Combined liquid chromatography/electron paramagnetic resonance spectrometry/electrospray ionization mass spectrometry for radical identification.

Electron paramagnetic resonance (EPR) spectrometry and mass spectrometry (MS) have been coupled together on-line with liquid chromatography (LC)/UV detection. These combined techniques have been applied to the determination of spin-trapped radical adducts, including phenyl, 2-, 3-, and 4-chlorophenyl, and 2-bromophenyl radicals trapped with alpha-(1-oxo-4-pyridyl)-N-tert-butylnitrone (4-POBN), and phenyl radicals trapped with 2-methyl-2-nitrosopropane (MNP), alpha-phenyl-N-tert-butylnitrone (PBN), and 5,5-dimethyl-1-pyrroline N-oxide (DMPO). Oxidized and reduced forms of the radical adducts were also detected by the on-line LC/EPR/MS system.     

An electron paramagnetic resonance study of defects in PECVD silicon oxides

Electron paramagnetic resonance (EPR) has been used to determine how the type and population of paramagnetic defects are altered firstly by changes to the composition of oxides grown on silicon by plasma enhanced chemical vapor deposition (PECVD) and secondly by subsequent anneal treatments of the various oxide films. Silicon oxide films with refractive index, n, of 1.464, 1.487, 1.508 and 1.536 and thickness of 1 m to 3 m were studied; those of higher index have a higher silicon content. Only E centers are detected in films with n=1.464 and 1.487. Raising n to 1.508 leads to the introduction of other types of paramagnetic centers and a large increase in the average total spin concentration. Increasing n further to 1.536 produces a further small increase in average spin concentration. Identities are proposed for the additional types of defect and the dependence of their population on anneal temperature is also reported.     

A study of electron paramagnetic resonance and optical absorption in calcium manganese phosphate glasses containing praseodymium

This paper reports on electron paramagnetic resonance (EPR) and optical absorption studies for Mn ions in praseodymium calcium manganese phosphate glasses. The EPR spectra exhibit three resonance signals at g2.0, g3.3 and g4.8. A six line hyperfine structure spectrum centered at g2.0 has been observed in the EPR spectra of all the glasses at lower concentration of Mn ions. The effects of the concentration of Mn ions and praseodymium oxide on resonance signals have been studied. The temperature dependence of EPR signals were also studied. The intensity of the resonance signals decreases with increase in temperature whereas the linewidths are found to be independent of temperature. As temperature is increased small fluctuations in hyperfine splitting are observed. From the optical absorption spectrum, the crystal field parameters and optical band gap energy were evaluated. The optical band gap energy is found to depend quite sensitively on added manganese content. The theoretical values of optical basicity were also evaluated.     

An in vitro L-band electron paramagnetic resonance study of highly irradiated whole teeth

Regarding in vivo L-band dosimetry with human teeth, a number of preliminary experiments were carried out that were linked to the resonators response and the relative contribution of enamel to the EPR signal intensity of irradiated whole teeth. The sensitivity of the extended loop resonator varies in the antenna plane, but this variation tends to vanish when the sample is moved away from this plane. When the loop antenna is placed just above the highly irradiated molar, around 88% of the dosimetric signal is due to the crown enamel. The sensitivity inside a birdcage cavity is approximately equal over the volume of a molar; only 30% of the molar's total dosimetric signal results from enamel. Some decrease in the intensity of the dosimetric signal from enamel is observed after irradiation. At room temperature, the signal is reduced by about 20% within 90 days and approaches a plateau with a time constant of about 35 days.     

Characterization of oligodeoxynucleotides by electron detachment dissociation fourier transform ion cyclotron resonance mass spectrometry

