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41.
Gancitano P Ciriminna R Testa ML Fidalgo A Ilharco LM Pagliaro M 《Organic & biomolecular chemistry》2005,3(13):2389-2392
Valuable organic compounds such as alpha-hydroxy acids are easily synthesised with relevant selectivity enhancement using a sol-gel hydrophobized nanostructured silica matrix doped with the organocatalyst TEMPO: A materials science based synthetic route which cannot be achieved via classical homogeneous synthesis. 相似文献
42.
Mass spectrometric identification and characterization of steroids using electrospray ionization and tandem mass spectrometry has advantages in drug testing and doping control analysis attributable to limitations of gas chromatography followed by electron ionization mass spectrometry. Steroids with an androstadiene-17beta-ol-3-one nucleus and double bonds located either at C-1 and C-4, C-4 and C-9, or C-4 and C-6 were used to determine characteristic fragmentation pathways. Diagnostic dissociation routes are proposed using deuterium labeling, MS3 experiments, and analyses of structurally closely related compounds. Steroids such as boldenone (androst-1,4-diene-17beta-ol-3-one) produced characteristic product ions at m/z 121, 135, and 147. Compounds with double bonds at C-4 and C-9 generated abundant product ions at m/z 145 and 147. Conjugated double bonds at C-4 and C-6 gave rise to an intense and characteristic signal at m/z 133. Stereochemical differentiation between 5alpha- and 5beta-isomers of androstan-17beta-ol-3-ones was possible because of significant differences in relative abundance of product ions generated by elimination of acetone from alpha,beta-saturated 3-keto steroids. 相似文献
43.
44.
A Trolox equivalent antioxidant capacity (TEAC) decolourisation assay was adapted to a flow injection analysis (FIA) system and a simple and rapid method for antioxidant activity evaluation was developed. To avoid the time consuming step of 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid)(ABTS) radical cation preparation by chemical oxidation of ABTS, as in the original TAEC assay, and hence, to shorten the analysis time, the ABTS radical cation was generated on-line by electrochemical oxidation of ABTS in the flow-through electrolysis cell forming a part of the FIA system. The proposed method was optimised with respect to a flow rate, injection volume and ABTS radical cation/carrier ratio. Under the optimised conditions linear calibration graphs for Trolox were obtained over the range 10-100 microM, with a limit of detection 1.6 microM. Good reproducibility (relative standard deviation 1.95%) and sample throughput (32 samples per hour) were achieved. The developed method was applied to the evaluation of the antioxidant activity of pure compounds and samples of some common beverages. In both cases a good correlation between the results obtained by the proposed method and TEAC values evaluated by the classic TAEC decolourisation assay was obtained (r(2)= 0.996 for pure compounds and r(2)= 0.957 for beverage samples). 相似文献
45.
Resinous materials, generally added to drying oils, were often employed as final protective films in paintings, both in tempera and oil techniques. Most of the resins used in fine arts come from exudates of plants. Natural resins are mainly composed by terpenoids. Among these resins, dammar, rosin, mastic, elemi gum, Venice turpentine were frequently employed in easel paintings. The aim of this work is the identification of natural resins in samples collected from works of art. In this paper we propose to use micro-FTIR spectrometry as a preliminary and non destructive technique to detect the presence of resinous materials in microsamples collected from paintings, followed by GC-MS analyses to obtain a precise identification of the resin. To reach this aim commercial resins, employed as standard, were analysed previously by micro-FTIR spectrometry and then analysed by GC-MS chromatography, searching characteristic chemical compounds used as "markers" of resins. The results obtained on standards allowed us to successfully analyse samples collected from two works of art: the "Portrait of a Young Gentleman", by Lorenzo Lotto (XVI century), and the "Madonna with the Infant Jesus and Saints": by Carlo Maratta (XVII secolo). 相似文献
46.
