Analysis of glass by UV laser ablation inductively coupled plasma atomic emission spectrometry. Part 1. Effects of the laser parameters on the amount of ablated material and the temporal behaviour of the signal for different types of laser

Two lasers working in the UV part of the spectrum have been used for the analysis of glass samples. An XeCl excimer laser (308 nm) and a Nd:YAG laser operating at the third harmonic (355 nm) and the fourth harmonic (266 nm) have been selected. The energy was 100 mJ and 5 mJ for the excimer laser and the Nd:YAG laser, respectively. Because of different spot sizes, the fluence was of the same magnitude for both lasers. Crater characterization indicated that the laser ablation efficiency was similar for the two lasers when normalized to the same energy. However, the XeCl was found to be more efficient when the results were normalized to irradiance unit. The amount of probed material and ablated material was measured, leading to an efficiency higher than 80%. The influence of the glass colour and the laser wavelength was evaluated. The XeCl laser provided the largest amount of material but was sensitive to the glass colour. This laser was mainly suitable for bulk analysis. In contrast, the Nd:YAG, particularly at 266 nm, was insensitive to the glass colour and was appropriate for localized analysis. Inductively coupled plasma atomic emission spectrometry was used for atomization and excitation of the ablated material. A good agreement was found between the temporal behaviour of the amount of ablated material and the analyte signal.     

Analysis of glass by UV laser ablation inductively coupled plasma atomic emission spectrometry. Part 2. Analytical figures of merit

Two lasers working in the UV part of the spectrum have been used for the direct analysis of glass samples by laser ablation ICP-AES. An XeCl excimer laser (308 nm) and a Nd:YAG laser operating at the third harmonic (355 nm) and the fourth harmonic (266 nm) have been selected. The energy was 70 mJ and 5 mJ for the excimer laser and the Nd:YAG laser, respectively, with a 10 Hz repetition rate. Figures of merit such as repeatability, reproducibility, accuracy and limits of detection have been studied. Si was used as an internal standard to improve the repeatability, the reproducibility and the accuracy. Use of internal standardardization led to an RSD of less than 1% for most elements and to a linear calibration graph irrespective of the colour of the glass samples. Limits of detection in the solid were of the same magnitude as those obtained using sample dissolution and pneumatic nebulization. Results confirmed that the XeCl laser provided the best results of detection whereas the Nd:YAG laser, particularly at 266 nm, was less sensitive to glass colour.     

Ionization of pesticides using a far-ultraviolet femtosecond laser in gas chromatography/time-of-flight mass spectrometry

The fourth harmonic emission (200 nm) of a femtosecond Ti:sapphire laser (35 fs) was generated and used in the multiphoton ionization of 49 pesticides in gas chromatography/time-of-flight mass spectrometry. The limit of detection was improved when the ionization source from the third harmonic emission (267 nm) was replaced with the fourth harmonic emission for several pesticide molecules that contained no conjugated double bonds since their absorption bands are located in the far-ultraviolet region. This analytical instrument was used in the analysis of a series of real samples including potatoes, carrots, and cabbage, and a signal suspected to arise from di-allate was observed for the potato sample.

Femtosecond laser time-of-flight mass spectrometry of labile molecular analytes: laser-desorbed nitro-aromatic molecules.

Femtosecond laser time-of-flight mass spectra of solid samples of trinitrobenzene (TNB), trinitrotoluene (TNT) and trinitrophenol (TNP) have been recorded. Desorption of the solid samples was enacted by the fourth harmonic output (266 nm) of a 5 ns Nd:YAG laser. Subsequent femtosecond post-ionisation of the plume of neutral molecules was achieved using 800 nm laser pulses of 80 fs duration. Mass spectra have been recorded for desorption laser intensities from 2-6 x 10(9) W cm(-2) with ionisation laser intensities between 2 x 10(14) and 6 x 10(15) W cm(-2). Femtosecond laser ionisation has been shown to be capable of generating precursor and characteristic high-mass fragment ions for labile nitro-aromatic molecules commonly used in high-explosive materials. This feature is critical in the future development of femtosecond laser-based analytical instruments that can be used for complex molecular identification and quantitative analysis of environmentally important labile molecules. Furthermore, a comparison of femtosecond post-ionisation mass spectra with standard 70 eV electron impact data has revealed similarities in the spectra and hence the fragmentation processes.     

