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1.
Ariel M. Sarotti 《Tetrahedron letters》2004,45(44):8203-8206
A two-step general approach to a new chiral auxiliary starting from levoglucosenone is reported. The compound is obtained by a [4+2] cycloaddition reaction with anthracene followed by a diastereoselective reduction of the C-2 keto function in high overall yield. The auxiliary has been used as chiral template in an asymmetric Diels-Alder reaction of the corresponding acrylic ester derivative with cyclopentadiene and shown to be efficient for asymmetric induction. 相似文献
2.
3.
Recently, the authors have proposed a new necessary and sufficient condition for turnpike optimality in calculus of variations
with singular Euler equation. The method is based on a characterization of the value function and generalizes the well known
method based on the Green theorem. Furthermore, it allows the optimality of a competition between several turnpikes to be
characterized. For a class of such problems not enjoying the turnpike property, we give an explicit formula for the value
function and show how to characterize the optimal solution as the limiting solution of a family of perturbed problems satisfying
the turnpike property. The considered problems are scalar with infinite horizon. 相似文献
4.
Ariel Fernández 《International Journal of Theoretical Physics》1991,30(2):129-136
We establish a mechanism for energy localization in regions of the sugar-phosphate RNA backbone which leads to the formation of transesterification or hydrolysis hot spots. In particular, our results account for the site specificity of the covalent cyclization and cycle reopening in the catalytic intervening sequence (IVS) of a ribosomal RNA. 相似文献
5.
In this paper we study the 2-dimension of a finite poset from the topological point of view. We use homotopy theory of finite
topological spaces and the concept of a beat point to improve the classical results on 2-dimension, giving a more complete answer to the problem of all possible 2-dimensions
of an n-point poset.
相似文献
6.
This paper focuses on the prediction of the dimensionless retention time of proteins (DRT) in hydrophobic interaction chromatography (HIC) by means of mathematical models based, essentially, only on aminoacidic composition. The results show that such prediction is indeed possible. Our main contribution was the design of models that predict the DRT using the minimal information concerning a protein: its aminoacidic composition. The performance is similar to that observed in models that use much more sophisticated information such as the three-dimensional structure of proteins. Three models that, in addition to the amino acid composition, use different assumptions about the amino acids tendency to be exposed to the solvent, were evaluated in 12 proteins with known experimental DRT. In all the cases analyzed, the model that obtained the best results was the one based on a linear estimation of the aminoacidic surface composition. The models were adjusted using a collection of 74 vectors of aminoacidic properties plus a set of 6388 vectors derived from these using two mathematical tools: k-means and self-organizing maps (SOM) algorithms. The best vector was generated by the SOM algorithm and was interpreted as a hydrophobicity scale based partly on the tendency of the amino acids to be hidden in proteins. The prediction error (MSE(JK)) obtained by this model was almost 35% smaller than that obtained by the model that supposes that all the amino acids are completely exposed and 40% smaller than that obtained by the model that uses a simple correction factor considering the general tendency of each amino acid to be exposed to the solvent. In fact, the performance of the best model based on the aminoacidic composition was 5% better than that observed in the model based on the three-dimensional structure of proteins. 相似文献
7.
Ariel Fernández 《Theoretical chemistry accounts》1985,67(3):229-233
A structurally stable model of the standard adiabatic gradient field of the potential energy surface for certain pericyclic reactions is derived.These reactions are not subjected to the principles of orbital isomerism or to the Woodward-Hoffmann rules.Use is made of a principle established by Ariel Fernández and Oktay Sinanolu which precludes direct meta-IRC connections between transition states.It is shown that Jahn-Teller isomers of the singlet biradicals involved in the process are not interconvertible since the biradical configuration is not a transition state but a critical point with Hessian matrix with two negative eigenvalues.The topological features of the PES obtained by combinatorial methods are in full agreement with earlier results obtained from MINDO calculations. 相似文献
8.
The system BaF2/AlF3 is investigated by X-ray and D.T.A., and the liquid-solid phase diagram is established. Five ternary fluorides are disclosed: trimorphic BaAlF5, Ba3Al2F12, Ba5AlF19, polymorphic Ba3AlF9 and Ba5AlF13. Neutron thermodiffractometry experiments are performed to specify some parts of the diagram. The cell parameters of the fluorides are given and the results are discussed and compared with those of the previous works. 相似文献
9.
Anodic stripping voltammetry at a glassy carbon disc electrode covered by a thin mercury film was adapted for use in a flow-through cell. The resulting system is characterized by extreme simplicity of set-up and operation, high sensitivity and excellent precision and stability. Its performance was tested via the determination of hydrated or labile complex ions of heavy metal ions in sea water, using short (2–10 min) deposition periods. The dependence of the stripping peak charge on metal ion concentration, length of deposition period, solution flow rate and other variables was examined and the reliability of the results obtained were evaluated under conditions resembling continuous monitoring. 相似文献
10.
Pb8FeIIFeF24 is triclinic: a = 20.118(3) Å, b = 5.597(1) Å, c = 9.440(2) Å, α = 89.75(2)°, β = 105.79(2)°, α = 89.38(2)°, Z = 2. The structure is solved in the unconventional space group C1 , from X-ray single crystal data using 1 641 independent reflections (R = 0.048, Rw = 0.051). It is built up from the stacking of two subnetworks along the a axis: fluorite-like [Pb8F10]n6n+ layers and infinite dimetallic [FeIIFeF14]n6n? double-chains of corner-sharing octahedra running along the b axis. 相似文献