Highly Efficient Transition Metal Nanoparticle Catalysts in Aqueous Solutions

A ligand design is proposed for transition metal nanoparticle (TMNP) catalysts in aqueous solution. Thus, a tris(triazolyl)‐polyethylene glycol (tris‐trz‐PEG) amphiphilic ligand, 2 , is used for the synthesis of very small TMNPs with Fe, Co, Ni, Cu, Ru, Pd, Ag, Pt, and Au. These TMNP‐ 2 catalysts were evaluated and compared for the model 4‐nitrophenol reduction, and proved to be extremely efficient. High catalytic efficiencies involving the use of only a few ppm metal of PdNPs, RuNPs, and CuNPs were also exemplified in Suzuki–Miyaura, transfer hydrogenation, and click reactions, respectively.     

Synthesis of pyridazine-based scaffolds as alpha-helix mimetics

The synthesis of several amphiphilic, nonpeptidic scaffolds that mimic the presentation of i, i + 3 or i + 4, and i + 7 residues of a peptide alpha-helix is described. The approach uses a pyridazine core, and the synthesis involves only a few steps and minimizes the number of C-C bond-forming reactions. The versatility of the synthesis makes it suitable for the preparation of small libraries of low molecular weight alpha-helix mimetics that could be targeted to certain protein/protein interactions.     

Post-source decay of alkylated and functionalized polycyclic aromatic compounds

Post-source decay (PSD) is a valuable tool for providing structural information from large molecules by time-of-flight mass spectrometry (TOFMS). We used PSD to obtain this type of data from small molecules in the laser desorption/ionization (LDI) study of diesel engine exhaust particles. As the original nitrogen laser (lambda = 337 nm, E = 3.5 eV/photon) of our TOF mass spectrometer does not yield sufficient energy to ionize polycyclic aromatic hydrocarbons (PAHs), a second laser with a shorter wavelength has been coupled to the instrument. The fourth harmonic of a Nd:YAG laser (lambda = 266 nm, 4.6 eV/photon) has been chosen to achieve two-photon single-step desorption/ionization of PAHs. The PSD fragmentation of functionalized, alkylated and sulfur PAHs is discussed. Diesel engine exhaust particles are also studied as an example of a real complex sample. This technique is presented herein as a way to identify small molecules in environmental samples. Information provided by LDI-PSD-TOFMS can be a way to distinguish pollutants with very close molecular weights even if the resolving power of a TOF mass spectrometer is not sufficient.     

Photoionization dynamics in pure helium droplets

The photoionization and photoelectron spectroscopy of pure He droplets were investigated at photon energies between 24.6 eV (the ionization energy of He) and 28.0 eV. Time-of-flight mass spectra and photoelectron images were obtained at a series of molecular beam source temperatures and pressures to assess the effect of droplet size on the photoionization dynamics. At source temperatures below 16 K, where there is significant production of clusters with more than 10(4) atoms, the photoelectron images are dominated by fast electrons produced via direct ionization, with a small contribution from very slow electrons with kinetic energies below 1 meV arising from an indirect mechanism. The fast photoelectrons from the droplets have as much as 0.5 eV more kinetic energy than those from atomic He at the same photon energy. This result is interpreted and simulated within the context of a "dimer model", in which one assumes vertical ionization from two nearest-neighbor He atoms to the attractive region of the He2+ potential energy curve. Possible mechanisms for the slow electrons, which were also seen at energies below IE(He), are discussed, including vibrational autoionizaton of Rydberg states comprising an electron weakly bound to the surface of a large HeN+ core.     

A Convenient Synthesis of the Echinacea‐Derived Immunostimulator and HIV‐1 Integrase Inhibitor (−)‐(2R,3R)‐Chicoric Acid

The Echinacea‐derived immunostimulator and HIV‐1 integrase inhibitor (−)‐chicoric acid (=2,3‐bis{[3‐(3,4‐dihydroxyphenyl)‐1‐oxoprop‐2‐enyl]oxy}butanedioic acid; 1a ) was conveniently prepared via a silane‐promoted Pd‐mediated chemoselective hydrogenolysis of its perbenzylated derivative 12a , which was generated from an efficient and reliable carbodiimide‐mediated coupling reaction between the caffeic acid dibenzyl ether derivative 7 and commercially available (+)‐dibenzyl L ‐tartrate ( 9a ). The other naturally occurring dextrorotatory chicoric acid ( 1b ) can be similarly prepared.     

