Laser-induced Desorption Research Articles

Production of highly charged ions of rare species by laser-induced desorption inside an electron beam ion trap.

This paper reports on the development and testing of a novel, highly efficient technique for the injection of very rare species into electron beam ion traps (EBITs) for the production of highly charged ions (HCI). It relies on in-trap laser-induced desorption of atoms from a sample brought very close to the electron beam resulting in a very high capture efficiency in the EBIT. We have demonstrated a steady production of HCI of the stable isotope 165Ho from samples of only 1012 atoms (∼300 pg) in charge states up to 45+. HCI of these species can be subsequently extracted for use in other experiments or stored in the trapping volume of the EBIT for spectroscopic measurements. The high efficiency of this technique extends the range of rare isotope HCIs available for high-precision atomic mass and spectroscopic measurements. A first application of this technique is the production of HCI of the synthetic radioisotope 163Ho for a high-precision measurement of the QEC-value of the electron capture in 163Ho within the "Electron Capture in Holmium" experiment [L. Gastaldo et al., J. Low Temp. Phys. 176, 876-884 (2014); L. Gastaldo et al., Eur. Phys. J.: Spec. Top. 226, 1623-1694 (2017)] (ECHo collaboration) ultimately leading to a measurement of the electron neutrino mass with an uncertainty on the sub electronvolt level.

Unraveling a self-assembling mechanism of isomeric aminothiophenol on Ag dendrite by correlated SERS and matrix-free LDI-MS

Correlated spectroscopic analysis can provide complementary chemical insights that are often unattainable by either approach used in isolation. We distinguished the different self-assembling behavior of isomeric aminothiophenols (ATPs) on Ag dendrite by the correlation of surface-enhanced Raman spectroscopy and laser-induced desorption ionization mass spectrometry, demonstrating that steric effect impinged significantly upon surface molecular density and plasmon-driven catalytic reaction yield, which led to drastic variations in the resulting SERS spectra. The correlative measurement shows that ortho-substitute barely formed a self-assemble monolayer, relative to the para-isomer, which can form a close-packed self-assembled monolayer and perform a decent azo-coupling reaction. Comparison between normal and SERS spectra of ATP isomers supports the fact that additional disulfide- or hydrogen-bonding interactions are established in para-ATP solid crystal, but neither of ortho- nor meta-isomers. This work is expected to create a significant impact on the development of an orthogonally correlated spectroscopic tool in deciphering chemical insights and underlying reaction mechanism. Graphical abstract.

Analogue spectra for impact ionization mass spectra of water ice grains obtained at different impact speeds in space.

Detecting ice grains with impact ionization mass spectrometers in space provides information about the compositions of ice grains and their sources. Depending on the impact speeds of the ice grains onto the metal target of a mass spectrometer, ionization conditions can vary substantially, resulting in changes to the appearance of the resulting mass spectra. Here we accurately reproduce mass spectra of water ice grains, recorded with the Cosmic Dust Analyzer (CDA) on board the Cassini spacecraft at typical impact speeds ranging between 4 km/s to 21 km/s, with a laboratory analogue experiment. In this Laser-Induced Liquid Beam Ion Desorption (LILBID) approach, a μm-sized liquid water beam is irradiated with a pulsed infrared laser, desorbing charged analyte and solvent aggregates and isolated ions, which are subsequently analyzed in a time-of-flight (TOF) mass spectrometer. We show that our analogue experiment can reproduce impact ionization mass spectra of ice grains obtained over a wide range of impact speeds, aiding the quantitative analyses of mass spectra from space. Spectra libraries created with the LILBID experiment will be a vital tool for inferring the composition of ice grains from mass spectra recorded by both past and future impact ionization mass spectrometers (e.g. the SUrface Dust Analyzer (SUDA) onboard NASA's Europa Clipper Mission or detectors on a future Enceladus Mission).

Dissipative quantum dynamics using the stochastic surrogate Hamiltonian approach.

