In the title compound, C24H36O6, the ester linkage in ring A is equatorial. The six‐membered rings A, B and C have chair conformations. The five‐membered ring D adopts a 13β,14α‐half‐chair conformation and the E ring adopts an envelope conformation. The A/B, B/C and C/D ring junctions are trans, whereas the D/E junction is cis. 相似文献
Summary: The range of validity of two popular versions of the nitroxide quasi‐equilibrium (NQE) approximation used in the theory of kinetics of alkoxyamine mediated styrene polymerization, are systematically tested by simulation comparing the approximate and exact solutions of the equations describing the system. The validity of the different versions of the NQE approximation is analyzed in terms of the relative magnitude of (dN/dt)/(dP/dt). The approximation with a rigorous NQE, kc[P][N] = kd[P N], where P, N and P N are living, nitroxide radicals and dormant species respectively, with kinetic constants kc and kd, is found valid only for small values of the equilibrium constant K (10−11–10−12 mol · L−1) and its validity is found to depend strongly of the value of K. On the other hand, the relaxed NQE approximation of Fischer and Fukuda, kc[P][N] = kd[P N]0 was found to be remarkably good up to values of K around 10−8 mol · L−1. This upper bound is numerically found to be 2–3 orders of magnitude smaller than the theoretical one given by Fischer. The relaxed NQE is a better one due to the fact that it never completely neglects dN/dt. It is found that the difference between these approximations lies essentially in the number of significant figures taken for the approximation; still this subtle difference results in dramatic changes in the predicted course of the reaction. Some results confirm previous findings, but a deeper understanding of the physico‐chemical phenomena and their mathematical representation and another viewpoint of the theory is offered. Additionally, experiments and simulations indicate that polymerization rate data alone are not reliable to estimate the value of K, as recently suggested.
Validity of the rigorous nitroxide quasi‐equilibrium assumption as a function of the nitroxide equilibrium constant. 相似文献
The objective of this study was to evaluate the effect of microwave treatment of crushed grapes on the yeast population of the must and on the development of alcoholic fermentation, as well as on the extraction of different compounds from the grapes such as polysaccharides and amino acids that can affect the organoleptic quality and stability of the wine. This study demonstrated for the first time the effect of the microwave treatment of grapes on native yeast species and their diversity, producing an increase in fermentation kinetics and a decrease in the lag phase. The microwave treatment produced a positive effect on the extraction of amino acids and polysaccharides from the grapes, resulting in significantly higher amounts of the main amino acids of the must and some major volatile compounds in the treated samples. The polysaccharides most affected by the microwave treatment were the PRAGs, the main polysaccharides liberated from grapes during the maceration. 相似文献
Optimal control theory (OCT) including nonresonant multiphoton transitions (NMT) in the femtosecond time regime has been implemented. The NMT process is modelled using an effective time-dependent Schrödinger equation, which considers a reduced space of the two levels which are involved in the transition, coupled to a density of high-lying off-resonant states. The specification of OCT to two-photon transitions is done within the rotating wave approximation. As an application, the transfer and displacement of a wavepacket in the organometallic system CpMn(CO)3, from the ground to an electronically excited state using two nonresonant photons, is simulated. 相似文献
In this work, we report the synthesis of a novel carbohydrate-lithocholic acid conjugate linked through of 1,2,3-triazole rings and its derivatives in good to excellent yields. The conjugate was synthesized via copper-catalyzed azide?alkyne cycloaddition (CuAAC) from methyl 4,6-O-benzylidene-2,3-di-O-propargyl-α-d-glucopyranoside and methyl 3-azidolithocholate. The structures of all new compounds were properly characterized by infrared (IR), high-resolution mass spectroscopy (HRMS) and one- and two-dimensional nuclear magnetic resonance (NMR). 相似文献
Electrophoretic, antioxidant, and FTIR profiles of some varieties of amaranth, quinoa, and buckwheat seeds and their by products were compared. Water extracts of these products were evaluated by the Folin–Ciocalteau method in order to determine total phenolic content. The antioxidant activities were determined by 2,2′-azobis-2-methyl-propanimidamide, ferric-reducing/antioxidant power, and cupric reducing antioxidant capacity radical scavenging assays. FTIR spectra showed the secondary structure of pseudocereals in the ranges of amides I, II, and III shifts. Results of evaluated methods could be used to control several products (seeds, flours, extracts, flakes, roasting) with high phenolic content and antioxidant activity suitable for supplementation in food applications.
An injector—commutator with a 0:1:2 section is employed to achieve intermittent flows without intermittent pumping. The resulting flow injection system is very simple, manually operated, and requires only one peristaltic pump. When applied to the spectrophotometric determination of nitrite in waters, the device leads to an enhancement of the sensitivity and sampling rate without affecting other analytical characteristics. The merging zones approach is employed to decrease consumption of reagents. 相似文献
[reaction: see text] Six-membered cyclic phosphates (2-phenoxy-2-oxo-1,3,2-dioxaphosphorinanes) bearing an internal protected or unprotected hydroxyl group were designed, synthesized, and studied by NMR and computational methods. Selective opening of O-isopropylidene-protected 1,2-diols at the primary site was achieved with either triethylsilane or trimethylallylsilane in the presence of BF3.OEt2. Applied to 5,6-O-isopropylidenepentofuranosides, this reaction gave rise to the formation of the corresponding 1,3-diol precursors for the six-membered ring phosphates containing an O-isopropyl or O-1,1-dimethyl-3-butenyl functional group at C-6. The O-1,1-dimethyl-3-butenyl protecting group was efficiently removed after the phosphorylation with BF3.OEt2, and the six-membered cyclic phosphates containing free hydroxyl groups were obtained. A cyclic phosphate with a free hydroxyl group oriented cis to the phosphoryl group shows a vicinal coupling constant 3J(HP) that is in accordance with the chair conformation. This is due to the formation of a seven-membered intramolecular hydrogen-bonded ring structure that stabilizes the chair conformation. Thus, the strong tendency of the phenoxy group to be in an axial position is diminished by the internal hydrogen bonding interaction. Computational studies provided strong support for the experimental observation. 相似文献
This paper investigates both theoretically and experimentally the effect of lattice bending on the output signals of a two-crystal x-ray interferometer of the Laue LLL type. The cross section intensity of the outgoing beams is modulated by the moiré effect produced by the overlapping of the analysing lattice on the x-ray standing field in front of it. Since the intensities of the transmitted and diffracted beams are integrated, the moiré pattern causes loss of visibility in the x-ray fringes and a non-linear phase shift, which depends on the pitch alignment of the analysing crystal with respect to the fixed crystal. The analysis of this phase shift allows the lattice curvature to be estimated. 相似文献
The proposed technique for hydrodynamic injection is based on commutation in a simple flow-injection system with only one peristaltic pump. Precise results (usually r.s.d. < 1%) are attained even when injected volumes are small (1–10 μl). Dead-volume effects are associated with the mechanical flexibility of the system and with diffusion; differences between effective sample size and the dimensions of the injection duct are emphasized, particularly for small volumes. The proposed technique is checked for a spectrophotometric model system and confirmed by the atomic absorption spectrometry of chromium in steels. With a sampling rate of 120 h?1, the precision is better than 99% for chromium contents in the 0.0–30.0% (w/w) range. The results agree well with those obtained by i.c.p./a/e/s. and conventional a.a.s. 相似文献