Recognition of Polycyclic Aromatic Hydrocarbons and Their Derivatives by the 1,3-Dinaphthalimide Conjugate of Calix4]arene: Emission, Absorption, Crystal Structures, and Computational Studies

Polycyclic aromatic hydrocarbons (PAHs) are environmental pollutants as well as well-known carcinogens. Therefore, it is important to develop an effective receptor for the detection and quantification of such molecules in solution. In view of this, a 1,3-dinaphthalimide derivative of calix4]arene (L) has been synthesized and characterized, and the structure has been established by single crystal XRD. In the crystal lattice, intermolecular arm-to-arm pi center dot center dot center dot pi overlap dominates and thus L becomes a promising receptor for providing interactions with the aromatic species in solution, which can be monitored by following the changes that occur in its fluorescence and absorption spectra. On the basis of the solution studies carried out with about 17 derivatives of the aromatic guest molecular systems, it may be concluded that the changes that occur in the fluorescence intensity seem to be proportional to the number of aromatic rings present and thus proportional to the extent of pi center dot center dot center dot pi interaction present between the naphthalimide moieties and the aromatic portion of the guest molecule. Though the nonaromatic portion of the guest species affects the fluorescence quenching, the trend is still based on the number of rings present in these. Four guest aldehydes are bound to L with K-ass of 2000-6000 M-1 and their minimum detection limit is in the range of 8-35 mu M. The crystal structure of a naphthaldehyde complex, L.2b, exhibits intermolecular arm-to-arm as well as arm-to-naphthaldehyde pi center dot center dot center dot pi interactions. Molecular dynamics studies of L carried out in the presence of aromatic aldehydes under vacuum as well as in acetonitrile resulted in exhibiting interactions observed in the solid state and hence the changes observed in the fluorescence and absorption spectra are attributable for such interactions. Complex formation has also been delineated through ESI MS studies. Thus L is a promising receptor that can recognize PAHs by providing spectral changes proportional to the aromatic conjugation of the guest and the extent of aromatic pi center dot center dot center dot pi interactions present between L and the guest.

Importance of orientational rearrangement during vitrification of hydrocarbons: dependence on molecular shape

On the basis of Monte Carlo calculations of 2,2-dimethylpropane (neopentane), n-pentane, and 2,2-dimethylbutane (neohexane) at several temperatures, thermodynamic properties and radial distribution functions as well as dimerization and bonding energy distribution functions are reported for both liquid and glassy states. Changes in the radial distribution functions on cooling depend on whether the groups are accessible (peripheral) or inaccessible. Peaks in the radial distribution functions corresponding to peripheral groups do not shift to lower distances on cooling and at times display a large increase in the intensity of the first peak. The peaks due to inaccessible groups, on the other hand, shift to lower distances on cooling. The magnitude of the reorientational contribution in determining the resulting structure of the glass is estimated for the different hydrocarbon molecules investigated. The reorientational contribution is highest for neopentane (26%) followed by isopentane (24%), neohexane (22%), and n-pentane (0%). It appears that molecular geometry has an important role in determining the magnitude of the reorientational contribution to the structure of the glass.

Molecular Dynamics Simulations of Orientational Relaxation in Dipolar Lattice: Lack of Diffusive Decay for Second and Higher Rank Correlation Functions

Extensive molecular dynamics simulations have been carried out to calculate the orientational correlation functions Cl(t), G(t) = [4n/(21 + l)]Ci=-l (Y*lm(sZ(0)) Ylm(Q(t))) (where Y,,(Q) are the spherical harmonics) of point dipoles in a cubic lattice. The decay of Cl(t) is found to be strikingly different from higher l-correlation functions-the latter do not exhibit diffusive dynamics even in the long time. Both the cumulant expansion expression of Lynden-Bell and the conventional memory function equation provide very good description of the Cl(t) in the short time but fail to reproduce the observed slow, long time decay of c1 (t) .

Higher twist and higher order contributions to the pion electromagnetic form factor

The O(m(pi)4/(m(u) + (d))2Q2) and O(alpha(S)2) corrections to the leading term of the perturbative QCD calculation of the pion electromagnetic form factor are examined numerically. Both sets of terms provide significant corrections for values of Q2 between 1 and 15 GeV2/c2.

Temperature-programmed desorption and surface reaction of thiophene over co-mo/.gamma.-Al2O3 hydrodesulfurization catalysts

The temperature-programmed desorption (TPD) and temperature-programmed surface reaction (TPSR) of thiophene over a series of Co-Mo/gamma-Al2O3, hydrodesulfurization (HDS) catalysts with varying Co to Mo ratios have been studied with the objective of understanding the promotional role of Co in the HDS reaction. As part of the study, the desorptions (TPD) and hydrogenations (TPSR) of butane, butene, and butadiene over these catalysts have also been investigated. The TPD of the hydrocarbons over catalysts containing no Co showed a single desorption profile while incorporation of Co created an additional site, with higher heats of desorption, without significantly affecting desorption from the original site. The TPSR measurements showed that the two sites had separate and independent activity for the hydrogenation of the C-4 hydrocarbons. The TPD of thiophene over catalysts with varying Co to Mo ratios showed a single desorption profile with identical heats of desorption, implying that Co does not affect or influence the adsorption sites for thiophene. The TPSR of the HDS of thiophene, however, showed that, although the products of the HDS reaction-butane, butene, and H2S-are the same irrespective of the Co content, the temperature profiles and the activation barriers for the formation of these species show considerable change with the Co/Co+Mo ratio. The results are discussed in light of the existing models for the promotional role of Co in the HDS reaction.

