Ultraviolet and Infrared Spectroscopy of Synthetic Foldamers, Aib Homopeptides, and Solvated 1,2-Diphenylethane in the Gas Phase

The work presented here implements a supersonic jet expansion source to funnel the population of model peptides and solvated-bichromophore clusters into their low lying structural minima and to collisionally cool these minima to their respective zero-point vibrational levels. Single-conformation ultraviolet and infrared spectroscopy techniques are then used to probe these systems and investigate their electronic properties and uncover their intrinsic conformational preferences in the gas phase. Model β/γ-peptides known as synthetic foldamers and aminoisobutyric acid (Aib) homopeptides incorporate structural constraints that are designed/known to impose particular structural motifs. Here the ability of a β/γ-dipeptide to replicate the backbone length of an α-tripeptide and subsequently form the first portion of an α-helix is presented. Additionally, tests of the propensity for (Aib)n homopeptides to form 310-helices, in spite of accumulation of a macrodipole moment are shown. In fact, Aib is a strong 310-helix former, but there appears to be a point around n = 6 where competing forces funnel the population into a competing conformational family. 1,2-Diphenylethane (DPE) is a model, flexible bichromophore comprising two phenyl rings bound by an ethane bridge. By complexing DPE with (H 2O)n (n = 1-3) the effects of step-wise solvation on the electronic spectroscopy (i.e. the impact of water on vibronically coupled chromophores) and the conformational preferences of both the DPE monomer and the (H2O)n structures were investigated. In three of the four resultant clusters, the water molecule(s) were found to bind symmetrically to the DPE host, and an S0-S2 origin transition was not observed. However, in the fourth case, in which the anti conformation of the DPE monomer serves as host, localization is observed, and the S0-S2 origin is detected. Also of note is that the water-trimer, which almost always adopts a cycle geometry, was found to exclusively adopt a chain-geometry in the presence of DPE

Interference-free coherence dynamics of gas-phase molecules using spectral focusing

Spectral focusing using broadband femtosecond pulses to achieve highly selective measurements has been employed for numerous applications in spectroscopy and microspectroscopy. In this work we highlight the use of spectral focusing for selective excitation and detection of gas-phase species. Furthermore, we demonstrate that spectral focusing, coupled with time-resolved measurements based upon probe delay, allows the observation of interference-free coherence dynamics of multiple molecules and gas-phase temperature making this technique ideal for gas-phase measurements of reacting flows and combustion processes

Simultaneous high-speed measurement of temperature and lifetime-corrected OH laserinduced fluorescence in unsteady flames

A means of performing simultaneous, high-speed measurements of temperature and OH lifetime-corrected laser-induced fluorescence (LIF) for tracking unsteady flames has been developed and demonstrated. The system uses the frequency-doubled and frequency-tripled output beams of an 80 MHz mode-locked Ti:sapphire laser to achieve ultrashort laser pulses (order 2 ps) for Rayleigh-scattering thermometry at 460 nm and lifetime-corrected OH LIF at 306.5 nm, respectively. Simultaneous, high-speed measurements of temperature and OH number density enable studies of flame chemistry, heat release, and flame extinction in unsteady, strained flames where the local fluorescence-quenching environment is unknown

A Threshold-Based Approach to Calorimetry in Helium Droplets: Measurement of Binding Energies of Water Clusters

Helium dropletbeam methods have emerged as a versatile technique that can be used to assemble a wide variety of atomic and molecular clusters. We have developed a method to measure the binding energies of clusters assembled in helium droplets by determining the minimum droplet sizes required to assemble and detect selected clusters in the spectrum of the dopeddropletbeam. The differences in the droplet sizes required between the various multimers are then used to estimate the incremental binding energies. We have applied this method to measure the binding energies of cyclic waterclusters from the dimer to the tetramer. We obtain measured values of D0 that are in agreement with theoretical estimates to within ∼20%. Our results suggest that this threshold-based approach should be generally applicable using either mass spectrometry or optical spectroscopy techniques for detection, provided that the clusters selected for study are at least as strongly bound as those of water, and that a peak in the overall spectrum of the beam corresponding only to the cluster chosen (at least in the vicinity of the threshold) can be located

Femtosecond coherent anti-Stokes Raman scattering measurement of gas temperatures from frequency-spread dephasing of the Raman coherence

Gas-phase temperatures and concentrations are measured from the magnitude and decay of the initial Raman coherence in femtosecond coherent anti-Stokes Raman scattering (CARS). A time-delayed probe beam is scattered from the Raman polarization induced by pump and Stokes beams to generate CARS signal; the dephasing rate of this initial coherence is determined by the temperature-sensitive frequency spread of the Raman transitions. Temperature is measured from the CARS signal decrease with increasing probe delay. Concentration is found from the ratio of the CARS and nonresonant background signals. Collision rates do not affect the determination of these quantities

Communication: Time-domain measurement of high-pressure N2 and O2 self-broadened linewidths using hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering

