Electronic spectroscopy of toluene-rare-gas clusters: the external heavy atom effect and vibrational predissociation

Toluene-X van der Waals clusters (where X = Ne, Ne2, Ar, Ar2, Kr, Xe) have been investigated by fluorescence excitation spectroscopy in the region of the S1-S0 transition. With the exception of Xe, for each rare-gas studied, we have assigned cluster transitions in the region of all the strong monomer vibrational bands up to 1000 cm(-1) above the origin band. We have further investigated the S1 relaxation dynamics for each vibrational level of each complex, via their fluorescence decay profiles. Clustering with neon has little appreciable effect on the vibrationless S1 lifetime. By contrast, the clusters with argon and krypton exhibit markedly shorter fluorescence lifetimes compared with the monomer. The effect is so severe in the case of toluene-Xe clusters that no fluorescence signals were observed. We interpret these results in terms of an external heavy atom effect in which the rate of intersystem crossing in toluene is influenced by the cluster partner. For clusters built upon excited S1 vibrational levels, the situation is potentially complicated by intramolecular vibrational redistribution and vibrational predissociation (VP). The majority of the fluorescence decay profiles were satisfactorily modeled using single exponential decays. The emission following pumping of the 37(1) level in the toluene-Kr cluster, however, is an exception. We have modeled the decay of this level with a simple kinetic scheme including VP and determined a predissociation rate of (1.04 +/- 0.54) x 10(7) s(-1).     

Restricted rotation of the olefin and amine ligands in cis-dichloro(p-toluidine)(ethyl vinyl ether)platinum(II)

cis-Dichloro(p-toluidine)(olefin)platinum(II) complexes, in which the olefin is either ethyl vinyl ether or ethylene, have been investigated by ¹H NMR spectroscopy over a range of temperatures (+50 to ?60° C) in order to study the rotation of the olefin ligand.The results give no evidence of rotation of the amine or vinyl ether ligands even at the highest temperature investigated, +50°C; only one of the two possible rotational isomers is present, and this is attributed to the presence of intramolecular hydrogen bonding between the oxygen atom of the vinyl ether and the -NH- group of the amine.In contrast, the amine and vinyl ligands in the ethylene complex rotate freely at room temperature, coalescence being observed above ?25° C for the ethylene protons.     

pH Switchable Water Dispersed Photocatalytic Nanoparticles

Photogeneration of Reactive Oxygen Species (ROS) finds applications in fields as different as nanomedicine, art preservation, air and water depollution and surface decontamination. Here we present photocatalytic nanoparticles (NP) that are active only at acidic pH while they do not show relevant ROS photo-generation at neutral pH. This dual responsivity (to light and pH) is achieved by stabilizing the surface of TiO₂ NP with a specific organic shell during the synthesis and it is peculiar of the achieved core shell-structure, as demonstrated by comparison with commercial photocatalytic TiO₂ NP. For the investigation of the photocatalytic activity, we developed two methods that allow real time detection of the process preventing any kind of artifact arising from post-treatments and delayed analysis. The reversibility of the pH response was also demonstrated as well as the selective photo-killing of cancer cells at acidic pH.     

Empirical properties of group preference aggregation methods employed in AHP: Theory and evidence

We study various methods of aggregating individual judgments and individual priorities in group decision making with the AHP. The focus is on the empirical properties of the various methods, mainly on the extent to which the various aggregation methods represent an accurate approximation of the priority vector of interest. We identify five main classes of aggregation procedures which provide identical or very similar empirical expressions for the vectors of interest. We also propose a method to decompose in the AHP response matrix distortions due to random errors and perturbations caused by cognitive biases predicted by the mathematical psychology literature. We test the decomposition with experimental data and find that perturbations in group decision making caused by cognitive distortions are more important than those caused by random errors. We propose methods to correct the systematic distortions.     

Substrate-directed asymmetric induction in the rhodium catalyzed hydroformylation of C-allyl-sugars: The influence of the glycoside-moiety on the selectivity of the reaction

α- and β-C-allylgalactopyranosides 1c and 1d, α-C-allylazaglucopyranoside 1e and α-C-allylfruttofuranoside 1f were hydroformylated at low temperatures affording a mixture of linear and branched aldehydes in regioisomeric and diastereoisomeric ratios depending on the starting alkene. The results obtained have allowed us to study the influence of the different structural features of the sugar moiety on the regio- and diastereoselectivity of the hydroformylation reaction.     

Paramagnetic-based NMR restraints lift residual dipolar coupling degeneracy in multidomain detergent-solubilized membrane proteins

Residual dipolar couplings (RDCs) are widely used as orientation-dependent NMR restraints to improve the resolution of the NMR conformational ensemble of biomacromolecules and define the relative orientation of multidomain proteins and protein complexes. However, the interpretation of RDCs is complicated by the intrinsic degeneracy of analytical solutions and protein dynamics that lead to ill-defined orientations of the structural domains (ghost orientations). Here, we illustrate how restraints from paramagnetic relaxation enhancement (PRE) experiments lift the orientational ambiguity of multidomain membrane proteins solubilized in detergent micelles. We tested this approach on monomeric phospholamban (PLN), a 52-residue membrane protein, which is composed of two helical domains connected by a flexible loop. We show that the combination of classical solution NMR restraints (NOEs and dihedral angles) with RDC and PRE constraints resolves topological ambiguities, improving the convergence of the PLN structural ensemble and giving the depth of insertion of the protein within the micelle. The combination of RDCs with PREs will be necessary for improving the accuracy and precision of membrane protein conformational ensembles, where three-dimensional structures are dictated by interactions with the membrane-mimicking environment rather than compact tertiary folds common in globular proteins.     

