Radiative and nonradiative decay rates of a molecule close to a metal particle of complex shape

We present a model to evaluate the radiative and nonradiative lifetimes of electronic excited states of a molecule close to a metal particle of complex shape and, possibly, in the presence of a solvent. The molecule is treated quantum mechanically at Hartree-Fock (HF) or density-functional theory (DFT) level. The metal/solvent is considered as a continuous body, characterized by its frequency dependent local dielectric constant. For simple metal shapes (planar infinite surface and spherical particle) a version of the polarizable continuum model based on the integral equation formalism has been used, while an alternative methodology has been implemented to treat metal particles of arbitrary shape. In both cases, equations have been numerically solved using a boundary element method. Excitation energies and nonradiative decay rates due to the energy transfer from the molecule to the metal are evaluated exploiting the linear response theory (TDHF or TDDFT where TD--time dependent). The radiative decay rate of the whole system (molecule + metal/solvent) is calculated, still using a continuum model, in terms of the response of the surrounding to the molecular transition. The model presented has been applied to the study of the radiative and nonradiative lifetimes of a lissamine molecule in solution (water) and close to gold spherical nanoparticles of different radius. In addition, the influence of the metal shape has been analyzed by performing calculations on a system composed by a coumarin-type molecule close to silver aggregates of complex shape.     

Direct minimization of the energy functional in LCAO-MO density matrix formalism

The general multiconfiguration self-consistent-field method is presented along the density matrix formalism. The proposed optimization procedure for orbitals makes use of an orthogonal transformation in the space spanned by the fixed basis set. Acting on the unconstrained parameters of the transformation a direct minimization of the energy expression is performed using a gradient approach. A similar method may also be applied to the optimization of the expansion coefficients. The method works not only for the ground state of a given system, but also for any excited state, yielding an upper bound to the true energy of the considered state.     

Aryl cations from aromatic halides. Photogeneration and reactivity of 4-hydroxy(methoxy)phenyl cation

The photochemistry of 4-chlorophenol (1) and 4-chloroanisole (2) has been examined in a range of solvents and found to lead mainly to reductive dehalogenation, through a homolytic path in cyclohexane and a heterolytic path in alcohols. Heterolysis of 1 and 2 in methanol and 2,2,2-trifluoroethanol offers a convenient access to triplet 4-hydroxy- and 4-methoxyphenyl cations. These add to pi nucleophiles, viz., 2,3-dimethyl-2-butene, cyclohexene, and benzene, giving the arylated products in medium to good yields. Wagner-Meerwein hydride and alkyl migration are evidence for the cationic mechanism of the addition to alkenes. Arylation (with no rearrangement) was obtained to some extent also in nonprotic polar solvents such as MeCN and ethyl acetate, reasonably via an exciplex and with efficiency proportional to the nucleophilicity of the trap (2,3-dimethyl-2-butene > cyclohexene > benzene).     

Supramolecular complexation of alkali cations through mechanochemical reactions between crystalline solids

The organometallic zwitterion [Co(III)(eta(5)-C(5)H(4)COOH)(eta(5)-C(5)H(4)COO)] reacts quantitatively as a solid polycrystalline phase with a number of crystalline alkali salts MX (M = K(+), Rb(+), Cs(+), NH(4) (+); X = Cl(-), Br(-), I(-), PF(6)(-), although not in all cation/anion permutations) to afford supramolecular complexes of the formula [Co(III)(eta(5)-C(5)H(4)COOH)(eta(5)-C(5)H(4)COO)](2).M(+)X(-). In some cases, the mechanochemical complexation requires kneading of the two solids with a catalytic amount of water. The characterization of the solid-state products has been achieved by a combination of X-ray single-crystal and powder-diffraction experiments. The hydrogen-bonding interactions have been investigated by solid-state NMR spectroscopy. The mechanochemical reactions imply a profound solid-state rearrangement accompanied by breaking and forming of O-H...O hydrogen-bonding interactions between the organometallic molecules. All compounds could also be obtained by solution crystallization of the inorganic salts in the presence of the organometallic unit. The solid-state complexation of alkali cations by the organometallic zwitterion has been described as a special kind of solvation process taking place in the solid state.     

A general criterion based on the implicit function theorem to model aggregation and adsorption in colloidal dispersions

This paper, which may interest not only colloid scientists and physical chemists but also applied mathematicians, completes some previous results on aqueous silicon nitride dispersions. Experimental data on adsorption from liquid solution were first obtained by a titration method and then used to derive the number of solid particles from an equilibrium constraint. To discuss the complex mechanisms affecting simultaneous solid particle aggregation and small ion adsorption at the solid/liquid interface, the Dini implicit function theorem (DT) has been applied to the equilibrium condition for a former suspension Gibbs free energy. It was able to relate the average particle number to the ion concentration adsorbed, but not to unequivocally specify their dependence on the liquid phase pH. We attempt here to model aggregation both through bulk and interfacial quantities. The generalized DT-based criterion has first been formulated in all generality, and then adopted according to a wider investigation. The results obtained confirm the original guess, i.e., to regard solid aggregation as dominated by interfacial mechanisms.     

