Ultraviolet Photodissociation of the N-Methylpyridinium Ion: Action Spectroscopy and Product Characterization

The ultraviolet photodissociation of gas-phase N-methylpyridinium ions is studied at room temperature using laser photodissociation mass spectrometry and structurally diagnostic ion-molecule reaction kinetics. The C5H5N-CH3+ (m/z 94), C5H5N-CD3+ (m/z 97), and C5D5N-CH3+(m/z 99) isotopologues are investigated, and it is shown that the N-methylpyridinium ion photodissociates by the loss of methane in the 36 000 - 43 000 cm(-1) (280 - 230 nm) region. The dissociation likely occurs on the ground state surface following internal conversion from the SI state. For each isotopologue, by monitoring the photofragmentation yield as a function of photon wavenumber, a broad vibronically featured band is recorded with origin (0-0) transitions assigned at 38 130, 38 140 and 38 320 cm(-1) for C5H5N-CH3+ C5H5N-CD3+ and C5D5N-CH3+, respectively. With the aid of quantum chemical calculations (CASSCF(6,6)/aug-cc-pVDZ), most of the observed vibronic detail is assigned to two in-plane ring deformation modes. Finally, using ion-molecule reactions, the methane coproduct at m/z 78 is confirmed as a 2-pyridinylium ion.

Thin-Layer Chromatography with Ultraviolet and Mass Spectrometric Detection: From Preparative-Layer to Miniaturized Ultra-Thin-Layer Technique

The present challenge in drug discovery is to synthesize new compounds efficiently in minimal time. The trend is towards carefully designed and well-characterized compound libraries because fast and effective synthesis methods easily produce thousands of new compounds. The need for rapid and reliable analysis methods is increased at the same time. Quality assessment, including the identification and purity tests, is highly important since false (negative or positive) results, for instance in tests of biological activity or determination of early-ADME parameters in vitro (the pharmacokinetic study of drug absorption, distribution, metabolism, and excretion), must be avoided. This thesis summarizes the principles of classical planar chromatographic separation combined with ultraviolet (UV) and mass spectrometric (MS) detection, and introduces powerful, rapid, easy, low-cost, and alternative tools and techniques for qualitative and quantitative analysis of small drug or drug-like molecules. High performance thin-layer chromatography (HPTLC) was introduced and evaluated for fast semi-quantitative assessment of the purity of synthesis target compounds. HPTLC methods were compared with the liquid chromatography (LC) methods. Electrospray ionization mass spectrometry (ESI MS) and atmospheric pressure matrix-assisted laser desorption/ionization MS (AP MALDI MS) were used to identify and confirm the product zones on the plate. AP MALDI MS was rapid, and easy to carry out directly on the plate without scraping. The PLC method was used to isolate target compounds from crude synthesized products and purify them for bioactivity and preliminary ADME tests. Ultra-thin-layer chromatography (UTLC) with AP MALDI MS and desorption electrospray ionization mass spectrometry (DESI MS) was introduced and studied for the first time. Because of the thinner adsorbent layer, the monolithic UTLC plate provided 10 100 times better sensitivity in MALDI analysis than did HPTLC plates. The limits of detection (LODs) down to low picomole range were demonstrated for UTLC AP MALDI and UTLC DESI MS. In a comparison of AP and vacuum MALDI MS detection for UTLC plates, desorption from the irregular surface of the plates with the combination of an external AP MALDI ion source and an ion trap instrument provided clearly less variation in mass accuracy than the vacuum MALDI time-of-flight (TOF) instrument. The performance of the two-dimensional (2D) UTLC separation with AP MALDI MS method was studied for the first time. The influence of the urine matrix on the separation and the repeatability was evaluated with benzodiazepines as model substances in human urine. The applicability of 2D UTLC AP MALDI MS was demonstrated in the detection of metabolites in an authentic urine sample.

Dynamics of I-asterisk(P-2(1/2)) production inthe ultraviolet photodissociation of alkyn iodides

The relative quantum yields, phi*, for the production of I*(P-2(1/2)) at 266, 280, and similar to 305 nm are reported for a series of primary alkyl iodides using the technique of two-photon laser-induced fluorescence for the detection of I(P-2(3/2)) and I*(P-2(1/2)) atoms. Results are analyzed by invoking the impulsive energy disposal model, which summarizes the dynamics of dissociation as a single parameter. Comparison of our data with those calculated by a more sophisticated time-dependent quantum mechanical model is also made. Near the red edge of the alkyl iodide A band, absorption contribution from the (3)Q(1) state is important and the dynamics near the (3)Q(0)-(1)Q(1) curve-crossing region seem to be influenced by the kinematics of the dissociation process

Time and space-resolved measurement of a gas-puff laser-plasma x-ray source

The dynamic interaction processes between a nano-second laser pulse and a gas-puff target, such as those of plasma formation, laser heating, and x-ray emission, have been investigated quantitatively. Time and space-resolved x-ray and optical measurement techniques were used in order to investigate time-resolved laser absorption and subsequent x-ray generation. Efficient absorption of the incident laser energy into the gas-puff target of 17%, 12%, 38%, and 91% for neon, argon, krypton, and xenon, respectively, was shown experimentally. It was found that the laser absorption starts and, simultaneously, soft x-ray emission occurs. The soft x-ray lasts much longer than the laser pulse due to the recombination. Temporal evolution of the soft x-ray emission region was analyzed by comparing the experimental results to the results of the model calculation, in which the laser light propagation through a gas-puff plasma was taken into account. (C) 2003 American Institute of Physics.

