Total spontaneous resolution of chiral covalent networks from stereochemically labile metal complexes

Stereochemically labile copper and zinc complexes with the N,N'-dimethylethylenediamine ligand (dmeda) have been shown to be promising precursors for the total spontaneous resolution of chiral covalent networks. (N,N')-[Cu(NO3)2(dmeda)]infinity crystallises as a conglomerate and yields either enantiopure (R,R)-1 or enantiopure (S,S)-1. A mixed-valence copper(I/II) complex, [{Cu(II)Br2(dmeda)}3(Cu(I)Br)2]infinity (2), which crystallises as a pair of interpenetrating chiral (10,3)-a nets, is formed from CuBr, CuBr2 and dmeda. One net contains ligands with solely (R,R) configuration and exhibits helices with (P) configuration while the other has solely (S,S)-dmeda ligands and gives rise to a net in which the helices have (M) configuration. The whole crystalline arrangement is racemic, because the interpenetrating chiral nets are of opposite handedness. With zinc chloride (R,S)-[ZnCl(dmeda)2]2[ZnCl4] (3) is obtained, which is a network structure, although not chiral. Total spontaneous resolution of stereochemically labile metal complexes formed from achiral or racemic building blocks is suggested as a viable route for the preparation of covalent chiral networks. Once the absolute structure of the compound has been determined by X-ray crystallography, a quantitative determination of the enantiomeric excess of the bulk product can be undertaken by means of solid-state CD spectroscopy.     

Nonspecific interactions of a carboxylate-substituted PPE with proteins. A cautionary tale for biosensor applications

Two carboxylate-substituted, fluorescent (Phi = 0.08), water-soluble poly(p-phenyleneethynylene)s (PPE) and a water-soluble model compound were exposed to a series of proteins and bovine serum. While the anionic PPEs do not have any specific binding sites, they form stable complexes with histone, lysozyme, myoglobin, and hemoglobin. The complex formation was evidenced by fluorescence quenching. Bovine serum albumin does not quench the fluorescence of the PPEs but enhances it, probably due to its surfactant character. These results imply that the use of charged conjugated polymers as biosensors, while an attractive proposition, has to take into account strong nonspecific interactions between conjugated polymers and the host of proteins that is found in cells and complex biological fluids.     

Enzymatic hydrolysis of heterocyclic nitriles

Chemoselective hydrolysis of heterocyclic nitriles can be achieved by an easy to use immobilized biocatalyst prepared from Rhodococcus sp. Pyrimidine-2-carbonitrile ( 2a ) and 3-chloropyridazine-4-carbonitrile ( 4a ) were converted into the corresponding amides while from 2-ethoxycarbonyl-4-pyridinecarbonitrile ( 1a ), 6-methylpyridazine-3-carbonitrile ( 3a ), 3-chloropyridazine-4-carbonitrile ( 4a ), 3-ethoxycarbonyl-4,5-dihydroisoxazole-5-carbonitrile ( 8a ), indole-3-carbonitrile ( 9a ) and indole-3-ylacetonitrile ( 10a ) the acids were formed.     

Electron-transfer in molecular functional materials

We discuss electron-transfer processes that govern the physics of several materials or systems of interest for advanced applications. The discussion touches upon several topics, ranging from solvatochromism to solvent-induced symmetry breaking, from excitonic to cooperative effects in molecular crystals, from phase transitions to vibrational contributions to the dielectric constant in organic materials, from spectroscopy to molecular transport. In all these diverse systems electron transfer (ET) plays a major role and is discussed with reference to simple models for delocalized charges.     

Asymmetry of electron transmission through monolayers of helical polyalanine adsorbed on gold surfaces

Polyalanine derivatives containing cysteamine linker R-(Ala)14NH-(CH2)2-SH, where R is ferrocenecarbonyl or hydrogen, were synthesized and then used to form self-assembled monolayers on gold. The tilt angles and the packing density of the molecules within monolayer assemblies were determined by FTIR spectroscopy and scanning tunneling microscopy, respectively. Electrochemical properties of monolayer-modified electrodes were studied using cyclic voltammetry and impedance spectroscopy. Measurements of electron-transfer rates using electrochemical techniques and scanning tunneling spectroscopy revealed asymmetry dependent on the applied voltage. It is suggested that the observed electron-transfer behavior is connected with the electric field generated by the molecular dipole of the polyalanine helix.     

