Enantioselective synthesis of secondary alcohols in the presence of chiral ligands

The synthesis of two S-proline derivatives is described together with their use as chiral ligands for lithium in reactions of n-butyllithium with benzaldehyde to give 1-phenyl-1-pentanol with moderate optical purity. The presence of lithium salts in the reaction mixture causes a decrease in asymmetric induction.     

Evaluation of the antioxidant activity by flow injection analysis method with electrochemically generated ABTS radical cation

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).     

Characterisation of fresh and aged terpenic resins by micro-FTIR and GC-MS analyses of varnishes in XVI-XVII centuries paintings

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).     

Synthetic Applications of 2-(1,3-Dithian-2-yl)indoles. 7. Synthesis of Aspidospermidine

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.     

Electrostatic lattice coefficients and binding energy of orthorhombic La2-x Sr x CuO4

Three valency models for orthorhombic La_2-x Sr _x CuO₄ were investigated for increasing Sr concentrationsx (0x0.21): 1. Cu²⁺Cu³⁺, 2. apex O^2–O^– and 3. in-plane O^2–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 La_2-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.     

The Green relations approach to congruences on completely regular semigroups

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.     

Homogenization of the heat equation for a domain with a network of pipes with a well-mixed fluid

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 r_g; 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.     

Some Normal Cryptogroups as Semigroups of Isomorphisms

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.