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321.
Cyclic voltammetry has been employed to investigate the mixed micellar behavior of the binary mixtures of different zwitterionic surfactants such as 3-(N,N-dimethylhexadecylammonio)propane sulfonate (HPS), 3-(N,N-dimethyltetradecylammonio)propane sulfonate (TPS) and 3-(N,N-dimethyldodecylammonio)propane sulfonate (DPS) with three triblock polymers (L64, F127 and P65) by using 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) as an electroactive probe at 25 °C. Critical micellar concentration (cmc) has been determined from the plots of variation in peak current (ip) versus the total concentration of surfactant/triblock polymer. Diffusion coefficient of the electroactive species has also been reported. The regular solution theory approximation has been used to determine various micellar parameters of ideal systems. The variation in micellar mole fraction (X1) of the zwitterionic surfactant supports the formation of mixed micelles, which are rich in triblock polymer component in the surfactant rich region of the mixture and vice versa. The regular solution interaction parameter (β) suggests the formation of mixed micelles due to the synergistic interactions in case of HPS/TPS/DPS + F127/P65 systems and gets affected by EO/PO ratio of triblock polymers. 相似文献
322.
The regio-, diastereo-, and π-facial selective Lewis acid mediated Diels-Alder reactions of cis/trans-3-butadienyl-2-azetidinones with unsymmetrical dienophiles viz. methyl acrylate, dimethyl fumarate, and acrolein leading to the synthesis of diastereomerically pure and biologically potent 1,3,4-trisubstituted-2-azetidinones are reported. Theoretical calculations at HF/6-31G∗∗ and 6-31G∗∗/DFT levels have been performed to support the observed π-facial selectivity. The formation of diastereomerically pure ‘endo’ adducts is supported by the X-ray diffraction studies. 相似文献
323.
Screening for conjugates formed by the tripeptide glutathione with new chemical entities is an essential step during the drug discovery process, as the formation of these conjugates serves as an indicator for the presence of reactive electrophilic intermediates. To increase the selectivity and throughput of this analysis, various mass spectral scan types have evolved over time. Historically, samples were analyzed under positive ionization conditions for the neutral loss of m/z 129 (loss of the pyroglutamic acid moiety from glutathione); however, more recently, negative precursor ion scanning for the loss of m/z 272 (deprotonated gamma-glutamyl-dehydroalanyl-glycine from glutathione) has emerged as a more selective tool. Further increasing the selectivity, we report on an extension of this methodology by incorporating a simultaneous dual negative precursor ion scan for two commonly observed ion fragments from glutathione conjugates, m/z 272 and 254 (the dehydrated form of m/z 272). This negative dual precursor ion scan methodology was first validated using substrates known to undergo metabolic bioactivation (diclofenac, carbamazepine, and 3-methyl indole) and has then been applied to the routine analysis of proprietary compounds undergoing active lead optimization. In comparison to alternative scan methodologies, the increased selectivity offered by this simultaneous dual precursor method results in a reduction in the generation of false positive results as well as reduced data interpretation time. 相似文献
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A.V. Mahajan H. Alloul G. Collin J.F. Marucco 《The European Physical Journal B - Condensed Matter and Complex Systems》2000,13(3):457-475
We present detailed data and analysis of the effects of Zn substitution on the planar Cu site in YBa2Cu3O6+x (YBCO6+x) as evidenced from our 89Y NMR measurements on oriented powders. For x << 1x \ll 1 we find additional NMR lines which are associated with the Zn substitution. From our data on the intensities and temperature dependence of the shift, width, and spin-lattice relaxation rate of these resonances, we conclude that the spinless Zn 3d 10 state induces local moments on the near-neighbour (nn) Cu atoms. Additionally, we conjecture that the local moments actually extend to the farther Cu atoms with the magnetization alternating in sign at subsequent nn sites. We show that this analysis is compatible with ESR data taken on dilute Gd doped (on the Y site) and on neutron scattering data reported recently on Zn substituted YBCO6 + x. For optimally doped compounds 89Y nn resonances are not detected, but a large T-dependent contribution to the 89Y NMR linewidth is evidenced and is also attributed to the occurence of a weak induced local moment near the Zn. These results are compatible with macroscopic magnetic measurements performed on YBCO6 + x samples prepared specifically in order to minimize the content of impurity phases. We find significant differences between the present results on the underdoped YBCO6 + x samples and 27Al NMR data taken on Al3+ substituted on the Cu site in optimally doped La2CuO4. Further experimental work is needed to clarify the detailed evolution of the impurity induced magnetism with hole content in the cuprates. 相似文献
326.