FIR system identification based on subspaces of a higher order cumulant matrix

A new linear algebraic approach for identification of a nonminimum phase FIR system of known order using only higher order (>2) cumulants of the output process is proposed. It is first shown that a matrix formed from a set of cumulants of arbitrary order can be expressed as a product of structured matrices. The subspaces of this matrix are then used to obtain the parameters of the FIR system using a set of linear equations. Theoretical analysis and numerical simulation studies are presented to characterize the performance of the proposed methods.

Oxidation of substituted benzylic hydrocarbons and naphthalenes by peroxydisulphate in the presence of metal ions

Oxidations of various substituted benzylic hydrocarbons with peroxydisulphate in the presence of metal ion catalysts like iron, nickel, copper, cobalt, silver and cerium were examined. Among the metal ions copper (II) catalysed reaction gives products in excellent yield, whereas oxidation of naphthalene and substituted naphthalenes gives low to moderate yield of the products with peroxydisulphate- copper (II).

Production of biosurfactant “Biosur-Pm” by Pseudomonas maltophila CSV89: characterization and role in hydrocarbon uptake

Pseudomonas maltophilia CSV89, a soil bacterium, produces an extracellular biosurfactant, ''Biosur-Pm''. The partially purified product is nondialyzable and chemically composed of 50% protein and 12-15% sugar, which indicates the complex nature of Biosur-Pm. It reduces the surface tension of water from 73 to 53 x 10(-3) N m(-1) and has a critical micellar concentration of 80 mg/l. Compared to aliphatic hydrocarbons, Biosur-Pm shows good activity against aromatic hydrocarbons. The emulsion formed is stable and does not require any metal ions for emulsification. The kinetics of Biosur-Pm production suggest that its synthesis isa growth-associated and pH-dependent process. At pH 7.0, cells produced more Biosur-Pm with less cell surface hydrophobicity. At pH 8.0, however, the cells produced less Biosur-Pm with more cell surface hydrophobicity and showed a twofold higher affinity for aromatic hydrocarbons compared to the cells grown at pH 7.0. The Biosur-Pm showed a pH-dependent release, stimulated growth of the producer strain on mineral salts medium with 1-naphthoic acid when added externally, and facilitated the conversion of salicylate to catechol. All these results suggest that Biosur-Pm is probably a cell-wall component and helps in hydrocarbon assimilation/uptake.

On the Impact of MIMO Diversity on Higher Layer Performance

In this paper, we shed light on the cross-layer interactions between the PHY, link and routing layers in networks with MIMO links operating in the diversity mode. Many previous studies assume an overly simplistic PHY layer model that does not sufficiently capture these interactions. We show that the use of simplistic models can in fact lead to misleading conclusions with regards to the higher layer performance with MIMO diversity. Towards understanding the impact of various PHY layer features on MIMO diversity, we begin with a simple but widely-used model and progressively incorporate these features to create new models. We examine the goodness of these models by comparing the simulated performance results with each, with measurements on an indoor 802.11 n testbed. Our work reveals several interesting cross-layer dependencies that affect the gains due to MIMO diversity. In particular, we observe that relative to SISO links: (a) PHY layer gains due to MIMO diversity do not always carry over to the higher layers, (b) the use of other PHY layer features such as FEC codes significantly influence the gains due to MIMO diversity, and (c) the choice of the routing metric can impact the gains possible with MIMO.

A cascaded discharge plasma-adsorbent technique for engine exhaust treatment

A cascaded system of electrical discharges (non-thermal plasma) and adsorption process was investigated for the removal of oxides of Nitrogen (NOx) and total hydrocarbons (THC) from an actual diesel engine exhaust. The non-thermal plasma and adsorption processes were separately studied first and then the cascaded process was studied. In this study, different types of adsorbents were used. The NOx removal efficiency was higher with plasma-associated adsorption (cascaded) process compared to the individual processes and the removal efficiency was found almost invariant in time. When associated by plasma, among the adsorbents studied, activated charcoal and MS-13X were more effective for NOx and THC removal respectively. The experiments were conducted at no load and at 50% load conditions. The plasma reactor was kept at room temperature throughout the experiment, while the temperature of the adsorbent reactor was varied. A relative comparison of adsorbents was discussed at the end.

Capturing higher modes of vibration of micromachined resonators

MEMS resonators have potential applications in the areas of RF-MEMS, clock oscillators, ultrasound transducers, etc. The important characteristics of a resonator are its resonant frequency and Q-factor (a measure of damping). Usually large damping in macro structures makes it difficult to excite and measure their higher modes. In contrast, MEMS resonators seem amenable to excitation in higher modes. In this paper, 28 modes of vibration of an electrothermal actuator are experimentally captured–perhaps the highest number of modes experimentally captured so far. We verify these modes with FEM simulations and report that all the measured frequencies are within 5% of theoretically predicted values.

Temperature effect on hydrocarbon-enhanced nitric oxide conversion using a dielectric barrier discharge reactor

Experimental investigations into the effect of temperature on conversion of NO in the presence of hydrocarbons (ethylene, acetylene and n-hexane) are presented. An AC energized dielectric barrier discharge reactor was used as the plasma reactor. The experiments were carried out at different temperatures up to 200 degreesC. The discharge powers were measured at all the temperatures. The discharge power was found to increase with temperature. NO conversion in the presence of ethylene and n-hexane was better than that of acetylene at all temperatures. The addition of acetylene at room temperature showed no better conversion of NO compared to no additive case. While at higher temperatures, it could enhance the conversion of NO. A slight enhancement in NO and NOx removal was observed in the presence of water vapor. (C) 2003 Elsevier Science B.V. All rights reserved.