A new fluorescence-based methodology for studying bioaerosol scavenging processes using a hyperspectral LIF-LIDAR remote sensing system.

This paper presents a novel experimental approach to in-situ study of atmospheric phenomena such as nucleation scavenging by biological seeds, bio-droplet dehydration, and bioaerosol's particle scavenging by raindrops. Our methodology is based on the analysis of the dynamical changes of fluorescence signal. We use a remote sensing system based on a homebuilt hyperspectral laser induced fluorescence (LIF) Lidar to measure the transient back-fluorescence and backscattering signals. The spectral line shape of the transient fluorescence associated with an aerosolized tryptophan solution was first analyzed in the laboratory. It then used to study bioaerosol phase transitions between wet and dry conditions. The experiments were first conducted in a dynamic aerosol cell where we repetitively create and monitor the droplets containing bioaerosol cloud starting from its early formation till its total evaporation. The LIF-Lidar was used to simultaneously measure back-fluorescence, scattering and transmission. These measurements were synchronized with the generation of droplets containing bioaerosol and with the monitoring of aerosol's size distribution and ambient conditions. A novel optical receiver design was used to simultaneously detect both back-fluorescence polarization components. Results showed that along with droplet's evaporation process, bioaerosol's fluorescence spectrum exhibit a blue shift, known as the dynamic Stokes-shifts, of ∼2000 cm-1 and an increase in its fluorescence anisotropy. To the best of our knowledge, this is the first report of fluorescence Stokes-shifts and anisotropy within microdroplets containing a biological solution due to wet-dry phase transitions. This method was also used to quantify scavenging of biological particle by raindrops from 100 m. It shows that valuable information can be derived from analyzing the fluorescence spectrum of bioaerosol within a cloud and demonstrate the potential of a LIF-LIDAR remote system to perform in-situ studies of scavenging processes.

Role of the P-F bond in fluoride-promoted aqueous VX hydrolysis: an experimental and theoretical study.

Following our ongoing studies on the reactivity of the fluoride ion toward organophosphorus compounds, we established that the extremely toxic and environmentally persistent chemical warfare agent VX (O-ethyl S-2-(diisopropylamino)ethyl methylphosphonothioate) is exclusively and rapidly degraded to the nontoxic product EMPA (ethyl methylphosphonic acid) even in dilute aqueous solutions of fluoride. The unique role of the P-F bond formation in the reaction mechanism was explored using both experimental and computational mechanistic studies. In most cases, the "G-analogue" (O-ethyl methylphosphonofluoridate, Et-G) was observed as an intermediate. Noteworthy and of practical importance is the fact that the toxic side product desethyl-VX, which is formed in substantial quantities during the slow degradation of VX in unbuffered water, is completely avoided in the presence of fluoride. A computational study on a VX-model, O,S-diethyl methylphosphonothioate (1), clarifies the distinctive tendency of aqueous fluoride ions to react with such organophosphorus compounds. The facility of the degradation process even in dilute fluoride solutions is due to the increased reactivity of fluoride, which is caused by the significant low activation barrier for the P-F bond formation. In addition, the unique nucleophilicity of fluoride versus hydroxide toward VX, in contrast to their relative basicity, is discussed. Although the reaction outcomes were similar, much slower reaction rates were observed experimentally for the VX-model (1) in comparison to VX.

Chirp effects on impulsive vibrational spectroscopy: a multimode perspective.

The well-documented propensity of negatively-chirped pulses to enhance resonant impulsive Raman scattering has been rationalized in terms of a one pulse pump-dump sequence which "follows" the evolution of the excited molecules and dumps them back at highly displaced configurations. The aim of this study was to extend the understanding of this effect to molecules with many displaced vibrational modes in the presence of condensed surroundings. In particular, to define an optimally chirped pulse, to investigate what exactly it "follows" and to discover how this depends on the molecule under study. To this end, linear chirp effects on vibrational coherences in poly-atomics are investigated experimentally and theoretically. Chirped pump-impulsive probe experiments are reported for Sulforhodamine-B ("Kiton Red"), Betaine-30 and Oxazine-1 in ethanol solutions with <10 fs resolution. Numerical simulations, including numerous displaced modes and electronic dephasing, are conducted to reproduce experimental results. Through semi-quantitative reproduction of experimental results in all three systems we show that the effect of group velocity dispersion (GVD) on the buildup of ground state wave-packets depends on the pulse spectrum, on the displacements of vibrational modes upon excitation, on the detuning of the excitation pulses from resonance, and on electronic dephasing rates. Akin to scenarios described for frequency-domain resonance Raman, within the small-displacement regime each mode responds to excitation chirp independently and the optimal GVD is mode-specific. Highly-displaced modes entangle the dynamics of excitation in different modes, requiring a multi-dimensional description of the response. Rapid photochemistry and ultrafast electronic dephasing narrow the window of opportunity for coherent manipulations, leading to a reduced and similar optimal chirp for different modes. Finally, non-intuitive coherent aspects of chirp "following" are predicted in the small-displacement and slow-dephasing regime, which remain to be observed in experiment.

Na(-) photolysis in THF: Charge transfer to solvent studied from the donors perspective in <10 fs detail.

Two and three pulse photolysis experiments on terahydrofuran (THF) solutions of Na(-), utilizing hyperspectral probing, are described. The objective is to probe the extent and duration of energetic correlations between the primary charge transfer to solvent (CTTS) fragments which are an e(-) and Na(0). The latter is characterized by an intense visible absorption spectrum with fine structure reflecting the atom's immediate solvent environment. Pump-probe experiments with approximately 6 fs pulses show that for the majority of irradiated ions, the electron ejection and production of unperturbed Na(0) is effectively over in approximately 15 fs, with no precursors. Three pulse experiments further demonstrate this to be true for nearly all ions irradiated at 3 eV. Thus, the 400 nm data provide a detailed spectral record of the formation and subsequent solvation and polarization of neutral sodium bubbles in THF. Measures are presented for parametrizing the ensuing spectral evolution. In contrast, exciting at 1.5 eV, the red edge of the CTTS band leads to charge transfer with less than unity quantum efficiency. The complementary fraction of absorbing ions is photostable at 800 nm, presumably due to preferential solvent stabilization. Prompt secondary irradiation at 2 microm can complete ionization of that population leading to additional generation of Na(0) but exhibiting much more pronounced spectral structure. Thus, at low photon energies, a short lived correlated and bound electronic excited state is produced with significant yield. These results are discussed in terms of classical models for CTTS spectra, as well as more recent simulations and experiments concerning CTTS in this and other related systems.