Based on the original Stochastic Surrogate Hamiltonian approach for the simulation of open quantum system dynamics, we present a modified algorithm for the swap procedure. The implementation is tested with nuclear relaxation dynamics of model systems known from literature, i.e., the harmonic oscillator and the Morse oscillator. Finally, the stochastic surrogate Hamiltonian is applied to simulate the dynamical electronic excitation and relaxation of a photodesorption process. This is the first application of the stochastic surrogate Hamiltonian in an ab initio context. A comparison to a surrogate Hamiltonian benchmark allows us to evaluate the results obtained. For this purpose, the well-studied laser-induced desorption of NO from NiO(100) is chosen.

Plasma-Material-Interaction Research Using PISCES Linear Plasma Devices

Recent plasma-material-interaction (PMI) studies of relevance to fusion PMI science are discussed. The results are a mix of science experiments and in situ diagnostic technology development. Scientific issues addressed include the nature of He and W atom migration in the evolution of W fuzz surfaces, understanding the nature of D retention in damaged W surfaces via modeling with the tritium migration and analysis program, and an examination of synergistic effects associated with D trapping on composite Be codeposit and W substrate surfaces. In situ diagnostic developments discussed include laser-induced desorption spectroscopy for the measurement of bulk hydrogen retention and laser-induced breakdown spectroscopy for the measurement of near-surface composition.

Internal Energy Deposition in Infrared Matrix-Assisted Laser Desorption Electrospray Ionization With and Without the Use of Ice as a Matrix.

The internal energy deposited into analytes during the ionization process largely influences the extent of fragmentation, thus the appearance of the resulting mass spectrum. The internal energy distributions of a series of para-substituted benzyl pyridinium cations in liquid and solid-state generated by infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) were measured using the survival yield method, of which results were subsequently compared with conventional electrospray ionization (ESI). The comparable mean internal energy values (e.g., 1.8-1.9eV at a collision energy of 15eV) and peak widths obtained with IR-MALDESI and ESI support that IR-MALDESI are essentially a soft ionization technique where analytes do not gain considerable internal energy during the laser-induced desorption process and/or lose energy during uptake into charged electrospray droplets. An unusual fragment ion, protonated pyridine, was only found for solid IR-MALDESI at relatively high collision energies, which is presumably resulted from direct ionization of the pre-charged analytes in form of salts. Analysis of tissue with an ice layer consistently yielded ion populations with higher internal energy than its counterpart without an ice layer, likely due to a substantially enhanced number of IR absorbers with ice. Further measurements with holo-myoglobin show that IR-MALDESI-MS retains the noncovalently bound heme-protein complexes under both native-like and denaturing conditions, while complete loss of the heme group occurred in denaturing ESI-MS, showing that the softness of IR-MALDESI is equivalent or superior to ESI for biomolecules.

Direct loading of nanoparticles under high vacuum into a Paul trap for levitodynamical experiments

Mechanical oscillators based on levitated particles are promising candidates for sensitive detectors and platforms for testing fundamental physics. The targeted quality factors for such oscillators correspond to extremely low damping rates of the center-of-mass motion, which can only be obtained if the particles are trapped in ultrahigh vacuum (UHV). In order to reach such low pressures, a noncontaminating method of loading particles in a UHV environment is necessary. However, loading particle traps at pressures below the viscous flow regime is challenging due to the conservative nature of trapping forces and reduced gas damping. We demonstrate a technique that allows us to overcome these limitations and load particles into a Paul trap at pressures as low as 4 × 10–7 mbar. The method is based on laser-induced acoustic desorption of nanoparticles from a metallic foil and temporal control of the Paul trap potential. We show that the method is highly efficient: More than half of the trapping attempts are successful. Moreover, since trapping attempts can be as short as a few milliseconds, the technique provides high throughput of loaded particles. Finally, the efficiency of the method does not depend on pressure, indicating that the method should be extensible to UHV.

