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排序方式: 共有133条查询结果,搜索用时 31 毫秒
61.
Marie-Pierre Gelin 《Journal of fluorine chemistry》2005,126(4):575-583
The radical copolymerisation in solution of vinylidene fluoride (or 1,1-difluoroethylene (VDF)) with hexafluoropropylene (HFP) initiated by di-tert-butyl peroxide is presented. A series of eight copolymerisation reactions was investigated with initial [VDF]o/[HFP]o molar ratios ranging from 5.0/95.0 to 85.2/14.8. Both co-monomers copolymerised in this range of copolymerisation. Moreover, only VDF homopolymerised in these conditions. The copolymer compositions of these random-type copolymers were calculated by means of 19F NMR spectroscopy which allowed the respective amount of each monomeric unit in the copolymer to be quantified. The Tidwell and Mortimer method led to the assessment of the reactivity ratios, ri, of both co-monomers showing a higher incorporation of VDF in the copolymer (rHFP = 0.12 ± 0.05 and rVDF = 2.9 ± 0.6 at 393 K). Alfrey-Price's Q and e values of HFP were calculated to be 0.002 (from QVDF = 0.008) or 0.009 (from QVDF = 0.015) and +1.44 (versus eVDF = 0.40) or +1.54 (versus eVDF = 0.50), respectively, indicating that HFP is an electron-accepting monomer. The thermal properties of these fluorinated copolymers were also determined. Except for those containing a high amount of VDF, they were amorphous. Each showed one glass transition temperature (Tg) only, and from known laws of Tg, that of the homopolymer of HFP was assessed. It was compared with that obtained from the literature after extrapolation and is discussed. 相似文献
62.
Using cyclodextrin-capillary zone electrophoresis (CD-CZE), baseline separation of baclofen, a potent GABA(B) agonist; was achieved. A method for the enantioresolution of this gamma-aminobutyric acid (GABA) and determination of enantiomeric purity was developed using CDs (highly sulfated-CD or highly S-CD) as chiral selectors and capillaries dynamically coated with polyethylene oxide (PEO). Operational parameters, such as the nature and concentration of the chiral selectors, buffer concentration, organic modifiers, and applied voltage, were investigated. The use of charged CDs provides a driving force in the opposite direction of the positively charged baclofen in the running buffer and enantiomeric resolution by inclusion of compounds in the CD cavity. Highly S-beta-CD was found to be the most effective complexing agent, allowing good enantiomeric resolution. The complete resolution was obtained using 25 mM phosphate buffer, pH 2.5, containing 3% w/v highly S-beta-CD at 25 degrees C with aN applied field of 0.40 kV/cm. The apparent association constants of the inclusion complexes were calculated. This optimized method was validated in terms of repeatability and limits of detection (0.13 microg x mL(-1)) and quantification. The migration order was determined. 相似文献
63.
Lipka E Daniel C Vaccher MP Glaçon V Ewing D Mackenzie G Len C Bonte JP Vaccher C 《Electrophoresis》2004,25(3):444-453
Baseline separation of some new acyclic nucleosides which are potential antiviral agents was achieved using cyclodextrin capillary zone electrophoresis (CD-CZE). A method for the enantiomeric resolution of these compounds and determination of their enantiomeric purity was developed using anionic CDs (highly sulfated-CD or highly S-CD) as chiral selectors and capillaries, which were dynamically coated with polyethylene oxide (PEO). Operational parameters including (i) the nature and concentration of the chiral selectors, (ii) organic modifiers, (iii) temperature, and (iv) applied voltage were investigated. The use of charged CDs provides (i) a supplementary driving force for the compounds in a running buffer and (ii) enantiomeric resolution by inclusion of compounds in the CD cavity. The highly S-CD was found to be the most effective complexing agent and allowed good enantiomeric resolution. The complete resolution of five nucleoside analogs was obtained using 25 mM phosphate buffer, pH 2.5, containing either highly S-alpha-CD, S-beta-CD or S-gamma-CD at 30 degrees C with an applied field of 0.30 kV/cm. The apparent association constants of the inclusion complexes were calculated. The enantiomer migration order for the molecules investigated was determined and the detection limit of enantiomeric impurities was found to vary between 0.34 to 3.56 ng.mL(-1) for the first enantiomer. 相似文献
64.
Dupouy C Iché-Tarrat N Durrieu MP Vigroux A Escudier JM 《Organic & biomolecular chemistry》2008,6(16):2849-2851
Introduction of alpha,beta-D-CNA featuring canonical values of the torsional angles alpha and beta within oligonucleotides leads to an overall stabilization and improved rigidity of the duplex DNA as demonstrated by UV experiments, circular dichroism and corroborated by molecular dynamics simulations. 相似文献
65.
The influence of structure and composition of a reverse SDS microemulsion on enzymatic activities and electrical conductivities 总被引:3,自引:0,他引:3
Bauduin P Touraud D Kunz W Savelli MP Pulvin S Ninham BW 《Journal of colloid and interface science》2005,292(1):244-254
The activity of the enzyme horse radish peroxidase (HRP) is studied in a series of reverse microemulsions composed of dodecane, aqueous buffer, sodium dodecylsufate (SDS) and alcohols of the homologous series 1-butanol to 1-octanol. The HRP catalyzed reaction is the oxidation of a classical water soluble substrate, the 2,2-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) by hydrogen peroxide. In parallel electrical conductivity measurements are performed on the same solutions. The structural changes in the microemulsions, as inferred by the conductivity measurements, correlate remarkably well with the changes in the enzymatic activities. In particular it is found that (a) the maximum activity of the enzyme is always related to its optimum hydration and that this hydration can be related to the microemulsion structures, (b) the enzyme inhibition caused by the alcohols in microemulsions is a consequence of both the solubility of the alcohols in the buffer and the rigidity of the interfacial film. Consequently, it can be concluded that enzymatic activity measurements are a valuable tool to study confined systems such as microemulsions and, in particular, the amount of available hydration water. Enzymatic activities can be finely tuned by small changes in microemulsion structures, probably in a predictive way. 相似文献
66.
