Vacuum ultraviolet laser-induced breakdown spectroscopy analysis of polymers

Laser-induced breakdown spectroscopy (LIBS) in the vacuum ultraviolet range (VUV, λ < 200 nm) is employed for the detection of trace elements in polyethylene (PE) that are difficult to detect in the UV/VIS range. For effective laser ablation of PE, we use a F₂ laser (wavelength λ = 157 nm) with a laser pulse length of 20 ns, a pulse energy up to 50 mJ, and pulse repetition rate of 10 Hz. The optical radiation of the laser-induced plasma is measured by a VUV spectrometer with detection range down to λ = 115 nm. A gated photon-counting system is used to acquire time-resolved spectra. From LIBS measurements of certified polymer reference materials, we obtained a limit of detection (LOD) of 50 µg/g for sulphur and 215 µg/g for zinc, respectively.The VUV LIBS spectra of PE are dominated by strong emission lines of neutral and ionized carbon atoms. From time-resolved measurements of the carbon line intensities, we determine the temporal evolution of the electronic plasma temperature, T_e. For this, we use Saha–Boltzmann plots with the electron density in the plasma, N_e, derived from the broadening of the hydrogen H-α line. With the parameters T_e and N_e, we calculate the intensity ratio of the atomic sulphur and carbon lines at 180.7 nm and at 175.2 nm, respectively. The calculated intensity ratios are in good agreement with the experimentally measured results.     

Laser desorption lamp ionization source for ion trap mass spectrometry

A two‐step laser desorption lamp ionization source coupled to an ion trap mass spectrometer (LDLI‐ITMS) has been constructed and characterized. The pulsed infrared (IR) output of an Nd:YAG laser (1064 nm) is directed to a target inside a chamber evacuated to ~15 Pa causing desorption of molecules from the target's surface. The desorbed molecules are ionized by a vacuum ultraviolet (VUV) lamp (filled with xenon, major wavelength at 148 nm). The resulting ions are stored and detected in a three‐dimensional quadrupole ion trap modified from a Finnigan Mat LCQ mass spectrometer operated at a pressure of ≥ 0.004 Pa. The limit of detection for desorbed coronene molecules is 1.5 pmol, which is about two orders of magnitude more sensitive than laser desorption laser ionization mass spectrometry using a fluorine excimer laser (157 nm) as the ionization source. The mass spectrum of four standard aromatic compounds (pyrene, coronene, rubrene and 1,4,8,11,15,18,22,25‐octabutoxy‐29H,31H‐phthalocyanine (OPC)) shows that parent ions dominate. By increasing the infrared laser power, this instrument is capable of detecting inorganic compounds. Copyright © 2015 John Wiley & Sons, Ltd.     

Significance of water quality and radiation wavelength for UV photolysis of PhCs in simulated mixed solutions

Ultraviolet (UV) photolysis of sixteen pharmaceutical compounds (PhCs) in mixed solutions with four types of water and two sets of UV radiation was investigated. UVC (254 nm) photolysis was ineffective at eliminating a large number of PhCs while a big number of them were refractory. However, vacuum UV (VUV: 185 nm + 254 nm) photolysis in the same experimental conditions eliminated the PhCs almost completely. The eliminations in ultrapure water (UPW), tap water (TW) and Neya River water (NRW) and their organic/inorganic contents were inversely correlated, which was more evident in VUV photolysis. Natural organic matter (NOM) in NRW did not have an impact in indirect photolysis, but effluent organic matter (EfOM) in secondary-treated effluent (NWTPE) enhanced indirect photolysis, which was more evident in VUV photolysis underlining the point that radiation wavelength/intensity can be a limiting factor in organic-rich waters. Moreover, VUV photolysis was far superior (90% mineralization) to UVC photolysis (10% mineralization) for PhCs mineralization. The greatly enhanced elimination and mineralization efficiencies observed for VUV photolysis were attributed to accelerated direct photolysis with 185 nm wavelength and indirect photolysis involving ^·OH. The results demonstrated efficacy of VUV photolysis in wastewater treatment and its potential use as a tertiary treatment.      

