Spatial resolution of a velocity-selected ion imaging microscope for surface reaction kinetics mapping.

Experimental validation of complex microkinetic models derived from quantum chemistry is crucial for the advancement of bottom-up approaches to heterogeneous catalysis. State-of-the-art velocity-resolved kinetics experiments have made tremendous progress in this arena but integrate reactivity over centimeter-scale single-crystal catalytic surfaces even when complex spatial phenomena may perturb the kinetic results. We report a new design, optimization, and analysis of an ion imaging microscope that can collect spatially resolved kinetic data from a catalytic surface.

Direct observation of coherence transfer and rotational-to-vibrational energy exchange in optically centrifuged CO super-rotors.

Optical centrifuges are laser-based molecular traps that can rotationally accelerate molecules to energies rivalling or exceeding molecular bond energies. Here we report time and frequency-resolved ultrafast coherent Raman measurements of optically centrifuged CO at 380 Torr spun to energies beyond its bond dissociation energy of 5.5 eV (J = 364, E = 6.

Class II malocclusion correction with Invisalign: Is it possible?

Introduction: This research aimed to determine whether Class II malocclusion can be treated with clear aligners after completing treatment with the initial set of aligners.

Methods: A sample of 80 adult patients were divided into Group 1 with Class I molar malocclusions (n = 40 [11 men and 29 women]; 38.70 ± 15.

1-D imaging of rotation-vibration non-equilibrium from pure rotational ultrafast coherent anti-Stokes Raman scattering.

We present one-dimensional (1-D) imaging of rotation-vibration non-equilibrium measured by two-beam pure rotational hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering (fs/ps CARS). Simultaneous measurements of the spatial distribution of molecular rotation-vibration non-equilibrium are critical for understanding molecular energy transfer in low temperature plasmas and hypersonic flows. However, non-equilibrium CARS thermometry until now was limited to point measurements.

Generation of narrowband pulses from chirped broadband pulse frequency mixing.

We extend an approach based upon sum-frequency generation of oppositely chirped pulses to narrow the bandwidths of broadband femtosecond pulses. We efficiently generate near-transform-limited pulses with durations of several picoseconds, while reducing the pulse bandwidth by a factor of 120, which is more than twice the reduction reported in previous literature. Such extreme bandwidth narrowing of a broadband pulse enhances the effects of dispersion nonlinearities.

Pure-rotational H thermometry by ultrabroadband coherent anti-Stokes Raman spectroscopy.

Coherent anti-Stokes Raman spectroscopy (CARS) is a sensitive technique for probing highly luminous flames in combustion applications to determine temperatures and species concentrations. CARS thermometry has been demonstrated for the vibrational Q-branch and pure-rotational S-branch of several small molecules. Practical advantages of pure-rotational CARS, such as multi-species detection, reduction of coherent line mixing and collisional narrowing even at high pressures, and the potential for more precise thermometry, have motivated experimental and theoretical advances in S-branch CARS of nitrogen (N), for example, which is a dominant species in air-fed combustion processes.

Design, synthesis, and evaluation of NO-donor containing carbonic anhydrase inhibitors to lower intraocular pressure.

The antiglaucoma drugs dorzolamide (1) and brinzolamide (2) lower intraocular pressure (IOP) by inhibiting the carbonic anhydrase (CA) enzyme to reduce aqueous humor production. The introduction of a nitric oxide (NO) donor into the alkyl side chain of dorzolamide (1) and brinzolamide (2) has led to the discovery of NO-dorzolamide 3a and NO-brinzolamide 4a, which could lower IOP through two mechanisms: CA inhibition to decrease aqueous humor secretion (reduce inflow) and NO release to increase aqueous humor drainage (increase outflow). Compounds 3a and 4a have shown improved efficacy of lowering IOP in both rabbits and monkeys compared to brinzolamide (2).

Split-probe hybrid femtosecond/picosecond rotational CARS for time-domain measurement of S-branch Raman linewidths within a single laser shot.