Time-resolved laser-induced desorption spectroscopy (LIDS) for quantified in-situ hydrogen isotope retention measurement and removal from plasma facing materials.

A laboratory scale laser induced thermal desorption spectroscopy system is developed and tested on tungsten-deuterium and titanium-deuterium codeposits, and its feasibility as a hydrogenic inventory measurement diagnostic is demonstrated over a range of retention values from 5 × 1019 m-2 to 7 × 1023 m-2 for absorbed laser power densities as low as 8 MW m-2. Codeposit layer samples are grown by magnetron sputtering and immersed in a weak argon rf plasma. A 1 kW fiber laser (λ = 1100 nm) heats the samples up to a peak surface temperature ranging from 900 to 1500 K using pulse widths of 0.5 and 1 s. Spectral line emission from Balmer series Dα and Hα from thermally desorbed deuterium and hydrogen, as well as line emission from argon, are monitored as a function of time using an optical spectrometer with maximum temporal resolution of 1 ms. To correct for wall recycling and pumping speed, and to accurately measure the time evolution of the laser-induced thermal desorption, the raw Dα signal is deconvolved with the system response function, which is obtained by injecting a short burst of D2 to approximate an impulse. Calibration is done with a standard D2 leak, and laser induced desorption spectroscopy deuterium retention values are found to be in good agreement with companion measurements made using conventional temperature programmed desorption on samples from the same codeposit batch.

LanI-Mediated Lantibiotic Immunity in Bacillus subtilis: Functional Analysis.

Lantibiotics subtilin and nisin are produced by Bacillus subtilis and Lactococcus lactis, respectively. To prevent toxicity of their own lantibiotic, both bacteria express specific immunity proteins, called SpaI and NisI. In addition, ABC transporters SpaFEG and NisFEG prevent lantibiotic toxicity by transporting the respective peptides to the extracellular space. Although the three-dimensional structures of SpaI and NisI have been solved, very little is known about the molecular function of either lipoprotein. Using laser-induced liquid bead ion desorption (LILBID)-mass spectrometry, we show here that subtilin interacts with SpaI monomers. The expression of either SpaI or NisI in a subtilin-nonproducing B. subtilis strain resulted in the respective strain being more resistant against either subtilin or nisin. Furthermore, pore formation provided by subtilin and nisin was prevented specifically upon the expression of either SpaI or NisI. As shown with a nisin-subtilin hybrid molecule, the C-terminal part of subtilin but not any particular lanthionine ring was needed for SpaI-mediated immunity. With respect to growth, SpaI provided less immunity against subtilin than is provided by the ABC transporter SpaFEG. However, SpaI prevented pore formation much more efficiently than SpaFEG. Taken together, our data show the physiological function of SpaI as a fast immune response to protect the cellular membrane.IMPORTANCE The two lantibiotics nisin and subtilin are produced by Lactococcus lactis and Bacillus subtilis, respectively. Both peptides have strong antimicrobial activity against Gram-positive bacteria, and therefore, appropriate protection mechanisms are required for the producing strains. To prevent toxicity of their own lantibiotic, both bacteria express immunity proteins, called SpaI and NisI, and in addition, ABC transporters SpaFEG and NisFEG. Whereas it has been shown that the ABC transporters protect the producing strains by transporting the toxic peptides to the extracellular space, the exact mode of action and the physiological function of the lipoproteins during immunity are still unknown. Understanding the exact role of lantibiotic immunity proteins is of major importance for improving production rates and for the design of newly engineered peptide antibiotics. Here, we show (i) the specificity of each lipoprotein for its own lantibiotic, (ii) the specific physical interaction of subtilin with its lipoprotein SpaI, (iii) the physiological function of SpaI in protecting the cellular membrane, and (iv) the importance of the C-terminal part of subtilin for its interaction with SpaI.

