extruder. The non-isothermal degradation kinetics was investigated by thermogravimetric analysis (TG and DTG) in the temperature range of 50–600 °C at five heating rates (2, 5, 10, 20 and 40 °C/min) and compared with the neat polymer. Significant differences were found since the nanocomposite showed three degradation steps instead of the two decomposition processes detected in the pristine sample. The onset mass loss temperature decreased in the nanocomposite due to the presence of the organo-modifier compound, but the presence of the silicate layers significantly decreased the degradation rate at the last stages of decomposition. Kinetic analysis was performed using the Kissinger method and the isoconversional (Kissinger–Akahira–Sunose and Friedman) methods. The true kinetic triplets (E, A, f(α)) were determined for the first two steps of degradation through the Coats–Redfern and the Invariant Kinetic Parameters methods. The results clearly indicated that the presence of the organo-modified clay modified the mechanisms of degradation. 相似文献
42.
Polycyclic aromatic hydrocarbons (PAH) from ambient air particulate matter (PM) were analyzed by a new method that utilized direct immersion (DI) and cold fiber (CF) SPME-GC/MS. Experimental design was used to optimize the conditions of extraction by DI-CF-SPME with a 100μm polydimethylsiloxane (PDMS) fiber. The optimal conditions included a 5min equilibration at 70°C time in an ultrasonic bath with an extraction time of 60min. The optimized method was validated by the analysis of a NIST standard reference material (SRM), 1649b urban dust. The results obtained were in good agreement with certified values. PAH recoveries for reference materials were between 88 and 98%, with a relative standard deviation ranging from 5 to 17%. Detection limits (LOD) varied from 0.02 to 1.16ng and the quantification limits (LOQ) varied from 0.05 to 3.86ng. The optimized and validated method was applied to the determination of PAH from real particulate matter (PM10) and total suspended particulate (TPS) samples collected on quartz fiber filters with high volume samplers. 相似文献
43.
Assis AC Couto N Duarte MF Rodrigues P Barros MT Costa ML Cabral BJ Fernandez MT 《Journal of mass spectrometry : JMS》2011,46(7):696-704
The relevance of metal interactions with azides has led us to the study of the complexation of some transition metals, nickel and cobalt, by azidoacetone by means of electrospray ionization mass spectrometry (ESI-MS). Complexes were obtained from solutions of NiCl(2) and CoCl(2) , in methanol/water. Nickel was electrosprayed with other counter ion, bromide (Br), as well as other solvent (ethanol/water). For nickel and cobalt, the complexes detected were single positively charged, with various stoichiometries, some resulted from the fragmentation of the ligand, the loss of N(2) being quite common. The most abundant species were [Ni(II)Az(2)X](+) where X = Cl, Br and Az = azidoacetone. Some of the complexes showed solvation with the solvent components. Metal reduction was observed in complexes where a radical was lost, resulting from the homolytic cleavage of a metal coordination bond. Collision-induced dissociation (CID) experiments followed by tandem mass spectrometry (MS-MS) analysis were not absolutely conclusive about the coordination site. However, terminal ions of the fragmentation routes were explained by a gas-phase mechanism proposed where a C-C bond was activated and the metal inserted subsequently. Density functional theory calculations provided structures for some complexes. In [Ni(II)Az(2)X](+) species, one azidoacetone ligand is monodentate and the dominant binding location is the alkylated nitrogen and not the carbonyl group. The other azidoacetone ligand is bidentate showing coordination through alkylated nitrogen and the carbonyl group. These are also the preferential binding sites for the most stable isomer of [Ni(II)AzX](+) species. 相似文献
44.
Reyes-Escogido Mde L Gonzalez-Mondragon EG Vazquez-Tzompantzi E 《Molecules (Basel, Switzerland)》2011,16(2):1253-1270
Capsaicin is a unique alkaloid found primarily in the fruit of the Capsicum genus and is what provides its spicy flavor. Generally extracted directly from fruit, high demand has driven the use of established methods to increase production through extraction and characterization. Over time these methods have improved, usually be applying existing techniques in conjunction. An increasingly wide range of potential applications has increased interest in capsaicin. Especially compelling are the promising results of medical studies showing possible beneficial effects in many diseases. Capsaicin's pungency has limited its use in clinical trials to support its biological activity. Characterization and extraction/ synthesis of non-pungent analogues is in progress. A review is made of capsaicin research focusing mainly on its production, synthesis, characterization and pharmacology, including some of its main potential clinical uses in humans. 相似文献
45.
Rocío Esquembre María Lourdes Renart Jos Antonio Poveda C. Reyes Mateo 《Molecules (Basel, Switzerland)》2022,27(19)
The nanostructuration of solid matrices with lipid nanoparticles containing membrane proteins is a promising tool for the development of high-throughput screening devices. Here, sol-gel silica-derived nanocomposites loaded with liposome-reconstituted KcsA, a prokaryotic potassium channel, have been synthesized. The conformational and functional stability of these lipid nanoparticles before and after sol-gel immobilization have been characterized by using dynamic light scattering, and steady-state and time-resolved fluorescence spectroscopy methods. The lipid-reconstituted KcsA channel entrapped in the sol-gel matrix retained the conformational and stability changes induced by the presence of blocking or permeant cations in the buffer (associated with the conformation of the selectivity filter) or by a drop in the pH (associated with the opening of the activation gate of the protein). Hence, these results indicate that this novel device has the potential to be used as a screening platform to test new modulating drugs of potassium channels. 相似文献
46.
