Photodimerization of coumarins in the solid state

Photochemical dimerization of 7-methoxycoumarin occurs in the solid state to give high yields of a syn-head-to-tail dimer although the potentially reactive double bonds are not favourably oriented in the crystal of the monomer.

Photodimerization of olefins in solid state

Photochemical transformations of organic solids provide an exciting area of research with new synthetic possibilities. These reactions are generally governed by topochemical factors rather than the normal rules of chemical reactivity. Defects play a crucial role in some of the reactions. Some of the transformations such as the photodimerization of 4, 4'-dimethoxystilbene occur in a single crystal fashion.

Decomposition of silane on solid P4O10

Silane undergoes thermal decomposition on the surface of “phosphorus pentoxide” ( P4O10) into its elements around 200–400°C. The hydrogen formed partially reduces the P4O10 forming lower oxides of phosphorus and water. Elemental silicon is precipitated as reddish-brown solid, which is separated by dissolving out the phosphorus oxides. Silica and disiloxane are not formed in the reaction.

Ultrafast Switching Time and Third Order Nonlinear Coefficients of Microwave Treated Single Walled Carbon Nanotube Suspensions

Microwave treated water soluble and amide functionalized single walled carbon nanotubes have been investigated using femtosecond degenerate pump-probe and nonlinear transmission experiments. The time resolved differential transmission using 75 femtosecond pulse with the central wavelength of 790 nm shows a bi-exponential ultrafast photo-bleaching with time constants of 160 fs (130 fs) and 920 fs (300 fs) for water soluble (amide functionalized) nanotubes. Open and closed aperture z-scans show saturation absorption and positive (negative) nonlinear refraction for water soluble (amide functionalized) nanotubes. Two photon absorption coefficient, beta(0) similar to 250 cm/GW (650 cm/GW) and nonlinear index, gamma similar to 15 cm(2)/pW (-30 cm(2)/pW) are obtained from the theoretical fit in the saturation limit to the data for two types of nanotubes.

Computational studies on new chemical species in the gas-phase and the solid-state.

There is intense activity in the area of theoretical chemistry of gold. It is now possible to predict new molecular species, and more recently, solids by combining relativistic methodology with isoelectronic thinking. In this thesis we predict a series of solid sheet-type crystals for Group-11 cyanides, MCN (M=Cu, Ag, Au), and Group-2 and 12 carbides MC2 (M=Be-Ba, Zn-Hg). The idea of sheets is then extended to nanostrips which can be bent to nanorings. The bending energies and deformation frequencies can be systematized by treating these molecules as an elastic bodies. In these species Au atoms act as an 'intermolecular glue'. Further suggested molecular species are the new uncongested aurocarbons, and the neutral Au_nHg_m clusters. Many of the suggested species are expected to be stabilized by aurophilic interactions. We also estimate the MP2 basis-set limit of the aurophilicity for the model compounds [ClAuPH_3]_2 and [P(AuPH_3)_4]^+. Beside investigating the size of the basis-set applied, our research confirms that the 19-VE TZVP+2f level, used a decade ago, already produced 74 % of the present aurophilic attraction energy for the [ClAuPH_3]_2 dimer. Likewise we verify the preferred C4v structure for the [P(AuPH_3)_4]^+ cation at the MP2 level. We also perform the first calculation on model aurophilic systems using the SCS-MP2 method and compare the results to high-accuracy CCSD(T) ones. The recently obtained high-resolution microwave spectra on MCN molecules (M=Cu, Ag, Au) provide an excellent testing ground for quantum chemistry. MP2 or CCSD(T) calculations, correlating all 19 valence electrons of Au and including BSSE and SO corrections, are able to give bond lengths to 0.6 pm, or better. Our calculated vibrational frequencies are expected to be better than the currently available experimental estimates. Qualitative evidence for multiple Au-C bonding in triatomic AuCN is also found.

