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101.
Carbon dioxide emulsion assisted loading of polymer microspheres toward sustained release materials 总被引:2,自引:0,他引:2
Baker GA Campbell ML Yates MZ McCleskey TM 《Langmuir : the ACS journal of surfaces and colloids》2005,21(9):3730-3732
An organic solvent-free method for encapsulating progesterone at high loadings within micron-sized inert latex polymer beads is reported. This approach makes use of a polymeric surfactant to emulsify carbon dioxide into an aqueous latex suspension. In this way, preformed approximately 4 microm polystyrene (PS) microparticles surface-grafted with poly(N-vinylpyrrolidone) (PVP) were plasticized and swollen followed by rapid partitioning of progesterone into the polymer matrix. The as-prepared polystyrene beads incorporated over 10% progesterone by weight while maintaining their initial size and morphological uniformity. Dissolution experiments were also carried out to obtain the release profile of progesterone entrapped within the PVP/PS particles. 相似文献
102.
Cappa CD Smith JD Wilson KR Messer BM Gilles MK Cohen RC Saykally RJ 《The journal of physical chemistry. B》2005,109(15):7046-7052
Measurements of the oxygen K-edge X-ray absorption spectrum (XAS) of aqueous sodium halide solutions demonstrate that ions significantly perturb the electronic structure of adjacent water molecules. The addition of halide salts to water engenders an increase in the preedge intensity and a decrease in the postedge intensity of the XAS, analogous to those observed when increasing the temperature of pure water. The main-edge feature exhibits unique behavior and becomes more intense when salt is added. Density functional theory calculations of the XAS indicate that the observed red shift of the water transitions as a function of salt concentration arises from a strong, direct perturbation of the unoccupied molecular orbitals on water by anions, and does not require significant distortion of the hydrogen bond network beyond the first solvation shell. This contrasts the temperature-dependent spectral variations, which result primarily from intensity changes of specific transitions due to geometric rearrangement of the hydrogen bond network. 相似文献
103.
Humphry T Forconi M Williams NH Hengge AC 《Journal of the American Chemical Society》2004,126(38):11864-11869
Kinetic isotope effects in the nucleophile and leaving group were obtained for the reaction of p-nitrophenyl phosphate monoester coordinated to a dinuclear Co(III) complex. The metal complex of the p-nitrophenyl phosphate monoester was found to hydrolyze by a single-step concerted mechanism, with significant nucleophilic participation in the transition state. By contrast, the hydrolysis of uncomplexed p-nitrophenyl phosphate occurs by a very loose transition state with little bond formation to the nucleophile. Previously, the metal complex of the diester methyl-p-nitrophenyl phosphate was found to hydrolyze via a two-step addition-elimination mechanism, in contrast to the concerted hydrolysis mechanism followed by uncomplexed diesters with the p-nitrophenolate leaving group. These results show that coordination to a metal complex can significantly alter the mechanism of phosphoryl transfer. 相似文献
104.
Monwar M Oh SJ Rinaldi PL McCord EF Hutchinson RA Buback MM Latz H 《Analytical and bioanalytical chemistry》2004,378(6):1414-1427
Poly(n-butylacrylate-co-carbon monoxide-co-ethylene) (polyEBC) samples prepared from 13C-labeled monomer, n-butyl acrylate, were characterized using two dimensional (2D) pulsed field gradient (PFG) 750 MHz NMR spectroscopy. To elucidate the complex structure of the terpolymer, 2D-1H/13C-heteronuclear single quantum coherence (HSQC) and heteronuclear multiple bond correlation (HMBC) experiments were conducted by selectively exciting the enhanced resonances in the spectra of two polymer samples, one polymer resulting from synthesis with 1-13C-n-butylacrylate monomer and a second polymer obtained from a synthesis with 2-13C-n-butylacrylate monomer. High-resolution 2D-NMR combined with 13C-labeling of the polymer greatly simplifies the 2D-NMR spectra, selectively enhances the weak peaks from low occurrence B-centered triad structures, and aids in their resonance assignments. In all experiments, the sample temperature was 120 degrees C, to ensure a homogeneous solution and sufficient molecular mobility. Electronic Supplementary Material: Supplementary material (1D 13C NMR spectra of the 13C-labeled and unlabeled polymers) is available in the online version of this article at http://dx.doi.org/100.1007/s00216-003-2402-3. 相似文献
105.