β-Phosphorus Hyperfine Coupling Constant in Nitroxides: Conformational Effects in 6-Membered Ring Nitroxides

Recently, we reported a significant solvent effect on the phosphorus hyperfine coupling constant a _P in β-phosphorylated 6-membered ring nitroxides (?a _P = 24 G in Org. Biomol. Chem. 2015). Thus, it led us to investigate the effect of solvent for several 6-membered ring nitroxides. Although smaller than mentioned above, a change of 5–7 G in a _P with the polarity of solvent was still observed for these nitroxides. As for other β-phosphorylated nitroxides, a _N increases with the polarity/polarizability π* and the Hydrogen Bond Donating α properties of the solvent whereas a _P exhibits the reverse trends. The change of a _P with the solvent depends a lot on a subtle interplay between the destabilizing steric hindrance due to the bulkiness of the substituents and the stabilizing hyperconjugation interactions SOMO → σ*_C–P between the anti-bonding orbitals of the C–P bond and the SOMO.     

Twistor Actions for Self-Dual Supergravities

We give holomorphic Chern-Simons-like action functionals on supertwistor space for self-dual supergravity theories in four dimensions, dealing with supersymmetries, the cases where different parts of the R-symmetry are gauged, and with or without a cosmological constant. The gauge group is formally the group of holomorphic Poisson transformations of supertwistor space where the form of the Poisson structure determines the amount of R-symmetry gauged and the value of the cosmological constant. We give a formulation in terms of a finite deformation of an integrable -operator on a supertwistor space, i.e., on regions in . For , we also give a formulation that does not require the choice of a background.     

Counterion Association and Structural Conformation Change of Charged PAMAM Dendrimer in Aqueous Solutions Revealed by Small Angle Neutron Scattering

Our previous study of the structure change of poly(amidoamine) starburst dendrimers (PAMAM) dendrimer of generation 5 (G5) have demonstrated that although the overall molecular size is practically unaffected by increasing DCl concentration, a configurational transformation, from a diffusive density profile to a more uniform density distribution, is clearly observed. In the current paper, the focus is placed on understanding the effect of counterion identity on the inter-molecular structure and the conformational properties by studying the effect due to DBr using small angle neutron scattering (SANS) and integral equation theory. While the overall molecular size is found to be essentially unaffected by the change in the pD of solutions, it is surprising that the intra-molecular configurational transformation is not observed when DBr is used. The overall effective charge of a dendrimer is nearly the same for α < 1, independent of the type of acids. However, when α > 1, the effect of counterion identity becomes significant, the effective charge carried by a charged G5 PAPAM protonated by DBr becomes smaller than that of solutions with DCl. As a consequence, a counterion identity dependence of counterion association is revealed: Under the same level of molecular protonation, the specific counterion association, which is defined as the ratio of bound chloride anions to positively charged amines per molecule, is larger for the G5 PAMAM dendrimer charged by DBr than the one by DCl.     

Bis{bis­[5‐tert‐butyl‐2‐oxido‐3‐(1‐pyridinio­methyl)­phenyl]­methane}­dioxouranium bis­(tri­fluoro­methane­sulfonate) pyridine disolvate: a uranyl bis­(diphenoxide) complex resulting from homooxacalixarene cleavage

The title compound, [UO₂(C₃₃H₃₈N₂O₂)₂](CF₃SO₃)₂·2C₅H₅N, has been obtained by reaction of U^IV tri­fluoro­methane­sulfonate with p‐tert‐butyl­tetrahomodioxacalix­[4]­arene in pyridine. The uranyl ion lies on an inversion centre and is bound to two O atoms from each diphenoxide ligand, which gives the usual square‐planar equatorial environment. The zwitterionic diphenoxide species results from nucleophilic attack by pyridine on the benzylic ether C atoms of the homooxacalixarene, assisted by initial U coordination to the ether groups, with subsequent metal oxidation giving the uranyl moiety.