Baker's yeast reduction of prochiral γ-nitroketones. II. straightforward enantioselective synthesis of 2,7-dimethyl-1,6-dioxaspiro[4.4]nonanes

The baker's yeast reduction of 5-nitro-2,8-nonanedione 2 afforded the corresponding (2S,8S)-5-nitro-2,8-nonanediol3 with complete diastereoselectivity and high enantioselectivity. The conversion of 3 into the thermodynamic (E,E)/(Z,Z) (3:1) mixture of optically active (95% e.e.) 2,7-dimethyl-1,6-dioxaspiro[4.4]nonanes 5 was then achieved by spontaneous cyclization under the acidic conditions of the Nef reaction.     

Apparent stoichiometry of water in proton hydration and proton dehydration reactions in CH3CN/H2O solutions

Gradual solvation of protons by water is observed in liquids by mixing strong mineral acids with various amounts of water in acetonitrile solutions, a process which promotes rapid dissociation of the acids in these solutions. The stoichiometry of the reaction XH(+) + n(H(2)O) = X + (H(2)O)(n)H(+) was studied for strong mineral acids (negatively charged X, X = ClO(4)ˉ, Clˉ, Brˉ, Iˉ, CF(3)SO(3)ˉ) and for strong cationic acids (uncharged X, X = R*NH(2), H(2)O). We have found by direct quantitative analysis preference of n = 2 over n = 1 for both groups of proton transfer reactions at relatively low water concentrations in acetonitrile. At high water concentrations, we have found that larger water solvates must also be involved in the solvation of the proton while the spectral features already observed for n = 2, H(+)(H(2)O)(2), remain almost unchanged at large n values up to at least 10 M of water.     

Statistical potential for modeling and ranking of protein-ligand interactions

Applications in structural biology and medicinal chemistry require protein-ligand scoring functions for two distinct tasks: (i) ranking different poses of a small molecule in a protein binding site and (ii) ranking different small molecules by their complementarity to a protein site. Using probability theory, we developed two atomic distance-dependent statistical scoring functions: PoseScore was optimized for recognizing native binding geometries of ligands from other poses and RankScore was optimized for distinguishing ligands from nonbinding molecules. Both scores are based on a set of 8,885 crystallographic structures of protein-ligand complexes but differ in the values of three key parameters. Factors influencing the accuracy of scoring were investigated, including the maximal atomic distance and non-native ligand geometries used for scoring, as well as the use of protein models instead of crystallographic structures for training and testing the scoring function. For the test set of 19 targets, RankScore improved the ligand enrichment (logAUC) and early enrichment (EF(1)) scores computed by DOCK 3.6 for 13 and 14 targets, respectively. In addition, RankScore performed better at rescoring than each of seven other scoring functions tested. Accepting both the crystal structure and decoy geometries with all-atom root-mean-square errors of up to 2 ? from the crystal structure as correct binding poses, PoseScore gave the best score to a correct binding pose among 100 decoys for 88% of all cases in a benchmark set containing 100 protein-ligand complexes. PoseScore accuracy is comparable to that of DrugScore(CSD) and ITScore/SE and superior to 12 other tested scoring functions. Therefore, RankScore can facilitate ligand discovery, by ranking complexes of the target with different small molecules; PoseScore can be used for protein-ligand complex structure prediction, by ranking different conformations of a given protein-ligand pair. The statistical potentials are available through the Integrative Modeling Platform (IMP) software package (http://salilab.org/imp) and the LigScore Web server (http://salilab.org/ligscore/).     

Innovative biotemplates for the synthesis of ZnO nanoparticles with versatile morphologies

Journal of Sol-Gel Science and Technology - ZnO nanoparticles with different morphologies were prepared via the biotemplate method. The microstructure of synthesized nanoparticles was found to...     

Fluorescent UO2(II) and ZrO(II) complexes: Synthesis,structural characterization,fluorescence, DNA binding studies and biological applications in cell probing

A new series of UO2(II) and ZrO(II) azo‐complexes based on 5‐nitro‐8‐hydroxyquinoline; [UO₂(H₂L¹)(NO₃)EtOH] (1), [ZrO(H₂L¹)(NO₃)H₂O] (2), [UO₂(HL²)(NO₃)EtOH]3H₂O (3), [ZrO(HL²)(NO₃)EtOH] (4), [UO₂(HL³)(NO₃)(H₂O)₃]2H₂O (5) and [ZrO(HL³)(NO₃)EtOH] (6); have been synthesized. The structure of these complexes has been characterized using elemental analysis, thermal analysis, molar conductance, UV–vis, IR, electron impact mass, X‐ray powder diffraction and NMR spectra. The results revealed the formation of non‐electrolyte mononuclear complexes via the N atom of the azo group or of the quinoline ring and the oxygen atom of the deprotonated OH. Fluorescence properties of the synthesized complexes have been examined and the fluorescence quantum yield (Φ_f) has been determined. The complexes have been tested as cell staining and imaging under the fluorescent microscope. The data showed that complexes 1 and 2 efficiently stain the nuclei in addition to some focal cytoplasmic areas. Other than complexes 3 and 4 exclusively stained the nuclei. On the other hand, complexes 5 and 6 stained the cytoplasm exclusively. It has been demonstrated that complex 4 was the most effective in cell staining. The binding constant (Kb) with DNA was calculated using UV–vis absorption titration and fluorescence spectral methods. It was concluded that complex 4 can be used effectively as fluorescent probes in studying cell biology.     

On problematic aspects in learning trigonometry

In this paper, research on some problematic aspects high school students have in learning trigonometry is presented. It is based on making sense of mathematics through perception, operation and reason in the case of trigonometry. We analyzed students' understanding of trigonometric concepts in the frame of triangle and circle trigonometry contexts, as well as the transition between these two contexts. In the conclusion, we present some new problematic aspects we noticed.

The research was carried out with two groups of high school students, one of them at the beginning of their trigonometry learning (17 years old) and the other at the end of their high school education (19 years old). The students were given a questionnaire similar to that of Chin and Tall, and we analyzed the students' response. In our research, we noticed that students have difficulties with properties of periodicity and the fact that trigonometric functions are not one-to-one. In addition, there is poor understanding of radian measure and a lack of its connection to the unit circle.     

Are the eigenvalues of preconditioned banded symmetric Toeplitz matrices known in almost closed form?

The problem of computing oscillatory integrals with general oscillators is considered. We employ a Filon-type method, where the interpolation basis functions are chosen in such a way that the moments are in terms of elementary functions and the oscillator only. This allows us to evaluate the moments rapidly and easily without needing to engage hypergeometric functions. The proposed basis functions form a Chebyshev set for any oscillator function even if it has some stationary points in the integration interval. This property enables us to employ the Filon-type method without needing any information about the stationary points if any. Interpolation by the proposed basis functions at the Fekete points (which are known as nearly optimal interpolation points), when combined with the idea of splines, leads to a reliable convergent method for computing the oscillatory integrals. Our numerical experiments show that the proposed method is more efficient than the earlier ones with the same advantages.