Even-dimensional topological gravity from Chern–Simons gravity

It is shown that the topological action for gravity in 2n  -dimensions can be obtained from the (2n+1)$(2n+1)$-dimensional Chern–Simons gravity genuinely invariant under the Poincaré group. The 2n  -dimensional topological gravity is described by the dynamics of the boundary of a (2n+1)$(2n+1)$-dimensional Chern–Simons gravity theory with suitable boundary conditions.     

Determination of gatifloxacin in bulk and tablet preparations by high-performance liquid chromatography

A sensitive, precise, and specific high-performance liquid chromatographic (HPLC) method was developed for the assay of gatifloxacin (GATX) in raw material and tablets. The method validation parameters yielded good results and included the range, linearity, precision, accuracy, specificity, and recovery. It was also found that the excipients in the commercial tablet preparation did not interfere with the assay. The HPLC separation was carried out by reversed-phase chromatography on a C18 absorbosphere column (250 x 4.6 mm id, 5 microm particle size) with a mobile phase composed of acetic acid 5%-acetonitrile-methanol (70 + 15 + 15, v/v/v) pumped isocratically at a flow rate of 1.0 mL/min. The effluent was monitored at 287 nm. The calibration graph for GATX was linear from 4.0 to 14.0 microg/mL. The interday and intraday precisions (relative standard deviation) were less than 1.05%.     

A novel Barton decarboxylation produces a 1,4-phenyl radical rearrangement domino reaction

A novel 1,4-Phenyl radical rearrangement (1,4-PhRR) is described in a typical Barton decarboxylation procedure. While carrying out this reaction in presence of a N,N-disubstituted β-amino acid derivative, the decarboxyphenyl rearranged derivative is obtained, as well as in presence of β-N,N-acylamide. On the other hand, secondary amines give the β-lactam derivative without rearrangement, as well as N-Fmoc derivatives give the normal decarboxylation reaction. In regards of amines which are far away from the carboxylic group, such as δ-amino acid derivatives, the reaction occur through a typical Barton decarboxylation without rearrangement. The diversity of the reaction proves synthetic usefulness paving the way to interesting biologically active compounds.     

Preparation of α,ω‐telechelic hexyl acrylate polymers with ?OH, ?COOH,and ?NH2 functional groups by RAFT

The design, synthesis, and use of two new, stable, functionalized chain transfer agents (CTA's) containing OH and amine end groups for the RAFT polymerization is reported: 2‐hydroxyethoxy‐carbonylphenylmethyl dithiobenzoate and 2‐(2‐(tert‐butoxycarbonyl)ethylamino)‐2‐oxo‐1‐phenylethyl benzodithioate, respectively. The RAFT polymerization of n‐hexyl acrylate (HA) using those CTA's, were compared to several other functionalized dithiobenzoate esters reported in the literature containing COOH and Ester groups. The performances of the dithiobenzoates were compared in terms of kinetics and molecular weight distribution control. Good control in polymerization of n‐hexyl acrylate with a linear increase of M_n with conversion mantaining polydispersity indices (PDI) below 1.1 was obtained by use of the new functionalized CTA's developed and also by use of some other CTA's tested, to produce well‐defined linear polymers with one specific chain‐end functionality: ? OH, ? COOH or Amine. Using a postpolymerization reaction with functionalized azocompounds in a 5 to 1 ratio, α,ω‐telechelic polymers, with ? OH or ? COOH as functional group at the second end were obtained. By using this synthetic strategy α,ω‐homotelechelic and heterotelechelic polymers were readily prepared. The chemical availability of functional end‐groups in the telechelics was demonstrated by reaction with methacrylic anhydride. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3033–3051, 2010     

Field preconcentration of cadmium from seawater by using a minicolumn packed with Amberlite XAD-4/4-(2-pyridylazo) resorcinol and its flow-injection-flame atomic absorption spectrometric determination at the ng L(-1) Level

