Fluorescence and visual sensing of nitroaromatic explosives using electron rich discrete fluorophores

Several pi-electron rich fluorescent aromatic compounds containing trimethylsilylethynyl functionality have been synthesized by employing Sonogashira coupling reaction and they were characterized fully by NMR (H-1, C-13)/IR spectroscopy. Incorporation of bulky trimethylsilylethynyl groups on the peripheral of the fluorophores prevents self-quenching of the initial intensity through pi-pi interaction and thereby maintains the spectroscopic stability in solution. These compounds showed fluorescence behavior in chloroform solution and were used as selective fluorescence sensors for the detection of electron deficient nitroaromatics. All these fluorophores showed the largest quenching response with high selectivity for nitroaromatics among the various electron deficient aromatic compounds tested. Quantitative analysis of the fluorescence titration profile of 9,10-bis(trimethylsilylethynyl) anthracene with picric acid provided evidence that this particular fluorophore detects picric acid even at ppb level. A sharp visual detection of 2,4,6-trinitrotoluene was observed upon subjecting 1,3,6,8-tetrakis (trimethylsilylethynyl) pyrene fluorophore to increasing quantities of 2,4,6-trinitrotoluene in chloroform. Furthermore, thin film of the fluorophores was made by spin coating of a solution of 1.0 x 10(-3) M in chloroform or dichloromethane on a quartz plate and was used for the detection of vapors of nitroaromatics at room temperature. The vapor-phase sensing experiments suggested that the sensing process is reproducible and quite selective for nitroaromatic compounds. Selective fluorescence quenching response including a sharp visual color change for nitroaromatics makes these fluorophores as promising fluorescence sensory materials for nitroaromatic compounds (NAC) with a detection limit of even ppb level as judged with picric acid.

Tidally compressed gas in centers of early-type and ultraluminous galaxies

In this paper we propose that the compressive tidal held in the centers of flat-core early-type galaxies and ultraluminous galaxies compresses molecular clouds producing dense gas observed in the centers of these galaxies. The effect of galactic tidal fields is usually considered disruptive in the literature. However, for some galaxies, the mass profile flattens toward the center and the resulting galactic tidal field is not disruptive, but instead it is compressive within the flat-core region. We have used the virial theorem to determine the minimum density of a molecular cloud to be stable and gravitationally bound within the tidally compressive region of a galaxy. We have applied the mechanism to determine the mean molecular cloud densities in the centers of a sample of flat-core, early-type galaxies and ultraluminous galaxies. For early-type galaxies with a core-type luminosity profile, the tidal held of the galaxy is compressive within half the core radius. We have calculated the mean gas densities for molecular gas in a sample of early-type galaxies which have already been detected in CO emission, and we obtain mean densities of [n] similar to 10(3)-10(6) cm(-3) within the central 100 pc radius. We also use our model to calculate the molecular cloud densities in the inner few hundred parsecs of a sample of ultraluminous galaxies. From the observed rotation curves of these galaxies we show that they have a compressive core within their nuclear region. Our model predicts minimum molecular gas densities in the range 10(2)-10(4) cm(-3) in the nuclear gas disks; the smaller values are applicable typically for galaxies with larger core radii. The resulting density values agree well with the observed range. Also, for large core radii, even fairly low-density gas (similar to 10(2) cm(-3)) can remain bound and stable close to the galactic center.

Unified approach to the constraint counting theory of glasses

An approach to the constraint counting theory of glasses is applied to many glass systems which include an oxide, chalcohalide, and chalcogenides. In this, shifting of the percolation threshold due to noncovalent bonding interactions in a basically covalent network and other recent extensions of the theory appear natural. This is particularly insightful and reveals that the chemical threshold signifies another structural transition along with the rigidity percolation threshold, thus unifying these two seemingly disparate toplogical concepts. [S0163-1829(99)11441-3].

Cyclic Prefix Based Cooperative Sequential Spectrum Sensing Algorithms for OFDM

This paper considers the problem of spectrum sensing in cognitive radio networks when the primary user is using Orthogonal Frequency Division Multiplexing (OFDM). For this we develop cooperative sequential detection algorithms that use the autocorrelation property of cyclic prefix (CP) used in OFDM systems. We study the effect of timing and frequency offset, IQ-imbalance and uncertainty in noise and transmit power. We also modify the detector to mitigate the effects of these impairments. The performance of the proposed algorithms is studied via simulations. We show that sequential detection can significantly improve the performance over a fixed sample size detector.

Non-Fermi-liquid theory for disordered metals near two dimensions

We consider the Finkelstein action describing a system of spin-polarized or spinless electrons in 2+2epsilon dimensions, in the presence of disorder as well as the Coulomb interactions. We extend the renormalization-group analysis of our previous work and evaluate the metal-insulator transition of the electron gas to second order in an epsilon expansion. We obtain the complete scaling behavior of physical observables like the conductivity and the specific heat with varying frequency, temperature, and/or electron density. We extend the results for the interacting electron gas in 2+2epsilon dimensions to include the quantum critical behavior of the plateau transitions in the quantum Hall regime. Although these transitions have a very different microscopic origin and are controlled by a topological term in the action (theta term), the quantum critical behavior is in many ways the same in both cases. We show that the two independent critical exponents of the quantum Hall plateau transitions, previously denoted as nu and p, control not only the scaling behavior of the conductances sigma(xx) and sigma(xy) at finite temperatures T, but also the non-Fermi-liquid behavior of the specific heat (c(v)proportional toT(p)). To extract the numerical values of nu and p it is necessary to extend the experiments on transport to include the specific heat of the electron gas.

