Structures of [M(Ura‐H)(H2O)n]+ (M = Mg,Ca, Sr,Ba; n = 1–3) complexes in the gas phase by IRMPD spectroscopy and theoretical studies

The structures of singly and doubly (and for Mg, triply) hydrated group 2 metal dications bound to deprotonated uracil were explored in the gas phase using infrared multiple photon dissociation spectroscopy in the mid‐infrared region (1000–1900 cm^?1) and the O–H/N–H stretching region (2700–3800 cm^?1) in a Fourier transform ion cyclotron resonance mass spectrometer. The infrared multiple photon dissociation spectra were then compared with the computed IR spectra for various isomers. Calculations were performed using B3LYP with the 6‐31 + G(d,p) basis set for all atoms except Ba²⁺ and Sr²⁺, for which the LANL2DZ or the def2‐TZVPP basis sets with relativistic core potentials were used. Atoms‐in‐molecules analysis was conducted for all lowest energy structures. The lowest energy isomers in all cases are those in which the one uracil is deprotonated at the N3 position, and the metal is coordinated to the N3 and O4 of uracil. Regardless of the degree of solvation, all water molecules are bound to the metal ion and participate in a hydrogen bond with a carbonyl of the uracil moiety. Copyright © 2016 John Wiley & Sons, Ltd.     

Discotic liquid crystals: a new generation of organic semiconductors

Discotic (disc-like) molecules typically comprising a rigid aromatic core and flexible peripheral chains have been attracting growing interest because of their fundamental importance as model systems for the study of charge and energy transport and due to the possibilities of their application in organic electronic devices. This critical review covers various aspects of recent research on discotic liquid crystals, in particular, molecular design concepts, supramolecular structure, processing into ordered thin films and fabrication of electronic devices. The chemical structure of the conjugated core of discotic molecules governs, to a large extent, their intramolecular electronic properties. Variation of the peripheral flexible chains and of the aromatic core is decisive for the tuning of self-assembly in solution and in bulk. Supramolecular organization of discotic molecules can be effectively controlled by the choice of the processing methods. In particular, approaches to obtain suitable macroscopic orientations of columnar superstructures on surfaces, that is, planar uniaxial or homeotropic alignment, are discussed together with appropriate processing techniques. Finally, an overview of charge transport in discotic materials and their application in optoelectronic devices is given.     

Structure and orientation changes of omega- and gamma-gliadins at the air-water interface: a PM-IRRAS spectroscopy and Brewster angle microscopy study

Microscopic and molecular structures of omega- and gamma-gliadin monolayers at the air-water interface were studied under compression by three complementary techniques: compression isotherms, polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS), and Brewster angle microscopy (BAM). For high molecular areas, gliadin films are homogeneous, and a flat orientation of secondary structures relative to the interface is observed. With increasing compression, the nature and orientation of secondary structures changed to minimize the interfacial area. The gamma-gliadin film is the most stable at the air-water interface; its interfacial volume is constant with increasing compression, contrary to omega-gliadin films whose molecules are forced out of the interface. gamma-Gliadin stability at a high level of compression is interpreted by a stacking model.     

Polyethylene glycol adsorption on silica: from bulk phase behavior to surface phase diagram

A characterization of the bulk-phase diagram from literature data and new NMR and DSC measurements provided us with valuable elements that are helpful for gaining, from aqueous solution, better insight into the surface behavior of polyethylene glycol on Aerosil 200. Adsorption isotherms built further to measurements by a depletion method showed a strong and temperature-dependent variation of the isotherm shape in agreement with the variations of interactions already evidenced in the bulk. In temperature-concentration areas, where water is behaving as a helix-promoting solvent, the finding of positive PEG adsorptions and stairlike isotherms agrees with observations reported in the literature. We identified some of the vertical parts as corresponding to the formation of monolayers of helix-shaped PEG molecules. In poor-solvent zones, adsorptions were null or negative, and the isotherms exhibited oscillations suggesting very different surface behavior. Our data analysis evidenced the presence of a much greater amount of water than in the previous surface states; however, the similar analysis of PEG behavior remains relevant. Indeed, the occurrence of first-order transitions in the surface layer implies some water reorganization, permitting the PEG molecules to move closer to the surface and become helix-shaped to rearrange in a monolayer. The surface phase diagram confirmed this analysis in a very satisfying way.     

Atomic force microscopy of microbial cells: application to nanomechanical properties, surface forces and molecular recognition forces

In recent years, the physical properties and interaction forces of microbial cell surfaces have been extensively studied using atomic force microscopy (AFM). A variety of AFM force spectroscopy approaches have been developed for investigating native cell surfaces with piconewton (nanonewton) sensitivity and nanometer lateral resolution, providing novel information on the nanomechanical properties of cell walls, on surface forces such as van der Waals and electrostatic forces, solvation and steric/bridging forces, and on the forces and localization of molecular recognition events. The intention of this article is to survey these different applications and to discuss related methodologies (how to prepare tips and samples, how to record and interpret force curves).     

