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151.
An approach based on on-line coupled liquid chromatography-gas chromatography (LC-GC) was developed for the rapid analysis of gamma-oryzanol in rice. Total lipids were extracted from rice and subjected to LC-GC without any prior purification. gamma-Oryzanol was pre-separated by HPLC from rice lipids and transferred on-line to GC analysis in order to separate its major constituents. 24-methylenecycloartanyl ferulate, cycloartenyl ferulate, campesteryl ferulate, beta-sitosteryl ferulate and campestanyl ferulate. The identities of the compounds were confirmed by off-line GC-MS analysis. Total gamma-oryzanol content could be quantified by HPLC-UV detection and the distribution of gamma-oryzanol constituents could be determined by on-line coupled GC analysis. The proposed methodology paves the way for high-throughput investigations providing information on natural variations in gamma-oryzanol content and its composition in different rice varieties. 相似文献
152.
Nickel-catalyzed reductive couplings of aldehydes with alkynes that contain tethered olefins are described, in which the degree and sense of regioselectivity are controlled by the length of the tether and the presence or absence of an additive. When the alkyne and alkene are separated by four bonds, very high (>95:5) regioselectivities are observed. Use of a monodentate phosphine as an additive leads to formation of the opposite regioisomer in equal and opposite selectivity (5: >95). These results provide strong evidence for an interaction between the remote alkene and the metal center during the regioselectivity-determining step and suggest that reactions with and without an additive proceed via fundamentally distinct mechanisms. 相似文献
153.
The separation of periodate, iodate and iodide can be easily achieved by HPLC on a C-18 column with a mobile phase consisting of acetonitrile and aqueous phosphoric acid, without the need of any mobile phase additives that are often employed. All three iodine species are well separated. Separation factors as high as 16 are observed, and retention factors k between ~0.5 and 8. The retention time of all three ions increases with increasing acetonitrile concentration. The retention time of periodate and iodide decreases with increasing temperature, however, it increases slightly for iodate. An application of the HPLC method that was developed is the monitoring of an oxidative cleavage reaction, the cleavage of the enone-group of the steroid 4-androstene-3,17-dione. Periodate is used as oxidative reagent for this reaction. During the reaction periodate is reduced to iodate, and eventually both iodine species will be present in the reaction mixture, besides the starting material and product. In the final product the remaining iodate ions will be reduced to iodide which can be quantified accurately using the developed HPLC method. 相似文献
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The crystal structures of the 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, TCNQF(4), electron transfer salts of meso-tetraphenylporphinatomagnesium(II), [MgTPP][TCNQF(4)].PhMe and [MgTPP][TCNQF(4)].3(1,2-C(6)H(4)Cl(2)), and meso-tetrakis(3,4,5-trimethoxyphenyl)porphinatomagnesium(II), [MgT(3,4,5-OMe)PP][TCNQF(4)].3(1,2-C(6)H(4)Cl(2)), provide the first structurally characterized examples of 1-D metal-radical chains involving [Mg(II)(porphyrin(*))](+). These salts possess [TCNQF(4)](*-) stabilized by trans-mu-coordination to Mg(II) and exhibit nu(CN) at 2199 and 2177, 2212 and 2187, and 2194 and 2172 cm(-1), respectively. The [TCNQF(4)](*-) species is planar and bridges two cations with MgN distances of 2.266(16), 2.221(2), and 2.276(3) A, respectively, which are shorter than the MnN 2.321(3) A distance observed for [MnT(3,4,5-OMe)PP][TCNQF(4)].3(1,2-C(6)H(4)Cl(2)). The room-temperature effective moments for [MgTPP][TCNQF(4)].xS (S = PhMe and 1,2-C(6)H(4)Cl(2)) and [MgTPP][C(4)(CN)(6)].PhMe are consistent with the calculated spin only value of 2.45 micro(B) with weak antiferromagnetic coupling (J(intra)/k(B) approximately -2.9 K; H = -2JSa.Sb) for these [TCNQF(4)](*-) salts and for this [C(4)(CN)(6)](*-) salt (J(intra)/k(B) approximately -0.8 K) on the basis of fits to several models. The coupling is significantly reduced with respect to that of the Mn analogues due to lack of spin on the metal site for [Mg(II)(por(*))](+). The antiferromagnetic coupling is enhanced for [MgT(3,4,5-OMe)PP][TCNQF(4)] with respect to [MgTPP][TCNQF(4)] as [TCNQF(4)](*-) gets closer to the [Mg(II)(por(*))](+) plane, which leads to greater interactions and coupling. 相似文献
157.
Harth E Van Horn B Lee VY Germack DS Gonzales CP Miller RD Hawker CJ 《Journal of the American Chemical Society》2002,124(29):8653-8660
A novel approach is presented for the controlled intramolecular collapse of linear polymer chains to give well-defined single-molecule nanoparticles whose structure is directly related to the original linear polymer. By employing a combination of living free radical polymerization and benzocyclobutene (BCB) chemistry, nanoparticles can be routinely prepared in multigram quantities with the size being accurately controlled by either the initial degree of polymerization of the linear chain or the level of incorporation of the BCB coupling groups. The latter also allows the cross-link density of the final nanoparticles to be manipulated. In analogy with dendritic macromolecules, a significant reduction of up to 75% in the hydrodynamic volume is observed on going from the starting random coil linear chains to the corresponding nanoparticles. The facile nature of the living free radical process also permits wide variation in monomer selection and functional group incorporation and allows novel macromolecular architectures to be prepared. Furthermore, the use of block copolymers functionalized with benzocyclobutene groups in only one of the blocks gives, after intramolecular collapse, a hybrid architecture in which a single linear polymer chain is attached to the globular nanoparticle. 相似文献
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J. Krägel J. B. Li R. Miller M. Bree G. Kretzschmar H. Möhwald 《Colloid and polymer science》1996,274(12):1183-1187
The surface viscoelastic properties of monolayers of two phospholipids DPPC (L--dipalmitoylphosphatidylcholine) and DMPE (L--dimyristoylphosphatidyl-ethanolamin), at the air-water interface have been investigated. Two techniques were used for the investigation. One involved use of an interfacial shear rheometer (torsion pendulum apparatus ISR1), to provide measurements of the shear viscosity s as a function of surface pressure, and the second, a modified LB trough with an oscillating barrier to generate periodie dilation and compression so as to measure the dilational elastic modulusE as a function of surface area.Results indicate a strong dependence of s andE upon monolayer phases. This suggests that the viscoelastic relaxation of monolayers can be understood as molecular rearrangements, domain exchange and molecular reorientations between different monolayer states. 相似文献