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.

Layer-by-layer self-assembly of modified hyaluronic acid/chitosan based on hydrogen bonding

The fabrication of hydrogen bonded polymer self-assembly for drug delivery has been accomplished via layer-by-layer sequential assembly from aqueous solution. In this study, the self-assembly was constructed based on hydrogen bonding between DNA base (adenine and thymine) pairs substituted on the backbone of chitosan and hyaluronic acid. Chitosan was modified with adenine, whereas hyaluronic acid was modified with thymine. Subsequently, these two polymers were sequentially absorbed on flat substrate by taking advantage of interactions of DNA base pairs via hydrogen bonding. Interlayer hydrogen bonding of these two polymers produces stable multilayer film without using any cross-linking agent. Thin film formation on quartz substrate has been monitored with UV-vis spectra and an AFM study. Formation of multilayer hydrogen-bonded thin film has been further confirmed with SEM. Encapsulation and release behavior of the therapeutic drug from the multilayer thin film at different conditions has been illustrated using UV-vis spectra. Cell viability of modified polymers using MTT assay confirmed no cytotoxic effect.

A Convenient Route for the Synthesis of Complex Metal Oxides Employing Solid-Solution Precursors

Synthesis of complex metal oxides by the thermal decomposition of solid-solution precursors (formed by isomorphous compounds of component metals) has been investigated since the method enables mixing of cations on an atomic scale and drastically reduces diffusion distances to a few angstroms. Several interesting oxides such as Ca2Fe03,5C, aCoz04,C a2C0205a, nd Ca,FeCo05 have been prepared by this technique starting from carbonate solid solutions of the type Ca,-,Fe,C03, Cal-,Co,C03, and Ca,-,,M,M'yC03 (M, M' = Mn, Fe, Co). The method has been extended to oxalate solid-solution precursors, and the possibility of making use of other kinds of precursor solid solutions is indicated.

Condensed phase reactions in solid propellants

The paper investigates the cause for the difference between differential scanning calorimetric results and mass spectrometric studies on polystyrene (PS) ammonium perchlorate (AP) propellants as related to the method of preparation of the propellant and the difference in experimental conditions by the use of mass spectrometry. Sufficient time is given for the product sublimates to interact with each other and attain equilibrium. It is shown that the propellant decomposition is a nonadditive phenomenon and that even a physical mixture of AP and PS does not yield additive decomposition products of its components. Results on the identification of a yellow compound containing chlorine in the bulk of the propellant suggest a condensed phase reaction. The occurrence of the reaction in the porous condensed phase of the propellant may explain the larger exothermicity of the propellant compared to the additive heats of decomposition of its components.

Nonlinear mode coupling of surface acoustic waves on an isotropic solid

The nonlinear mode coupling between two co-directional quasi-harmonic Rayleigh surface waves on an isotropic solid is analysed using the method of multiple scales. This procedure yields a system of six semi-linear hyperbolic partial differential equations with the same principal part governing the slow variations in the (complex) amplitudes of the two fundamental, the two second harmonic and the two combination frequency waves at the second stage of the perturbation expansion. A numerical solution of these equations for excitation by monochromatic signals at two arbitrary frequencies, indicates that there is a continuous transfer of energy back and forth among the fundamental, second harmonic and combination frequency waves due to mode coupling. The mode coupling tends to be more pronounced as the frequencies of the interacting waves approach each other.

Nonlinear surface acoustic waves on an isotropic solid

A systematic derivation of the approximate coupled amplitude equations governing the propagation of a quasi-monochromatic Rayleigh surface wave on an isotropic solid is presented, starting from the non-linear governing differential equations and the non-linear free-surface boundary conditions, using the method of mulitple scales. An explicit solution of these equations for a signalling problem is obtained in terms of hyperbolic functions. In the case of monochromatic excitation, it is shown that the second harmonic amplitude grows initially at the expense of the fundamental and that the amplitudes of the fundamental and second harmonic remain bounded for all time.

Thermal Decomposition of hydrazinium monoperchlorate in the solid state

Hydrazinium monoperchlorate (HP-1) has been shown to decompose thermally in the solid state according to the chemical equation: 5N2H5CIO4 = 4NH4CIO4+1HCI+3N2+4H2O The activation energy for the evolution of HCl as determined mass spectrometrically is 8.05 kcal mol−1 in the temperature range of 80 to 120°C. The rate of decomposition is seen to be altered by doping HP-1 with small concentrations of SO2−4, Ca2+ and Al3+.