Nadia Anik Marc Airiau Marie-Pierre Labeau Chi-Thanh Vuong Hervé Cottet 《Journal of chromatography. A》2012
For many industrial applications, the combination of two different monomers in statistical or diblock copolymers enhances the properties of the corresponding polymer. However, during the polymerization reaction, homopolymers might be formed and can influence the properties for the applications. Consequently, the separation and the quantification of the homopolymers contained in copolymer samples are crucial. In addition, the charge density distribution of the statistical copolymer is an important characteristic for the applications. The purpose of this work was to study the characterization of a statistical copolymer of acrylic acid (AA) and diallyldimethyl ammonium chloride (DADMAC) by capillary electrophoresis (CE) in acidic conditions (cationic copolymers). For that purpose, a free solution electrophoretic separation was carried out according to the charge rate (chemical composition) independently of the molar mass. The second objective was to compare contactless conductivity detection and indirect UV absorbance modes for the quantification of DADMAC homopolymers present in copolymer samples. Different coated capillaries based on neutral or positively charged modification were also compared. The comparison of indirect absorbance UV and contactless conductimetric detection demonstrated that both detection modes can be used for a complete CE characterization of non-UV absorbing PAA-DADMAC copolymers. 相似文献
67.
Sabine Gei? Max Schneider Gerhild Donnevert Jürgen W. Einax Nicole Lettmann Aurélien Rey Herbert Lepper Birgit K?rner Theodor Prey Bettina Hilger Moana Engelke Marie-Pierre Strub Herve Adrien George Sawal Dirk L?ffler Tom Schillings Ines Hussy Philipp Steinbichl Sigrid Scharf Alexander Ruderisch Jorge E. Olmos F. Javier Santos Arantxa Bartolome Josep Caixach 《Accreditation and quality assurance》2012,17(1):15-25
A validation interlaboratory trial was carried out to prepare ISO 12010: Water quality??Determination of short-chain polychlorinated alkanes (SCCP) in water??Method using gas chromatography/mass spectrometry (GC-MS) and electron capture negative ionisation (ECNI). The task was to determine the sum of short-chain polychlorinated n-alkanes with carbon chain lengths of C10?CC13 and a chlorine content between 49% (g/100?g) and 67% (g/100?g) in water by GC-ECNI-MS. The quantification had to be performed by multiple linear regression as described in ISO/DIS 12010, the compulsory method. Samples distributed were real river samples, and waste water spiked with a target concentration of 0.4 and 0.6???g/L for the sum of SCCPs, i.e. a concentration around the environmental quality target level according to the European Water Framework Directive. The different types of water samples tested were surface water with <150?mg/L suspended matter, surface water with 0.5?g/L suspended matter, and filtered waste waster. The interlaboratory trial included the extraction of the water samples, a column chromatographic clean up, a concentration step, and integration of chromatographic unresolved complex mixtures as well as the calibration and quantification by multiple linear regression. The reproducibility standard deviation of the standard concentration was 11.9%. Reproducibility standard deviations of concentrations in the three different water samples between 27.8 and 34.2% were achieved by 10?C12 participating laboratories from six countries. 相似文献
68.
Interaction between GUVs and catanionic nanocontainers: new insight into spontaneous membrane fusion
Mauroy C Castagnos P Blache MC Teissié J Rico-Lattes I Rols MP Blanzat M 《Chemical communications (Cambridge, England)》2012,48(53):6648-6650
Spontaneous receptor-free membrane fusion with pure lipid systems, used as a cell membrane model, is demonstrated with easy-to-handle lactose-derived catanionic vesicles. This fusion, mediated and controlled by phospholipids, emphasizes the great value of these nanovesicles for enhanced direct cytosolic drug delivery without the shortcomings linked with endocytic pathways. 相似文献
69.
Santoni MP Pal AK Hanan GS Tang MC Venne K Furtos A Ménard-Tremblay P Malveau C Hasenknopf B 《Chemical communications (Cambridge, England)》2012,48(2):200-202
Pd(II)-directed self-assembly of a 3-pyridyl grafted Lindqvist hexavanadate led to the formation of a unique trimeric species, as confirmed by a variety of techniques, including pulsed-field gradient NMR spectroscopy and high-resolution ESI mass spectrometry. 相似文献
70.
Et Taouil A Mahmoud MM Lallemand F Lallemand S Gigandet MP Hihn JY 《Ultrasonics sonochemistry》2012,19(6):1186-1193
A variety of coatings based on electrosynthesized polypyrrole were deposited on zinc coated steel in presence or absence of ultrasound, and studied in terms of corrosion protection. Cr III and Cr VI commercial passivation were used as references. Depth profiling showed a homogeneous deposit for Cr III, while SEM imaging revealed good surface homogeneity for Cr VI layers. These chromium-based passivations ensured good protection against corrosion. Polypyrrole (PPy) was also electrochemically deposited on zinc coated steel with and without high frequency ultrasound irradiation in aqueous sodium tartrate-molybdate solution. Such PPy coatings act as a physical barrier against corrosive species. PPy electrosynthesized in silent conditions exhibits similar properties to Cr VI passivation with respect to corrosion protection. Ultrasound leads to more compact and more homogeneous surface structures for PPy, as well as to more homogeneous distribution of doping molybdate anions within the film. Far better corrosion protection is exhibited for such sonicated films. 相似文献