Hybrid dendritic molecules with confined chromophore architecture to tune fluorescence efficiency.

The aim of this publication is to present a general strategy to engineer more efficient photoluminescent dendritic molecules based on polyhedral oligomeric silsesquioxane (POSS) cores. A series of chromophores were grafted on POSS cores to form dendritic molecules for which steric hindrance was used as a trigger to tune their photophysical properties. For fluorescence in the blue/near-UV spectral ranges, 4-vinylbiphenyl molecules were chosen as model chromophores to present a general approach based on stable chemistry and bulky groups grafted to the chromophores to enhance photoluminescence efficiency of the dendritic molecules. Photoluminescence quantum yields as well as steady-state and time-resolved solution spectroscopy along with molecular dynamics investigation and electronic structure calculations on a family of new materials are reported. We highlight an apparent contrast between free chromophore and dendritic molecules photophysical properties and show that chromophores' engineering and confinement around an inorganic core allows the design of more efficient photoluminescent dendritic molecules relevant to sensors and hybrid light-emitting diodes.

Electrochemical deposition of poly(trans-[RuCl2(4-vinylpyridine)4]) and its reductive desorption: cyclic voltammetry and electrochemical quartz crystal microbalance studies.

The electropolymerization of trans-[RuCl(2)(vpy)(4)](vpy = 4-vinylpyridine) on Au or Pt electrodes was studied by cyclic voltammetry and the electrochemical quartz crystal microbalance (EQCM) technique. Cyclic voltammetry of the monomer in DMSO on Au shows reductions at -2.0 and -2.2 V. Potential cycling over the first wave leads to polymer formation; however, scanning over the second wave leads to desorption of the polymer. These observations were confirmed by EQCM measurements which also revealed a high polymerization efficiency. Electrolysis, EQCM and XPS measurements showed that desorption was associated with substitution of chloride ligands by DMSO when the polymer was in a highly reduced state. The film also showed reversible mass changes due to the oxidation and accompanying ingress of charge-balancing anions and solvent into the film. Measurements on the dried films revealed that large quantities of solvent are trapped in the film during the electropolymerization process.

New pyridine carboxamide ligands and their complexation to copper(II). X-Ray crystal structures of mono-, di, tri- and tetranuclear copper complexes.

Seven new pyridine dicarboxamide ligands H2L(1-7) have been synthesised from condensation reactions involving pyridine-2,6-dicarboxylic acid (H2dipic), pyridine-2,6-dicarbonyl dichloride or 2,6-diaminopyridine with heterocyclic amine or carboxylic acid precursors. Crystallographic analyses of N,N'-bis(2-pyridyl)pyridine-2,6-dicarboxamide monohydrate (H2L8 x H2O), N,N'-bis[2-(2-pyridyl)methyl]pyridine-2,6-dicarboxamide and N,N'-bis[2-(2-pyridyl)ethyl]pyridine-2,6-dicarboxamide monohydrate revealed extensive intramolecular hydrogen bonding interactions. 2,6-Bis(pyrazine-2-carboxamido)pyridine (H2L6) and 2,6-bis(pyridine-2-carboxamido)pyridine (H2L7) reacted with copper(II) acetate monohydrate to give tricopper(II) complexes [Cu3(L)2(mu2-OAc)2]. X-Ray crystallography confirmed deprotonation of the amidic nitrogen atoms and that the (L6,7)2- ligands and acetate anions hold three copper(II) ions in approximately linear fashion. H2L8. Reacted with copper(II) tetrakis(pyridine) perchlorate to give [Cu(L8)(OH2)]2 x 2H2O, in which (L8)2- was tridentate through the nitrogen atoms of the central pyridine ring and the deprotonated carboxamide groups at one copper centre, with one of the terminal pyridyl rings coordinating to the other copper atom in the dimer. The corresponding reaction using H2L7 gave [Cu3(L7)2(py)2][ClO4]2, which transformed during an attempted recrystallisation from ethanol under aerobic conditions to a tetracopper(II) complex [Cu4(L7)2(L7-O)2].

A resonance Raman, surface-enhanced resonance Raman, IR, and ab initio vibrational spectroscopic study of nickel(II) tetraazaannulene complexes.

The IR and resonance Raman spectra of the nickel(II) complexes of dibenzo[b,i][1,4,8,11]tetraaza[14]annulene (TAA) and 5,7,12,14-tetramethyldibenzo[b,i][1,4,8,11]tetraaza[14]annulene (TMTAA) have been measured and compared with ab initio calculations of the vibrational wavenumbers at the B3-LYP level using the LanL2DZ basis set. An excellent fit is found between the experimental and calculated data, enabling precise vibrational assignments to be made. Surface-enhanced resonance Raman spectra were obtained following adsorption on Ag electrodes, with potentials in the range -0.1 to -1.1 V vs Ag/AgCl. There is evidence for contributions from both the electromagnetic and charge transfer (CT) surface enhancement mechanisms. The data indicate that variations in band intensities with electrode potential can be interpreted in terms of the CT mechanism.

A three-enzyme microelectrode sensor for detecting purine release from central nervous system.

As the purines, in particular adenosine, are important signaling agents in the nervous system we have devised a new biosensor for directly measuring their production in real time during physiological activity. Our amperometric adenosine biosensor is made by entrapping 3 enzymes (xanthine oxidase, purine nucleoside phosphorylase and adenosine deaminase) in a composite lactobionamide and amphiphillic polypyrrole matrix around a Pt microelectrode. The resulting sensors are small (25-100 microm diameter), fast responding (10-90% rise time, 2+/-0.23 s), sensitive (100-222 mA M(-1) cm(-2)) and stable (100% activity after 5 days). The sensor was used in vivo to demonstrate the spatial localization of release of adenosine from Xenopus embryo spinal cord during fictive swimming.