Search results for "Photochemistry"
showing 10 items of 2034 documents
Proton Transfer versus Hydrogen Bonding: The Reduction of Ubiquinone Q2Incorporated in a Self-Assembled Monolayer in Unbuffered Aqueous Solution
2014
The electrochemical reduction of ubiquinone Q2 (UQ2) in unbuffered aqueous media was investigated over a pH range of 2 to 11, and the results were compared to those obtained in our previous work in buffered solutions. The short isoprene chains of UQ2 were incorporated in a self-assembled monolayer. Analysis of the mechanism and a study in D2O solutions allowed us to demonstrate the important role of hydrogen bonding in the stabilization of the reduced species, also in water. If the concentration of H+ is low relative to that of the quinone, the electrochemical reaction does not proceed through proton-coupled electron transfer, as it does in buffered medium or at low pH values (pH<4.4). We p…
Complexation and Extraction of PAHs to the Aqueous Phase with a Dinuclear Pt II Diazapyrenium‐Based Metallacycle
2010
New palladium and platinum metallacycles have been synthesized by reaction between a 2,7-diazapyrenium-based ligand and Pd(II) and Pt(II) complexes. The inclusion complexes between the metallacycles and polycyclic aromatic hydrocarbons (PAHs) in CD(3)NO(2) and D(2)O were studied by NMR spectroscopy. The structures of the inclusion complexes of the Pt metallacycle as host with pyrene, phenanthrene, and triphenylene were confirmed by single crystal X-ray crystallography. The association constants between the Pt metallacycle and the selected PAHs were determined in CH(3)CN following the characteristic charge-transfer band displayed in their UV/Vis absorption spectrum. Although in aqueous solut…
Reversible Cluster Formation of Colloidal Nanospheres by Interparticle Photodimerization
2004
Crosslinked spherical nanoparticles based on trimethoxysilane monomers have been prepared by polycondensation in aqueous emulsion. These particles have been labeled chemically at their surface region with two different types of organic dye molecules (cinnamate, coumarin), which both are well known for their ability to undergo a reversible photodimerization if irradiated with light of a suitable wavelength. Upon irradiation of dilute solutions of these nanoparticles with UV light, the photodimerization of labels belonging to different colloidal nanoparticles caused the formation of large colloidal clusters consisting of chemically bound individual nanospheres. This process has been quantitat…
Entropy of transfer of n-nitroalkanes from n-octane to water at 25�C
1984
Entropy of transfer of nitromethane, nitroethane, 1-nitrobutane, 1-nitropentane, and 1-nitrohexane from n-octane to water at 25°C is calculated using an electrostatic model. The calculations indicate that the electrostatic transfer entropy depends primarily on the dipole moment and the size of the-C−NO2 group, showing a trend which is similar to that previously found for the transfer free energy of the same process.
Oxidation of oxalate ion in aqueous suspensions of TiO2 by photocatalysis and ozonation
2005
Abstract Oxalate anion has been oxidized in aqueous alkaline solution by using ozonation and photocatalysis in the presence of TiO 2 . A batch annular reactor has been used for carrying out reactivity runs in the presence of air/ozone, air/ozone/near UV irradiation, air/ozone/TiO 2 , air/near UV-irradiated TiO 2 and air/ozone/near UV-irradiated TiO 2 . The Langmuir–Hinshelwood kinetic model adequately describes the photocatalytic results obtained at different reaction conditions and allows determining the values of the kinetic and equilibrium adsorption constants. The contemporary presence of photocatalysis and ozonation shows a significant improvement of the process performance as the oxid…
Solubilization control by redox-switching of polysoaps
2008
Reversible changes in the self-organization of polysoaps may be induced by controlling their charge numbers via covalently bound redox moieties. This is illustrated with two viologen polysoaps, which in response to an electrochemical stimulus, change their solubility and aggregation in water, leading from homogeneously dissolved and aggregated molecules to collapsed ones and vice verse. Using the electrochemical quartz crystal microbalance (EQCM), it could be shown that the reversibility of this process is better than 95% in 16 cycles.
Probing the internal environment of PVP networks generated by irradiation with different sources
2010
Poly(N-vinyl-2-pyrrolidone) (PVP) hydrogels have been synthesised from the aqueous solutions of the same linear polymer by two different radiation sources: electron beams and UV rays. The present investigation couples conventional hydrogel characterisation techniques with the study of the partition equilibria, fluorescence behaviour and release of two different molecular probes, 1-anilino-8-naphthalene sulphonate (ANS) and Thioflavin T (ThT). The two probes have comparable molecular weight and different structural and optical properties. The chemical networks produced upon irradiation in different experimental conditions presented quite distinctive mechanical spectra, yielded to different…
Single Molecule Spectroscopy of Oriented Recombinant Trimeric Light Harvesting Complexes of Higher Plants
2002
The bleaching dynamics of reconstituted single light-harvesting chlorophyll a/b investigated. The complexes containing one histidine6 tag per monomeric subunit were immobilised predominantly in a defined orientation with their symmetry axis perpendicular to a Ni-ion-containing surface allowing for the first time the examination of single LHCIIb in an aqueous environment. Most complexes exhibit photobleaching in one step, indicating coupling between the monomeric subunits leading to an energy transfer between adjacent subunits. Differences in bleaching behaviour between these and previous observations with single LHCIIb are discussed.
Spectroscopic study of molecular associations between riboflavin and some (dihydro) β-carboline derivatives
1993
Abstract The spectrophotometric and thermodynamic properties of molecular complexes of riboflavin (RFN) with some dihydro β-carboline derivatives have been investigated by using electronic absorption and fluorescence spectroscopic methods in aqueous solution. The molecular associations have been examined by means of eletronic absorption spectra, since in each, a new charge transfer-like band has been located, and also by observing the variation of the fluorescence emission of RFN on the solutions. The formation constants for the molecular complexes were determined from absorption data, using the Forster—Hammick—Wardley method. The quenching phenomenon observed in RFN fluorescence is related…
Thermal and Chemical Stability of Thiol Bonding on Gold Nanostars
2015
The stability of thiol bonding on the surface of star-shaped gold nanoparticles was studied as a function of temperature in water and in a set of biologically relevant conditions. The stability was evaluated by monitoring the release of a model fluorescent dye, Bodipy-thiol (BDP-SH), from gold nanostars (GNSs) cocoated with poly(ethylene glycol) thiol (PEG-SH). The increase in the BDP-SH fluorescence emission, quenched when bound to the GNSs, was exploited to this purpose. A maximum 15% dye release in aqueous solution was found when the bulk temperature of gold nanostars solutions was increased to T = 42 °C, the maximum physiological temperature. This fraction reduces 3-5% for temperatures …