Excited state intramolecular proton transfer of novel conjugated derivatives containing hydroxy and imino groups

<正>This letter presents excited state intramolecular proton transfer(ESIPT) of new conjugated derivatives containing hydroxy and imino groups.ESIPT occurrence in one photon process is confirmed by well-separated emission band for the derivatives.Twophoton absorption(TPA) induced ESIPT emission has been determined by Ti:sapphire femtosecond laser tuning from 700 nm to 800 nm at the internals of 20 nm.     

Two-color two-photon excitation using femtosecond laser pulses

The use of two-color two-photon (2c2p) excitation easily extends the wavelength range of Ti:sapphire lasers to the UV, widening the scope of its applications especially in biological sciences. We report observation of 2c2p excitation fluorescence of p-terphenyl (PTP), 2-methyl-5-t-butyl-p-quaterphenyl (DMQ) and tryptophan upon excitation with 400 and 800 nm wavelengths using the second harmonic and fundamental wavelength of a mode-locked Ti:sapphire femtosecond laser. This excitation is energetically equivalent to a one-photon excitation wavelength at 266 nm. The fluorescence signal is observed only when both wavelengths are spatially and temporally overlapping. Adjustment of the relative delay of the two laser pulses renders a cross correlation curve which is in good agreement with the pulse width of our laser. The fluorescence signal is linearly dependent on the intensity of each of the two colors but quadratically on the total incident illumination power of both colors. In fluorescence microscopy, the use of a combination of intense IR and low-intensity blue light as a substitute for UV light for excitation can have numerous advantages. Additionally, the effect of differently polarized excitation photons relative to each other is demonstrated. This offers information about different transition symmetries and yields deeper insight into the two-photon excitation process.     

Determination of additives in PVC material by UV laser ablation inductively coupled plasma atomic emission spectrometry

UV laser ablation inductively coupled plasma atomic emission spectrometry (LA-ICP-AES) has been applied to the direct determination of additives in solid poly(vinyl chloride) materials. A Nd:YAG laser, operating at its fourth harmonic (266 nm), was used with a beam masking device, in the most reproducible conditions, to introduce solid particles into the plasma torch of a simultaneous ICP-AES system. Emphasis was placed on both precision and accuracy in the analysis of PVC materials by LA-ICP-AES. A series of six in-house PVC reference materials was prepared by incorporating several additives in increasing concentrations. Three alternative methods were evaluated to certify the amount of incorporated elements: ICP-AES with sample dissolution, NAA and XRF. Satisfactory results and good agreement were obtained for seven elements (Al, Ca, Cd, Mg, Sb, Sn and Ti) among the ten incorporated. Sample homogeneity appeared to be satisfactory, and calibration graphs obtained by LA-ICP-AES for several elements are presented. Finally, the performance of the technique in terms of repeatability (1.6-5%), reproducibility (2–5%), and limits of detection was investigated.     

Study of laser ablation of brass materials using inductively coupled plasma atomic emission spectrometric detection

A XeCl laser and a Q-switched Nd:YAG laser operating at 1064, 532, 355 and 266 nm were used to ablate brass materials with varying concentrations of Zn and Cu. The ablated material was transported to an inductively coupled plasma for further atomization, excitation and ionization with an atomic emission spectrometric detection. A Zn enhancement was observed, which could be suppressed by using a Nd:YAG laser working at 266 nm with fluences higher than 400 J cm⁻² (equivalent to 80 GW cm⁻²). In contrast, a lack of linearity was observed for Cu as a function of the concentration, regardless of the wavelength and the fluence. The Cu problem seemed to occur during the ablation and was related to the structure of the brass material. Lack of linearity was also observed for Zn and other contained elements when samples from different origins were used.     

