Molecular dynamics and simulations study on the vibrational and electronic solvatochromism of benzophenone

Solvent plays a key role in diverse physico-chemical and biological processes. Therefore, understanding solute-solvent interactions at the molecular level of detail is of utmost importance. A comprehensive solvatochromic analysis of benzophenone (Bzp) was carried out in various solvents using Raman and electronic spectroscopy, in conjunction with Density Functional Theory (DFT) calculations of supramolecular solute-solvent clusters generated using classical Molecular Dynamics Simulations (c-MDSs). The >C=O stretching frequency undergoes a bathochromic shift with solvent polarity. Interestingly, in protic solvents this peak appears as a doublet: c-MDS and ad hoc explicit solvent ab initio calculations suggest that the lower and higher frequency peaks are associated with the hydrogen bonded and dangling carbonyl group of Bzp, respectively. Additionally, the dangling carbonyl in methanol (MeOH) solvent is 4 cm(-1) blue-shifted relative to acetonitrile solvent, despite their similar dipolarity/polarizability. This suggests that the cybotactic region of the dangling carbonyl group in MeOH is very different from its bulk solvent structure. Therefore, we propose that this blue-shift of the dangling carbonyl originates in the hydrophobic solvation shell around it resulting from extended hydrogen bonding network of the protic solvents. Furthermore, the 1(1)n pi* (band I) and 1(1)pi pi* (band II) electronic transitions show a hypsochromic and bathochromic shift, respectively. In particular, these shifts in protic solvents are due to differences in their excited state-hydrogen bonding mechanisms. Additionally, a linear relationship is obtained for band I and the >C=O stretching frequency (cm(-1)), which suggests that the different excitation wavelengths in band I correspond to different solvation states. Therefore, we hypothesize that the variation in excitation wavelengths in band I could arise from different solvation states leading to varying solvation dynamics. This will have implications for ultrafast processes associated with electron-transfer, charge transfer, and also the photophysical aspects of excited states. (C) 2016 AIP Publishing LLC.

New insight into the architecture of oxy-anion pocket in unliganded conformation of GAT domains: A MD-simulation study

Human Guanine Monophosphate Synthetase (hGMPS) converts XMP to GMP, and acts as a bifunctional enzyme with N-terminal ``glutaminase'' (GAT) and C-terminal ``synthetase'' domain. The enzyme is identified as a potential target for anticancer and immunosuppressive therapies. GAT domain of enzyme plays central role in metabolism, and contains conserved catalytic residues Cys104, His190, and Glu192. MD simulation studies on GAT domain suggest that position of oxyanion in unliganded conformation is occupied by one conserved water molecule (W1), which also stabilizes that pocket. This position is occupied by a negatively charged atom of the substrate or ligand in ligand bound crystal structures. In fact, MD simulation study of Ser75 to Val indicates that W1 conserved water molecule is stabilized by Ser75, while Thr152, and His190 also act as anchor residues to maintain appropriate architecture of oxyanion pocket through water mediated H-bond interactions. Possibly, four conserved water molecules stabilize oxyanion hole in unliganded state, but they vacate these positions when the enzyme (hGMPS)-substrate complex is formed. Thus this study not only reveals functionally important role of conserved water molecules in GAT domain, but also highlights essential role of other non-catalytic residues such as Ser75 and Thr152 in this enzymatic domain. The results from this computational study could be of interest to experimental community and provide a testable hypothesis for experimental validation. Conserved sites of water molecules near and at oxyanion hole highlight structural importance of water molecules and suggest a rethink of the conventional definition of chemical geometry of inhibitor binding site.

Triplet excited electronic state switching induced by hydrogen bonding: A transient absorption spectroscopy and time-dependent DFT study

The solvent plays a decisive role in the photochemistry and photophysics of aromatic ketones. Xanthone (XT) is one such aromatic ketone and its triplet-triplet (T-T) absorption spectra show intriguing solvatochromic behavior. Also, the reactivity of XT towards H-atom abstraction shows an unprecedented decrease in protic solvents relative to aprotic solvents. Therefore, a comprehensive solvatochromic analysis of the triplet-triplet absorption spectra of XT was carried out in conjunction with time dependent density functional theory using the ad hoc explicit solvent model approach. A detailed solvatochromic analysis of the T-T absorption bands of XT suggests that the hydrogen bonding interactions are different in the corresponding triplet excited states. Furthermore, the contributions of non-specific and hydrogen bonding interactions towards differential solvation of the triplet states in protic solvents were found to be of equal magnitude. The frontier molecular orbital and electron density difference analysis of the T-1 and T-2 states of XT indicates that the charge redistribution in these states leads to intermolecular hydrogen bond strengthening and weakening, respectively, relative to the S-0 state. This is further supported by the vertical excitation energy calculations of the XT-methanol supra-molecular complex. The intermolecular hydrogen bonding potential energy curves obtained for this complex in the S-0, T-1, and T-2 states support the model. In summary, we propose that the different hydrogen bonding mechanisms exhibited by the two lowest triplet excited states of XT result in a decreasing role of the n pi* triplet state, and are thus responsible for its reduced reactivity towards H-atom abstraction in protic solvents. (C) 2016 AIP Publishing LLC.

