We demonstrate that optical trapping combined with confocal Raman spectroscopy using a single laser source is a powerful tool for the rapid identification of micrometer-sized particles in an aqueous environment. Optical trapping immobilizes the particle while maintaining it in the center of the laser beam path and within the laser focus, thus maximizing the collection of its Raman signals. The single particle is completely isolated from other particles and substrate surfaces, therefore eliminating any unwanted background signals and ensuring that information is collected only from the selected, individual particle. In this work, an inverted confocal Raman microscope is combined with optical trapping to probe and analyze bacterial spores in solution. Rapid, reagentless detection and identification of bacterial spores with no false positives from a complex mixed sample containing polystyrene and silica beads in aqueous suspension is demonstrated. In addition, the technique is used to analyze the relative concentration of each type of particle in the mixture. Our results show the feasibility for incorporating this technique in combination with a flow cytometric-type scheme in which the intrinsic Raman signatures of the particles are used instead of or in addition to fluorescent labels to identify cells, bacteria, and particles in a wide range of applications.
Resonance Raman spectra of chlorine dioxide (OClO) dissolved in cyclohexane obtained with excitation throughout the 2 B 1 -2 A 2 electronic transition are presented. Resonance Raman intensity corresponding to all vibrational degrees of freedom (the symmetric stretch, bend, and asymmetric stretch) is observed, demonstrating that excited-state structural evolution along all three coordinates occurs upon photoexcitation. The electronic absorption and absolute resonance Raman cross sections are reproduced employing the time-dependent formalism for Raman scattering using an anharmonic description of the 2 A 2 , excited-state potential-energy surface. Analysis of the resonance Raman cross-sections demonstrates that both homogeneous and inhomogeneous broadening mechanisms are operative in cyclohexane. Comparison of the experimentally determined, gas-phase 2 A 2 surface to that in solution defined by the analysis presented here shows that although displacements along the symmetric stretch and bend are similar in both phases, evolution along the asymmetric stretch is dramatically altered in solution. Specifically, employing the gas-phase potential along this coordinate, the predicted intensity of the overtone transition is an order of magnitude larger than that observed. The analysis presented here demonstrates that the asymmetric stretch overtone intensity is consistent with a reduction in excited-state frequency along this coordinate from 1100 to 750 ( 100 cm -1 . This comparison suggests that differences in evolution along the asymmetric stretch may be responsible for the phase-dependent reactivity of OClO. In particular, the absence of substantial evolution along the asymmetric stretch in solution results in the ground-state symmetry of OClO being maintained in the 2 A 2 excited state. The role of symmetry in defining the reaction coordinate and the nature of the solvent interaction responsible for modulation of the excited-state potential energy surface are discussed.
The photochemical reaction dynamics of chlorine dioxide (OClO) are investigated using absorption and
resonance Raman spectroscopy. The first Raman spectra of gaseous OClO obtained directly on resonance
with the 2B1−2A2 electronic transition are reported. Significant scattering intensity is observed for all vibrational
degrees of freedom (the symmetric stretch, bend, and asymmetric stretch), demonstrating that structural
evolution occurs along all three normal coordinates following photoexcitation. The experimentally measured
absorption and resonance Raman intensities are compared to the intensities predicted using both empirical
and ab initio models for the optically active 2A2 surface. Comparison of the experimental and theoretical
absorption spectra demonstrates that the frequencies and intensities of transitions involving the asymmetric
stretch are well reproduced by the empirical model characterized by a double-minimum along the asymmetric
stretch. However, the ab initio model is also found to reproduce a subset of the experimental intensities. In
addition, the extremely large resonance Raman intensity of the asymmetric stretch overtone transition is
predicted by both models. The results presented here taken in combination with the model for the 2A2 surface
in condensed environments suggest that the phase-dependent photochemical reactivity of OClO is due to
environment-dependent excited-state structural evolution along the asymmetric stretch coordinate.
The resonance Raman depolarization ratios of chlorine dioxide (OClO) dissolved in cyclohexane are measured and analyzed to establish the existence of a A12 excited state that is nearly degenerate with the optically stronger, A22 excited state. The depolarization ratio of the symmetric stretch fundamental transition is measured at several excitation wavelengths spanning the lowest-energy electronic transition centered at ∼360 nm. The depolarization ratio of this transition reaches a maximum value of 0.25±0.04 directly on resonance suggesting that scattered intensity is not derived from a single excited state. The depolarization ratios are modeled utilizing the time-dependent formalism for Raman scattering. This analysis demonstrates that the observed Raman depolarization ratios are derived from contributions of two excited states of A12 and A22 symmetry to the observed scattering. The results presented here support the emerging picture of OClO excited-state reaction dynamics in which photoexcitation to the A22 excited state is followed by internal conversion from this state to the A12 surface. Both the role of the A12 state in the photochemistry of OClO and the importance of this state in modeling resonance Raman intensities are discussed.
We have measured the reaction propagation rate (RPR), or deflagration rate, in octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine (HMX) powder in a diamond anvil cell over the pressure range 0.7–35 GPa. Numerical simulations of the RPR of pressurized HMX were also performed for comparison to the experimental results obtained. The simulated RPR values closely approximate the observed rates at pressures up to 3 GPa, and serve as a bridge to lower‐pressure deflagration rates for HMX in the literature. However, at higher pressures the simulated RPR values deviate significantly from our experimental results. This suggests that further refinement to the computational model is required for the calculated RPR values to approach those observed at higher pressures.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.