Synthesis and Characterization of ZnO Nanowires

Zinc oxide is a wide bandgap (3.37 eV) semiconductor with a hexagonal wurtzite crystal structure. ZnO prepared in nanowire form may be used as a nanosized ultraviolet light-emitting source. In this study, ZnO nanowires were prepared by vapor-phase transport of Zn vapor onto gold-coated silicon substrates in a tube furnace heated to 900 ?C. Gold serves as a catalyst to capture Zn vapor during nanowire growth. Size control of ZnO nanowires has been achieved by varying the gold film thickness…     

Basic investigations for laser microanalysis: IV. The dependence on the laser wavelength in laser ablation

The fourth harmonic wavelength at 266 nm as well as the fundamental radiation at 1.06 m of a pulsed Nd: YAG laser has been used for ablation of solid samples. Using different buffer gases and different samples, the ablated masses and plasma temperatures obtained with the two different laser wavelengths are compared. The analytical application of 266-nm laser pulses is studied by the measurement of aluminium and manganese in steel and boraxglass (Na₂B₄O₇) samples.     

Trace element analysis of synthetic mono- and poly-crystalline CaF2 by ultraviolet laser ablation inductively coupled plasma mass spectrometry at 266 and 193 nm

The analytical figures of merit for ultraviolet laser ablation-inductively coupled plasma mass spectrometry (UV-LA-ICP-MS) at 266 nm with respect to the trace element analysis of high-purity, UV-transmitting alkaline earth halides are investigated and discussed. Ablation threshold energy density values and ablation rates for mono- and poly-crystalline CaF₂ samples were determined. Furthermore, Pb-, Rb-, Sr-, Ba- and Yb-specific analysis was performed. For these purposes, a pulsed Nd:YAG laser operated at the fourth harmonic of the fundamental wavelength (λ=266 nm) and a double-focusing sector field ICP-MS detector were employed. Depending on the background noise and isotope-specific sensitivity, the detection limits typically varied from 0.7 ng/g for Sr to 7 ng/g in the case of Pb. The concentrations were determined using a glass standard reference material (SRM NIST612). In order to demonstrate the sensitivity of the arrangement described, comparative measurements by means of a commercial ablation system consisting of an ArF excimer laser (λ=193 nm) and a quadrupole-type ICP-MS (ICP-QMS) instrument were carried out. The accuracy of both analyses was in good agreement, whereas ablation at 266 nm and detection using sector-field ICP-MS led to a sensitivity that was one order of magnitude above that obtained at 193 nm with ICP-QMS.     

Recent trends and developments in laser ablation-ICP-mass spectrometry

The increased interest in laser technology (e.g. for micro-machining, for medical applications, light shows, CD-players) is a tremendous driving force for the development of new laser types and optical set-ups. This directly influences their use in analytical chemistry. For direct analysis of the elemental composition of solids, mostly solid state lasers, such as Nd:YAG laser systems operating at 1064 nm (fundamental wavelength), 266 nm (frequency quadrupled) and even 213 nm (frequency quintupled) have been investigated in combination with all available inductively coupled plasma mass spectrometers. The trend towards shorter wavelengths (1064 nm - 157 nm) was initiated by access to high quality optical materials which led to the incorporation of UV gas lasers, such as excimer lasers (XeCl 308 nm, KrF 248 nm, ArF 193 nm, and F2 157 nm) into laser ablation set-ups. The flexibility in laser wavelengths, output energy, repetition rate, and spatial resolution allows qualitative and quantitative local and bulk elemental analysis as well as the determination of isotope ratios. However, the ablation process and the ablation behavior of various solid samples are different and no laser wavelength was found suitable for all types of solid samples. This article highlights some of the successfully applied systems in LA-ICP-MS. The current fields of applications are explained on selected examples using 266 nm and 193 nm laser ablation systems.     

