Proton controlled intramolecular communication in dinuclear ruthenium(II) polypyridine complexes

The synthesis and characterization of two dinuclear ruthenium polypyridyl complexes based on the bridging ligands 5,5'-bis(pyridin-2' '-yl)-3,3'-bis(1H-1,2,4-triazole) and 5,5'-bis(pyrazin-2' '-yl)-3,3'-bis(1H-1,2,4-triazole) and of their mononuclear precursors are reported. The dinuclear compounds have been prepared by a Ni(0) catalyzed coupling of a mononuclear ruthenium(II) polypyridyl complex containing a brominated triazole moiety. Electrochemical and photophysical studies indicate that, in these dinuclear complexes, the protonation state of the bridge may be used to tune the intercomponent interaction between the two metal centers and that these species act as proton driven three-way molecular switches that can be read by electrochemical or luminescence techniques.     

Model reactions for stereochemistry of Ziegler-Natta polymerization: Asymmetric hydroisomerization of α-olefins by chiral titanium tetra-alkoxides/tri-isobutyl aluminum catalytic systems

Homogeneous catalytic systems based on optically active low-molecular-weight and macromolecular titanium alcoholates and tri-isobutyl aluminum were used in the isomerization and hydrogenation of chiral and prochiral olefins. The reactions performed in a nitrogen and hydrogen atmosphere show a different behavior in regard to reaction rate, composition of reaction mixture, and stereochemical control. The catalyst based on macromolecular titanium alcoholate displays lower activity and a varying influence on the stereochemical pathway with respect to the catalysts based on low- molecular-weight alcoholates. The data obtained in both cases strongly support the absence of a stereocontrol by the growing chain in the stereoelective polymerization of racemic α-olefins by Ziegler-Natta catalysts based on optically active precursors. Finally evidence is provided in favor of the intermediate step responsible for asymmetric isomerization which does not occur via η-allyl complex.     

Selective spectrofluorimetric method for paracetamol determination through coumarinic compound formation

A spectrofluorimetrical selective method was designed for determination of paracetamol in tablets. This important technique can be characterized by its sensitivity, simplicity, celerity and cheaper cost than current official methods. The employed methodology involves coumarinic compound formation obtained by reaction between paracetamol and ethylacetoacetate (EAA) in the presence of sulphuric acid as catalyst. The reaction product is highly fluorescent at 478 nm, being excited at 446 nm.The linear concentration range of the application was 0.1-0.4 μg/ml of paracetamol and the detection limit was 57 ng/ml.The influence of different variables was studied and optimized through chemometric techniques. Applying the above-mentioned method good results were obtained with regard to pharmaceutical formulations containing paracetamol. Therefore, it is relevant to suggest this profitable technique for medicament control analysis.     

Relating atomic energy,radius and electronegativity through compression

Trends in atomic properties are well-established tools for guiding the analysis and discovery of materials. Here, we show how compression can reveal a long sought-after connection between two central chemical concepts – van-der-Waals (vdW) radii and electronegativity – and how these relate to the driving forces behind chemical and physical transformations.

Compression is used to derive a long sought-after connection between two central chemical concepts – van-der-Waals (vdW) radii and electronegativity – and how these relate to the driving forces behind chemical and physical transformations.     

From achiral porphyrins to template-imprinted chiral aggregates and further. Self-replication of chiral memory from scratch

The presence of 10-13 M of chiral clusters of aromatic amino acids addresses aggregation of opposite-charged achiral porphyrin towards the formation of smart chiral assemblies. The latter supramolecular complexes are able to self-propagate and transfer their chiral information with a 100% yield. The chiral bias occurs through a correlated sequence of induction, memory, and amplification of chirality that strongly recalls possible prebiotic scenarios.     

Can the pi-facial selectivity of solvation be predicted by atomistic simulation?

