Ultrasonics promoted synthesis of thiazolidinones from 2-aminopyridine and 2-picolilamine

The efficient multicomponent synthesis of thiazolidinones from the reaction of arenealdehydes, mercaptoacetic acid and 2-picolilamine or 2-aminopyridine under ultrasound irradiation are reported. The reaction with 2-aminopyridine needs a Lewis acid catalysis to afford the corresponding 2-aryl-3-(pyridin-2-yl)-1,3-thiazolidin-4-ones. All novel compounds were identified and characterized by (1)H and (13)C NMR spectra. Applying the sonochemical methodology, two series of heterocyclic thiazolidinones were synthesized in good yields after short reaction times.     

A recursive algorithm for Bernstein operators of second kind

The Bernstein operators of second kind were introduced by Paolo Soardi in 1990, in terms of a random walk on a certain hypergroup. They have the same relation with Chebyshev polynomials of second kind as the classical Bernstein operators have with Chebyshev polynomials of first kind. In this paper we describe a de Casteljau type algorithm for these operators.     

Sparse Biclustering of Transposable Data

We consider the task of simultaneously clustering the rows and columns of a large transposable data matrix. We assume that the matrix elements are normally distributed with a bicluster-specific mean term and a common variance, and perform biclustering by maximizing the corresponding log-likelihood. We apply an ?₁ penalty to the means of the biclusters to obtain sparse and interpretable biclusters. Our proposal amounts to a sparse, symmetrized version of k-means clustering. We show that k-means clustering of the rows and of the columns of a data matrix can be seen as special cases of our proposal, and that a relaxation of our proposal yields the singular value decomposition. In addition, we propose a framework for biclustering based on the matrix-variate normal distribution. The performances of our proposals are demonstrated in a simulation study and on a gene expression dataset. This article has supplementary material online.     

Chiral flavanones from Amygdalus lycioides Spach: structural elucidation and identification of TNFalpha inhibitors by bioactivity-guided fractionation

Phytochemical investigation on the Amygdalus lycioides Spach branchelets resulted in the isolation of four chiral flavanones: (2R,3R)-Taxifolin, (2R,3R)-aromadendrin, (S)-5,7,3',5'-tetrahydroxyflavanone and (S)-naringenin. The flavanones were isolated by semi-preparative HPLC, their structures elucidated based on spectroscopic data and their absolute configuration assigned. As a part of our ethnobotanical-directed search for novel TNFα inhibitors, the bioassay-guided fractionation of the n-hexane-acetone (n-Hex-Ac, 1:1 v/v) Amygdalus lycioides Spach branchelets extract was performed. In this way, (S)-naringenin was identified as the constituent responsible for the TNFα blocking effect, being effective in vitro and in vivo after oral administration. This is the first investigation on bioactive secondary metabolites of Amygdalus lycioides Spach branchelets.     

Characterization by fourier transform infrared spectroscopy (FT-IR) and 2D IR correlation spectroscopy of PAMAM dendrimer

FT-IR and 2D correlation spectroscopy were employed to study the microstructural changes occurring during phase transitions of a liquid crystal poly(amidoamine) codendrimer (PAMAM (L1)16(L2)16) generation 3, functionalized on the terminal groups by one-chain promesogenic calamitic units (4-(4'-decyloxybenzoyloxy)salicylaldehyde (L1)) and two-chain promesogenic calamitic units (4-(3',4'-didecyloxybenzoyloxy)salicylaldehyde (L2)). Spectral modifications associated with molecular conformation rearrangements allowing for molecular shape change on going from a liquid-crystalline organization to another were found. The transition temperatures were calculated, and they are in good agreement with the DSC data. Spectral analysis gives evidence of the LC phase transitions and to an additional transition associated with the existence of conformers. Various types of hydrogen bonding have been established.     

Protonation of carbonate in aqueous tetraalkylammonium salts at 25 degrees C

Protonation constants of carbonate were determined in tetramethylammonium chloride (Me₄NCl_aq 0.1 ≤ I/mol kg⁻¹ ≤ 4) and tetraethylammonium iodide (Et₄NI_aq 0.1 ≤ I/mol kg⁻¹ ≤ 1) by potentiometric ([H⁺]-glass electrode) measurements. Dependence of protonation constants on ionic strength was taken into account by modified specific ion interaction theory (SIT) and by Pitzer models. Literature data on the protonation of carbonate in NaCl_aq (0.1 ≤ I/mol kg⁻¹ ≤ 6) were also critically analysed. Both protonation constants of carbonate follow the trend Et₄NI > Me₄NCl > NaCl. An ion pair formation model designed to take into account the different protonation behaviours of carbonate in different supporting electrolytes was also evaluated.     

Coordinated and reversible reduction of enzymes involved in terminal oxidative metabolism in skeletal muscle mitochondria from a riboflavin-responsive, multiple acyl-CoA dehydrogenase deficiency patient

In this case report we studied alterations in mitochondrial proteins in a patient suffering from recurrent profound muscle weakness, associated with ethylmalonic-adipic aciduria, who had benefited from high dose of riboflavin treatment. Morphological and biochemical alterations included muscle lipid accumulation, low muscle carnitine content, reduction in fatty acid beta-oxidation and reduced activity of complexes I and II of the respiratory chain. Riboflavin therapy partially or totally reversed these symptoms and increased the level of muscle flavin adenine dinucleotide, suggesting that aberrant flavin cofactor metabolism accounted for the disease. Proteomic investigation of muscle mitochondria revealed decrease or absence of several flavoenzymes, enzymes related to flavin cofactor-dependent mitochondrial pathways and mitochondrial or mitochondria-associated calcium-binding proteins. All these deficiencies were completely rescued after riboflavin treatment. This study indicates for the first time a profound involvement of riboflavin/flavin cofactors in modulating the level of a number of functionally coordinated polypeptides involved in fatty acyl-CoA and amino acid metabolism, extending the number of enzymatic pathways altered in riboflavin-responsive multiple acyl-CoA dehydrogenase deficiency.