We introduce a multiplex technique for the single-laser-shot determination of S-branch Raman linewidths with high accuracy and precision by implementing hybrid femtosecond (fs)/picosecond (ps) rotational coherent anti-Stokes Raman spectroscopy (CARS) with multiple spatially and temporally separated probe beams derived from a single laser pulse. The probe beams scatter from the rotational coherence driven by the fs pump and Stokes pulses at four different probe pulse delay times spanning 360 ps, thereby mapping collisional coherence dephasing in time for the populated rotational levels. The probe beams scatter at different folded BOXCARS angles, yielding spatially separated CARS signals which are collected simultaneously on the charge coupled device camera.

Communication: Simplified two-beam rotational CARS signal generation demonstrated in 1D.

We explore a novel phase matching scheme for gas-phase rotational coherent anti-Stokes Raman spectroscopy (CARS). The scheme significantly simplifies the employment of the technique in general. Two laser beams, one broadband and one narrowband, are crossed at arbitrary angle and the generated rotational CARS signal, copropagating with the probe beam, is isolated using a polarization gating technique.

400 µJ 79 ns amplified pulses from a Q-switched fiber laser using an Yb(3+)-doped fiber saturable absorber.

We report a passively Q-switched all-fiber laser using a large mode area (LMA) Yb(3+)-doped fiber cladding-pumped at 915 nm and an unpumped single-mode Yb(3+)-doped fiber as the saturable absorber (SA). The saturable absorber fiber and gain fiber were coupled with a free-space telescope to optimize the coupling efficiency between the disparate fibers, preferentially bleaching the SA fiber before gain depletion in the pumped fiber. Using this scheme we first demonstrate a Q-switched oscillator with 40 μJ 79 ns pulses at 1026 nm, and show that pulses can be generated from 1020 nm to 1040 nm.

High-power all-fiber passively Q-switched laser using a doped fiber as a saturable absorber: numerical simulations.

We report a design for a power-scalable all-fiber passively Q-switched laser that uses a large mode area Yb-doped fiber as a gain medium adiabatically tapered to an unpumped single-mode Yb-doped fiber, which serves as a saturable absorber. Through the use of a comprehensive numerical simulator, we demonstrate a passively Q-switched 1030 nm pulsed laser with 14 ns pulse duration and 0.5 mJ pulse energy operating at 200 kHz repetition rate.

Quantitative one-dimensional imaging using picosecond dual-broadband pure-rotational coherent anti-Stokes Raman spectroscopy.

We employ picosecond dual-broadband pure-rotational coherent anti-Stokes Raman spectroscopy (CARS) in a one-dimensional (1D) imaging configuration. Temperature and O(2):N(2) concentration ratios are measured along a 1D line of up to 12 mm in length. The images consist of up to 330 individual rotational CARS (RCARS) spectra, corresponding to 330 spatially resolved volume elements in the probe volume.

Suppression of Raman-resonant interferences in rotational coherent anti-Stokes Raman spectroscopy using time-delayed picosecond probe pulses.

We measure time-dependent pure-rotational coherent anti-Stokes Raman spectroscopy (CARS) spectra for room-temperature N(2), O(2), CO(2), C(2)H(4), and C(3)H(8), as well as in a C(3)H(8) diffusion flame, using picosecond lasers. Because Raman coherences for N(2) and O(2) persist significantly longer than those for the other species, delayed probing can significantly reduce unwanted resonant contributions to rotational coherent anti-Stokes Raman spectroscopy spectra, enabling temperature and relative O(2)/N(2) concentration determination in fuel-rich gas mixtures. Delayed probing also eliminates interference from smeared vibrational CARS.

Picosecond time-resolved pure-rotational coherent anti-Stokes Raman spectroscopy for N(2) thermometry.

Time-resolved pure-rotational coherent anti-Stokes Raman spectroscopy using picosecond-duration laser pulses is investigated for gas thermometry. The use of picosecond laser pulses significantly reduces background caused by scattering of the probe beam, and delayed probing of the Raman coherence enables elimination of interference from nonresonant four-wave mixing processes. Temperatures inferred from rotational spectra are sensitive to the probe delay because of the rotational-level dependence of collisional dephasing of Raman coherences.