Natural Abundant Solid State NMR Studies in Designed Tripeptides for Differentiation of Multiple Conformers

Solid state NMR (SSNMR) experiments on heteronuclei in natural abundance are described for three synthetically designed tripeptides Piv-(L)Pro_(L)Pro-(L)Phe-OMe (1), Piv-(D)Pro_(L)Pro_(L)Phe-OMe (2), and Piv-(D)Pro_(L)Pro_(L)Phe-NHMe (3). These peptides exist in different conformation as shown by solution state NMR and single crystal X-ray analysis (Chatterjee et al., Chem Eur J 2008, 14, 6192). In this study, SSNMR has been used to probe the conformations of these peptides in their powder form. The C-13 spectrum of peptide (1) showed doubling of resonances corresponding to cis/cis form, unlike in solution where the similar doubling is attributed to cis/trans form. This has been confirmed by the chemical shift differences of C-beta and C-gamma carbon of Proline in peptide (1) both in solution and SSNMR. Peptide (2) and (3) provided single set of resonances which represented all transform across the di-Proline segment. The results are In agreement with the X-ray analysis. Solid state N-15 resonances, especially from Proline residues provided additional information, which is normally not observable in solution state NMR. H-1 chemical shifts are also obtained from a two-dimensional heteronuclear correlation experiment between H-1-C-13. The results confirm the utility of NMR as a useful tool for identifying different conformers in peptides in the solid state. (C) 2009 Wiley Periodicals, Inc. Biopolymers 91: 851-860, 2009.

Mechanoformation of ammonium perchlorate-potassium perchlorate solid solutions

Ammonium perchlorate-potassium perchlorate mixtures, upon pelletization, form a series of homogeneous solid solutions as manifested by X-ray powder diffractograms. Scanning electron microscopic studies throw light on the mechanism of the solid-solution formation. Solid solutions of ammonium perchlorate-potassium perchlorate have also been obtained by a modified cocrystallization technique. The thermal and combustion behavior of the solid solutions have also been studied, using the DTA technique and the Crawford strand burner.

Gas-Solid Reactions: Photochemical Oxidation of Thioketones in the Crystalline State

Photochemical oxidation of 11 diaryl thioketones (1-11) was conducted in the solid state. Quite interestingly, of these only six were oxidized to the corresponding carbonyl compound whereas the rest were photostable. However, in solution all were readily oxidized. The difference in behavior between the thioketones in the solid state has been rationalized on the basis of molecular arrangement in the crystal. X-ray crystal structure analyses of four thioketones were carried out in this connection.

Novel solid hypergolic fuels for hybrid propellants

A new class of compounds, viz., monothiocarbohydrazones, have been found to be hypergolic with anhydrous and red fuming nitric acids. A study of the ignition delays of the various thiocarbohydrazonenitric acid systems as a function of particle size and fuel/oxidizer ratio reveals no significant effect by these parameters. The observed ignition delays have been explained in terms of the chemical reactivity and structure of these compounds.

Spectroscopy and photochemistry of hydrogen peroxide and its complexes in solid rare gases

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Viscoelastic Properties of Nanocrystalline Films of Semiconducting Chalcogenides at Liquid/Liquid Interface

The interfacial shear rheological properties of a continuous single-crystalline film of CuS and a 3D particulate gel of CdS nanoparticles (3−5 nm in diameter) formed at toluene−water interfaces have been studied. The ultrathin films (50 nm in thickness) are formed in situ in the shear cell through a reaction at the toluene−water interface between a metal−organic compound in the organic layer and an appropriate reagent for sulfidation in the aqueous layer. Linear viscoelastic spectra of the nanofilms reveal solid-like rheological behavior with the storage modulus higher than the loss modulus over the range of angular frequencies probed. Large strain amplitude sweep measurements on the CdS nanofilms formed at different reactant concentrations suggest that they form a weakly flocculated gel. Under steady shear, the films exhibit a yield stress, followed by a steady shear thinning at high shear rates. The viscoelastic and flow behavior of these films that are in common with those of many 3D “soft” materials like gels, foams, and concentrated colloidal suspensions can be described by the “soft” glassy rheology model.