Enantioselective HF loss promoted by resonant two photon ionization of supersonically expanded (R)-1-phenyl-2,2,2-trifluoroethanol clusters.

(R)-1-Phenyl-2,2,2-trifluoroethanol and its hydrogen bonded adducts with achiral (water, tetrahydrofuran) and chiral solvent mols. ((R)- and (S)-butan-2-ol, (R)- and (S)-3-hydroxy-tetrahydrofuran) have been ionized by resonant two-photon absorption. The presence of photofragments, attributable to the occurrence of a hydrogen fluoride loss reaction, has been interpreted with the aid of theor. predictions at the DFT level of theory with the inclusion of dispersive terms. The HF elimination process takes place by a mechanism involving the preliminary C.alpha.-H hydrogen transfer to an hydroxyl oxygen assisted by the solvent mol. which is followed by extrusion of the HF mol. The calcd. energy barriers depend on the type of solvent as well as on its configuration and are consistent with the obsd. fragmentation ratios

Cu-catalyzed Si-NWS grown on “carbon paper” as anodes for Li-ion cells

The very high theoretical capacity of the silicon (4200mAh/g more than 10 times larger than graphite), environmental-friendly, abundant and low-cost, makes it a potential candidate to replace graphite in high energy density Li-ion batteries. As a drawback, silicon suffers from huge volume changes (300%) on alloying and dealloying with Li, leading a structural deformation that induces disruption. The use of nanostructured silicon materials has been shown to be an effective way to avoid this mechanical degradation of the active material. In this paper the synthesis of silicon nanowires, grown on a highly porous 3D-like carbon paper substrate by CVD using Cu as the catalyst, is presented. The use of carbon paper allows to achieve remarkable loadings of active material (2-5 mg/cm2) and, consequently, high capacity densities. The silicon electrode was investigated both morphologically and electrochemically. To improve the electrochemical performance various strategies have been carried out. It was observed that a very slow first cycle (C/40), which helps the formation of a stable solid electrolyte interphase on the silicon surface, improves the performance of the cells; nevertheless, their cycle life has been found not fully satisfactory. Morphological analysis of the Si-NWs electrodes before and after cycling showed the presence of a dense silicon layer below the nanowires which could reduce the electrical contact between the active material and the substrate

Molecular and supramolecular chirality: R2PI spectroscopy as a tool for the gas-phase recognition of chiral systems of biological interest.

A review. In life sciences, diastereomeric chiral mol./chiral receptor complexes are held together by a different combination of intermol. forces and are therefore endowed with different stability and reactivity. Detn. of these forces, which are normally affected in the condensed phase by solvent and supramol. interactions, can be accomplished through the generation of diastereomeric complexes in the isolated state and their spectroscopic investigation. This review presents a detailed discussion of the mass resolved Resonant Two Photon Ionization (R2PI-TOF) technique in supersonic beams and introduces an overview of various other technologies currently available for the spectroscopic study of gas phase chiral mols. and supramol. systems. It reports case studies primarily from the authors' recent work using R2PI-TOF methodol. for chiral recognition in clusters contg. mols. of biol. interest. The measurement of absorption spectra, ionization and fragmentation thresholds of diastereomeric clusters by this technique allow the detn. of the nature of the intrinsic interactions, which control their formation and which affect their stability and reactivity

Chirality effects on the IRMPD spectra of basket resorcinarene/nucleoside complexes

The IRMPD spectra of the ESI-formed proton-bound complexes of the R,R,R,R- and S,S,S,S-enantiomers of a bis(diamido)-bridged basket resorcin[4]arene (R and S) with cytosine (1), cytidine (2), and cytarabine (3) were measured in the region 2800– 3600 cm1. Comparison of the IRMPD spectra with the corresponding ONIOM (B3LYP/6-31(d):UFF)-calculated absorption frequencies allowed the assessment of the vibrational modes that are responsible for the observed spectroscopic features. All of the complexes investigated, apart from [R·H·3]+, showed similar IRMPD spectra, which points to similar structural and conformational landscapes. Their IRMPD spectra agree with the formation of several isomeric structures in the ESI source, wherein the N(3)-protonated guest establishes noncovalent interactions with the host amidocarbonyl groups that are either oriented inside the host cavity or outside it between one of the bridged side-chains and the upper aromatic nucleus. The IRMPD spectrum of the [R·H·3]+ complex was clearly different from the others. This difference is attributed to the effect of intramolecular hydrogen bonding interactions between the C(2’)-OH group and the aglycone oxygen atom of the nucleosidic guest upon repulsive interactions between the same oxygen atom and the aromatic rings of the host

Chiral recognition between 1-(4-fluorophenyl)ethanol and 2-butanol: higher binding energy of homochiral complexes in the gas phase