Laser-induced acoustic desorption

Abstract

Laser-Induced Desorption of co-deposited Deuterium in Beryllium Layers on Tungsten

Abstract For the development of the tritium monitoring system in ITER the hydrogen isotope release by Laser-Induced Desorption (LID) from Be layers is studied to determine the laser parameters for a high desorption efficiency while minimising dust production and surface modifications is also pursued. Be layers of 1 µm thickness with 25–30 at% D and 3 × 1022 D/m2 comparable to JET-ILW areal concentrations [1] have been produced by High Power Impulse Magnetron Sputtering (HiPIMS) on ITER grade W. Laser pulses of 1, 5 and 10 ms duration heat the layer in vacuum in the Fuel REtention DIagnostic Setup (FREDIS) and release the retained D thermally. By mass spectrometry in FREDIS and subsequent Nuclear Reaction Analysis (NRA) inside the laser spot the desorbed and remaining D is quantified. While a pulse duration of 1 ms cannot fully desorb the deuterium, it is found that a single 5 or 10 ms laser pulse with an absorbed energy density of ca. 1.5 MJ/m2 corresponding to a heat flux factor around 20 MW√s/m2 leads to nearly complete desorption of the retained D. This encourages the development of a useful tritium monitoring system, although the present layers produce some dust due to local delamination of the layer on at least 11% of the heated surface (at 1.4 MJ/m2 absorbed energy within 5 ms) and lead to unavoidable crack formation.

Fuel Retention Diagnostic Setup (FREDIS) for desorption of gases from beryllium and tritium containing samples

In fusion devices, the retention of the fusion fuel deuterium (D) and tritium (T) in plasma-facing components (PFCs) is a major concern. Measurement of their hydrogen isotope content gives insight into the retention physics.In FREDIS, two methods of thermal desorption are used for retention measurements: In Thermal Desorption Spectrometry (TDS) the samples are heated by 6 infrared lamps up to 1433 K with linear temperature ramps of up to 1.67 K/s. The desorbed gases are detected up to 100 amu/e with a double-QMS (Quadrupole Mass Spectrometer) that can distinguish between helium and D2 and uses an innovative differential pumping system.In a connected vacuum chamber, a ∅3 mm spot can be heated on the sample surface by a high energy Nd:YAG laser pulse (E0 < 100 J) within milliseconds (0.1–20 ms) to several thousand degrees. This method of Laser-Induced Desorption (LID) can also be applied inside the fusion chamber and is planned as in situ retention diagnostic for ITER. In FREDIS, LID is thus tested and used as ex situ analysis method utilising the same double-QMS for absolute quantification. FREDIS is capable of handling beryllium (Be) by means of glove boxes and in the future also tritium using a tritium trap to analyse also samples from JET and ITER. In this contribution we present the specifications of FREDIS and compare TDS and LID.

Ultrafast Vibrational Dynamics of CO Ligands on RuTPP/Cu(110) under Photodesorption Conditions

We have studied CO coordinated to ruthenium tetraphenylporphyrin (RuTPP)/Cu(110) and directly adsorbed to Cu(110), using femtosecond pump-sum frequency probe spectroscopy, to alter the degree of electron-vibration coupling between the metal substrate and CO. We observe the facile femtosecond laser-induced desorption of CO from RuTPP/Cu(110), but not from Cu(110). A change in the vibrational transients, in the first few picoseconds, from a red- to blue-shift of the C–O stretching vibration under photodesorption conditions, was also observed. This drastic change can be explained, if the cause of the C–O frequency redshift of Cu(110) is not the usually-assumed anharmonic coupling to low frequency vibrational modes, but a charge transfer from hot electrons to the CO 2π* state. This antibonding state shifts to higher energies on RuTPP, removing the C–O redshift and, instead, reveals a blueshift, predicted to arise from electron-mediated coupling between the coherently excited internal stretch and low frequency modes in the system.

Photochemical Etching of Carbonyl Groups from a Carbon Matrix: The (001) Diamond Surface.