A new method of synthesizing the alkaloid aspidospermidine (1), based on building ring E on the pyridocarbazole [ABCD] ring structure, is reported. The preparation of the pyridocarbazole framework of Aspidosperma alkaloids is a new three-step synthetic application of 2-(1,3-dithian-2-yl)indoles. A tandem conjugate addition-alkylation reaction starting from indolyldithiane (4), 3-methylenelactam 6, and EtI yields the adduct 17. Treatment of lactam 17 with DIBALH leads to formation of the naphthyridoindole 18. Compound 18 isomerizes in aqueous AcOH to yield pyridocarbazole 3. Finally, closure of ring E and subsequent reduction of the dithiane ring produces aspidospermidine. Pyridocarbazoles 2 and 10 were prepared as models. 相似文献
47.
Three valency models for orthorhombic La2-x
Sr
x
CuO4 were investigated for increasing Sr concentrationsx (0x0.21): 1. Cu2+Cu3+, 2. apex O2–O– and 3. in-plane O2–O–. All calculations were done by using structural parameters valid for the temperature range from 10 to 22 K. We thereby calculated the electrostatic interaction energy which, next to ionization potentials and electron affinities, comprises a major of the binding energyE
B
of crystals. Second-order effects were accounted for by calculating the strength of ionic dipole moments induced by crystal electric fields at relevant lattice sites. Their largest strengths are comparable to the dipole moment of the water molecule. Three out of five dipoles in La2-x
Sr
x
CuO4 vanish during the transition from the orthorhombic to the tetragonal phase. The binding energy differences between the different models suggest that the system is in a state of model 1. However, the differences are very small, being in the order of 0.3 to 0.76 eV atx=0.13. 相似文献
48.
Mario Petrich 《Annali di Matematica Pura ed Applicata》1994,167(1):117-146
On the congruence lattice (2(5) of a completely regular semigroup S the following mappings are considered p: P and p: VP, whereP is any of the Green relationsH, L, R orD. The equivalence relationsP
andP
V induced by these maps represent the main object of study in the paper. The former is a complete -congruence whereas the latter is a complete congruence onC(S). In particularH
,H
V,L
V,R
V coincide with the kernel, trace, left trace and right trace relations onC(S), respectively. All essential properties known for the latter relations carry over to the new relationsP
andP
V. In addition, some interesting interplays of these provide for more richness in the theory of congruences on completely regular than is the case for the kernel-trace approach to congruences on regular semigroups. 相似文献
49.
We consider the linear heat equation in a domain occupied by a solid material with a network of pipes in which a well-mixed fluid is circulating. The temperature of the fluid in the pipe is uniform and its time variation is determined by the thermal flux on the wall of the pipe, plus a given internal source; continuity of the temperature across the pipe is also assumed. We suppose that we deal with a periodic geometry, with cells of size with inclusions of size rg; we study in detail in the case r, referring to a previous paper for the case r In the limit »0 we get a homogenized equation. The limit depends strongly on the ratio between the time variation of the temperature in the inclusions and the thermal flux through the interface. The homogenized equation has a new specific heat, which depends on the porosity and the constant of proportionality between the time variation of temperature and the flux on the boundary of the pipe. We also have a new thermal conductivity depending on the microstructure, and volume sources appear. The main tool is the energy method and we generalize the classical results for the more standard boundary conditions for parabolic equations. Finally, we consider the network of pipes forming a random ball structure. We prove convergence for this case. The homogenized equation is of the same form as in the periodic case but auxiliary problems are stochastic. 相似文献
50.
Mario Petrich 《Results in Mathematics》1996,30(1-2):102-121
Given a Clifford semigroup G, we construct special G-operands L and R which we term conformai. Certain suboperands of L and R we call threads and fix some special G-isomorphisms, which we term coherent, of threads in R onto threads in L. On the set of all coherent G-isomorphisms of threads in L onto threads in R we define a sandwich-type multiplication. When we restrict our threads to be cyclic suboperands of L and R, this construction produces a normal cryptogroup which we represent as $ S=[Y;S_{\alpha},\chi_{{\alpha},{\beta}}] $ -Without any restriction on the threads this produces a semigroup isomorphic with a remarkable ideal of the translational hull of S. Conversely, given a strong semilattice of completely simple semigroups, satisfying certain conditions, we can represent it isomorphically as indicated above. 相似文献