Communication: vacuum ultraviolet laser photodissociation studies of small molecules by the vacuum ultraviolet laser photoionization time-sliced velocity-mapped ion imaging method

We demonstrate that the vacuum ultraviolet (VUV) photodissociation dynamics of N(2) and CO(2) can be studied using VUV photoionization with time-sliced velocity-mapped ion imaging (VUV-PI-VMI) detection. The VUV laser light is produced by resonant sum frequency mixing in Kr. N(2) is used to show that when the photon energy of the VUV laser is above the ionization energy of an allowed transition of one of the product atoms it can be detected and characterized as the wavelength is varied. In this case a β parameter = 0.57 for the N((2)D°) was measured after exciting N(2)(o(1)Π(u), v(') = 2, J(') = 2) ← N(2)(X(1)Σ(g) (+), v(") = 0, J(") = 1). Studies with CO(2) show that when there is no allowed transition, an autoionization resonance can be used for the detection of a product atom. In this case it is shown for the first time that the O((1)D) atom is produced with CO((1)Σ(+)) at 92.21 nm. These results indicate that the VUV laser photodissociation combined with the VUV-PI-VMI detection is a viable method for studying the one-photon photodissociation from the ground state of simple molecules in the extreme ultraviolet and VUV spectral regions.     

Radiofrequency field enhanced chemical ionization with vacuum ultraviolet lamp for miniature time-of-flight mass spectrometer

Radiofrequency field enhanced chemical ionization enhances the sensitivity of benzene, toluene, hydrogen sulfide and other compounds by 2–3 orders of magnitude and expanded the detection range of the compounds with ionization energy from 10.6 eV to 12.0 eV.     

Formation and Fragmentation of Radical Peptide Anions: Insights from Vacuum Ultra Violet Spectroscopy

We have studied the photodissociation of gas-phase deprotonated caerulein anions by vacuum ultraviolet (VUV) photons in the 4.5 to 20 eV range, as provided by the DESIRS beamline at the synchrotron radiation facility SOLEIL (France). Caerulein is a sulphated peptide with three aromatic residues and nine amide bonds. Electron loss is found to be the major relaxation channel at every photon energy. However, an increase in the fragmentation efficiency (neutral losses and peptide backbone cleavages) as a function of the energy is also observed. The oxidized ions, generated by electron photodetachment were further isolated and activated by collision (CID) in a MS³ scheme. The branching ratios of the different fragments observed by CID as a function of the initial VUV photon energy are found to be independent of the initial photon energy. Thus, there is no memory effect of the initial excitation energy on the fragmentation channels of the oxidized species on the time scale of our tandem MS experiment. We also report photofragment yields as a function of photon energy for doubly deprotonated caerulein ions, for both closed-shell ([M–2H]^2–) non-radical ions and open-shell ([M–3H]^2–•) radical ions. These latter ions are generated by electron photodetachment from [M–3H]^3– precursor ions. The detachment yield increases monotonically with the energy with the appearance of several absorption bands. Spectra for radical and non-radical ions are quite similar in terms of observed bands; however, the VUV fragmentation yield is enhanced by the presence of a radical in caerulein peptides.     

Use of radiation sources with mercury isotopes for real-time highly sensitive and selective benzene determination in air and natural gas by differential absorption spectrometry with the direct Zeeman effect

A new analytical portable system is proposed for the direct determination of benzene vapor in the ambient air and natural gas, using differential absorption spectrometry with the direct Zeeman effect and innovative radiation sources: capillary mercury lamps with different isotopic compositions (¹⁹⁶Hg, ¹⁹⁸Hg, ²⁰²Hg, ²⁰⁴Hg, and natural isotopic mixture). Resonance emission of mercury at a wavelength of 254 nm is used as probing radiation. The differential cross section of benzene absorption in dependence on wavelength is determined by scanning of magnetic field. It is found that the sensitivity of benzene detection is enhanced three times using lamp with the mercury isotope ²⁰⁴Hg in comparison with lamp, filled with the natural isotopic mixture. It is experimentally demonstrated that, when benzene content is measured at the Occupational Exposure Limit (3.2 mg/m³ for benzene) level, the interference from SO₂, NO₂, O₃, H₂S and toluene can be neglected if concentration of these gases does not exceed corresponding Occupational Exposure Limits. To exclude the mercury effect, filters that absorb mercury and let benzene pass in the gas duct are proposed. Basing on the results of our study, a portable spectrometer is designed with a multipath cell of 960 cm total path length and detection limit 0.5 mg/m³ at 1 s averaging and 0.1 mg/m³ at 30 s averaging. The applications of the designed spectrometer to measuring the benzene concentration in the atmospheric air from a moving vehicle and in natural gas are exemplified.     