The surface of diamond is reported to undergo nonablative photochemical etching when exposed to ultraviolet (UV) radiation which allows controlled single and partial layer removal of lattice layers. Oxygen termination of surface dangling bonds is known to be crucial for the etching process; however, the exact mechanism of carbon ejection remains unclear. We investigate the interaction of UV laser pulses with oxygen-terminated diamond surfaces using atomic-scale surface characterization combined with first-principles time-dependent density functional theory calculations. We present evidence for laser-induced desorption (LID) from carbonyl functional groups at the diamond {001} surface. The doubly bonded carbonyl group is photoexcited into a triply bonded CO-like state, including scission of the underlying C─C bonds. The carbon removal process in LID is atom by atom; therefore, this mechanism provides a novel "top-down" approach for creating nanostructures on the surface of diamond and other carbon-containing semiconductors.

Sweep Jet Collection Laser-Induced Acoustic Desorption Atmospheric Pressure Photoionization for Lipid Analysis Applications.

Laser-induced acoustic desorption coupled to microplasma-based atmospheric pressure photoionization (LIAD-APPI) using a nebulized sweep jet to aid in dopant introduction and ion transmission has been applied to the analysis of model, apolar lipid compounds. Specifically, several sterols, sterol esters, and triacylglycerols were detected using dopants such as anisole and toluene. Additionally, several triacylglycerols, sterols, carboxylic acids, and hopanoids were detected from complex mixtures of olive oil and Australian shale rock extract as a first demonstration of the applicability of LIAD-APPI on real-world samples. Detection limits using a sweep jet configuration for α-tocopherol and cholesterol were found to be 609 ± 61 and 292 ± 29fmol, respectively. For sterol esters and triacylglycerols with a large number of double bonds in the fatty acid chain, LIAD-APPI was shown to yield greater molecular ion or [M+NH4]+ abundances than those with saturated fatty acid chains. Dopants such as anisole and toluene, with ionization potentials (IPs) of 8.2 and 8.8eV, respectively, were tested. A greater degree of fragmentation with several of the more labile test compounds was observed using toluene. Overall, LIAD-APPI with a nebulized sweep jet requires minimal sample preparation and is a generally useful and sensitive analysis technique for low-polarity mixtures of relevance to biochemical assays and geochemical profiling. Graphical Abstract.

Quantifying Surface Temperature of Thermoplasmonic Nanostructures.

Precise measurement of the temperature right at the surface of thermoplasmonic nanostructures is a grand challenge but extremely important for the photochemical reaction and photothermal therapy. We present here a method capable of measuring the surface temperature of plasmonic nanostructures with surface-enhanced Raman spectroscopy, which is not achievable by existing methods. We observe a sensitive shift of stretching vibration ofa phenyl isocyanide molecule with temperature (0.232 cm-1/°C) as a result of the temperature-dependent molecular orientation change. We develop this phenomenon into a method capable of measuring the surface temperature of Au nanoparticles (NPs) during plasmonic excitation, which is validated by monitoring the laser-induced desorption process of the adsorbed CO on Au NP surface. We further extend the method into a more demanding single living cell thermometry that requires a high spatial resolution, which allows us to successfully monitor the extracellular temperature distribution of a single living cell experiencing cold resistance and the intracellular temperature change during the calcium ion transport process.

Development and Characterization of a Laser-Induced Acoustic Desorption Source.

A laser-induced acoustic desorption source, developed for use at central facilities, such as free-electron lasers, is presented. It features prolonged measurement times and a fixed interaction point. A novel sample deposition method using aerosol spraying provides a uniform sample coverage and hence stable signal intensity. Utilizing strong-field ionization as a universal detection scheme, the produced molecular plume is characterized in terms of number density, spatial extend, fragmentation, temporal distribution, translational velocity, and translational temperature. The effect of desorption laser intensity on these plume properties is evaluated. While translational velocity is invariant for different desorption laser intensities, pointing to a nonthermal desorption mechanism, the translational temperature increases significantly and higher fragmentation is observed with increased desorption laser fluence.