2,2'-Biphosphinines and 2,2'-bipyridines in homoleptic dianionic Group 4 complexes and neutral 2,2'-biphosphinine Group 6 d(6) metal complexes: octahedral versus trigonal-prismatic geometries

The geometric and electronic structure of formally d(6) tris-biphosphinine [M(bp)(3)](q) and tris-bipyridine [M(bpy)(3)](q) complexes were studied by means of DFT calculations with the B3LYP functional. In agreement with the available experimental data, Group 4 dianionic [M(bp)(3)](2-) complexes (1P-3P for M=Ti, Zr, and Hf, respectively) adopt a trigonal-prismatic (TP) structure, whereas the geometry of their nitrogen analogues [M(bpy)(3)](2-) (1N-3N) is nearly octahedral (OC), although a secondary minimum was found for the TP structures (1N'-3N'). The electronic factors at work in these systems are discussed by means of an MO analysis of the minima, MO correlation diagrams, and thermodynamic cycles connecting the octahedral and trigonal-prismatic limits. In all these complexes, pronounced electron transfer from the metal center to the lowest lying pi* ligand orbitals makes the d(6) electron count purely formal. However, it is shown that the bp and bpy ligands accommodate the release of electron density from the metal in different ways because of a change in the localization of the HOMO, which is a mainly metal-centered orbital in bp complexes and a pure pi* ligand orbital in bpy complexes. The energetic evolution of the HOMO allows a simple rationalization of the progressive change from the TP to the OC structure on successive oxidation of the [Zr(bp)(3)](2-) complex, a trend in agreement with the experimental structure of the monoanionic complex. The geometry of Group 6 neutral complexes [M(bp)(3)] (4P and 5P for M=Mo and W, respectively) is found to be intermediate between the TP and OC limits, as previously shown experimentally for the tungsten complex. The electron transfer from the metal center to the lowest lying pi* ligand orbitals is found to be significantly smaller than for the Group 4 dianionic analogues. The geometrical change between [Zr(bp)(3)](2-) and [W(bp)(3)] is analyzed by means of a thermodynamic cycle and it is shown that a larger ligand-ligand repulsion plays an important role in favoring the distortion of the tungsten complex away from the TP structure.     

Synthesis and biological evaluation of indoloquinolines and pyridocarbazoles: a new example of unexpected photoreduction accompanying photocyclization

Indoloquinoline alkaloid cryptolepine and pyridocarbazole alkaloid ellipticine are of great interest because in vitro and in vivo studies revealed their good cytotoxic properties. In order to obtain some biologically active analogs of these compounds, we developed a synthesis based on the photocyclization of tertiary N-substituted enaminones derived from 1,3-cyclohexandione and 3 or 6-aminoquinoline. The angular cyclized compounds thus obtained were tested in vitro on K 562 cells and A 2780 doxorubicin sensitive and resistant cells. All compounds were less effective than doxorubicin in sensitive cells but their activity wasn't decreased by MDR resistance.     

Thermal and electrochemically assisted Pd-Cl bond cleavage in the d9-d9 Pd2dppm2Cl2 complex by Pd3 dppm3COn+ clusters (n = 2, 1, 0)

A new aspect of reactivity of the cluster [Pd3(dppm)3(micro3-CO)]n+, ([Pd3]n+, n = 2, 1, 0) with the low-valent metal-metal-bonded Pd2(dppm)2Cl2 dimer (Pd2Cl2) was observed using electrochemical techniques. The direct reaction between [Pd3]2+ and Pd2Cl2 in THF at room temperature leads to the known [Pd3(dppm)3(micro3-CO)(Cl)]+ ([Pd3(Cl)]+) adduct and the monocationic species Pd2(dppm)2Cl+ (very likely as Pd2(dppm)2(Cl)(THF)+, [Pd2Cl]+) as unambiguously demonstrated by UV-vis and 31P NMR spectroscopy. In this case, [Pd3]2+ acts as a strong Lewis acid toward the labile Cl- ion, which weakly dissociates from Pd2Cl2 (i.e., dissociative mechanism). Host-guest interactions between [Pd3]2+ and Pd2Cl2 seem unlikely on the basis of computer modeling because of the strong screening of the Pd-Cl fragment by the Ph-dppm groups in Pd2Cl2. The electrogenerated clusters [Pd3]+ and [Pd3]0 also react with Pd2Cl2 to unexpectedly form the same oxidized adduct, [Pd3(Cl)]+, despite the known very low affinity of [Pd3]+ and [Pd3]0 toward Cl- ions. The reduced biproduct in this case is the highly reactive zerovalent species "Pd2(dppm)2" or "Pd(dppm)" as demonstrated by quenching with CDCl3 (forming the well-known complex Pd(dppm)Cl2) or in presence of dppm (forming the known Pd2(dppm)3 d10-d10 dimer). To bring these halide-electron exchange reactions to completion for [Pd3]+ and [Pd3]0, 0.5 and 1.0 equiv of Pd2Cl2 are necessary, respectively, accounting perfectly for the number of exchanged electrons. The presence of a partial dissociation of Pd2Cl2 into the Cl- ion and the monocation [Pd2Cl]+, which is easier to reduce than Pd2Cl2, is suggested to explain the overall electrochemical results. It is possible to regulate the nature of the species formed from Pd2Cl2 by changing the state of charge of the title cluster.     

PEG400 novel phase description in water

The behavior of hydroxyl-terminated PEG400 in water was investigated by surface tension measurements and 13C NMR as a function of concentration and temperature. PEG400 exhibited a critical aggregative concentration (cac) that evidenced both its amphiphilic character and its aggregation capacity. Moreover, the chemical shifts of the different carbons of the PEG were followed by NMR versus concentration at various temperatures. We observed a plateau between 20 and 35 degrees C at concentrations above 0.2 mol L(-1) and ascribed it to the aggregation process. A good correlation was found between the NMR spectra in the region of aggregation and the cac region in the phase diagram. Our investigations were also focused on the solid-liquid region of the phase diagram at lower temperatures. These experimental data, together with conclusions available in the literature, led us to propose explanations for the conformation/hydration/aggregation in the PEG400-water solutions phenomena.