Axial CID and high pressure resonance CID in a miniature ion trap mass spectrometer using a discontinuous atmospheric pressure interface

Axial collision induced dissociation (CID) and high-pressure resonance CID were implemented and compared with normal low-pressure resonance CID in a miniature ion trap mass spectrometer to obtain more complete fragmentation spectra. Axial CID was realized simply by applying a potential to the discontinuous atmospheric pressure interface (DAPI) capillary without performing parent ion isolation before dissociation. High-pressure resonance CID employed a double-introduction pulse scan function, by means of which precursor ions isolated at low-pressure (<10⁻³ torr) were dissociated at high-pressure (0.1 torr-1 torr) with higher excitation energy, so that tandem MS of isolated precursor ions was achieved and extensive fragmentation was obtained. A simple peptide (Leu-enkephalin) and dye molecule (rhodamine B) ionized by ESI were used to investigate both methods and compare them with normal low-pressure resonance CID.     

Application of prominent spectral lines in the 125-180 nm range for inductively coupled plasma optical emission spectrometry

A new axially viewed ICP optical emission spectrometer featuring an argon-filled optic and CCD detectors was evaluated for the application of prominent spectral lines in the 125-180 nm range. This wavelength range was investigated for several analytical applications of inductively coupled plasma optical emission spectrometry (ICP-OES). There are different advantages for the application of spectral lines below 180 nm. A number of elements, such as Al, Br, Cl, Ga, Ge, I, In, N, P, Pb, Pt, S and Te, were found to have the most intense spectral lines in the wavelength range from 125-180 nm. Compared with lines above 180 nm higher signal-to-background ratios were found. Low limits of detection using pneumatic nebulization of aqueous solutions for sample introduction were calculated for Al II 167.080 nm (0.04 microg L(-1)), Br I 154.065 nm (9 microg L(-1)), Cl I 134.724 nm (19 microg L(-1)), Ga II 141.444 nm (0.8 microg L(-1)), Ge II 164.919 nm (1.3 microg L(-1)), II 142.549 nm (13 microg L(-1)), In II 158.583 nm (0.2 microg L(-1)), P I 177.500 nm (0.9 microg L(-1)), Pb II 168.215 nm (1.5 microg L(-1)), Pt II 177.709 nm (2.6 microg L(-1)), S I 180.731 nm (1.9 microg L(-1)) and Te I 170.00 nm (4.6 microg L(-1)). Numerous application examples for the use of those lines and other important spectral lines below 180 nm are given. Because of fewer emission lines from transition elements, such as Fe, Co, Cr, lines below 180 nm often offer freedom from spectral interferences. Additional lines of lower intensity for the determination of higher elemental concentrations are also available in the vacuum ultraviolet spectral range. This is specially useful when the concentrations are not in the linear range of calibration curves obtained with commonly used lines.     

Wavelength-tunable ultraviolet photodissociation (UVPD) of heparin-derived disaccharides in a linear ion trap

A set of three heparin-derived disaccharide deprotonated ions was isolated in a linear ion trap and subjected to UV laser irradiation in the 220–290 nm wavelength range. The dissociation yields of the deprotonated molecular ions were recorded as a function of laser wavelength. They revealed maximum absorption at 220 nm for the nonsulfated disaccharide, but centered at 240 nm for the sulfated species. The comparison of the fragmentation patterns between ultraviolet photodissociation (UVPD) at 240 nm and CID modes showed roughly the same distribution of fragment ions resulting from glycosidic bond cleavages. Interestingly, UVPD favored additional cross ring cleavages of A and X type ion series enabling easier sulfate group location. It also reduced small neutral losses (H₂O).     