A flow injection analysis-flame atomic absorption spectrometric method for the determination of cadmium in seawater was developed with the aim of yielding a sensitive assay with a low detection limit. The method employs a field flow preconcentration technique involving a minicolumn containing Amberlite XAD-4 impregnated with the complexing agent 4-(2-pyridylazo) resorcinol. A Plackett-Burman 2(7)x3/32 design for seven factors (sample pH, sample flow rate, eluent volume, eluent concentration, eluent flow rate, ethanol percentage in the eluent and minicolumn diameter) was carried out in order to find the significant variables affecting the field continuous preconcentration system (FCPS) and the flow injection elution manifold for cadmium determination in seawater samples by flame atomic absorption spectrometry. Cadmium can be preconcentrated with an enrichment factor of 1053 for a sample volume of 200 mL and a preconcentration time of 57 min. In these experimental conditions, the method provides a linear relationship between absorbance and cadmium concentration in the range from 22-1900 ng L(-1), with a detection limit (3SD) of 6 ng L(-1). The precision (expressed as relative standard deviation) for eleven independent determinations reached values of 8.9-0.8% in cadmium solutions of 50-700 ng L(-1). Analysis of certified reference materials (SLEW-3 and NASS-5) showed good agreement with the certified value. This procedure was applied to the determination of cadmium in seawater from Galicia (Spain).     

A convenient synthesis of novel pyrido(1′,2′:1,2)imidazo[5,4‐d]‐1,2,3‐triazinones from imidazo[1,2‐a]pyridines

The imidazo[1,2‐a]pyridine system was investigated as a synthon for the building of very attractive fused triazines, a planar, angular tri‐heterocycle with potential biological activity. Thus ethyl 3‐nitroimidazo[1,2‐a]pyridine‐2‐carboxylate was treated with ammonia or with an excess of primary amines to generate the corresponding substituted nitro carboxamidoimidazopyridines. The nitro substituent in the latter products, was reduced to yield 3‐amino‐2‐carboxamidoimidazo[1,2‐a]pyridine derivatives, which in turn were treated with nitrous acid to furnish 1‐oxo‐2‐substituted pyrido(1′,2′:1,2)imidazo[5,4‐d]‐1,2,3‐triazines.     

Influence of protonation on substrate and inhibitor interactions at the active site of human monoamine oxidase-A

Although substrate conversion mediated by human monoaminooxidase (hMAO) has been associated with the deprotonated state of their amine moiety, data regarding the influence of protonation on substrate binding at the active site are scarce. Thus, in order to assess protonation influence, steered molecular dynamics (SMD) runs were carried out. These simulations revealed that the protonated form of the substrate serotonin (5-HT) exhibited stronger interactions at the protein surface compared to the neutral form. The latter displayed stronger interactions in the active site cavity. These observations support the possible role of the deprotonated form in substrate conversion. Multigrid docking studies carried out to rationalize the role of 5-HT protonation in other sites besides the active site indicated two energetically favored docking sites for the protonated form of 5-HT on the enzyme surface. These sites seem to be interconnected with the substrate/inhibitor cavity, as revealed by the tunnels observed by means of CAVER program. pK(a) calculations in the surface loci pointed to Glu32?, Asp32?, His???, and Asp132 as candidates for a possible in situ deprotonation step. Docking analysis of a group of inhibitors (structurally related to substrates) showed further interactions with the same two docking access sites. Interestingly, the protonated/deprotonated amine moiety of almost all compounds attained different docking poses in the active site, none of them oriented to the flavin moiety, thus producing a more variable and less productive orientations to act as substrates. Our results highlight the role of deprotonation in facilitating substrate conversion and also might reflect the necessity of inhibitor molecules to adopt specific orientations to achieve enzyme inhibition.     

Separation of brombuterol enantiomers in capillary electrophoresis with cyclodextrin‐type chiral selectors and investigation of structure of selector‐selectand complexes using nuclear magnetic resonance spectroscopy

The major goal of this study was to determine the affinity pattern of brombuterol (BB) enantiomers toward various cyclodextrins (CD) and to evaluate the potential of NMR spectroscopy for understanding fine mechanisms of interactions between CDs and BB enantiomers. Separation of BB enantiomers was performed in a fused‐silica capillary using a phosphate buffer, pH 2.5, at the room temperature in the normal polarity mode. It was shown once again that CE in combination with NMR spectroscopy represents a very sensitive tool for studies of affinity patterns and structure of CD complexes with chiral guests. Although opposite affinity patterns of BB enantiomers were observed toward native β‐ and γ‐CDs, no significant differences between the structures of the complexes of these two CDs with BB were detected by NMR spectroscopy. In contrary to this, the opposite affinity pattern of BB enantiomers toward β‐CD and its two sulfated derivatives, heptakis (2,3‐O‐diacetyl‐6‐sulfo)‐β‐CD (HDAS‐β‐CD) and heptakis (2‐O‐methyl‐3,6‐di‐O‐sulfo)‐β‐CD (HMDS‐β‐CD) was associated with major differences in the structure of the complexes. In addition, it was shown again that HMDS‐β‐CD provides separation of enantiomers without formation of inclusion‐type complex with the chiral analyte.