Collisional quenching of NO A 2Sigma+(v' = 0) between 125 and 294 K.

We report measurements of the temperature-dependent cross sections for the quenching of fluorescence from the A (2)Sigma(+)(v(')=0) state of NO for temperatures between 125 and 294 K. Thermally averaged cross sections were measured for quenching by NO(X (2)Pi), N(2), O(2), and CO in a cryogenically cooled gas flow cell. Picosecond laser-induced fluorescence was time resolved, and the thermally averaged quenching cross sections were determined from the dependence of the fluorescence decay rate on the quencher-gas pressure.

Comparison of nanosecond and picosecond excitation for interference-free two-photon laser-induced fluorescence detection of atomic hydrogen in flames.

Two-photon laser-induced fluorescence (TP-LIF) line imaging of atomic hydrogen was investigated in a series of premixed CH4/O2/N2, H2/O2, and H2/O2/N2 flames using excitation with either picosecond or nanosecond pulsed lasers operating at 205 nm. Radial TP-LIF profiles were measured for a range of pulse fluences to determine the maximum interference-free signal levels and the corresponding picosecond and nanosecond laser fluences in each of 12 flames. For an interference-free measurement, the shape of the TP-LIF profile is independent of laser fluence.

Total synthesis of leucascandrolide a: a new application of the Mukaiyama aldol-Prins reaction.

A total synthesis of the marine natural product leucascandrolide A has been completed. The titanium tetrabromide-mediated Mukaiyama aldol-Prins (MAP) reaction with aldehydes developed in our group provided a highly convergent and stereoselective method for assembling the core of the molecule. A new class of MAP reactions with acetals is introduced, and mechanistic considerations for both MAP methods are described.

Influence of connectivity and porosity on ligand-based luminescence in zinc metal-organic frameworks.

Applications of metal-organic frameworks (MOFs) require close correlation between their structure and function. We describe the preparation and characterization of two zinc MOFs based on a flexible and emissive linker molecule, stilbene, which retains its luminescence within these solid materials. Reaction of trans-4,4'-stilbene dicarboxylic acid and zinc nitrate in N,N-dimethylformamide (DMF) yielded a dense 2-D network, 1, featuring zinc in both octahedral and tetrahedral coordination environments connected by trans-stilbene links.

Branching ratios for quenching of nitric oxide A 2Sigma+ (nu' = 0) to X 2Pi(nu' = 0).

We describe experiments designed to measure the fraction of nitric oxide molecules that undergo quenching from A 2Sigma+ (nu' = 0) directly to X 2Pi(nu" = 0). This quenching channel was investigated for room temperature collisions with O2, CO, CO2, and H2O by measuring recovery of the ground-state population following intense laser excitation. Experiments were conducted in a room temperature flow cell containing dilute mixtures of NO, N2, and the quenching gases.

Temperature- and species-dependent quenching of NO A 2Sigma+(v'=0) probed by two-photon laser-induced fluorescence using a picosecond laser.

We report improved measurements of the temperature-dependent cross sections for the quenching of fluorescence from the A 2Sigma+(v'=0) state of NO. Cross sections were measured for gas temperatures ranging from 294 to 1300 K for quenching by NO(X (2)Pi), H(2)O, CO(2), O(2), CO, N(2), and C(2)H(2). The A 2Sigma+(v'=0) state was populated via two-photon excitation with a picosecond laser at 454 nm, and the decay rate of the fluorescence originating from A 2Sigma+(v'=0) was measured directly.

Comparison of nanosecond and picosecond excitation for two-photon laser-induced fluorescence imaging of atomic oxygen in flames.

Two-photon laser-induced fluorescence (LIF) imaging of atomic oxygen is investigated in premixed hydrogen and methane flames with nanosecond and picosecond pulsed lasers at 226 nm. In the hydrogen flame, the interference from photolysis is negligible compared with the LIF signal from native atomic oxygen, and the major limitations on quantitative measurements are stimulated emission and photoionization. Excitation with a nanosecond laser is advantageous in the hydrogen flames, because it reduces the effects of stimulated emission and photoionization.