Amphibious sensor of temperature and refractive index based on D-shaped photonic crystal fibre filled with liquid crystal

ABSTRACT

A D-shaped photonic crystal fibre filled with liquid crystal was demonstrated as an amphibious sensor for detection of both temperature and refractive index, when combined with plasma materials. Specifically, the optical component is implanted into a complete optical system ensuring modulation of the external electric field. When the refractive index of the external solution changes from 1.0 to 1.6, the y-polarised mode has a loss spectrum with a wavelength sensitivity of up to 2275 nm/RIU, and the corresponding amplitude sensitivity is ?88.2RIU^?1. When the perceived temperature changes from 15°C to 50°C, the temperature of the sensor is correspondingly expressed as the maximum wavelength sensitivity of 9.09 nm/°C and the amplitude sensitivity of ?0.311°C^?1. In addition, the actual micro-operation processes have been studied in detail, such as polishing depth, coating thickness and coating method. This provides practical ideas for real-time sensing analysis that requires harsh environments.     

Simultaneous multi-element determination with coherent forward scattering spectrometry employing chromatically corrected polarizers and a fast scanning spectrometer

A new coherent forward scattering spectrometer for simultaneous multi-element determination on up to 20 atomic lines has been constructed and evaluated. The apparatus consists of a continuum primary source, calcite Glan-Taylor polarizers equipped with a laboratory-designed chromatic correction for the wavelength range 214–766 nm, an electrothermal atomizer with magnet and autosampler and a laboratory-constructed wavelength modulated polychromator with medium resolving power. Light intensities of up to 20 resonance lines in the wavelength range of 214–500 nm are transferred from the focal plane to an array of 20 miniature photomultipliers by optical fiber-bundles. The instrumentation is controlled by a computer. Owing to modular construction the graphite furnace can be exchanged by a flame. Simultaneous multi-element determinations of Ag, Al, Ca, Cd, Co, Cr, Cu, Fe, K, Mn, Na, Ni, Pb, Sr, Tl and Zn are carried out. The received analytical curves cover 1.5–2.5 orders of magnitude per atomic line, which is in the same order as with multi-element measurements with electrothermal atomic absorption spectrometry (ETAAS). Further working range expansions are demonstrated with determining on resonance lines with different strengths. The detection limits for the strongest resonance line of most elements are in the μg l⁻¹-range and are one order of magnitude higher than those measured with commercially available ETAAS instrumentation when determining four elements simultaneously. The crossed-to-open extinction ratio of the chromatically corrected Glan-Taylor polarizers is determined to approximately 2.5×10⁻⁵ under installed conditions with the graphite furnace and its two windows in between. The spectral transmissions of these polarizers and the optical fiber-bundles are measured with a photometer. It shows a steep decay for wavelengths below 220 nm.     

VUV-transitions in ionic rare-gas alkali molecules

Mixtures of rare-gases (Rg) and alkali vapors (A) were excited by helium and argon ions. VUV transitions observed between 131.1 nm and 189.9 nm were ascribed to the decay of (RgA)⁺ ions where Rg=Kr, Xe and A=Cs, Rb, K, Na, Li. In the (ArA)⁺ systems (A=Rb, K, Na, Li) transitions appeared between 114.1 nm and 124.7 nm. Since the final state is only weakly bound, the (RgA)⁺ ions seem to be promising candidates for storage media of VUV lasers.     

Vacuum-ultraviolet induced oxidation of the polymers polyethylene and polypropylene