Surbhi Mahajan Byoung‐Ki Cho Jürgen Allgaier Lewis J. Fetters Geoffrey W. Coates Ulrich Wiesner 《Macromolecular rapid communications》2004,25(22):1889-1894
Summary: Stepwise anionic polymerization, catalytic hydrogenation, and atom transfer radical polymerization were performed to synthesize an amphiphilic ABC triblock copolymer, poly(ethylene‐alt‐propylene)‐block‐poly(ethylene oxide)‐block‐poly(hexyl methacrylate) (PEP‐b‐PEO‐b‐PHMA), with hydrophilic PEO as the middle block. The resulting block copolymers have well‐defined molecular weights and narrow molecular weight distributions as revealed by 1H NMR spectroscopy and gel permeation chromatography.
327.
Anomalous amino acids not only play central roles as mimics of natural amino acids but also offer opportunities as unique building blocks for combinatorial chemistry. This paper describes the chiral syntheses and solid-phase applications of a versatile atypical amino acid, 4-azalysine (2,6-diamino-4-azahexanoic acid) 1. The syntheses of differentially protected 4-azalysine derivatives 28a-e have been developed by two efficient and inexpensive routes that start either from Garner's aldehyde 16 or the chiron (S)-N(alpha)-Cbz-2,3-diaminopropionic acid 23. Both approaches employ the convergent modular concept and exploit reductive amination of aldehydes with amines as the key step for the fusion of the two segments. In the first route, the overall process inverts the chirality of the starting material, L-serine, and thus provides an excellent route to the unnatural D-isomers. The alternative route starting from L-asparagine provides a shorter and high-yielding route to orthogonally protected 4-azalysine derivatives. The corresponding N(2)-Fmoc-4-azalysines 31a-e, readily derived from the key intermediate 27, are compatible with the Fmoc-based solid-phase peptide synthesis (SPPS) and solid-phase organic chemistry (SPOC) protocols. Furthermore, the utility and versatility of another key structure, tris-Boc-4-azalysine 2 in the engineering of novel high-loading dendrimeric polystyrene resins 33 and 36, have been demonstrated. Following derivatization with the Rink amide linker 34, the stability and robustness of these resin-bound dendrimers 35 and 37 in the synthesis of small molecules using a range of reaction conditions (e.g., Mitsunobu and Suzuki reactions) have been effectively illustrated. 相似文献
328.
329.
Ghanshyam S. Chauhan Harinder Lal Swati Mahajan Monica Bansal 《Journal of polymer science. Part A, Polymer chemistry》2000,38(24):4506-4518
To get highly reactive polymeric materials for selective studies of enzyme immobilization, water purification, separation, and enrichment technologies, we attempted to graft 4‐vinyl pyridine (4‐VP) onto Teflon‐PFA by simultaneous γ‐ray initiation. The resulting graft copolymers were quaternized by treatment with some alkylating agents. Optimum conditions for grafting were evaluated through the variation of the total dose of radiation, the amount of water, and the monomer concentration. The effect of the solvent composition (H2O/MeOH) was also studied. In the presence of MeOH, grafting occurred less often and was nonselective as 4‐VP was incorporated on both sides in comparison with highly selective grafting in an aqueous medium. The percentages of the grafting, total conversion, and grafting efficiency and the rates of the polymerization, grafting, and homopolymerization were also evaluated. Some other monomers such as methacrylic acid, methyl methacrylate, maleic acid, acrylonitrile, and vinyl imidazole were not incorporated onto the backbone film under the optimum grafting reaction conditions evaluated for the grafting of 4‐VP. Although some grafting occurred, the graft yield was too low to be considered of any significance. The grafted films were quaternized with benzyl chloride, and quaternized and unquaternized films were used for the immobilization of lipase. The former showed high activity with lipase and has potential for development as a bioreactor. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4506–4518, 2000 相似文献
330.