Diastereomeric adducts between (S)-1-(4-fluorophenyl)-ethanol and R and S 2-butanol, formed by supersonic expansion, were studied by a combination of mass selected resonant two-photon ionization-spectroscopy and IR depletion spectroscopy. Chiral recognition is evidenced by the specific spectroscopic signatures of the S1 S0 electronic transition as well as different frequencies and intensities of the OH stretch vibrational mode in the ground state. D-DFT calcns. were performed to assist in the anal. of the spectra and the detn. of the structures. The homochiral and heterochiral complexes show slight structural differences, in particular in the interaction of the alkyl groups of 2-butanol with the arom. ring. The homochiral [FESBS] complex is more stable than the heterochiral [FESBR] diastereomer in both the ground and excited states. The binding energy difference was evaluated to be >0.60 kcal mol-1

Solvent free interactions in contact pairs of molecules of biological interest: Laser spectroscopic and electrospray mass spectrometric studies

A laser spectroscopic and mass spectrometric study of ionic and molecular clusters of biological interest is reported. The molecules of interest and their aggregates were generated in a supersonic beam and analyzed by mass resolved resonant two photon absorption and ionization (R2PI) and by collision induced mass spectrometry (CID-MS). The absence of the solvent allows to study these systems in the isolated state free of undesired solvent effects which may level off the differences in their properties. The gas phase results have been compared to theoretical estimates of the structure and stability of the systems under investigation

Probing the competition among different coordination motifs in metal-ciprofloxacin complexes through IRMPD spectroscopy and DFT calculations

The vibrational spectra of ciprofloxacin complexes with monovalent (Li+, Na+, K+, Ag+) and polyvalent (Mg2+, Al3+) metal ions are recorded in the range 1000-1900 cm(-1) by means of infrared multiple-photon dissociation (IRMPD) spectroscopy. The IRMPD spectra are analyzed and interpreted in the light of density functional theory (DFT)-based quantum chemical calculations in order to identify the possible structures present under our experimental conditions. For each metal-ciprofloxacin complex, four isomers are predicted, considering different chelation patterns. A good agreement is found between the measured IRMPD spectrum and the calculated absorption spectrum of the most stable isomer for each complex. Metal ion size and charge are found to drive the competition among the different coordination motifs: small size and high charge density metal ions prefer to coordinate the quinolone between the two carbonyl oxygen atoms, whereas large-size metal ions prefer the carboxylate group as a coordination site. In the latter case, an intramolecular hydrogen bond compensates the weaker interaction established by these cations. The role of the metal cation on the stabilization of ionic and nonionic structures of ciprofloxacin is also investigated. It is found that large-size metal ions preferentially stabilize charge separated motifs and that the increase of metal ion charge has a stabilizing effect on the zwitterionic form of ciprofloxacin

Probing trinitrotoluene (TNT) by low-energy electrons: Strong fragmentation following attachment of electrons near 0 eV

Electron attachmentto gas phase trinitrotoluene (TNT) is studiedbymeansof a crossedelectron-molecular beam experiment at high-energy resolution. TNT shows unique features in the way that electrons right at threshold (near 0 eV) generate both the non-decomposed anion and a variety of anions arising from dissociative electron attachment (DEA). While the parent anion is formed within a very narrowresonance near 0 eV, the DEA reactions extend to higher energies and are operative via several resonant features in the energy range 0–10 eV. They involve remarkably complex reaction sequences associated with multiple bond cleavages and formation of new bonds. By far the dominant DEA reaction generates an ion formed by the loss of a neutral OH radical from the precursor ion. Further strong ion signals arise from the loss of up to three neutral NO units. The remarkable instability of TNT following attachment of electrons with virtually no energy underlines the explosive nature of this compound

Chiral clusters in a supersonic beam: R2PI-TOF spectroscopy of diastereomeric carboxylic esters/(R)-(+)-1-phenyl-1-propanol complexes

Wavelength and mass resolved resonance-enhanced two photon ionization (R2PI) excitation spectra of (R)-(+)-1-phenyl-1-propanol (P-R) and its complexes with some chiral esters, i.e. methyl lactates (L-R and L-S), methyl 3-hydroxybutyrates (H-R and H-S), and methyl 2-chloropropionates (C-R and C-S), have been recorded after a supersonic molecular beam expansion and interpreted in the light of DFT calculations. The spectral features of the selected complexes were found to depend on the nature of hydrogen-bond interactions within the diasteromeric complexes, whose intensity in turn depends upon the structure and the configuration of the estereal moiety. The study further confirms resonant two-photon ionization spectroscopy, coupled with time-of-flight mass resolution (R2PI-TOF), as an excellent tool for gathering valuable information on the interactive forces in molecular clusters and for the enantiodiscrimination of chiral molecules in the gas phase