NT230 series High Energy Broadly Tunable DPSS Lasers

Hydrated singly charged magnesium ions [Mg(H₂O)_n]⁺ are thought to consist of an Mg²⁺ ion and a hydrated electron for n > 15. This idea is based on mass spectra, which exhibit a transition from [MgOH(H₂O)_n−1]⁺ to [Mg(H₂O)_n]⁺ around n = 15 – 22, black-body infrared radiative dissociation, and quantum chemical calculations. Here, we present photodissociation spectra of size-selected [Mg(H₂O)_n]⁺ in the range of n = 20 – 70 measured for photon energies of 1.0 – 5.0 eV. The spectra exhibit a broad absorption from 1.4 to 3.2 eV, with two local maxima around 1.7 – 1.8 eV and 2.1 – 2.5 eV, depending on cluster size. The spectra shift slowly from n = 20 to n = 50, but no significant change is observed for n = 50 – 70. Quantum chemical modeling of the spectra yields several candidates for the observed absorptions, including five- and six-fold coordinated Mg²⁺ with a hydrated electron in its immediate vicinity, as well as a solvent-separated Mg²⁺/e⁻ pair. The photochemical behavior resembles that of the hydrated electron, with barrierless interconversion into the ground state following the excitation.

Here we report gas-phase action and luminescence spectra of cationic dyes derived from oxazine: cresyl violet (CV⁺), oxazine 170 (Ox-170⁺), nile blue (NB⁺), darrow red (DR⁺), oxazine 1 (Ox-1⁺), oxazine 4 (Ox-4⁺), and brilliant cresyl blue (BCB⁺). The first four have a benzofused structure, which results in asymmetric charge distributions along the long axis. The positive charge is also asymmetrically distributed in BCB⁺ while Ox-1⁺ and Ox-4⁺ are symmetric. As the ions are isolated in vacuo, there are no interactions with solvent molecules or counter ions, and the effect of chemical modifications is therefore more easily revealed than from solution-phase experiments. The transition energy decreases in the order: DR⁺ > CV⁺ > Ox-4⁺ > Ox-170⁺ > BCB⁺ > Ox-1⁺ > NB⁺, and the fluorescence from BCB⁺ is less than from the others. We discuss the results based on electron delocalisation, degree of charge-transfer character, rigidity of the chromophore structure, and substituents.

Hydrated singly charged magnesium ions Mg⁺(H₂O)_n, n ≤ 5, in the gas phase are ideal model systems to study photochemical hydrogen evolution since atomic hydrogen is formed over a wide range of wavelengths, with a strong cluster size dependence. Mass selected clusters are stored in the cell of an Fourier transform ion cyclotron resonance mass spectrometer at a temperature of 130 K for several seconds, which allows thermal equilibration via blackbody radiation. Tunable laser light is used for photodissociation. Strong transitions to D_1 – 3 states (correlating with the 3s-3p_x,y,z transitions of Mg⁺) are observed for all cluster sizes, as well as a second absorption band at 4 – 5 eV for n = 3-5. Due to the lifted degeneracy of the 3p_x,y,z energy levels of Mg⁺, the absorptions are broad and red shifted with increasing coordination number of the Mg⁺ center, from 4.5 eV for n = 1 to 1.8 eV for n = 5. In all cases, H atom formation is the dominant photochemical reaction channel. Quantum chemical calculations using the full range of methods for excited state calculations reproduce the experimental spectra and explain all observed features. In particular, they show that H atom formation occurs in excited states, where the potential energy surface becomes repulsive along the O⋯H coordinate at relatively small distances. The loss of H₂O, although thermochemically favorable, is a minor channel because, at least for the clusters n = 1-3, the conical intersection through which the system could relax to the electronic ground state is too high in energy. In some absorption bands, sequential absorption of multiple photons is required for photodissociation. For n = 1, these multiphoton spectra can be modeled on the basis of quantum chemical calculations.

Marine aerosols consist of a variety of compounds and play an important role in many atmospheric processes. In the present study, sodium iodide clusters with their simple isotope pattern serve as model systems for laboratory studies to investigate the role of iodide in the photochemical processing of sea-salt aerosols. Salt clusters doped with camphor, formate and pyruvate are studied in a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) coupled to a tunable laser system in both UV and IR range. The analysis is supported by ab initio calculations of absorption spectra and energetics of dissociative channels. We provide quantitative analysis of IRMPD measurements by reconstructing one-photon spectra and comparing them with the calculated ones. While neutral camphor is adsorbed on the cluster surface, the formate and pyruvate ions replace an iodide ion. The photodissociation spectra revealed several wavelength-specific fragmentation pathways, including the carbon dioxide radical anion formed by photolysis of pyruvate. Camphor and pyruvate doped clusters absorb in the spectral region above 290 nm, which is relevant for tropospheric photochemistry, leading to internal conversion followed by intramolecular vibrational redistribution, which leads to decomposition of the cluster. Potential photodissociation products of pyruvate in the actinic region may be formed with a cross section of <2×10⁻²⁰ cm², determined by the experimental noise level.

Time-resolved serial femtosecond crystallography using an X-ray free electron laser (XFEL) in conjunction with a photosensitive caged-compound offers a crystallographic method to track enzymatic reactions. Here we demonstrate the application of this method using fungal NO reductase, a heme-containing enzyme, at room temperature. Twenty milliseconds after caged-NO photolysis, we identify a NO-bound form of the enzyme, which is an initial intermediate with a slightly bent Fe-N-O coordination geometry at a resolution of 2.1 Å. The NO geometry is compatible with those analyzed by XFEL-based cryo-crystallography and QM/MM calculations, indicating that we obtain an intact Fe³⁺-NO coordination structure that is free of X-ray radiation damage. The slightly bent NO geometry is appropriate to prevent immediate NO dissociation and thus accept H⁻ from NADH. The combination of using XFEL and a caged-compound is a powerful tool for determining functional enzyme structures during catalytic reactions at the atomic level.

