S. S. Alimpiev

On the mechanism of laser-induced desorption–ionization of organic compounds from etched silicon and carbon surfaces

The laser-induced desorption/ionization of organic compounds from etched carbon and silicon substrate surfaces was investigated. Two different etching procedures were used. Silicon surfaces were etched either by galvanostatic anodization to produce porous silicon or by a hyperthermal (∼5 eV) F-atom beam to produce nonporous silicon. Atomic force microscopy (AFM) images showed that both etching procedures yielded surfaces with sub-micrometer structures. Highly oriented pyrolytic graphite was etched with hyperthermal O atoms. A 337 nm ultraviolet (UV) laser and a 3.28 μm infrared (IR) laser were used for desorption. Analytes were deposited on the substrates either from the liquid or the gas phase. Mass spectra were obtained provided that three conditions were fulfilled. First, sufficient laser light had to be absorbed. When the IR laser was employed, a thin physisorbed solvent layer was required for sufficient laser light absorption to occur. Though the required fluence of IR and UV light differed by a fact...

Infrared, surface-assisted laser desorption ionization mass spectrometry on frozen aqueous solutions of proteins and peptides using suspensions of organic solids.

Surface-assisted, laser desorption ionization (SALDI) time-of-flight mass spectra of proteins and peptides have been obtained from bulk frozen aqueous solutions by adding solid organic powders to the solutions before freezing. Abundant analyte ions were obtained with a 3.28 µm Nd:YAG/OPO laser. 20 compounds were evaluated as solid additives, and 16 yielded protein mass spectra. Successful solids included compounds like pyrene, aspartic acid, and polystyrene. The best results were obtained with nicotinic acid and indole-2-carboxylic acid, which yielded protein mass spectra anywhere on the sample and with every laser shot. Compared with ultraviolet-matrix-assisted laser desorption ionization on the same instrument, cryo-IR-SALDI had a comparable detection limit (≈1 µM), a lower mass resolution for peptides, and a higher mass resolution for large proteins. Approximately 2500 cryo-IR-SALDI mass spectra were obtained from a single spot on a 0.3-mm-thick frozen sample before the metal surface was reached. About 0.1 nL of frozen solution was desorbed per laser shot. The extent of protein charging varied between the SALDI solids used. With thymine, myoglobin charge states up to MH12+12 were observed. It is tentatively concluded that observed ions are preformed in the frozen sample.

Direct observation of ultraviolet laser induced photocurrent in oxygen deficient silica and germanosilicate glasses

UV laser induced inonization of silicon oxygen deficient centers (SODC) in silica glasses and germanium oxygen deficient centers (GODC) in germanosilicate glasses has been studied by direct displacement photocurrent measurements. For both SODC and GODC the two‐photon (two‐step) nature of photoionization has been established. The cross sections of transitions from first excited to upper (ionizable) states were estimated as σ12=6×10−18 cm2 for SODC and (0.5–1.0)×10−19 cm2 for GODC. The effect of pulse‐to‐pulse degradation of the photocurrent signal caused by the screening effect is applied to estimate the lifetimes and ranges of the free carriers. The conclusion was drawn, that ionized SODC and GODC play the key role for free charge trapping.

Gas Chromatography/Surface-Assisted Laser Desorption Ionization Mass Spectrometry of Amphetamine-like Compounds

A variety of amphetamine-like compounds were analyzed by gas chromatography/surface-assisted laser desorption ionization mass spectrometry, GC/SALDI-MS. In the SALDI method, compounds are adsorbed on a solid SALDI substrate and directly ionized from the substrate by means of a laser pulse. The interfacing of a SALDI ion source with a gas chromatograph is presented here for the first time. The end of the GC column is situated 20 mm from the silicon substrate in the vacuum of the ion source of a time-of-flight mass spectrometer, and the compounds eluted from the GC capillary are adsorbed onto the nanostructured silicon surface. The mass spectra show very low levels of background noise and no reagent ions. GC/SALDI-MS detection limits are several orders of magnitude lower than those previously reported for GC/MS analysis of amphetamine-like compounds. The extent of fragmentation is under experimental control by changing the laser fluence.

