A novel sulfonamidoglycosylation of glycals

[reaction: see text] The sulfonamidoglycosylation of benzylated glycals using a catalytic amount of triphenylphosphine hydrobromide proceeded in a highly stereoselective fashion to give the beta anomers with good to high yields. This process was demonstrated with d-galactal and d-glucal. Two of the new N-2-(deoxyglycosyl)sulfonamides were tested as inhibitors of tumor cell growth in vitro and showed antiproliferative properties in the micromolar range.     

Biomimetic synthesis of biatractylolide and biepiasterolide

[reaction: see text] The biomimetic synthesis of the bisesquiterpenoids biatractylolide 1 and biepiasterolide 2 is reported.     

Finite element approximation of spectral problems with Neumann boundary conditions on curved domains

This paper deals with the finite element approximation of the spectral problem for the Laplace equation with Neumann boundary conditions on a curved nonconvex domain . Convergence and optimal order error estimates are proved for standard piecewise linear continuous elements on a discrete polygonal domain in the framework of the abstract spectral approximation theory.

     

Correlations in a Mozart's music score (K-73x) with palindromic and upside-down structure

In this work, we study long-range correlations in a “Scherzo-Duetto di Mozart” score (K-73x) for two violins. This is a fascinating piece, as the second violin part is upside down on the same sheet below the first violin, and some parts are like a palindrome. Given such ingenious structure, it is expected the existence of long-range correlations in the score structure. In order to quantify long-range correlations, we considered the music score as a sequence of integer numbers, each of them corresponding to last common denominator units of note. By using detrended fluctuation analysis (DFA), correlations are quantified by means of the scaling exponent that reflects the type of correlations for a given distance between neighbors note. The following conclusions can be drawn from the analysis: (a) For about 10-25 neighbor note distances, correlations are similar to 1/f-noise. This is an interesting finding since it has been shown that pleasant sounds for humans display a behavior similar to 1/f noise. (b) As the neighbor note distance increases, the long-range correlations decays continuously. For some score sections, the music score behaves like non-correlated (i.e., purely random) noise. Summing up, the results show that the studied Mozart's score contains a certain degree of correlation for relatively small note distances, and becomes close to non-correlated behavior for long note distances. We considered also the sequence constructed by considering the distance between the simultaneously played notes of the two violins. Interestingly, for relatively small neighbor note distances, a scaling behavior similar to that found for individual violins is also displayed. In some sense, this is an expression of the specific structure (palindromes plus upside down construction) used by Mozart in the composition of this music score. Although we focused on a particular high-art music score, our results suggest that modern methods borrowed from statistical physics can be useful for the systematic study of music composition techniques.     

Measurements of the density and refractive index for 1-n-butyl-3-methylimidazolium-based ionic liquids

Correlations between density and refractive index of pure systems of ionic liquids were examined in this work. To this end, the density and refractive index of four 1-n-butyl-3-imidazolium-based ionic liquids were measured at atmospheric pressure and temperature up to 353.2 K. Densities and refractive indices of the ionic liquids investigated are presented as a function of temperature. A group contribution-based equation was modified to calculate the density as a function of temperature. An empirical equation was used to study the temperature-dependence of refractive index. The Lorentz–Lorenz, Dale–Gladstone, Eykman, Oster, Arago–Biot, and Newton equations, as well as a modified Eykman were used to correlate the relation between the densities and refractive indices of the different ionic liquid systems. The correlations give satisfactory results. The results of this study can add to the newly organized database for ionic liquids and can also be used for various process design calculations.     

Zur maassanalytischen Bestimmung des Quecksilbers

Ohne Zusammenfassung     

Regioselectivity in isoquinoline alkaloid synthesis

Regioselectivity in isoquinoline alkaloid synthesis is analyzed here. Our experiments have shown that substituents on the aromatic ring of the starting amine are determinant in isoquinoline synthesis. The use of dicyclohexylcarbodiimide in activating carboxylic acids for electrophilic aromatic substitution reactions is presented for the first time.     

First-principles prediction of the pK(a)s of anti-inflammatory oxicams

The gas- and aqueous-phase acidities of a series of oxicams have been computed by combining M05-2X/6-311+G(3df,2p) gas-phase free energies with solvation free energies from the CPCM-UAKS, COSMO-RS, and SMD solvent models. To facilitate accurate gas-phase calculations, a benchmarking study was further carried out to assess the performance of various density functional theory methods against the high-level composite method G3MP2(+). Oxicams are typically diprotic acids, and several tautomers are possible in each protonation state. The direct thermodynamic cycle and the proton exchange scheme have been employed to compute the microscopic pK(a)s on both solution- and gas-phase equilibrium conformers, and these were combined to yield the macroscopic pK(a) values. Using the direct cycle of pK(a) calculation, the CPCM-UAKS model delivered reasonably accurate results with MAD ~ 1, whereas the SMD and COSMO-RS models' performance was less satisfactory with MAD ~ 3. Comparison with experiment also indicates that direct cycle calculations based on solution conformers generally deliver better accuracy. The proton exchange cycle affords further improvement for all solvent models through systematic error cancellation and therefore provides better reliability for the pK(a) prediction of compounds of these types. The latter approach has been applied to predict the pK(a)s of several recently synthesized oxicam derivatives.     

Crystal structure ofcis-diaqua bis(2,2′-bipyridyl)chromium(III) nitrate, [Cr(bipy)2(H2O)2] (NO3)3

cis-Diaquabis(2,2-bipyridyl)chromium(III) nitrate crystallizes in the mono-clinic system, space groupP2₁/c, witha=16.102(6),b=10.792(5),c=15.076(6) Å,=112.90(5)°, andZ=4. The saltlike structure was determined from X-ray crystallography and refined toR=7.5% for 3342 observed reflections. The Cr atom is octahedrally surrounded by twocis water molecules and by two chelated 2,2-bypiridyl ligands forming two nearly orthogonal planes. Selected bond distances are: Cr-O, 2.00(1) and 1.98(1) Å, Cr-N, 2.04 Å (mean).