Toward fully synthetic carbohydrate-based HIV antigen design: on the critical role of bivalency

Synthetic gp120331-335 glycopeptide fragments carrying hybrid and high-mannose type N-linked glycans were evaluated for binding to broadly neutralizing antibody 2G12 using surface plasmon resonance technology. None of the hybrid-type constructs demonstrated binding to 2G12. In the high-mannose series, the "Cys dimer" construct, presenting two undecasaccharide glycans, showed significantly higher binding than the Cys-protected monomer. The binding of the dimeric structure was further investigated in competition with recombinant gp120. The data suggest that gp120 and its designed synthetic epitope construct bind to the same site on 2G12.     

Synthesis,characterisation and ferric ion complexation studies of chelating probes for oxidative stress

The ferric ion binding characteristics of a novel chelating probe for detecting reactive oxygen and nitrogen species are reported. The probe comprises a polyaminocarboxylic acid chelator (EDTA) conjugated with aromatic amino acids. The probe (i) complexes redox-active and non-redox active metal ions and (ii) differentiates between different reactive oxygen/nitrogen species based upon the reaction products with same. The ferric ion binding characteristics were measured using species distribution and electronic absorption spectroscopic investigations. Over the physiological pH range a favoured one to one complex exists.     

Chemo-enzymatic synthesis of 4-methylumbelliferyl beta-(1-->4)-D-xylooligosides: new substrates for beta-D-xylanase assays

Transglycosylation catalyzed by a beta-D-xylosidase from Aspergillus sp. was used to synthesize a set of 4-methylumbelliferyl (MU) beta-1-->4-D-xylooligosides having the common structure [beta-D-Xyl-(1-->4)]2-5-beta-D-Xyl-MU. MU xylobioside synthesized chemically by the condensation of protected MU beta-D-xylopyranoside with ethyl 2,3,4-tri-O-acetyl-1-thio-beta-D-xylopyranoside was used as a substrate for transglycosylation with the beta-D-xylosidase from Aspergillus sp. to produce higher MU xylooligosides. The structures of oligosaccharides obtained were established by 1H and 13C NMR spectroscopy and electrospray tandem mass spectrometry. MU beta-D-xylooligosides synthesized were tested as fluorogenic substrates for the GH-10 family beta-D-xylanase from Aspergillus orizae and the GH-11 family beta-D-xylanase I from Trichoderma reesei. Both xylanases released the aglycone from MU xylobioside and the corresponding trioside. With substrates having d.p. 4 and 5, the enzymes manifested endolytic activities, splitting off MU, MUX, and MUX2 primarily.     

Conformational equilibria and photoinduced tautomerization in 2-(2′-pyridyl)pyrrole

Depending on the polarity and protic abilities of the solvent, 2-(2′-pyridyl)pyrrole can exist in either syn or anti rotameric forms. In nonpolar solvents, intramolecular excited state single proton transfer is observed, manifested by the appearance of low-energy tautomeric emission. The solvent-assisted excited state double proton transfer reaction is also detected. DFT calculations confirm low barriers for both single and double proton transfer processes in the lowest excited singlet state and show different character of the tautomerization in both cases: in the intramolecular reaction, mutual approach of two nitrogen atoms plays an important role.     

Polystyrene prepared by reactive extrusion: kinetics and effect of processing parameters

The conversion and residence time were investigated during the bulk polymerization of styrene in a twin screw extruder. It was found that polymerization mainly occurred in the zone between 400 and 1000 mm along the screw axis in the extruder, corresponding to the residence time of the reactants ranging from 1 to 4 min in the extruder. Furthermore, the processing conditions (feed rate, screw rotation rate) and average molecular weight of the polymer have a great effect on the residence time. Based on dimensionless analysis, a model of the residence time has been built‐up, which has been confirmed by the results of realistic measurements. A kinetic model of the polymerization has also been established under the assumption that the screw extruder can be regarded as an ideal plug flow reactor. Copyright © 2004 John Wiley & Sons, Ltd.