Gas-phase basicity: Parameter determining the efficiency of laser desorption/ionization from silicon surfaces

The efficiency of laser desorption/ionization of twenty compounds from the surface of amorphous silicon is studied as a function of proton affinity (PA) and gas-phase basicity (GB). The values of GB and PA are obtained from quantum-chemical calculations using the density functional theory in the B3LYP model with the 6–311++G(3df,3pd) basis set. The values of GB lie in the range from 845 to 977 kJ/mol. The efficiency of laser desorption/ionization exponentially depends on the GB and PA values and for the studied compounds varies from 7 × 10−6 to 1.4 × 10−2.

Negative-ion emission during laser ablation of multicomponent materials

The time of flight technique coupled with an electrostatic energy filter has been used for composition and energy-distribution analysis of the ion species emitted during laser ablation of multicomponent materials Y-Ba-Cu-O, Pb-Sn-Te. The negative-ion output and kinetic-energy distribution as a function of the laser wavelength and the laser fluence on the target were measured. A high output of the negative ions of matrix elements comparable with the positive-ion emission was detected. The barium negative-ion formation was observed in spite of the negative electron affinity of alkaline earth elements in the ground electronic state. The mechanism of negative-ion formation based on the ternary collisional recombination in the laser plasma is analyzed.

Biocompatibility of Laser-deposited Hydroxyapatite Coatings on Titanium and Polymer Implant Materials

We have investigated the biocompatibility of calcium phosphate coatings deposited by pulsed laser ablation from hydroxyapatite (HA) targets onto polyethylene and Teflon substrates. It was found that the cell density, attachment, and morphology of primary rat calvaria osteoblasts were influenced by both the original polymer and by the nature of the apatite coatings. HA coatings on Teflon were found to have higher biocompatibility in terms of cell adhesion and spreading. In vivo studies of bone response to coatings deposited by KrF excimer and CO2 lasers on commercial Ti6A14V alloy implants show that both deposition techniques suppress fibrous tissue formation and promote osteogenesis.

Investigation of thin ZnO layers in view of laser desorption-ionization

Thin zinc oxide films (ZnO) were developed as a matrix-free platform for surface assisted laser desorption-ionization (SALDI) time-of-flight mass spectrometry. The ZnO films were deposited by RF magnetron sputtering of ZnO ceramic targets in Ar atmospheres on monocrystalline silicon. The generation under UV (355 nm) laser irradiation of positive ions of atenolol, reserpine and gramicidin S from the ZnO layers deposited was studied. All analytes tested were detected as protonated molecules with no or very structure-specific fragmentation. The mass spectra obtained showed low levels of chemical background noise. All ZnO films studied exhibited high stability and good reproducibility. The detection limits for test analytes are in the 10 femtomol range.

On the Mechanism of Ion Desorption in the Process of Laser Desorption/Ionization from Silicon Surfaces

The mechanism of ion desorption in the process of laser desorption/ionization from silicon surfaces is studied using pyridine and N,N-dimethyl-1-phenylethylamine as examples. Based on the experimental and theoretical results, dependences of ion signal on the surface temperature are obtained for two different wavelengths of laser radiation, 355 nm and 532 nm. The theoretical part of the work includes numerical calculations of surface temperatures of amorphous silicon using the SLIM software package and quantum-chemical calculations of binding energy between the ions and silicon surface using the Hartree-Fock method and Firefly software package. It is demonstrated that the ions are desorbed via a thermal mechanism at temperatures much lower than the melting point of amorphous silicon.

Some aspects of space-charge effect calculation in high-resolution mass spectrometry

A variational 3D approach to the problem of simulating stationary distributions of ions in the radiofrequency low-vacuum ion traps with regard to Coulomb interaction and collisions of ions with buffer gas molecules is proposed. The software developed in the course of this work is employed to study the structure of stationary ion ensembles in the radiofrequency ion traps of various types. The effect of high-frequency and constant voltages, space-charge density, and buffer gas temperature on the formation of stationary distributions in the radiofrequency ion traps and their limiting capacitance is investigated. It is shown that the use of electrodes with a constant voltage in the presence of high enough ion density allows pre-filtering of ions directly in a high-frequency trap-accumulator.