The emission from low-pressure microwave plasmas in the vacuum-ultraviolet (VUV) region (λ < 200 nm) was investigated in order to use these plasmas as light sources for the study of the VUV photochemistry of polyethylene (PE) and polypropylene (PP) as part of the study of plasma-polymer interaction. These polymers, immersed in low-presure oxygen, were exposed to radiation with wavelengths down to 112 nm, the cut off of magnesium fluoride used as a window to separate the polymer specimen from the plasma light source. Total oxygen incorporation in the surface [O], and the formation of hydroxyl, carbonyl, and carboxyl groups were measured using XPS in combination with chemical derivatizations, particularly their dependence upon the radiation spectrum and the oxygen pressure around the sample. In most experiments the surface oxygen concentration [O] attained a constant value that appears to be related to the initial oxidation rate; this suggests a competition between oxygen incorporation and chain scission reactions, followed by the removal of volatile oxidation products. PE is usually oxidized to a higher level than PP, the latter appearing to be more susceptible to reaction with atomic oxygen than PE. A general initiation mechanism for the VUV experiments is proposed that allows us to explain the observed differences in behavior between PE and PP, and the results obtained under different irradiation conditions. The nature of oxidation products is in both cases very similar to what is observed after direct plasma treatment of the polymers. We conclude that short wavelength radiation contributes very appreciably to the observed surface modification effects during plasma treatment of PE and PP. © 1995 John Wiley & Sons, Inc.     

Evaluation of piezoelectric PVDF polymers for use in space environments. III. Comparison of the effects of vacuum UV and gamma radiation

Films of piezoelectric PVDF and P(VDF‐TrFE) were exposed to vacuum UV (115–300 nm VUV) and γ‐radiation to investigate how these two forms of radiation affect the chemical, morphological, and piezoelectric properties of the polymers. The extent of crosslinking was almost identical in both polymers after γ‐irradiation, but surprisingly, was significantly higher for the TrFE copolymer after VUV‐irradiation. Changes in the melting behavior were also more significant in the TrFE copolymer after VUV‐irradiation due to both surface and bulk crosslinking, compared with only surface crosslinking for the PVDF films. The piezoelectric properties (measured using d₃₃ piezoelectric coefficients and D‐E hysteresis loops) were unchanged in the PVDF homopolymer, while the TrFE copolymer exhibited more narrow D‐E loops after exposure to either γ‐ or VUV‐radiation. The more severe damage to the TrFE copolymer in comparison with the PVDF homopolymer after VUV‐irradiation is explained by different energy deposition characteristics. The short wavelength, highly energetic photons are undoubtedly absorbed in the surface layers of both polymers, and we propose that while the longer wavelength components of the VUV‐radiation are absorbed by the bulk of the TrFE copolymer causing crosslinking, they are transmitted harmlessly in the PVDF homopolymer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3253–3264, 2006     

High-resolution Absorption Spectra of Acetylene in 142.8-152.3 nm

The absorption spectra of acetylene molecules was measured under jet-cooled conditions in the wavelength range of 142.8-152.3 nm,with a tunable and highly resolved vacuum ultraviolet (VUV) laser generated by two-photon resonant four wave difference frequency mixing processes. Due to the sufficient vibrational and rotational cooling effect of the molecular beam and the higher resolution VUV laser, the observed absorption spectra exhibit more distinct spectral features than the previous works measured at room temperature. The major three vibrational bands are assigned as a CC symmetry stretching vibrational progress (v2=0-2) of the C1Ⅱu state of acetylene.The observed shoulder peak at 148.2 nm is assigned to the first overtone band of the trans-bending mode v4 of the C1Ⅱu state of acetylene. Additionally,the two components, 420 (μ1Ⅱu) and 420(к1Ⅱu),are suggested to exhibit in the present absorption spectra,due to their Renner-Teller effect and transition selection rule.All band origins and bandwidths are obtained subsequently,and it is foundthat bandwidths are broadened and lifetimes decrease gradually with the excitation of vibration.     

Photolysis of a fluorinated polymer film by vacuum ultraviolet radiation

We studied the photolysis of a fluoroethylene–fluoropropylene copolymer (FEP) film by vacuum ultraviolet (VUV) radiation from a resonance Xe lamp at a wavelength of 147 nm and air pressures of 0.05 and 2.5 Torr. The chemical changes in the FEP surface layer were investigated by Fourier-transform infrared spectroscopy with attenuated total reflection attachment and X-ray photoelectron spectroscopy. Double bonds were found to be the main product in the case of VUV treatment at 0.05 Torr, while photo-oxidation of FEP occurred predominantly by VUV treatment at 2.5 Torr under formation of the —CF₂C(O)F group. This oxygen-containing group was more effectively formed in the FEP surface layer by VUV photo-oxidation than by conventional surface oxidation techniques such as treatments by plasma and corona discharge and ozone. Storage of the VUV-treated polymers in air at 50% relative humidity resulted in hydrolysis of —CF₂C(O)F to the —CF₂COOH group. Substantial improvement of the film wettability was noticed after VUV photo-oxidation. These findings suggest that VUV irradiation provides a high potential for surface modification of fluorinated polymers which are known to be particularly resistant against functionalization by conventional surface modification techniques such as plasma treatment. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2215–2222, 1998     