Non-stationary multifractality in stock returns

We perform an extensive empirical analysis of scaling properties of equity returns, suggesting that financial data show time varying multifractal properties. This is obtained by comparing empirical observations of the weighted generalised Hurst exponent (wGHE) with time series simulated via Multifractal Random Walk (MRW) by Bacry et al. [E. Bacry, J. Delour, J.-F. Muzy, Multifractal random walk, Physical Review E 64 (2) (2001) 026103]. While dynamical wGHE computed on synthetic MRW series is consistent with a scenario where multifractality is constant over time, fluctuations in the dynamical wGHE observed in empirical data are not in agreement with a MRW with constant intermittency parameter. We test these hypotheses of constant multifractality considering different specifications of MRW model with fatter tails: in all cases considered, although the thickness of the tails accounts for most of the anomalous fluctuations of multifractality, it still cannot fully explain the observed fluctuations.     

Catalytic effect of sulfoxides on the fluxional motion of 2,9-dimethyl-1,10-phenanthroline in a platinum(II) complex: evaluation of steric and electronic contributions

Addition of external weak nucleophiles to a chloroform solution of the cationic complex ion [Pt(Me)(dmphen)(PPh(3))](+) (1) accelerates the fluxional motion of the symmetric chelating ligand 2,9-dimethyl-1,10-phenanthroline (dmphen) between nonequivalent exchanging sites. The rates of the dynamic process can be measured by line-shape analysis of the (1)H NMR spectra. Concentration-dependent measurements were carried out with the ligands SOMe(2), SO(CH(2))(4), SO(n-Bu)(2), SO(sec-Bu)(2), SO(i-Pr)(2), SOEt(Ph), SOPr(Ph), SO(Bz)(2), SO(p-MeC(6)H(4))(2), SOPh(2), SO(p-ClC(6)H(4))(2), SOMe(p-MeOC(6)H(4)), SOMe(p-MeC(6)H(4)), SOMe(Ph), SOMe(p-BrC(6)H(4)), and SOMe(p-ClC(6)H(4)). The rate constants k(obsd), when plotted against the concentration of the added ligands SOR(R'), give a family of straight lines with a common intercept, indicating that the two-term rate law k(obsd) = k(1) + k(2)[SOR(R')] is obeyed. The same rate law applies to the displacement of SOMe(2) from [Pt(Me)(phen)(SOMe(2))](+) (2) (phen = 1,10-phenanthroline) by sulfoxides (SOMe(2), SO(i-Pr)(2), SOMe(p-MeOC(6)H(4)), SO(p-MeC(6)H(4))(2), SOPh(2), SO(p-ClC(6)H(4))(2), and SO(sec-Bu)(2)). The fluxional rates in 1 are 6-7 orders of magnitude higher than the substitution rates in 2. The values of the rate constants for the two processes were resolved quantitatively into steric and electronic contributions by use of quantitative analysis of ligand effects (QALE). Inhibitory steric effects are linearly operative for the entire set of ligands, the rates of the reactions are enhanced with increasing electron donor capacity of the sulfoxides, and there is a small but significant E(ar) effect that enhances the reactivity of the aryl sulfoxides. The strict similarity of the patterns of the two processes and of their dependence upon the stereoelectronic properties of the ligands, combined with the intrinsic lability of the platinum-nitrogen bonds, would suggest the operation of stereospecific consecutive ring-opening and ring-closure steps for the fluxional motion of dmphen in 1. However, the available evidence does not allow alternative mechanisms involving intramolecular rearrangements of the five-coordinate intermediate to be ruled out.     

Synthesis of 5,6,7,8‐tetrahydroindolizines via a domino‐type transformation based on the rhodium catalyzed hydroformylation of N‐(β‐methallyl)pyrroles

Variously substituted 5,6,7,8‐tetrahydroindolizines can be easily synthesized via a domino reactions sequence under rhodium catalyzed hydroformylation of N‐(β‐methallyl)pyrroles. The later are readily prepared from properly functionalized pyrroles via phase‐transfer N‐allylation in the presence of 18‐crown‐6 and potassium tert‐butoxide.     

beta-Hydrogen Kinetic Effect

A combined kinetic and DFT study of the uncatalyzed isomerization of cationic solvent complexes of the type cis-[Pt(R')(S)(PR3)2]+ (R' = linear and branched alkyls or aryls and S = solvents) to their trans isomers has shown that the reaction goes through the rate-determining dissociative loss of the weakly bonded molecule of the solvent and the interconversion of two geometrically distinct T-shaped 14-electron three-coordinate intermediates. The Pt-S dissociation energy is strongly dependent on the coordinating properties of S and independent of the nature of R'. The energy barrier for the fluxional motion of [Pt(R')(PR3)2]+ is comparatively much lower ( approximately 8-21 kJ mol-1). The presence of beta-hydrogens on the alkyl chain (R' = Et, Prn, and Bun) produces a great acceleration of the reaction rate. This accelerating effect has been defined as the beta-hydrogen kinetic effect, and it is a consequence of the stabilization of the transition state and of the cis-like three-coordinate [Pt(R')(PR3)2]+ intermediate through an incipient agostic interaction. The DFT optimization of [Pt(R')(PMe3)2]+ (R' = Et, Prn, and Bun) reproduces a classical dihapto Pt....eta2-HC agostic mode between the unsaturated metal and a dangling C-H bond. The value of the agostic stabilization energy (in the range of approximately 21-33 kJ mol-1) was estimated by both kinetic and computational data and resulted in being independent of the length of the hydrocarbon chain of the organic moiety. A better understanding of such interactions in elusive reaction intermediates is of primary importance in the control of reaction pathways, especially for alkane activation by metal complexes.