Conformational studies of a bombolitin III-derived peptide mimicking the four-helix bundle structural motif of proteins

Bombolitins are five structurally related heptadecapeptides originally isolated from the venom of a bumblebee. In aqueous solution, bombolitins at sufficiently high concentration form oligomeric aggregates with consequent conformational transition from a random coil to the alpha-helical structure. Previous studies suggested that oligomeric aggregates could mimic the four-helix bundle structural motif of proteins. In the present work, we synthesized the following peptide sequence formed by two bombolitin III sequences linked head-to-tail by the tetrapeptide bridge -Gly-Pro-Val-Asp-: I(1)-K(2)-I(3)-M(4)-D(5)-I(6)-L(7)-A(8)-K(9)-L(10)-G(11)-K(12)-V(13)-L(14)-A(15)-H(16)-V(17)-G(18)-P(19)-V(20)-D(21)-I(22)-K(23)-I(24)-M(25)-D(26)-I(27)-L(28)-A(29)-K(30)-L(31)-G(32)-K(33)-V(3)(4)-L(35)-A(36)-H(37)-V(38)-NH(2). The tetrapeptide GPVD connecting the two helical peptide sequences was chosen to facilitate the formation of the helix-loop-helix structural motif. The conformational properties of the peptide were studied by CD, NMR, and molecular dynamics calculations. The results indicate the presence of a helix-loop-helix conformation at 10(-)(5) M concentration. At higher concentrations, NOESY connectivities were detected which are compatible with the presence of dimers or higher aggregates of peptide molecules in the helix-loop-helix structure packed in an antiparallel fashion. Molecular dynamics simulation were run either with NOE distance restraints or without restraints in explicit solvent for extended time. The results of these simulations support the dimerization of the molecules in the helix-loop-helix structure with formation of the four-helix bundle motif.     

Excess enthalpies of binary mixtures containing poly(propylene glycols) + benzyl alcohol, or + m-cresol, or + anisole at 308.15 K and at atmospheric pressure

Excess enthalpies, H^E, of binary mixtures containing poly(propylene glycols) of different molecular masses + benzyl alcohol, or + m-cresol, or + anisole were determined using a flow microcalorimeter at 308.15 K and at atmospheric pressure. Data was correlated using the Redlich–Kister polynomial. Results were qualitatively discussed in terms of molecular interactions and of the regular solution model.     

The proficiency testing programme for trace elements of the CORILA project

Harmonised quality schemes are being implemented in the framework of the thematic area Organization and Dissemination of Data of the Consorzio per la Gestione del Centro di Coordinamento delle Attività di Ricerca Inerenti il Sistema Lagunare di Venezia (Consortium for the Management of the Coordination Centre of Research Activities on the Venice Lagoon System, CORILA). Over the last 2 years, two proficiency tests were completed at the time of writing (while a third one is still in progress) to assess the capabilities of the analytical laboratories involved in the determination of trace elements in environmental inorganic matrices from the Lagoon of Venice.Both interlaboratorial trials were based on the determination of As, Cd, Cr, Cu, Fe, Hg, Pb and Zn in aqueous acidic, matrix-enriched solutions at concentrations within the ranges generally found in marine water and in sediment after chemical digestion, respectively. The proficiency of participants was assessed on the basis of the z score criterion (|z|≤2, acceptable results; 2<|z|<3, questionable results; |z|≥3, unacceptable results). In the two trials, the relevant percentages for the laboratories scoring |z|≤2 and |z|<3 were 61% and 71% and 65% and 77%, respectively. These first two proficiency tests, on the one hand, clearly pointed to the benefits the laboratories had from their participation in these exercises, and on the other hand, provided sound evidence of the need for further trials based on real environmental matrices.     

Total assignment of 1H and 13C NMR data for the sesquiterpene lactone 15-deoxygoyazensolide

We describe a complete analysis of the 1H and 13C spectra of the anti-inflamatory, schistossomicidal and trypanosomicidal sesquiterpene lactone 15-deoxygoyazensolide. This lactone, with a structure similar to other important ones, was studied by NMR techniques such as COSY, HMQC, HMBC, Jres and NOE experiments. The comparison of the data with some computational results led to an unequivocal assignment of all hydrogen and carbon chemical shifts, even eliminating some previous ambiguities. We were able to determine all hydrogen coupling constants (J) and signal multiplicities and to confirm the stereochemistry. A new method for the determination of the relative position of the lactonization and the position of the ester group on a medium-sized ring by NMR was developed.     

Double addition of grignard reagents to N-glycosyl nitrones: a new tool for the construction of enantiopure azaheterocycles

[Reaction: see text] C-Phenyl-N-erythrosylnitrone 3 behaves as a C1,C1' bis-electrophile, undergoing a double addition of Grignard reagents in a domino fashion to afford acyclic hydroxylamines 4. The reaction proceeds at 0 degrees C with variable degrees of diastereoselectivity, from moderate to good, mainly depending on the organomagnesium reagent used. The usefulness of compounds 4 has been exemplified with the synthesis of pyrroloazepine 12 through a ring closing metathesis key step.