The first total synthesis of the marine dolabellane diterpene (+)-4,5-deoxyneodolabelline (1) has been accomplished. The highly efficient approach is characterized by the convergent assembly of dihydropyrans 2ab and cyclopentylsilanes 3ab. Allylic silane 3a was prepared from 2-methyl-2-cyclopentenone via a copper-catalyzed 1,4-addition followed by diastereoselective alkylation of the resulting enolate. A chemical resolution of racemic cyclopentanone 8 was effected by (S)-CBS-catalyzed borohydride reduction. Direct hydroxymethylation of the enantioenriched ketone 8 to form allylic alcohol 14 was achieved by a Stille palladium-catalyzed cross-coupling from the cyclopentenyl triflate 13. Treatment of the corresponding allylic phosphate 15 with trimethylsilylcopper reagent provided for displacement with allylic transposition yielding the exocyclic allylsilane 3a with excellent diastereoselectivity. Dihydropyrans 2a and 2b were prepared from optically pure acyclic acetals via ring-closing metathesis. Coupling of 3a and 2a or 2b via the carbon-Ferrier protocol gave trans-2,6-disubstituted dihydropyrans 30 and 35 with complete stereoselectivity. Vanadium-based pinacol coupling reactions were explored for closure of the medium-sized carbocycle to yield syn-diol 33. X-ray diffraction studies of the monobenzoate 34 have provided unambiguous stereochemical assignments. Substantial ring strain accounted for the lack of alkene products typical of reductive elimination using TiCl(3) and zinc-copper couple (McMurry) conditions leading to 37. Finally, the natural product 1 was obtained via Swern oxidation of the diol 37. 相似文献
106.
This review covers recent progress in polyelectrolyte multilayer (PEM) coatings applied to analytical separations using open-tubular capillary electrochromatography (OT-CEC). The simple preparation procedure involved in the PEM approach has provided some attractive features over other modes of capillary electrophoresis-based separations including packed column capillary electrochromatography (PC-CEC) and micellar electrokinetic chromatography (MEKC). PEM coatings have been used to alleviate the adsorption of basic analytes, to improve separations, and to improve the stability of the electroosmotic flow. Fundamental aspects of PEM coatings on surfaces and analytical separation platforms are briefly outlined in this review. In addition, applications of PEM coatings to fused-silica capillaries or microchip separation devices for the separation of small achiral or chiral analytes, as well as large biomolecules, are discussed. 相似文献
107.
[reaction: see text]. In the copper salt catalyzed ether formation from aryl bromides or iodides and phenols, 2,2,6,6-tetramethylheptane-3,5-dione (TMHD) was found to greatly accelerate the ordinarily difficult reaction, making it occur under more moderate temperatures and reaction times. A series of aryl halides and phenols were shown to form ethers in NMP as the solvent, cesium carbonate as the base, and CuCl and TMHD as the catalysts. The reaction was shown to tolerate electron-rich aryl bromides and electron-neutral phenols. 相似文献
108.
The synthesis of 5,8-difluoronaphtho[2,3-c]thiophene-4,9-dione ( 2a ) has been accomplished. Treatment of 2a with 2,2-dimethylaminoethylamine leads to 2-[2-(dimethylamino)ethyl]-5-[2-(dimethylamino)ethylamino]-8-fluoronaphtho[2,3-c]pyrrole-4,9-dione ( 6 ). 相似文献
109.
Recent highlights in stationary phase design for open-tubular capillary electrochromatography 总被引:1,自引:0,他引:1
This review examines the most recent innovations made to achieve high performance in open-tubular capillary electrochromatography (OT-CEC) separations, focusing on the ingenious chemical and physical solutions made to increase the surface area and equip the stationary phase with exploitable selectivity. Among the approaches taken are chemically bonded ligands, etching with chemical bonding, sol-gels, molecularly imprinted polymers, porous layers, physically attached or adsorbed phases, and nanoparticle coatings. Particularly noteworthy are modern developments with macrocyclic receptor ligands, nanoparticles and open channel electrochromatography on-chip. 相似文献
110.
Terrence G. Vargo Daniel J. Hook Joseph A. Gardella Mary A. Eberhardt Anne E. Meyer Robert E. Baier 《Journal of polymer science. Part A, Polymer chemistry》1991,29(4):535-545
Recent work in our laboratories has fully characterized the surface region of a segmented poly(ether-urethane) (PEU) extending from the air/polymer interfacial region through bulk depths in the micron range. This characterization utilized energy and angle dependent Electron Spectroscopy for Chemical Analysis (ESCA), Attenuated Total Reflectance–Fourier Transform Infrared Spectroscopy (ATR–FTIR), and Comprehensive Wettability Profiling (contact angle using a homologous series of liquids) as defined by Zisman. In this study this same multi-analytical-technique approach is used to elucidate changes in these PEU surfaces induced through an H2O Radio Frequency Glow Discharge (RFGD) plasma. This investigation reports both qualitative and quantitative changes due to the modification treatments as well as the permanency of the changes effected on these surfaces through the plasma treatment. From our analyses, the amount of surface residing polyurethane (hard segment) is observed to increase due to a proposed plasma etching mechanism. Further, the addition of oxygen containing functionality is detected at the modified surfaces unique with respect to the unmodified PEU. These surface modifications which show large increases in wettability, are finally observed to be semi-permanent over a time period of 6 months. 相似文献