Polarity dependence of the radiative and nonradiative rates of flavone derivatives comprising structurally similar amino moieties: change in the nature of the emitting state

Photophysical behavior of several structurally related electron donor-acceptor flavone derivatives, which have been synthesized and characterized, has been studied as a function of the polarity of the media. Significant variation of the absorption and fluorescence response of the systems has been observed with change in the polarity of the medium. The results show an increase in the radiative rate constant and a decrease in the nonradiative rate constant of the systems with increase in the polarity of the media. This finding has been attributed to the change in the nature of the emitting state from a mixed n-pi* and pi-pi* state to a dominant pi-pi* state with increase in the polarity of the medium. The results of single-crystal diffraction studies and theoretical calculations based on density functional method support the idea of close proximity of the n-pi* and pi-pi* states and the change in their relative contributions toward the emission process with the polarity of the medium. Laser flash photolysis studies show that the triplet state is not involved in the variation of the fluorescence response of the systems.     

Unexpectedly large binding constants of azulenes with fullerenes

In spite of having small pi-conjugation systems, azulenes show large binding constants (10(4)-10(5)) to C(60) and C(70), which are larger than those of monoporphyrins and alternant aromatic hydrocarbons.     

Spectroscopic investigation of 3-pyrazolyl 2-pyrazoline derivative in homogeneous solvents

How solvent conditions such as solvent polarity and hydrogen-bonding affect the fluorescence of a newly synthesized 3-pyrazolyl 2-pyrazoline derivative (Pyz) having pharmaceutical activity has been explored. The solvatochromic effect of Pyz is due to a change in dipole moment of the compound in the excited state. The relaxation of S1 state is perturbed in hydrogen-bonding solvents. The fluorescence properties of the systems are strongly dependent on the polarity of the media. The non-radiative relaxation process is facilitated by an increase in the polarity of the media. The photophysical response of Pyz in different solvents has been explained considering solute-solvent interactions.     

PCR-based detection in a micro-fabricated platform

We present a novel, on-chip system for the electrokinetic capture of bacterial cells and their identification using the polymerase chain reaction (PCR). The system comprises a glass-silicon platform with a set of micro-channels, -chambers, and -electrodes. A platinum thin film resistor, placed in the proximity of the chambers, is used for temperature monitoring. The whole chip assembly is mounted on a Printed Circuit Board (PCB) and wire-bonded to it. The PCB has an embedded heater that is utilized for PCR thermal cycle and is controlled by a Lab-View program. Similar to our previous work, one set of electrodes on the chip inside the bigger chamber (0.6 microl volume) is used for diverting bacterial cells from a flowing stream into to a smaller chamber (0.4 nl volume). A second set of interdigitated electrodes (in smaller chamber) is used to actively trap and concentrate the bacterial cells using dielectrophoresis (DEP). In the presence of the DEP force, with the cells still entrapped in the micro-chamber, PCR mix is injected into the chamber. Subsequently, PCR amplification with SYBR Green detection is used for genetic identification of Listeria monocytogenes V7 cells. The increase in fluorescence is recorded with a photomultiplier tube module mounted over an epifluorescence microscope. This integrated micro-system is capable of genetic amplification and identification of as few as 60 cells of L. monocytogenes V7 in less than 90 min, in 600 nl volume collected from a sample of 10(4) cfu ml(-1). Specificity trials using various concentrations of L. monocytogenes V7, Listeria innocua F4248, and Escherichia coli O157:H7 were carried out successfully using two different primer sets specific for a regulatory gene of L. monocytogenes, prfA and 16S rRNA primer specific for the Listeria spp., and no cross-reactivity was observed.     

Excited-state proton-transfer dynamics of 7-hydroxyquinoline in room temperature ionic liquids

Excited-state proton transfer (ESPT) reaction of 7-hydroxyquinoline (7-HQ) mediated by methanol molecules has been studied in two room temperature ionic liquids (RTILs) using steady-state and time-resolved fluorescence measurements. While no ESPT is observable in neat RTILs, characteristic tautomer fluorescence of 7-HQ could be observed in the presence of small quantity of methanol (0.5-4.1 M). The observation of a rise time (350 ps-1.4 ns) associated with the tautomer fluorescence suggests that proton transfer in 7-HQ is indeed an excited-state phenomenon that requires considerable solvent reorganization prior to the relay of proton from the hydroxyl group to the distant ring nitrogen atom through suitably organized dimeric chain of methanol molecules. The rise time of the tautomer fluorescence, which has been found to decrease with increasing methanol concentration, is attributed to the change of viscosity of the medium upon methanol addition. While the influence of viscosity on the ESPT kinetics is evident from the data, lack of any definite correlation between the bulk viscosity and the rise time has been interpreted in terms of the microheterogeneous nature of the media that does not allow assessment of the microviscosity around 7-HQ from the bulk viscosity.     

Trapping and cooling a mirror to its quantum mechanical ground state

We propose a technique aimed at cooling a harmonically oscillating mirror to its quantum mechanical ground state starting from room temperature. Our method, which involves the two-sided irradiation of the vibrating mirror inside an optical cavity, combines several advantages over the two-mirror arrangements being used currently. For comparable parameters the three-mirror configuration provides a stiffer trap for the oscillating mirror. Furthermore, it prevents bistability from limiting the use of higher laser powers for mirror trapping, and also partially does so for mirror cooling. Lastly, it improves the isolation of the mirror from classical noise so that the quantum mechanical dynamics of the mirror become easier to observe. These improvements are expected to bring the task of achieving and detecting ground state occupation for the mirror closer to completion.     

Using a Laguerre-Gaussian beam to trap and cool the rotational motion of a mirror

We show theoretically that it is possible to trap and cool the rotational motion of a macroscopic mirror made of a perfectly reflecting spiral phase element using orbital angular momentum transfer from a Laguerre-Gaussian optical field. This technique offers a promising route to the placement of the rotor in its quantum mechanical ground state in the presence of thermal noise. It also opens up the possibility of simultaneously cooling a vibrational mode of the same mirror. Lastly, the proposed design may serve as a sensitive torsional balance in the quantum regime.     

Population transfer to excited vibrational levels of H2 molecule by stimulated hyper-Raman passage with chirped laser pulses

We have theoretically investigated the population transfer from the initial ground rovibrational level v(g)=0, J(g)=0 to the final rovibrational levels v(f)=1,2, J(f)=0 of the ground electronic state X (1)Sigma(g) (+) via the resonant intermediate level v(i)=6, J(i)=0 of the excited electronic state EF (1)Sigma(g) (+) of H(2) molecule by (2+2)-photon stimulated hyper-Raman passage (STIHRP). The density matrix technique has been employed to evaluate the population transfer to the final target levels using linearly chirped pump and Stokes laser pulses with different chirp rates. Both the pulses are considered to have the same temporal shape, pulse width, and linear parallel polarizations. We have studied in detail the dependence of the population transfer on the set of laser parameters for pulse (peak) intensities in the ranges of 1.5 x 10(11)-1.0 x 10(12) and 1.0 x 10(12)-7.0 x 10(12) W/cm(2). The corresponding pulse widths (full width at half maximum) are of the order of 115-200 and 15-30 ps. We have found that the chirp rate parameters can be optimized to achieve almost complete population transfer from the ground (g) to the final (f) target levels. This, to our knowledge, is the first application of a (2+2)-photon STIHRP process with chirpings to a model molecular system (H(2)). The study demonstrates the suitability of the chirped (2+2)-photon STIHRP technique for selective and almost total inversion of vibrational population in a diatomic molecule.