The structure of N-fluorobis(trifluoromethylsulfonyl)imide, prepared by a relatively safe and easy method, has been determined by gas-phase electron diffraction (GED), employing the SARACEN method, with flexible restraints based on the MP2/6-311G* structure, and by X-ray crystallography at 150 K. The strongly electron-withdrawing CF(3) and SO(2)CF(3) groups make the C-S and N-S distances long, averaging 187.7(3) and 171.7(3) pm, respectively, in the gas phase. The gas consists of two conformers, one (75%) with a CF(3) group on each side of the SNS plane, one anti-periplanar and one syn-periplanar to the further N-S bond (ap, sp), and the other with both CF(3) groups on the same side, i.e. denoted ap, ap. These conformers have very different SNS angles, 126.9(9) degrees and 117.1(17) degrees respectively. In the crystal all molecules have the ap, sp conformation, with parameters similar to those found for this conformer in the gas phase. 相似文献
Ostwald ripening in n-alkane oil-in-water emulsions stabilized by sodium caseinate at neutral pH has been studied by monitoring time-dependent changes in the number-average droplet diameter and the droplet-size distribution. In qualitative agreement with theory, the destabilization rate has been shown to increase with reduction of the n-alkane chain length and on addition of ethanol to the aqueous phase. Replacement of caseinate by β-lactoglobulin also leads to improved stability, but addition of calcium ions does not. The potential use of transglutaminase-induced crosslinking of adsorbed protein as a way of inhibiting the Ostwald ripening of caseinate-stabilized emulsions has been examined. It is shown that enzymic crosslinking before emulsification can lead to a modest reduction in the coarsening rate at long storage times. Crosslinking of caseinate after emulsification produces enhanced stability at short times, but there is a catastrophic loss of stability at long times due to droplet coalescence. 相似文献
The synthesis of a range of 3‐(phenylsulfonimidoyl)propanoate derivatives is described. A number of strategies for the imination of the key sulfoxide methyl 3‐(penylsulfinyl)propanoate are discussed including the use of O‐(mesitylsulfonyl)hydroxylamine (MSH) and iminoiodane reagents (Ph IN SO2R). A successful strategy for the preparation of the target compounds was the use of MSH followed by in situ coupling with a N‐Boc‐protected amino acid. The pseudo‐dipeptides thus formed exhibited interesting conformational properties in CDCl3 solution giving evidence of intramolecular H‐bonds in all cases, except for the proline derivative. 相似文献
Reaction of lithium phenylselenothiolate, generated in situ from the reductive cleavage of PhSe‐SiMe3 with alkyl lithium reagents and insertion of elemental sulfur, with triphenylphosphine solubilized CuCl affords the molecular cluster complex [Cu20Se4 (μ3‐SePh)12(PPh3)6] ( 1 ). The analogous reaction with AgCl yields the extended structure [Ag(SePh)]∞ ( 2 ) in which an infinite layer of AgI atoms is capped on either side by μ4‐SePh ligands. 1: space group P¯1, a = 17.9510(6), b = 18.1712(7), c = 31.4311(11) Å, a = 78.098(2), β = 82.905(2), γ = 70.012(2)°. 2: space group C2/c, a = 5.8762(6), b = 7.2989(7), c = 29.124(2) Å, β = 95.790(3)°. 相似文献
The rapid synthesis of cis-2,6-disubstituted dihydropyrans is achieved in a three-component, one-pot cascade reaction. BiBr3-mediated addition of ketene silyl acetals or silyl enol ethers to β,γ-unsaturated cis-4-trimethylsilyl-3-butenal provides a Mukaiyama aldol adduct containing a vinylsilane moiety tethered to a silyl ether. Addition of a second aldehyde initiates a domino sequence involving intermolecular addition followed by an intramolecular silyl-modified Sakurai (ISMS) reaction. Isolated yields of this one-pot reaction vary from 44 to 80% and all compounds were isolated as the cis-diastereomers (10 examples). 相似文献
N-arachidonoyl glycine (NAGly) is an endogenous signaling lipid with a wide variety of biological activity whose biosynthesis
is poorly understood. Two primary biosynthetic pathways have been proposed. One suggests that NAGly is formed via an enzymatically
regulated conjugation of arachidonic acid (AA) and glycine. The other suggests that NAGly is an oxidative metabolite of the
endogenous cannabinoid, anandamide (AEA), through an alcohol dehydrogenase. Here using both in vitro and in vivo assays measuring metabolites with LC/MS/MS we test the hypothesis that both pathways are present in mammalian cells. 相似文献
Viscous fingering is an important fluid transport phenomenon that manifests itself when two fluids having different viscosities move in the same direction. Their interface is unstable and a complex fingering pattern may arise. This phenomenon is important in chromatography because it may lead to a decrease or even a failure in separations. The onset of viscous fingering was visually observed by packing a glass column with particles having the same refractive index as the mobile phase and injecting plugs of dye solutions having viscosities different from that of the mobile phase. Severe fingering effects are observed if the viscosity difference exceeds 0.17 cP. However, for smaller viscosity differences, band distortions are observed that may affect retention data, band efficiency, and band resolution. Careful attention should be paid to matching the mobile phase viscosity and that of the injection plug when accurate chromatographic information is required. 相似文献