The direct measurement of self-broadened linewidths using the time decay of pure-rotational hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering (fs/ps RCARS) signals is demonstrated in gas-phase N2 and O2 from 1–20 atm. Using fs pump and Stokes pulses and a spectrally narrowed ps probe pulse, collisional dephasing rates with time constants as short as 2.5 ps are captured with high accuracy for individual rotational transitions. S-branch linewidths of N2 and O2 from ∼0.06 to 2.2 cm−1 and the line separation of O2 triplet states are obtained from the measured dephasing rates and compared with high-resolution, frequency-domain measurements and S-branch approximations using the modified exponential gap model. The accuracy of the current measurements suggests that the fs/ps RCARS approach is well suited for tracking the collisional dynamics of gas-phase mixtures over a wide range of pressures

ASSESSING THE IMPACT OF BACKBONE LENGTH AND CAPPING AGENT ON THE CONFORMATIONAL PREFERENCES OF A MODEL PEPTIDE: CONFORMATION SPECIFIC IR AND UV SPECTROSCOPY OF 2-AMINOISOBUTYRIC ACID

2-Aminoisobutyric acid (Aib) is an achiral, ${alpha}$-amino acid having two equivalent methyl groups attached to C$_{alpha}$. Extended Aib oligomers are known to have a strong preference for the adoption of a 3$_{10}$-helical structure in the condensed phase.footnote{Toniolo, C.; Bonora, G. M.; Barone, V.; Bavoso, A.; Benedetti, E.; Di Blasio, B.; Grimaldi, P.; Lelj, F.; Pavone, V.; Pedone, C., Conformation of Pleionomers of $alpha$-Aminoisobutyric Acid. textit{Macromolecules} textbf{1985}, textit{18}, 895-902.} Here, we have taken a simplifying step and focused on the intrinsic folding propensities of Aib by looking at a series of capped Aib oligomers in the gas phase, free from the influence of solvent molecules and cooled in a supersonic expansion. Resonant two-photon ionization and IR-UV holeburning have been used to record single-conformation UV spectra using the Z-cap as the UV chromophore. Resonant ion-dip infrared (RIDIR) spectroscopy provides single-conformation IR spectra in the OH stretch and NH stretch regions. Data have been collected on a set of Z-(Aib)$_{n}$-X oligomers with n = 1, 2, 4, 6 and X = -OH and -OMethyl. The impacts of these capping groups and differences in backbone length have been found to dramatically influence the conformational space accessed by the molecules studied here. Oligomers of n=4 have sufficient backbone length for a full turn of the 3$_{10}$-helix to be formed. Early interpretation of the data collected shows clear spectroscopic markers signaling the onset of 3$_{10}$-helix formation as well as evidence of structures incorporating C7 and C14 hydrogen bonded rings

Fast-framing ballistic imaging of velocity in an aerated spray

We describe further development of ballistic imaging adapted for the liquid core of an atomizing spray. To fully understand spray breakup dynamics, one must measure the velocity and acceleration vectors that describe the forces active in primary breakup. This information is inaccessible to most optical diagnostics, as the signal is occluded by strong scattering in the medium. Ballistic imaging mitigates this scattering noise, resolving clean shadowgram-type images of structures within the dense spray region. We demonstrate that velocity data can be extracted from ballistic images of a spray relevant to fuel-injection applications, by implementing a simple, targeted correlation method for determining velocity from pairs of spray images. This work presents the first ballistic images of a liquid-fuel injector for scramjet combustion, and the first velocity information from ballistic images relevant to breakup in the near-field of a spray

Interference-free gas-phase thermometry at elevated pressure using hybrid femtosecond/picosecond rotational coherent anti- Stokes Raman scattering

Rotational-level-dependent dephasing rates and nonresonant background can lead to significant uncertainties in coherent anti-Stokes Raman scattering (CARS) thermometry under high-pressure, lowtemperature conditions if the gas composition is unknown. Hybrid femtosecond/picosecond rotational CARS is employed to minimize or eliminate the influence of collisions and nonresonant background for accurate, frequency-domain thermometry at elevated pressure. The ability to ignore these interferences and achieve thermometric errors of \u3c5% is demonstrated for N2 and O2 at pressures up to 15 atm. Beyond 15 atm, the effects of collisions cannot be ignored but can be minimized using a short probe delay (~6.5 ps) after Raman excitation, thereby improving thermometric accuracy with a time- and frequency-resolved theoretical model

Communication: Hybrid femtosecond/picosecond rotational coherent anti-Stokes Raman scattering thermometry using a narrowband time-asymmetric probe pulse

A narrowband, time-asymmetric probe pulse is introduced into the hybrid femtosecond/picosecond rotational coherent anti-Stokes Raman scattering (fs/ps RCARS) technique to provide accurate and precise single-shot, high-repetition-rate gas-phase thermometric measurements. This narrowband pulse-generated by inserting a Fabry-Pérot étalon into the probe-pulse beam path-enables frequency-domain detection of pure-rotational transitions. The unique time-asymmetric nature of this pulse, in turn, allows for detection of resonant Raman-active rotational transitions free of signal contamination by nonresonant four-wave-mixing processes while still allowing detection at short probe-pulse delays, where collisional dephasing processes are negligible. We demonstrate that this approach provides excellent single-shot thermometric accuracy (1 error) and precision (∼2.5) in gas-phase environments