This work is concerned with the rationalization and prediction of solvent and temperature effects in nucleophilic addition to alpha-chiral carbonyl compounds leading to facial diastereoselectivity. We study, using molecular dynamics simulations, the facial solvation of (R)-2-phenyl-propionaldehyde in n-pentane and n-octane at a number of temperatures and compare it with experimental selectivity data for the nBuLi addition leading to syn- and anti-(2R)-2-phenyl-3-heptanol, which give nonlinear Eyring plots with the presence of inversion temperatures. We have found from simulations that the facial solvation changes with temperature and alkane. Moreover, by introducing a suitable molecular chirality index we have been able to predict break temperatures (T(CI)) for the two solvents within less than 20 degrees of the inversion temperatures experimentally observed in the diastereoselective nBuLi addition. We believe this could lead to a viable approach for predicting inversion temperatures and other subtle solvent effects in a number of stereoselective reactions.     

Solvent-induced supramolecular isomerism in [Pt(S=C(NH2)2)4]2+ croconate salts

The role of solvent (and other species) in the formation of networks from tetrakis(thiourea)platinum(II) cations and croconate anions is examined, with crystallisations from DMSO giving rise to a structure containing solvent filled channels.     

Inoculum studies in production of penicillin g acylase by Bacillus megaterium ATCC 14945

This article reports studies concerning the production of penicillin G acylase (PGA) by Bacillus megaterium. This enzyme has industrial use in the hydrolysis of penicillin G to obtain 6-aminopenicillanic acid, an essential intermediate for the production of semisynthetic β-lactam antibiotics. Although most microorganisms produce the enzyme intracellularly, B. megaterium provides extracellular PGA. The enzyme production by microorganisms involves several steps, resulting in a many operational variables to be studied. The study of the inoculum is an important step to be accomplished, before addressing other issues such as culture optimization and downstream processing. In this study, using a standard inoculum as reference, several runs were performed aiming at the definition of operational conditions in the PGA production. Cell concentration and PGA activity in the production medium were measured after 24, 48, and 72 h of the beginning of the production phase. This study encompasses the duration of the inoculum germination phase and the concentration of cells used to startup the germination. Based on these results, PGA productivity during the production phase was maximized. The selected values for these variables were 1.5 × 10⁷ spores/mL of germination medium, germination during 24 h, and 72 h for the production phase.     

A new tripodal receptor for molecular recognition of monosaccharides. A paradigm for assessing glycoside binding affinities and selectivities by 1H NMR spectroscopy

A new tripodal receptor for the recognition of monosaccharides is described. The prototypical host 1 features a 1,3,5-substituted 2,4,6-triethylbenzene scaffold bearing three convergent H-bonding units. The binding ability of the t-octyl derivative 1a toward a set of octylglycosides of biologically relevant monosaccharides, including Glc, Gal, Man, and GlcNAc, was investigated by 1H NMR in CDCl3. A protocol for the correct evaluation of binding affinities was established, which can be generally applied for the recognition of monosaccharides by 1H NMR spectroscopy. A three-constant equilibrium model, including 1:1 and 2:1 host-guest association and dimerization of the receptor, was ascertained for the interaction of 1a with all the investigated glycosides. An affinity index, which we defined median binding concentration BC50 in analogy to the IC50 parameter, intended to address the general issue of comparing dimensionally heterogeneous binding data, and a limiting BC0(50)quantity describing intrinsic binding affinities were developed for evaluating the results. BC0(50) values for 1a range from 1 to 6 mM, indicating an intrinsic binding affinity in the millimolar range and a selectivity factor of 5 toward the investigated glycosides. The treatment has been extended to include any generic host-guest system involved in single or multiple binding equilibria.     

Conformation of bicyclo [n.1.0] Derivatives: Part 3. Dioxa- and trioxa-bicyclo[5.1.0] octanes

The conformational geometries and possible interconversion paths for some oxa derivatives of bicyclo[5.1.0] octane have been studied by the molecular mechanics method. The theoretical results are compared with the experimental data for the molecular geometry of bicyclo[5.1.0] octane and 3,5,8-trioxabicyclo[5.1.0] octane, the free energy of activation for cycloheptene epoxide and 3,5-dioxabicyclo[5.1.0] octane, the dipole moments and molar Kerr constants in solution for cycloheptene epoxide, 3,5-dioxa- and 3,5,8-trioxabicyclo[5.1.0] octane.