Experimental determination of laser induced breakdown thresholds of metals under nanosecond Q-switched laser operation

Laser-induced breakdown thresholds for several pure metals were determined using a nanosecond laser. A Q-switched pulsed Nd:YAG laser operating at infrared (1064 nm), visible (532 nm) and ultraviolet (266 nm) wavelengths has been used. The plasma was generated by focusing the Nd:YAG laser on the target in air at atmospheric pressure. The dispersed plasma light was detected using a two-dimensional intensified charge-coupled device (CCD) detector. The studied elements were chosen according to their different thermal and physical properties, particularly boiling point, melting point and thermal conductivity. The effect of wavelength on the plasma threshold has been discussed. Laser fluence thresholds in the ultraviolet were larger than those obtained using visible and infrared radiation, while the energy threshold is larger using infrared radiation. Correlations between the plasma threshold of metal targets and the melting point and boiling point at 266, 532 and 1064 nm have been established. The results indicate that thermal effects have an important influence on the ablation behavior of metals at the three wavelengths used.     

Photocrosslinking of copolymers of vinyloxyethyl methacrylate–styrene initiated by sulfonium salts. I. Transient species formed on photolysis of sulfonium salt

Benzyl cation was detected by transient absorption spectroscopy with a spectroscopic multichannel analyzer on pulse excitation (fourth harmonic of Nd:YAG laser, 266 nm; 10 ns fwhm) of benzyl(4-hydroxyphenyl) methylsulfonium hexafluoroantimonate(BSS) in 1,2-dichloroethane (EDC). The benzyl cation was long-lived (lifetime, 59 ms) at room temperature and quenched by a vinyl ether compound. The formation of the benzyl cation as active species on photolysis of BSS is in contrast to the formation of Brønsted acids in other sulfonium salts so far reported. © 1992 John Wiley & Sons, Inc.     

The luminescence response of Eu(III)-thenoyltrifluoroacetonate complexes upon preresonant excitation with femtosecond laser pulses

The luminescence of thenoyltrifluoroacetonate (TTA) coordination complexes of trivalent europium ion (Eu(III)) in aqueous solutions and in solid-state polymeric films is probed upon single- and two-photon preresonant excitation with Ti:sapphire femtosecond laser. Particularly, diamine-liganded Eu(III)(TTA)₃ and poly(oxyethylene phosphate)tris(β-diketonate)Eu(III) complexes are examined aiming their possible applications as luminescent labels for sensing and imaging of biological molecules. Even at a pre-resonance, the excitation of these compounds with high-intensity, broadband light of frequency-doubled Ti:sapphire femtosecond laser centered around 400 nm results in a luminescence response suitable for fluorometric applications.     

Recent trends and developments in laser ablation-ICP-mass spectrometry

The increased interest in laser technology (e.g. for micro-machining, for medical applications, light shows, CD-players) is a tremendous driving force for the development of new laser types and optical set-ups. This directly influences their use in analytical chemistry. For direct analysis of the elemental composition of solids, mostly solid state lasers, such as Nd:YAG laser systems operating at 1064 nm (fundamental wavelength), 266 nm (frequency quadrupled) and even 213 nm (frequency quintupled) have been investigated in combination with all available inductively coupled plasma mass spectrometers. The trend towards shorter wavelengths (1064 nm– 157 nm) was initiated by access to high quality optical materials which led to the incorporation of UV gas lasers, such as excimer lasers (XeCl 308 nm, KrF 248 nm, ArF 193 nm, and F₂ 157 nm) into laser ablation set-ups. The flexibility in laser wavelengths, output energy, repetition rate, and spatial resolution allows qualitative and quantitative local and bulk elemental analysis as well as the determination of isotope ratios. However, the ablation process and the ablation behavior of various solid samples are different and no laser wavelength was found suitable for all types of solid samples. This article highlights some of the successfully applied systems in LA-ICP-MS. The current fields of applications are explained on selected examples using 266 nm and 193 nm laser ablation systems.     