Theoretical investigation of single attosecond pulse generation in an orthogonally polarized two-color laser field

We theoretically demonstrate the generation of extreme ultraviolet supercontinua in an orthogonally polarized two-color few-cycle laser field. We show that the ionized electrons can be driven back to their parent ion after traveling along curved trajectories in a plane perpendicular to the beam propagation direction, giving rise to a train of attosecond pulses at different polarization angles. A single isolated attosecond pulse can be obtained by blocking the low-order high harmonics, which contribute to the formation of the satellite pulses. (C) 2008 Optical Society of America.

Optical breakdown of 6H SiC induced by wavelength-tunable femtosecond laser pulses

The damage mechanisms and micromachining of 6H SiC are studied by using femtosecond laser pulses at wavelengths between near infrared (NIR) and near ultraviolet (NUV) delivered from an optical parametric amplifier (OPA). Our experimental results indicate that high quality microstructures can be fabricated in SiC crystals. On the basis of the dependence of the ablated area and the laser pulse energy, the threshold fluence of SiC is found to increase with the incident laser wavelength in the visible region, while it remains almost constant for the NIR laser. For the NIR laser pulses, both photoionization and impact ionization play important roles in electronic excitation, while for visible lasers, photoionization plays a more important role.

Temporal confinement and enhancement of high-order harmonic emission with a synthesized laser field

We demonstrated that a synthesized laser field consisting of an intense long (45 fs, multi-optical-cycle) laser pulse and a weak short (7 fs, few-optical-cycle) laser pulse can control the electron dynamics and high-order harmonic generation in argon, and generate extreme ultraviolet supercontinuum towards the production of a single strong attosecond pulse. The long pulse offers a large amplitude field, and the short pulse creates a temporally narrow enhancement of the laser field and a gate for the highest energy harmonic emission. This scheme paves the way to generate intense isolated attosecond pulses with strong multi-optical-cycle laser pulses.

Red laser-induced domain inversion in MgO-doped lithium niobate crystals

A laser beam at wavelength 647 nm is focused on a sample of 5 mol% MgO-doped lithium niobate crystal for domain inversion by a conventional external electric field. In this case, a reduction of 36% in the electric field required for domain nucleation (nucleation field) is observed. To the best of our knowledge, it is the longest wavelength reported for laser-induced domain inversion. This extends the spectrum of laser inducing, and the experimental results are helpful to understand the nucleation dynamics under laser illumination. The dependence of nucleation fields on intensities of laser beams is analysed in experiments.

Blue emission from Eu2+ -doped high silica glass by near-infrared femtosecond laser irradiation

Eu2+-doped high silica glass (HSG) is fabricated by sintering porous glass which is impregnated with europium ions. Eu2+-doped HSG is revealed to yield intense blue emission excited by ultraviolet (UV) light and near-infrared femtosecond laser. The emission profile obtained by UV excitation can be well traced by near-infrared femtosecond laser. The upconversion emission excited by 800 nm femtosecond laser is considered to be related to a two-photon absorption process from the relationship between the integrated intensity and the pump power. A tentative scheme of upconverted blue emission from Eu2+-doped HSG was also proposed. The HSG materials presented herein are expected to find applications in high density optical storage and three-dimensional color displays. (c) 2008 American Institute of Physics.

Blue upconversion luminescence generation in Ce3+: Gd2SiO5 crystals by infrared femtosecond laser irradiation

Blue frequency-upconversion fluorescence emission has been observed in Ce3+-doped Gd2SiO5 single crystals, pumped with 120-fs 800 nm IR laser pulses. The observed fluorescence emission peaks at about 440nm is due to 5d -> 4f transition of Ce3+ ions. The intensity dependence of the blue fluorescence emission on the IR excitation laser power obeys the cubic law, demonstrating three-photon absorption process. Analysis suggested that three-photon simultaneous absorption induced population inversion should be the predominant frequency upconversion mechanism. (c) 2006 Optical Society of America.

Three-photon-excited upconversion luminescence of Ce3+: YAP crystal by femtosecond laser irradiation

Infrared to ultraviolet and visible upconversion luminescence was demonstrated in trivalent cerium doped YAlO3 crystal (Ce3+: YAP) under focused infrared femtosecond laser irradiation. The fluorescence spectra show that the upconverted luminescence comes from the 5d-4f transitions of trivalent cerium ions. The dependence of luminescence intensity of trivalent cerium on infrared pumping power reveals that the conversion of infrared radiation is dominated by three-photon excitation process. It is suggested that the simultaneous absorption of three infrared photons pumps the Ce3+ ion into upper 5d level, which quickly nonradiatively relax to lowest 5d level. Thereafter, the ions radiatively return to the ground states, leading to the characteristic emission of Ce3+. (c) 2005 Optical Society of America.

Photoreduction of Ag+ in aluminoborate glasses induced by irradiation of a femtosecond laser

We report on photoreduction of Ag+ in aluminoborate glasses induced by irradiation of a femtosecond laser. Novel fluorescence was observed in the femtosecond laser irradiated glass when excited by a 365 nm ultraviolet lamp. Optical absorption, emission, and electron spin resonance spectra of the glass samples demonstrated that after the laser irradiation, portions of silver ions near the focused part of the laser beam inside the glass were reduced to silver atoms, which resulted in the formation of the characteristic fluorescence. The observed phenomenon may have promising applications in the fabrication of functional optical devices.