Is the formation of N-heterocyclic carbenes (NHCs) a feasible mechanism for the distillation of imidazolium ionic liquids?

We describe the synthesis of two tetrachloroindate ionic liquids used as probes to study the involvement of NHCs (N-heterocyclic carbenes) in the distillation of imidazolium derivatives. Atmospheric-pressure chemical ionization mass spectrometry (APCI-MS), electrospray ionization mass spectrometry (ESI-MS), atmospheric-pressure thermal desorption ion mass spectrometry (APTDI-MS) and laser-induced acoustic desorption (LIAD) were used to depict the possibility of the involvement of NHCs during the distillation process. Each type of imidazolium derivative showed a particular mechanism of distillation, pointing firmly to the dependence of both the cation and the anion natures to distil as ion pairs or NHCs. Ionic liquid 1-n-butyl-3-methylimidazolium tetrachloroindate (1a) exhibited a preference to distil as ion pairs, whereas 3,3'-(ethane-1,2-diyl)bis(1-methyimidazolium)bis-tetrachloroindate (1b) may react with the Lewis acid anion, affording a bidentate NHC complex to distil. Thermodynamics, quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analyses of the ionic liquid 1a were also conducted and helped understand the preference for ion pairs instead of NHCs. The performed theoretical calculations did not forwent the possibility of NHC formation; however, they clearly indicated the high stability of the anions (Lewis acids in nature) and also indicated that the possible reaction between NHC and the anion is not favoured. The calculated thermodynamic values were in accordance with the features observed by MS and indicated ion pairs as the feasible species for the distillation of imidazolium-based ionic liquids.

Peptidomimetics That Inhibit and Partially Reverse the Aggregation of Aβ1-42.

The peptide sequence KLVFF resembles the hydrophobic core of the Aβ peptide known to form amyloid plaques in Alzheimer's disease. Starting from its retro-inverso peptide, we have synthesized three generations of peptidomimetics. Step by step natural amino acids have been replaced by aromatic building blocks accessible from the Pd-catalyzed Catellani reaction. The final compound 18 is stable against proteolytic decay and largely prevents the aggregation of Aβ1-42 over extended periods of time. The activity of the new inhibitors was tested first by fluorescence correlation spectroscopy. For closer examination of compound 18, additional techniques were also applied: laser-induced liquid bead ion desorption mass spectrometry, confocal laser scanning microscopy, thioflavin T fluorescence, and gel electrophoresis. Compound 18 not only retards the aggregation of chemically synthesized Aβ but also can partially dissolve the oligomeric structures. Thioflavin binding mature fibrils, however, seem to resist the inhibitor.

Laser-stimulated desorption of organic molecules from surfaces, as a method of increasing the efficiency of ion mobility spectrometry analysis.

Application of laser-induced desorption was investigated as a method of increasing the efficiency of gas phase analyzers on principles of field asymmetric ion mobility spectrometry. Mass spectrometric data of investigations of laser desorption of pentaerythritoltetranitrate molecules and cyclotetramethylenetetranitramine molecules from quartz substrate under vacuum were obtained. Laser sources a Nd3+:YAG with nanosecond pulse duration (λ = 532 nm) and a continuous wave diode laser (λ = 440 nm) were used. It was shown that both laser sources have different desorption abilities. This is expressed in various time of appearance of desorbed products that is caused by different heating mechanisms of surface layer. The desorbed quantity under action of both laser sources exceeds the detection threshold for all modern gas phase analyzers. It should be noted that despite the presence of surface dissociation of explosives under laser radiation, the quantity of nondissociated molecules is large enough for detection by ion mobility and field asymmetric ion mobility spectrometers. The optimal parameters of laser radiation for effective removal (evaporation) molecules of low-volatile compounds from surfaces are defined. The conclusion about preferable use of a Nd3+:YAG laser for increasing the detection ability of detectors based on ion mobility spectrometry was made.