The treatment of trialkyl phosphate with different alkyl bromides provides facile access to mixed phosphate esters. The presence of substoichiometric amounts of lithium bromide was found to be critical to this transesterification process, supporting a mechanism involving initial generation of phosphate anion, followed by its nucleophilic attack on alkyl bromide. 相似文献
N,N,N′,N′-Tetrabutyl-3,6-dioxaoctane-dithioamide, an Ionophore with Selectivity for Cd2+ The dioxa-dithioamide 3 behaves as a highly selective ionophore for Cd2+ in solvent polymeric membranes. It induces cation-permselectivity in these membranes with a transference number of 1 for Cd(NO3)2- and of 2 for CdCl2-solutions. In the presence of a proton carrier, 3 may be used to selectively pump Cd2+ through membranes by coupling with a pH gradient. 相似文献
(−)-Neplanocin F, the natural isomer of a component of the neplanocin family was enantioselectively synthesized starting from d-γ-ribonolactone. The synthetic approach was based on the preparation of a suitable carbocyclic precursor bearing three hydroxyl groups orthogonally protected. The key steps of the synthesis were the regioselective protection of a secondary allylic alcohol over a homoallylic one and the coupling of the nucleobase with a triflate intermediate. 相似文献
Tristannanes used as photochemical precursors for the synthesis of organic compounds react via triplet states followed by homolytic CSn and SnSn bond scission. 相似文献
Condensation of γ-tocopherol with aldehydes provides 2,4-disubstituted 1,3,8-trioxaphenanthrenes in a simple one-pot reaction. The reaction proceeded under acid catalysis according to a two-step alkylation-acetalisation mechanism in yields between 58 and 81%. The title compounds are precursors for the thermal generation of ortho-quinone methides, which can be in situ reduced to give antioxidants of the 5a-substituted α-tocopherol-type. The products were analytically characterized by NMR and HRMS. 相似文献
Redox reactions are still a challenge for biochemical engineers. A personal view for the development of this field is given. Cofactor regeneration was an obstacle for quite some time. The first technical breakthrough was achieved with the system formate/formate dehydrogenase for the regeneration of NADH2. In cases where the same enzyme could be used for chiral reduction as well as for cofactor regeneration, isopropanol as a hydrogen source proved to be beneficial. The coproduct (acetone) can be removed by pervaporation. Whole-cell reductions (often yeast reductions) can also be used. By proper biochemical reaction engineering, it is possible to apply these systems in a continuous way. By cloning a formate dehydrogenase and an oxidoreductase "designer bug" can be obtained where formate is used instead of glucose as the hydrogen source. Complex sequences of redox reactions can be established by pathway engineering with a focus on gene overexpression or with a focus on establishing non-natural pathways. The success of pathway engineering can be controlled by measuring cytosolic metabolite concentrations. The optimal exploitation of such systems calls for the integrated cooperation of classical and molecular biochemical engineering. 相似文献
The Rb/K ion exchange in micro-structured K(TiO)PO4 single crystals in contact with Rb containing nitrate melts results in ion-exchanged zones with enlarged refractive index which works as an optical phase grating. The knowledge of the diffusion behavior was the prerequisite for the generation of optimum refractive index profiles. Therefore, the local Rb/K concentration of ion-exchanged single crystals was determined with an electron probe microanalyzer (EPMA). The observed degree of ion exchange and the calculated Rb/K counterdiffusion coefficients were used to estimate the optimum ion exchange conditions. The diffusion-generated optical phase gratings show very narrow and deep ion-exchanged zones. The ratio of the ion penetration depths results in an extreme diffusion anisotropy DRb/K(c):DRb/K(b) ≈ 500:1.
Electron energy distribution functions (EEDF) and related properties in the bulk region of the rf CO plasma at the reduced rf field frequency /p0=×107 sec–1 torr–1 have been calculated by solving the time-dependent spatially homogeneous Boltzmann equation in the presence of second-kind collisions and have been interpreted on a microphysical basis. The results show that second-kind collisions (vibrational and electronic) strongly affect the temporal evolution of EEDF, of the mean energy, and of the mean collision frequencies for vibrational and electronic excitation processes, as well as for ionization. In particular, second-kind collisions in the CO rf bulk plasma strongly decrease the modulation of the mean ionization frequency during its periodical alteration in the rf field. Furthermore, the effect of second-kind collisions on an approximate determination of the time-averaged EEDF in the rf bulk plasma using the so-called effective-field appriximation has been estimated. 相似文献
The nitronyl nitroxide 2-cyano-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (1) crystallises in the tetragonal P42(1)m space group with a=7.4050(7), c=8.649(1) A. In the crystal the molecules form layers parallel to the ab plane in which they are orthogonal to each other. In the layers there are close contacts, 2.953(2) A, between the NO groups and the bridging carbon atoms of the O-N-C-N-O fragment of neighbouring radicals. The calculated spin density shows a positive population mainly and equally localised on the NO groups and small but significant negative spin densities on the bridging carbon atom and the cyano nitrogen. Absorption spectra show temperature-dependent transitions related to the magnetic behaviour. The temperature dependence of the magnetic susceptibility in the range 2-300 K reveals that couplings between the radicals are antiferromagnetic, and is interpreted by considering a two-dimensional square array of spin S=1/2 antiferromagnetically coupled (J=-10 cm(-1) and g=2.01). This is interpreted as an exchange coupling through close contact between positive and negative spin densities in orthogonal orbitals on oxygen and carbon atoms, respectively. 相似文献
Summary The function of solid sampling graphite furnace atomic absorption spectrometry (SS-GFAAS) in the laboratory-internal preparation, production and standardization of bovine liver reference material is described. Analytical quality assurance was achieved by using a wet digestion decomposition procedure and GFAAS (WD-GFAAS) as well as three different methods of SS-GFAAS. It will be shown, that SS-GFAAS is an adequate and efficacious method of analytical quality control in the production of reference materials. Details are given about the preliminary steps of sample selection and preparation, applying SS-GFAAS both as a screening method and for the detection of contamination during the production of the reference materials. The element contents of the four bovine liver materials measured after decomposition with nitric acid in the open system by GFAAS and also by Flame-AAS, using the slotted tube atom trap, are compared statistically with the results obtained by SS-GFAAS. In solid sampling analyses three different systems were applied: a solid sampling ZAA-spectrometer with platform-boat, a D2AA-spectrometer with solid sampling graphite tube and platform-drawer and an autoprobe-D2AA-spectrometer with solid sampling autoprobe and graphite tube. 相似文献