Low-temperature growth of carbon nanotubes by plasma-enhanced chemical vapor deposition

Vertically aligned carbon nanotubes were grown at temperatures as low as 120degreesC by plasma-enhanced chemical vapor deposition. A systematic study of the temperature dependence of the growth rate and the structure of the as-grown nanotubes is presented using a C2H2/NH3 system and nickel as the catalyst. The activation energy for the growth rate was found to be 0.23 eV, much less than for thermal chemical vapor deposition (1.2-1.5 eV). This suggests growth occurs by surface diffusion of carbon on nickel. The result could allow direct growth of nanotubes onto low-temperature substrates like plastics, and facilitate the integration in sensitive nanoelectronic devices. (C) 2003 American Institute of Physics.

Effects of pre-treatment and plasma enhancement on chemical vapor deposition of carbon nanotubes from ultra-thin catalyst films

We report a detailed study of surface-bound chemical vapor deposition of carbon nanotubes and nanofibers from evaporated transition metal catalysts exposed to ammonia diluted acetylene. We show that a reduction of the Fe/Co catalyst film thickness below 3 nm results into a transition from large diameter (> 40 nm), bamboo-like nanofibers to small diameter (similar to 5 nm) multi-walled carbon nanotubes. The nanostructuring of ultrathin catalyst films critically depends on the gas atmosphere, with the resulting island distribution initiating the carbon nucleation. Compared to purely thermal chemical vapor deposition, we find that, for small diameter nanotube growth, DC plasma assistance is detrimental to graphitization and sample homogeneity and cannot prevent an early catalyst poisoning. (c) 2006 Elsevier B.V. All rights reserved.

Nano-Tribological Study on a Super-Hydrophobic Film Formed on Rough Aluminum

A novel super-hydrophobic stearic acid (STA) film with a water contact angle of 166° was prepared by chemical adsorption on aluminum wafer coated with polyethyleneimine (PEI) film. The micro-tribological behavior of the super-hydrophobic STA monolayer was compared with that of the polished and PEI-coated Al surfaces. The effect of relative humidity on the adhesion and friction was investigated as well. It was found that the STA monolayer showed decreased friction, while the adhesive force was greatly decreased by increasing the surface roughness of the Al wafer to reduce the contact area between the atomic force microscope (AFM) tip and the sample surface to be tested. Thus the friction and adhesion of the Al wafer was effectively decreased by generating the STA monolayer, which indicated that it could be feasible and rational to prepare a surface with good adhesion resistance and lubricity by properly controlling the surface morphology and the chemical composition. Both the adhesion and friction decreased as the relative humidity was lowered from 65% to 10%, though the decrease extent became insignificant for the STA monolayer.

Micro- and macro-tribological study on a self-assembled dual-layer film

A novel self-assembled dual-layer film as apotential excellent lubricant for micromachines was successfully prepared on single-crystal silicon substrate by chemical adsorption of stearic acid (STA) molecules on self-assembled monolayer of 3-aminopropyltri

Chemical kinetics and self-ignition in a model supersonic hydrogen-air combustor

Self-ignition tests of a model scramjet combustor were conducted by using parallel sonic injection of gaseous hydrogen from the base of a blade-like strut into a supersonic vitiated airstream. The range of stagnation pressure and temperature studied varied from 1.0 to 4.5 MPa and from 1300 to 2200 K, respectively. Experimental results show that the self-ignition limit, in terms of either global or local quantities of pressure and temperature, exhibits a nonmonotonic behavior resembling the classical homogeneous explosion limit of the hydrogen-oxygen system. Specifically, for a given temperature, increasing pressure from a low value can render a nonignitable mixture to first become ignitable, then nonignitable again, This correspondence shows that, despite the globally supersonic nonpremixed configuration studied herein, ignition is strongly influenced by the intricate chemical reaction mechanism and thereby exhibits the homogeneous explosion character. Consequently, self-ignition criteria based on a global reaction rate approximating the complex chemistry are inadequate. An auxiliary computational study on counterflow ignition was also conducted to systematically investigate the contamination effects of vitiated air. Results indicate that the net contamination effects for the present experimental data are expected to be substantially smaller than contributions from the individual contamination species because of the counterbalancing influences of the H2O-inhibition and NO-promotion reactions in effecting ignition.

