Electron impact ionization in helium nanodroplets: controlling fragmentation by active cooling of molecular ions

Reported here is a study of the effects of liquid helium cooling on the fragmentation of ions formed by electron impact mass ionization. The molecules of interest are picked up by the helium nanodroplets as they pass through a low pressure oven. Electron impact ionization of a helium atom in the droplet is followed by resonant charge transfer to neighboring helium atoms. When the charge is transferred to the target molecule, the difference in the ionization potentials between helium and the molecule results in the formation of a vibrationally hot ion. In isolation, the hot parent ion would undergo subsequent fragmentation. On the other hand, if the cooling due to the helium is fast enough, the parent ion will be actively cooled before fragmentation occurs. The target molecule used in the present study is triphenylmethanol (TPM), an important species in synthetic chemistry, used to sterically protect hydroxyl groups. Threshold PhotoElectron PhotoIon COincidence (TPEPICO) experiments are also reported for gas-phase TPM to help quantify the ion energetics resulting from the cooling effects of the helium droplets.     

State selective electron injection in non-aggregated titanium phthalocyanine sensitised nanocrystalline TiO2 films

We describe a novel titanium phthalocyanine that shows no aggregation when anchored to nanocrystalline TiO2 films through its axial carboxylated ligand without the use of co-adsorbents; state selective electron injection into the TiO2 is demonstrated, resulting in efficient photocurrent generation in dye sensitised photoelectrochemical solar cells.     

Critical properties of lattices of diffusively coupled quadratic maps

We study the critical properties of lattices of coupled logistic maps in the regime where the individual maps are closely above the onset of chaos. We discuss both spatial and temporal characteristics and especially the link between them. We show that the mutual information function between two points on the lattice decays exponentially with distance. In this way we find support for the relation xi approximately lambda(-1/2) between the coherence length xi and the largest Lyapunov exponent lambda which is further corroborated by a detailed study of the spreading of small perturbations. Finally we study the structure function of the lattice field variable. It shows that at the onset of chaos the lattice remains smooth.     

A total synthesis of hydroxylysine in protected form and investigations of the reductive opening of p-methoxybenzylidene acetals

A synthesis of (2S,5R)-5-hydoxylysine, based on (R)-malic acid and Williams glycine template as chiral precursors, has been developed. This afforded hydroxylysine, suitably protected for direct use in peptide synthesis, in 32% yield over the 13-step sequence. Regioselective reductive opening of a p-methoxybenzylidene acetal and alkylation of the Williams glycine template were key steps in the synthetic sequence. Surprisingly, the regioselectivity in opening of the p-methoxybenzylidene acetal was reversed as compared to what was expected. It was found that this was due to chelation of the trialkylsilyl choride, used as an electrophile in the reductive opening, to an adjacent azide functionality. It was also discovered that an equivalent amount of trialkylsilyl hydride was formed in the reaction, a finding that led to additional mechanistic insight into reductive openings of p-methoxybenzylidene acetals with sodium cyanoborohydride as reducing agent.     

Connecting pairwise and positional election outcomes

General conclusions relating pairwise tallies with positional (e.g., plurality, antiplurality (“vote-for-two”)) election outcomes were previously known only for the Borda Count. While it has been known since the eighteenth century that the Borda and Condorcet winners need not agree, it had not been known, for instance, in which settings the Condorcet and plurality winners can disagree, or must agree. Results of this type are developed here for all three-alternative positional rules. These relationships are based on an easily used method that connects pairwise tallies with admissible positional outcomes; e.g., a special case provides the first necessary and sufficient conditions ensuring that the Condorcet winner is the plurality winner; another case identifies when there must be a profile whereby each candidate is the “winner” with some positional rule.     

Expanding the Chemical Space of Tetracyanobuta-1,3-diene (TCBD) through a Cyano-Diels-Alder Reaction: Synthesis,Structure, and Physicochemical Properties of an Anthryl-fused-TCBD Derivative

Tetracyanobuta-1,3-diene (TCBD) is a powerful and versatile electron-acceptor moiety widely used for the preparation of electroactive conjugates. While many reports addressing its electron-accepting capability have appeared in the literature, significantly scarcer are those dealing with its chemical modification, a relevant topic which allows to broaden the chemical space of this interesting functional unit. Here, we report on the first example of a high-yielding cyano-Diels-Alder (CDA) reaction between TCBD, that is, where a nitrile group acts as a dienophile, and an anthryl moiety, that is, acting as a diene. The resulting anthryl-fused-TCBD derivative, which structure was unambiguously identified by X-ray diffraction, shows high thermal stability, remarkable electron-accepting capability, and interesting electronic ground- and excited-state features, as characterized by a thorough theoretical, electrochemical, and photophysical investigation. Moreover, a detailed kinetic analysis of the intramolecular CDA reaction transforming the anthryl-TCBD-based reactant into the anthryl-fused-TCBD product was carried out at different temperatures.