Theory of polymer breaking under tension

We consider the breaking of a polymer molecule which is fixed at one end and is acted upon by a force at the other. The polymer is assumed to be a linear chain joined together by bonds which satisfy the Morse potential. The applied force is found to modify the Morse potential so that the minimum becomes metastable. Breaking is just the decay of this metastable bond, by causing it to go over the barrier. Increasing the force causes the potential to become more and more distorted and eventually leads to the disappearance of the barrier. The limiting force at which the barrier disappears is D(e)a/2,D-e with a the parameters characterizing the Morse potential. The rate of breaking is first calculated using multidimensional quantum transition state theory. We use the harmonic approximation to account for vibrations of all the units. It includes tunneling contributions to the rate, but is valid only above a certain critical temperature. It is possible to get an analytical expression for the rate of breaking. We have calculated the rate of breaking for a model, which mimics polyethylene. First we calculate the rate of breaking of a single bond, without worrying about the other bonds. Inclusion of other bonds under the harmonic approximation is found to lower this rate by at the most one order of magnitude. Quantum effects are found to increase the rate of breaking and are significant only at temperatures less than 150 K. At 300 K, the calculations predict a bond in polyethylene to have a lifetime of only seconds at a force which is only half the limiting force. Calculations were also done using the Lennard-Jones potential. The results for Lennard-Jones and Morse potentials were rather different, due to the different long-range behaviors of the two potentials. A calculation including friction was carried out, at the classical level, by assuming that each atom of the chain is coupled to its own collection of harmonic oscillators. Comparison of the results with the simulations of Oliveira and Taylor [J. Chem. Phys. 101, 10 118 (1994)] showed the rate to be two to three orders of magnitude higher. As a possible explanation of discrepancy, we consider the translational motion of the ends of the broken chains. Using a continuum approximation for the chain, we find that in the absence of friction, the rate of the process can be limited by the rate at which the two broken ends separate from one another and the lowering of the rate is at the most a factor of 2, for the parameters used in the simulation (for polyethylene). In the presence of friction, we find that the rate can be lowered by one to two orders of magnitude, making our results to be in reasonable agreement with the simulations.

Ab initio, DFT and transition state theory calculations on 1,2-HF, HCI and CIF elimination reactions from CH2F-CH2Cl

This paper reports ab intio, DFT and transition state theory (TST) calculations on HF, HCI and CIF elimination reactions from CH2Cl-CH2F molecule. Both the ground state and the transition state for HX elimination reactions have been optimized at HF, MP2 and DFT calculations with 6-31G*, 6-31G** and 6-311++G** basis sets. In addition, CCSD(T) single point calculations were carried out with MP2/6-311++G** optimized geometry for more accurate determination of the energies of the minima and transition state, compared to the other methods employed here. Classical barriers are converted to Arrhenius activation energy by TST calculations for comparisons with experimental results. The pre-exponential factors, A, calculated at all levels of theory are significantly larger than the experimental values. For activation energy, E-a DFT gives good results for HF elimination, within 4-8 W mol(-1) from experimental values. None of the methods employed, including CCSD(T), give comparable results for HCI elimination reactions. However, rate constants calculated by CCSD(T) method are in very good agreement with experiment for HCI elimination and they are in reasonable agreement for HF elimination reactions. Due to the strong correlation between A and E., the rate constants could be fit to a lower A and E-a (as given by experimental fitting, corresponding to a tight TS) or to larger A and E-a (as given by high level ab initio calculations, corresponding to a loose TS). The barrier for CIF elimination is determined to be 607 U mol(-1) at HF level and it is unlikely to be important for CH2FCH2Cl. Results for other CH2X-CH2Y (X,Y = F/Cl) are included for comparison.

A waveguide problem involving a thick iris in the theory of electromagnetism

The problem of electromagnetic wave propagation in a rectangular waveguide containing a thick iris is considered for its complete solution by reducing it to two suitable integral equations, one of which is of the first kind and the other is of the second kind. These integral equations are solved approximately, by using truncated Fourier series for the unknown functions. The reflection coefficient is computed numerically from the two integral equation approaches, and almost the same numerical results are obtained. This is also depicted graphically against the wave number and compared with thin iris results, which are computed by using complementary formulations coupled with Galerkin approximations. While the reflection coefficient for a thin iris steadily increases with the wave number, for a thick iris it fluctuates and zero reflection occurs. The number of zeros of the reflection coefficient for a thick iris increases with the thickness. Thus a thick iris becomes completely transparent for some discrete wave numbers. This phenomenon may be significant in the modelling of rectangular waveguides.