Study of multi-walled carbon nanotube structures fabricated by PMMA suspended dispersion

We report on the electrical characteristics of plasma enhanced chemical vapour deposition (PECVD)-grown, multi-walled carbon nanotube (MWCNT) devices made by a new fabrication method, PMMA suspended dispersion. This method makes it possible to suspend nanotubes between metal electrodes and to remove unwanted nanotubes from the substrate. The measurements show that the MWCNTs are metallic and able to maintain a current density ∼2×106 A/cm2 for more than 15 days with a maximum current density of ∼1.8×107 A/cm2. This high current density and reliability will make PECVD-grown MWCNTs applicable to field emission cathodes. © 2002 Elsevier Science B.V. All rights reserved.

Quantum Monte Carlo study of the CO interaction with a dimer model surface for Cr(110)

The chemisorption of CO on a Cr( 110) surface is investigated using the quantum Monte Carlo method in the diffusion Monte Carlo (DMC) variant and a model Cr2CO cluster. The present results are consistent with the earlier ab initio HF study with this model that showed the tilted/ near-parallel orientation as energetically favoured over the perpendicular arrangement. The DMC energy difference between the two orientations is larger (1.9 eV) than that computed in the previous study. The distribution and reorganization of electrons during CO adsorption on the model surface are analysed using the topological electron localization function method that yields electron populations, charge transfer and clear insight on the chemical bonding that occurs with CO adsorption and dissociation on the model surface.

Shock tube study of JP-10 ignition delay time

JP-10 (exo-tetrahydrodicyclopentadiene, C10H16) ignition delay times were measured in a preheated shock tube. The vapor pressures of the JP-10 were measured directly by using a high-precision vacuum gauge, to remedy the difficulty in determining the gaseous concentrations of heavy hydrocarbon fuel arising from the adsorption on the wall in shock tube experiments. The whole variation of pressure and emission of the OH or CH radicals were observed in the ignition process by a pressure transducer and a photomultiplier with a monochromator. The emission of the OH or CH radicals was used to identify the time to ignition. Experiments were performed over the pressure range of 151-556 kPa, temperature range of 1000-2100 K, fuel concentrations of 0.1%-0.55% mole fraction, and stoichiometric ratios of 0.25, 0.5, 1.0 and 2.0. The experimental results show that for the lower and higher temperature ranges, there are different dependency relationships of the ignition time on the temperature and the concentrations of JP-10 and oxygen.

Numerical analysis of spatial evolution of the small signal gain in a chemical oxygen-iodine laser operating without primary buffer gas

A chemical oxygen iodine laser (COIL) that operates without primary buffer gas has become a new way of facilitating the compact integration of laser systems. To clarify the properties of spatial gain distribution, three-dimensional (3-D) computational fluid dynamics (CFD) technology was used to study the mixing and reactive flow in a COIL nozzle with an interleaving jet configuration in the supersonic section. The results show that the molecular iodine fraction in the secondary flow has a notable effect on the spatial distribution of the small signal gain. The rich iodine condition produces some negative gain regions along the jet trajectory, while the lean iodine condition slows down the development of the gain in the streamwise direction. It is also found that the new configuration of an interleaving jet helps form a reasonable gain field under appropriate operation conditions. (c) 2007 Elsevier Ltd. All rights reserved.

A new dynamic model for study of dislocation pattern formation

Based on the principle given in nonlinear diffusion-reaction dynamics, a new dynamic model for dislocation patterning is proposed by introducing a relaxation time to the relation between dislocation density and dislocation flux. The so-called chemical potential like quantities, which appear in the model can be derived from variation principle for free energy functional of dislocated media, where the free energy density function is expressed in terms of not only the dislocation density itself but also their spatial gradients. The Linear stability analysis on the governing equations of a simple dislocation density shows that there exists an intrinsic wave number leading to bifurcation of space structure of dislocation density. At the same time, the numerical results also demonstrate the coexistence and transition between different dislocation patterns.

Chemical recycling of municipal packaging waste by pyrolysis

[EN]The present doctoral thesis centers on studying pyrolysis as a chemical recycling technique for rejected packaging waste fractions coming from separation and sorting plants. The pyrolysis experiments have been carried out in a lab-scale installation equipped with a 3.5 L semi-batch reactor and a condensation and collection system for the liquids and gases generated. In the present thesis, an experimental study on the conventional pyrolysis process applied to the aforementioned waste fractions has been conducted, as well as the study of non-conventional or advanced pyrolysis processes such as catalytic and stepwise pyrolysis. The study of the operating parameters has been carried out using a mixed plastics simulated sample, the composition of which is similar to that found in real fractions, and subsequently the optimized process has been applied to real packaging waste. An exhaustive characterization of the solids, liquids and gases obtained in the process has been made after each experiment and their potential uses have been established. Finally, an empirical model that will predict the pyrolysis yields (% organic liquid, % aqueous liquid, % gases, % char, % inorganic solid) as a function of the composition of the initial sample has been developed. As a result of the experimental work done, the requirements have been established for an industrial packaging waste pyrolysis plant that aims to be sufficiently versatile as to generate useful products regardless of the nature of the raw material.