We report a target-enclosing, hybrid tomograph with a total of 768 elements based on capacitive micromachined ultrasound transducer technology and providing fast, high-resolution 2-D/3-D photoacoustic and ultrasound tomography tailored to finger imaging.A freely programmable ultrasound beamforming platform sampling data at 80 MHz was developed to realize plane wave transmission under multiple angles. A multiplexing unit enables the connection and control of a large number of elements. Fast image reconstruction is provided by GPU processing. The tomograph is composed of four independent and fully automated movable arc-shaped transducers, allowing imaging of all three finger joints. The system benefits from photoacoustics, yielding high optical contrast and enabling visualization of finger vascularization, and ultrasound provides morphologic information on joints and surrounding tissue. A diode-pumped, Q-switched Nd:YAG laser and an optical parametric oscillator are used to broaden the spectrum of emitted wavelengths to provide multispectral imaging. Custom-made optical fiber bundles enable illumination of the region of interest in the plane of acoustic detection. Precision in positioning of the probe in motion is ensured by use of a motor-driven guide slide. The current position of the probe is encoded by the stage and used to relate ultrasound and photoacoustic signals to the corresponding region of interest of the suspicious finger joint. The system is characterized in phantoms and a healthy human finger in vivo. The results obtained promise to provide new opportunities in finger diagnostics and establish photoacoustic/ultrasoundtomography in medical routine.

Protonated leucine enkephalin (YGGFL) was studied by ultraviolet photodissociation (UVPD) from 225 to 300 nm utilizing an optical parametric oscillator tunable wavelength laser system (OPO). Fragments were identified by absolute mass measurement in a 9.4 T Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). Bond cleavage was preferred in the vicinity of the two aromatic residues, resulting in high ion abundances for a₄, a₁, b₃, y₂ and y₁ fragments. a, b and y ions dominated the mass spectrum, and full sequence coverage was achieved for those types. Photodissociation was most effective at the short wavelength end of the studied range, which is assigned to the onset of the L_a π–π* transition of the tyrosine chromophore, but worked well also at the L_b π–π* chromophore absorption maxima in the 35 000 – 39 000 cm⁻¹ region. Several side-chain and internal fragments were observed. H atom loss is observed only above 41 000 cm⁻¹, consistent with the requirement of a curve crossing to a repulsive ¹πσ* state. It is suggested that the photochemically generated mobile H atom plays a role in further backbone cleavages, similar to the mechanism for electron capture dissociation. The b₄ fragment is most intense at the L_b chromophore absorptions, undergoing additional fragmentation at higher photon energies. The high resolution of the FT-ICR MS revealed that out of all x and z-type fragments only x₃ and x₄ were formed, with low intensity. Other previously reported x- and z-fragments were re-assigned to internal fragments, based on exact mass measurement.

A relatively simple setup for collection and detection of light emitted from isolated photo-excited molecular ions has been constructed. It benefits from a high collection efficiency of photons, which is accomplished by using a cylindrical ion trap where one end-cap electrode is a mesh grid combined with an aspheric condenser lens. The geometry permits nearly 10% of the emitted light to be collected and, after transmission losses, approximately 5% to be delivered to the entrance of a grating spectrometer equipped with a detector array. The high collection efficiency enables the use of pulsed tunable lasers with low repetition rates (e.g., 20 Hz) instead of continuous wave (cw) lasers or very high repetition rate (e.g., MHz) lasers that are typically used as light sources for gas-phase fluorescence experiments on molecular ions. A hole has been drilled in the cylinder electrode so that a light pulse can interact with the ion cloud in the center of the trap. Simulations indicate that these modifications to the trap do not significantly affect the storage capability and the overall shape of the ion cloud. The overlap between the ion cloud and the laser light is basically 100%, and experimentally >50% of negatively charged chromophore ions are routinely photodepleted. The performance of the setup is illustrated based on fluorescence spectra of several laser dyes, and the quality of these spectra is comparable to those reported by other groups. Finally, by replacing the optical system with a channeltron detector, we demonstrate that the setup can also be used for gas-phase action spectroscopy where either depletion or fragmentation is monitored to provide an indirect measurement on the absorption spectrum of the ion.

Benzhydryl radicals and cations are reactive intermediates central to the under-standing of organic reactivity. They can be generated from benzhydryl halides by UV irradi-ation. We performed transient absorption (TA) measurements over the range from femto -seconds to microseconds to unravel the complete reaction scheme. The 290 – 720-nm proberange allows the unambiguous monitoring of all fragments. The appearance of the radical isdelayed to the optical excitation, the onset of the cation signal is found even later. Ab initiocalculations show that this non-rate behavior in the 100 fs range is due to wavepacket motionfrom the Franck–Condon region to two distinct conical intersections. The rise of the opticalsignal with a quasi-exponential time of 300 fs is assigned to the planarization and solvationof the photoproducts. The bond cleavage predominantly generates radical pairs. A subse-quent electron transfer (ET) transforms radical pairs into ion pairs. Due to the broad inter-radical distance distribution and the distance dependence, the ET is strongly non-exponen-tial. Part of the ion pairs recombine geminately. The ET and the recombination are terminatedby the depletion of close pairs and diffusional separation. The remaining free radicals and cations undergo further reactions in the nanosecond to microsecond regime.