Reactivity between biphenyl and precursor of solvated electrons in tetrahydrofuran measured by picosecond pulse radiolysis in near-ultraviolet, visible, and infrared

The initial decrease of solvated electrons in tetrahydrofuran (THF) upon addition of biphenyl was investigated by picosecond pulse radiolysis. Transient absorption spectra derived from the biphenyl radical anion (centered at 408 and 655 nm) and solvated electrons of THF (infrared) were successfully measured in the wavelength region from 400 to 900 nm by the extension of a femtosecond continuum probe light to near-ultraviolet using a second harmonic generation of Ti:sapphire laser and a CaF2 plate. From the analysis of kinetic traces at 1300 nm considering the overlap of primary solvated electrons and partial biphenyl radical anion, C37, which is defined by the solute concentration to reduce the initial yield of solvated electrons to 1/e, was found to be 87 +/- 3 mM. The rate constant of solvated electrons with biphenyl was determined as 5.8 +/- 0.3 x 10(10) M(-1) s(-1). We demonstrate that the kinetic traces at both 408 nm mainly due to biphenyl radical anion and 1300 nm mainly due to solvated electrons are reproduced with high accuracy and consistency by a simple kinetic analysis. Much higher concentrations of biphenyl (up to 2 M) were examined, showing further increase of the initial yield of biphenyl radical anion accompanying a fast decay component. This observation is discussed in terms of geminate ion recombination, scavenging, delayed geminate ion recombination, and direct ionization of biphenyl at high concentration.     

N4+的生成与检测

用从Nd:YAG激光器发出的波长532nm的激光(能量约为10mJ/pulse)溅射由BN、ZrN粉末分别压成的直径13mm、厚度约2～5mm的固体压片样品,生成了含氮团簇N4+。实验中,用高纯氮气为载气,辅助含氮团簇的生成并冷却激光溅射所产生的团簇。反射式飞行时间质谱仪监测反应过程证实N4+的存在,且其存在时间超过200μs。     

Analysis of pesticides by gas chromatography/multiphoton ionization/mass spectrometry using a femtosecond laser

Gas chromatography/multiphoton ionization/time-of-flight mass spectrometry (GC/MPI/TOFMS) was utilized for analysis of a standard mixture sample containing 49 pesticides and 4 real samples using the third-harmonic emission (267 nm) of a femtosecond Ti:sapphire laser (100 fs) as the ionization source. A sample of a standard mixture of n-alkane was also measured for calibration of the retention time indices of the pesticides. Two photons are required for the excitation of n-alkane due to an absorption band located in the far ultraviolet region (140 nm). The n-alkane molecule in the excited state was subsequently ionized either directly or by absorbing another photon because of a high ionization potential. Due to a large excess of energy, the molecular ion was decomposed and formed many fragment ions. Compared to n-alkanes, most of the pesticides were softly ionized by the femtosecond laser; one photon was used for excitation and another was used for the subsequent ionization. The pesticides with no conjugated double bond had a lower ionization efficiency. The present analytical instrument was applied to several samples prepared from a variety of vegetables and a single fruit after pretreatment with solid-phase extraction. Three pesticides were found in these samples, although some of them were not detected by conventional GC/EI/MS–MS due to insufficient sensitivity and selectivity.     

4,5-二(2',4'-二硝基苯硫基)-1,3-二硫杂环戊烯-2-酮的合成, 晶体结构及其激光倍频性质

首次合成了具有激光倍频性质的BNPT-DTO,并测定了结构.BNPT-DTO是电子给体-受体型手性分子,它的两个苯环几乎与二硫杂环戊烯的平面垂直,用1064nm YAG:Nd激光照射晶体产生532nm的倍频光,其强度与KDP的倍频光强度相当