Ultraviolet photodissociation of protonated pharmaceuticals in a pressurized linear quadrupole ion trap

Ultraviolet photodissociation (UVPD) was evaluated as a technique for generating ion fragmentation information that is alternative and/or complementary to the information obtained by collision‐induced dissociation (CID). Ions trapped in a pressurized linear ion trap were dissociated using a 355 nm or a 266 nm pulsed laser. Comparisons of UVPD and CID spectra using a set of aromatic chromophore‐containing compounds (desmethyl bosentan, haloperidol, nelfinavir) demonstrated distinct characteristic fragmentation patterns resulting from photodissociation. The wavelength of light and the pressure of the buffer gas in the UVPD cell are important parameters that control fragmentation pathways. The wavelength effect is related to the absorption cross section, location of the chromophore and the energy carried by one photon. Thus, UV irradiation wavelength affects fragmentation pathways as well as the fragmentation rate. The pressure effect can be explained by collisional quenching of ‘slow’ fragmentation pathways. We observed that higher pressure of the buffer gas during UVPD experiments highlights unique fragment ions by suppressing slow fragmentation pathways responsible for CID‐like fragmentation patterns. Copyright © 2010 John Wiley & Sons, Ltd.     

An Ion Mobility/Ion Trap/Photodissociation Instrument for Characterization of Ion Structure

A new instrument that combines ion mobility spectrometry (IMS) separations with tandem mass spectrometry (MS(n)) is described. Ion fragmentation is achieved with vacuum ultraviolet photodissociation (VUV PD) and/or collision-induced dissociation (CID). The instrument is comprised of an approximately 1 m long drift tube connected to a linear trap that has been interfaced to a pulsed F(2) laser (157 nm). Ion gates positioned in the front and the back of the primary drift region allow for mobility selection of specific ions prior to their storage in the ion trap, mass analysis, and fragmentation. The ion characterization advantages of the new instrument are demonstrated with the analysis of the isomeric trisaccharides, melezitose and raffinose. Mobility separation of precursor ions provides a means of separating the isomers and subsequent VUV PD generates unique fragments allowing them to be distinguished.     

Analysis of vitamin E in food and phytopharmaceutical preparations by HPLC and HPLC-APCI-MS-MS

Summary The analysis of α, β, γ, δ-tocopherols, trienols, α-tocopheryl acetate and nicotinate (vitamin E) in complex matrices was carried out using a new liquid chromatographic (HPLC) method giving better separation efficiency, selectivity and sensitivity than that described in the literature. The use of normal-phase (NP)-HPLC on silica gel with issoctane-diisopropylether-1,4-dioxane as optimized mobilepphase yielded higher resolution than conventional reversed-phase (RP)-HPLC using methanol mobile phase. Identification of peaks was by UV-absorbance at 295 nm, diode array, or fluorescence detection (λ _ex = 295 nm,λ _ex = 330 nm). The latter was found to be more selective and ten times more sensitive than UV-absorbance detection. A quadrupole, ion-trap mass spectrometer with an atmospheric-pressure ionization (APCl) interface was used to detect vitamin E constituents in the femtomole range. With collision-induced dissociation (CID) in the ion source, which gave characteristic fragmentation, the identity of the investigated compounds could be confirmed. Plots of peak area versus amount injected allowed quantitation of α, β, γ, δ-tocopherols and-trienols, α-tocopheryl acetate and nicotinate in real samples such as peanut, almond, spinach, spelt grain bran, latex and tablets. The method described offers fast identification and quantitation of vitamin E constituents of complex biological origin. Dedicated to Professor Dr. Heinz Engelhardt on the occasion of his 65^th birthday.