Volumetric and infrared measurements on amorphous ice structure

We have simultaneously used adsorption isotherm volumetry and Fourier transform infrared spectroscopy in order to take the investigations on amorphous ice structure a step further, especially concerning porosity and annealing-induced modifications. We have studied surface reorganization during annealing and found that the number of surface sites decreases before crystallization, their relative ratios being different for amorphous and crystalline ice. We also present results confirming that ice can have a large specific surface area and nevertheless be non-microporous.     

H atom transfer along an ammonia chain: tunneling and mode selectivity in 7-hydroxyquinoline.(NH3)3

Excitation of the 7-hydroxyquinoline(NH(3))(3) [7HQ(NH(3))(3)] cluster to the S(1) (1)pi pi(*) state results in an O-H-->NH(3) hydrogen atom transfer (HAT) reaction. In order to investigate the entrance channel, the vibronic S(1)<-->S(0) spectra of the 7HQ.(NH(3))(3) and the d(2)-7DQ.(ND(3))(3) clusters have been studied by resonant two-photon ionization, UV-UV depletion and fluorescence techniques, and by ab initio calculations for the ground and excited states. For both isotopomers, the low-frequency part of the S(1)<--S(0) spectra is dominated by ammonia-wire deformation and stretching vibrations. Excitation of overtones or combinations of these modes above a threshold of 200-250 cm(-1) for 7HQ.(NH(3))(3) accelerates the HAT reaction by an order of magnitude or more. The d(2)-7DQ.(ND(3))(3) cluster exhibits a more gradual threshold from 300 to 650 cm(-1). For both isotopomers, intermolecular vibrational states above the threshold exhibit faster HAT rates than the intramolecular vibrations. The reactivity, isotope effects, and mode selectivity are interpreted in terms of H atom tunneling through a barrier along the O-H-->NH(3) coordinate. The barrier results from a conical intersection of the optically excited (1)pi pi(*) state with an optically dark (1)pi sigma(*) state. Excitation of the ammonia-wire stretching modes decreases both the quinoline-O-H...NH(3) distance and the energetic separation between the (1)pi pi(*) and (1)pi sigma(*) states, thereby increasing the H atom tunneling rate. The intramolecular vibrations change the H bond distance and modulate the (1)pi pi(*)<-->(1)pi sigma(*) interaction to a much smaller extent.     

Storage impulsive processes in the merging phase space

The storage impulsive processes given by a sum of random variables on a superposition of two renewal processes are considered on increasing time intervals. The averaging, diffusion approximation, and large deviation problem are studied in the series scheme with a small parameter series under suitable scaling.     

Stabilization of the Triphosphallyl Ligand η3‐P3{P(O)H} at Iridium via Alkaline Activation of P4

The selective functionalization of the polyphosphorus moiety Ph₂PCH₂PPh₂PPPP present as a tetrahapto‐ligand in complex [Ir(dppm)(Ph₂PCH₂PPh₂PPPP)]⁺ ( 1 , dppm=Ph₂PCH₂PPh₂) was obtained by reaction of 1 with water under basic conditions at room temperature. The formation of the new triphosphaallyl moiety η³‐P₃{P(O)H} was determined in solution by NMR spectroscopy, and confirmed in the solid state by a single‐crystal X‐ray structure of the stable product [Ir(κ²‐dppm)(κ¹‐dppm)(η³‐P₃{P(O)H})] ( 2 ). In solution, 2 has a fluxional behavior attributable to the four P atoms belonging to the tetraphosphorus moiety in 1 and exhibits a chemical exchange process involving the two PPh₂ moieties of the same bidentate ligand, as determined by 1D and 2D NMR spectroscopy experiments carried out at variable temperature. The mechanism of the reaction was investigated at the DFT level, which suggested a selective attack of an in‐situ generated OH^? anion on one of the non‐coordinated phosphorus atoms of the P₄ moiety. The reaction then evolves through an acid‐assisted tautomerization, which leads to the final compound 2 . Bonding analysis pointed out that the new unsubstituted P₃‐unit in the η³‐P₃{P(O)H} moiety behaves as a triphosphallyl ligand.     

Synthesis and cytotoxicity evaluation of diastereoisomers and N-terminal analogues of tubulysin-U

Tubulysins are potent anti-mitotic natural compounds and a scalable and efficient synthetic route for generation of its analogues has been developed and extended to the synthesis of diastereoisomers and N-terminal analogues of tubulysin-U. Structure–activity-relationship studies on these synthetic analogues reaffirmed the significance of native stereochemistry of tubulysins for optimal biological activity and cytotoxicity. However, while modification of Tup stereochemistry has only minor effect on the tubulysins cytotoxicity, Tuv stereochemistry is critically important and modification of either Tuv stereocentre produced a dramatic drop in cytotoxicity.     