Gonzalo Martínez‐García Verónica Serafín Lourdes Agüí Paloma Yáñez‐Sedeño José M. Pingarrón 《Electroanalysis》2015,27(5):1119-1126
An electrochemical immunosensor for ghrelin (GHRL) determination in saliva is reported. Anti‐GHRL was immobilized onto Protein G‐magnetic beads and a competitive immunoassay involving biotinylated GHRL and alkaline phosphatase‐streptavidin was implemented. Once conjugate was magnetically captured on a screen‐printed carbon electrode, GHRL quantization was accomplished by DPV of 1‐naphtol formed upon addition of 1‐naphtyl phosphate. A linear range between 10?3 and 103 ng/mL GHRL, and a LOD of 7 pg/mL, much smaller than those from commercial ELISA kits, were found. The usefulness of the immunosensor was demonstrated by analyzing human saliva spiked with GHRL at 0.01, 0.1, 1 and 10 ng/mL. 相似文献
47.
Iván da Silva Cristina González-Silgo Juan Rodríguez-Carvajal Lourdes Mestres 《Journal of solid state chemistry》2005,178(5):1601-1608
The crystal structure of potassium, rubidium and caesium fluoroberyllates have been re-examined by neutron powder diffraction at room temperature and at 1.5 K. Previously, their structures, obtained from X-ray data, were described in the Pn21a space group. However, the results obtained from Rietveld refinements, using powder neutron diffraction, at both temperatures, indicated that all structures are orthorhombic with space group Pnma. The known phase transition at high temperature is probably related to the appearance of a hexagonal pseudo-symmetry instead of the elimination of the mirror plane between the above mentioned orthorhombic space groups. A possible phase transition, at very low temperature, was discarded considering the stereochemical criteria concerning the structural stability of A2BX4 compounds. This was confirmed by thermal analysis. On the other hand, a modulated background has been detected in all samples during the refinements. This is compatible with the presence of an amorphous phase, coexisting with the crystalline phase, or with a disordered component within the main crystalline phase. Instead of using a polynomial function, the background was modelled by Fourier filtering improving the fit for all patterns. The radial distribution function (RDF) was obtained from the analysis of the calculated background and compared with the RDF from the average crystal structure. The advantages of neutron with respect to X-ray diffraction were evidenced for this type of compound with β-K2SO4-type structure. 相似文献
48.
Sannomiya M Rodrigues CM Coelho RG dos Santos LC Hiruma-Lima CA Souza Brito AR Vilegas W 《Journal of chromatography. A》2004,1035(1):47-51
The methanolic extract of the leaves of the medicinal plant Byrsonima crassa (Malpighiaceae) contain flavonoids with antioxidant activity. They were separated in a preparative scale using high-speed counter-current chromatography. The optimum solvent system used was composed of a mixture of ethyl acetate-n-propanol-water (140:8:80 (v/v/v)) and led to a successful separation between monoglucosilated flavonoids (quercetin-3-O-alpha-L-arabinoside, quercetin-3-O-beta-D-galactoside) and the biflavonoid amentoflavone in only 3.5 h. The purities of quercetin-3-O-alpha-L-arabinoside (95 mg), quercetin-3-O-beta-D-galactoside (16 mg) and the biflavonoid amentoflavone (114 mg) were all isolated at purity over 95%. Identification was performed by 1H NMR, 13C NMR and UV analyses. 相似文献
49.
The feasibility of comprehensive two-dimensional gas chromatography with electron-capture detection (GC x GC-ECD) for the enantioseparation of chiral PCBs from other possible interfering compounds has been evaluated. Three commercially available enantioselective beta-cyclodextrin-based capillary columns (Chirasil-Dex, BGB-172 and BGB-176SE) have been tested as first-dimension columns. Three non-enantioselective stationary phases (HT-8, BPX-50 and Supelcowax-10) were combined with the enantioselective columns to allow the unambiguous determination of the enantiomers of the target chiral PCBs. Each enantioselective first-dimension column tested was able to separate into enantiomers different PCB congeners, but in all cases, the use of Supelcowax-10 as second-dimension column provided the most satisfactory results. The Chirasil-Dex x Supelcowax-10 column combination allowed the determination of the enantiomeric fraction (EF) of PCBs 84, 91, 95, 132, 136, 149, 174 and 176 in the working standard solution, while that of congener 135 was hindered. The BGB-172 x Supelcowax-10 column set allowed a proper EF determination of congeners 45, 84, 131, 132, 135, 171, 174 and 183, while that of PCB 91 was interfered with co-elutants. The column combination BGB-176SE x Supelcowax-10 allowed the determination of all congeners that this enantioselective stationary phase was able to separate into enantiomers, i.e. PCBs 45, 91, 95, 136, 149 and 176. These column combinations have also been evaluated for the simultaneous determination of the 12 congeners with a toxic equivalency factor assigned by the WHO (PCBs 77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169, 189) and the seven indicator congeners (PCBs 28, 52, 101, 118, 138, 153 and 180), and evaluated for the analysis of food samples. 相似文献