Storage stability of solid rocket fuels. 2. Effect of oxidizer loadings

Ageing behaviour, leading to ballistic changes, has been studied as a function of oxidizer loading in polystyrene/ammonium perchlorate solid-propellants. The ageing studies were carried out at 100 °C in air. Change in burning rate decreased as the oxidizer loading increased from 75 to 80%. The change in thermal decomposition rates both at 230 and 260 °C also decreased as the oxidizer loading in the propellants increased. The shapes of the plots of the changes in burning rate and thermal decomposition rate (230 and 260 °C) at different storage times for different oxidizer-loaded propellants seem to be exactly similar. These results lead to the conclusion that the thermal decomposition of the propellant may be responsible for bringing about the ballistic changes during the ageing process. Infrared studies of the binder portion of the aged propellant indicate that peroxide formation takes place during the course of ageing and that peroxide formation for a particular storage time and temperature increases as the loading decreases.

Conformationally Restricted Nucleocyclitols: a Study into their Conformational Preferences and Supramolecular Architecture in the Solid State

With the intent of probing the feasibility of employing annulation as a tactic to engender axial rich conformations in nucleoside analogues, two adenine-derived, ``conformationally restricted'' nucleocylitols, 9 and 10, have been conceptualized as representatives of a hitherto unexplored class of nucleic acid base-cyclitol hybrids. A general synthetic strategy, with an inherent scope for diversification, allowed rapid functionalization of indane and tetralin to furnish 9 and 10 respectively in fair yield. Single-crystal X-ray diffraction analysis revealed that the two nucleocyclitols under study, though homologous, present completely dissimilar modes of molecular packing, marked, in particular, by the nature of involvement of the adenynyl NH2 group in the supramolecular assembly. In addition, the crystal structures of 9 and 10 also exhibit two different conformations of the functionalized cyclohexane ring. Thus, while the six-membered carbocycle in cyclopenta-annulated 9 exists in the expected chair (C) conformation that in cyclohexaannulated 10, which crystallizes as a dihydrate, shows an unusual twist-boat (TB) conformation. From a close analysis of the (HNMR)-H-1 spectroscopic data recorded for 9 and 10 in CD3OD, it was possible to put forth a putative explanation for the uncanny conformational preferences of crystalline 9 and 10.

Review of continuum, finite element and hybrid techniques in the analysis of stress concentrations in structures

When a uniform flow of any nature is interrupted, the readjustment of the flow results in concentrations and rare-factions, so that the peak value of the flow parameter will be higher than that which an elementary computation would suggest. When stress flow in a structure is interrupted, there are stress concentrations. These are generally localized and often large, in relation to the values indicated by simple equilibrium calculations. With the advent of the industrial revolution, dynamic and repeated loading of materials had become commonplace in engine parts and fast moving vehicles of locomotion. This led to serious fatigue failures arising from stress concentrations. Also, many metal forming processes, fabrication techniques and weak-link type safety systems benefit substantially from the intelligent use or avoidance, as appropriate, of stress concentrations. As a result, in the last 80 years, the study and and evaluation of stress concentrations has been a primary objective in the study of solid mechanics. Exact mathematical analysis of stress concentrations in finite bodies presents considerable difficulty for all but a few problems of infinite fields, concentric annuli and the like, treated under the presumption of small deformation, linear elasticity. A whole series of techniques have been developed to deal with different classes of shapes and domains, causes and sources of concentration, material behaviour, phenomenological formulation, etc. These include real and complex functions, conformal mapping, transform techniques, integral equations, finite differences and relaxation, and, more recently, the finite element methods. With the advent of large high speed computers, development of finite element concepts and a good understanding of functional analysis, it is now, in principle, possible to obtain with economy satisfactory solutions to a whole range of concentration problems by intelligently combining theory and computer application. An example is the hybridization of continuum concepts with computer based finite element formulations. This new situation also makes possible a more direct approach to the problem of design which is the primary purpose of most engineering analyses. The trend would appear to be clear: the computer will shape the theory, analysis and design.