Solid‐state NMR as a tool to describe and quantify the morphology of photoactive layers used in plastic solar cells

The optimization and control of the nanomorphology of thin films used as active layer in bulk heterojunction (BHJ) plastic solar cells is of key importance for a better understanding of the photovoltaic mechanisms and for increasing the device performances. Hereto, solid‐state NMR relaxation experiments have been evaluated to describe the film morphology of one of the “work‐horse” systems poly(2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylene‐vinylene)/[6, 6]‐phenyl‐C₆₁butyric acid methyl ester (MDMO‐PPV/PCBM) in a quantitative way. Attention is focused on the influence of the processing solvent (toluene vs. chlorobenzene), the blend composition, and the casting technique, that is, spin coating versus doctor blading. It is demonstrated that independently of the solvent and casting technique, part of the PCBM becomes phase separated from the mixed phase. Whereas casting from toluene results in the development of well‐defined PCBM crystallites, casting from chlorobenzene leads to the formation of PCBM‐rich domains that contain substructures of weakly organized PCBM nanoclusters. The amount and physico‐chemical state of the phase separated PCBM is quantified by solid‐state NMR relaxation times experiments. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

HPLC determination of plasma taurine

Summary The taurine content in plasma was determined by high performance liquid chromatographic analysis of its dansyl derivative with fluorometric detection. After the reaction with dansyl chloride, the derivative was extracted from an aqueous mixture by using tetrabutylammonium as a counter-ion. The influences of different tetrabutylammonium salts and of the eluent mixture composition were studied. Omotaurine, added as the internal standard to the plasma samples, assured good reproducibility. The procedure was applied to the determination of taurine in specimens from different mammalian species.     

Hyperbranched anatase TiO2 nanocrystals: nonaqueous synthesis, growth mechanism, and exploitation in dye-sensitized solar cells

A colloidal crystal-splitting growth regime has been accessed, in which TiO(2) nanocrystals, selectively trapped in the metastable anatase phase, can evolve to anisotropic shapes with tunable hyperbranched topologies over a broad size interval. The synthetic strategy relies on a nonaqueous sol-gel route involving programmed activation of aminolysis and pyrolysis of titanium carboxylate complexes in hot surfactant media via a simple multi-injection reactant delivery technique. Detailed investigations indicate that the branched objects initially formed upon the aminolysis reaction possess a strained monocrystalline skeleton, while their corresponding larger derivatives grown in the subsequent pyrolysis stage accommodate additional arms crystallographically decoupled from the lattice underneath. The complex evolution of the nanoarchitectures is rationalized within the frame of complementary mechanistic arguments. Thermodynamic pathways, determined by the shape-directing effect of the anatase structure and free-energy changes accompanying branching and anisotropic development, are considered to interplay with kinetic processes, related to diffusion-limited, spatially inhomogeneous monomer fluxes, lattice symmetry breaking at transient Ti(5)O(5) domains, and surfactant-induced stabilization. Finally, as a proof of functionality, the fabrication of dye-sensitized solar cells based on thin-film photoelectrodes that incorporate networked branched nanocrystals with intact crystal structure and geometric features is demonstrated. An energy conversion efficiency of 6.2% has been achieved with standard device configuration, which significantly overcomes the best performance ever approached with previously documented prototypes of split TiO(2) nanostructures. Analysis of the relevant photovoltaic parameters reveals that the utilized branched building blocks indeed offer light-harvesting and charge-collecting properties that can overwhelm detrimental electron losses due to recombination and trapping events.     

Vibrational Behaviour of the CrO3- 4 Anion in Different Crystalline Environments

The powder-infrared spectra of different crystalline compounds containing the tetrahedral Cro^3- ₄, anion have been recorded and analyzed with the aid of the site symmetry rules. In some cases Raman data are also reported. The effect of the different crystalline environments is discussed in detail and comparisons with isostructural phases are also made. A definitive assignment for the internal vibrations of the CrO^3- ₄, ion is proposed and a new set of force constants has been calculated fron a modified valence force field.     

A relation between the binding energy and the band-gap energy in semiconductors of diamond or zinc-blende structure

From an empirical calculation of bond energy, of semiconductors of diamond and zinc-blende structures, and of some wurtzite-type, it is revealed that between the gap energy E_g and single-bond energy E_s there exists a linear correlation which, for the different series of binary semiconductors of tetrahedral coordination taken into consideration here, can be expressed by a relation of the type : E_g = a(E_s−b) where a and b are characteristic constants of the series A^ivA^iv, AⁱⁱⁱB^v,AⁱⁱB^vi. The correlation found for the said semiconductors are not valid for the compounds AⁱB^vii of zinc-blende type structure and for the two oxides ZnO, CdO of wurtzite-type structure. This fact is attributed to the almost completely ionic character of the bond in these compounds, because of which the localization of the electrons along the valence bonds is negligible.