Electron detachment dissociation (EDD), recently introduced by Zubarev and co-workers for the dissociation of multiply charged biomolecular anions via a radical ion intermediate, has been shown to be analogous to electron capture dissociation (ECD) in several respects, including more random peptide fragmentation and retention of labile posttranslational modifications. We have previously demonstrated unique fragmentation behavior in ECD compared to vibrational excitation for oligodeoxynucleotide cations. However, that approach is limited by the poor sensitivity for oligonucleotide ionization in positive ion mode. Here, we show implementation of EDD on a commercial Fourier transform ion cyclotron resonance mass spectrometer utilizing two different configurations: a heated filament electron source and an indirectly heated hollow dispenser cathode electron source. The dispenser cathode configuration provides higher EDD efficiency and additional fragmentation channels for hexamer oligodeoxynucleotides. As in ECD, even-electron d/w ion series dominate the spectra, but we also detect numerous a/z (both even-electron and radical species), (a/z - B), c/x, (c/x - B), and (d/w - B) ions with minimal nucleobase loss from the precursor ions. In contrast to previous high-energy collision-activated dissociation (CAD) and ion trap CAD of radical oligonucleotide anions, we only observe minimum sugar cross-ring cleavage, possibly due to the short time scale of EDD, which limits secondary fragmentation. Thus, EDD provides fragmentation similar to ECD for oligodeoxynucleotides but at enhanced sensitivity. Finally, we show that noncovalent bonding in a DNA duplex can be preserved following EDD, illustrating another analogy with ECD. We believe the latter finding implies EDD has promise for characterization of nucleic acid structure and folding.     

Dose reconstruction with electron paramagnetic resonance spectroscopy of deciduous teeth

In the present study the feasibility of using whole, naturally loose deciduous incisors for dose reconstruction with electron paramagnetic resonance (EPR) spectroscopy was investigated. The properties of EPR signals were analysed before and after laboratory irradiation. The parameters of the native EPR signal of deciduous incisors was found to be different from those from enamel of permanent molars. The native EPR signal of deciduous incisors with peak-to-peak line width of 0.65 mT was located at g = 2.0050. The evaluated parameters of the dosimetric EPR signal (CO2-) of deciduous incisors were in agreement with those for enamel of permanent molars. A detection threshold for absorbed dose of about 100 mGy was estimated.     

Analysis of protein solvent accessible surfaces by photochemical oxidation and mass spectrometry

Protein surfaces are important in most biological processes, including protein-protein interactions, enzymatic catalysis, and protein-ligand binding. We report a method in which hydroxyl radicals generated by a rapid-UV irradiation of a 15% hydrogen peroxide solution were utilized to oxidize specific amino acid side chains of two model proteins (lysozyme, beta-lactoglobulin A), according to the residues' chemical reactivities and the solvent accessibility of the reactive carbons and sulfurs in the residue. Oxidized peptides generated by tryptic digestion were identified by electrospray-Fourier transform mass spectrometry. The specific sites of the stable modification were then identified by reverse-phase liquid chromatography coupled to quadropole ion trap tandem mass spectrometry. The solvent accessibility of the residue was shown to directly affect the rate of oxidation by this method (with the exception of methionine), supporting its use as a rapid measure of the solvent accessibility of specific residues, and in some cases, individual atoms.     

A method for applying strong electric fields in electron paramagnetic resonance at low temperatures

A method is described for studying epr spectra in crystals under the action of an external electric field which is applicable to a RE-1301 spectrometer, in the resonator of which a quartz cryostat extension is housed. A viscous electrically insulating grease is used, making it possible to carry out investigations in electric fields up to 700 kV cm^?1 at T = 77 and 4.2 K.     

Lateral diffusion of thiol ligands on the surface of au nanoparticles: an electron paramagnetic resonance study

The lateral mobility of the thiolate ligands on the surface of Au nanoparticles was probed by EPR spectroscopy. This was achieved by using bisnitroxide ligands, which contained a disulfide group (to ensure attachment to the Au surface) and a cleavable ester bridge connecting the two spin-labeled branches of the molecule. Upon adsorption of these ligands on the surface of Au nanoparticles, the two spin-labeled branches were held next to each other by the ester bridge as evidenced by the spin-spin interactions. Cleavage of the bridge removed the link that kept the branches together. CW and pulsed EPR (DEER) experiments showed that the average distance between the adjacent thiolate branches on the Au nanoparticle surface only marginally increased after cleaving the bridge and thermal treatment. This implies that the lateral diffusion of thiolate ligands on the nanoparticle surface is very slow at room temperature and takes hours even at elevated temperatures (90 degrees C). The changes in the distance distribution observed at high temperature are likely due to ligands hopping between the nanoparticles rather than diffusing on the particle surface.     

Manganese in apatites,chemical, ligand-field and electron paramagnetic resonance spectroscopy studies

Hydroxapatites precipitated with different amounts of carbonate and Mn²⁺ were studied. Infrared spectra, X-ray diffraction lattice parameters and thermal behaviour indicate that the presence of Mn²⁺ does not have any effect on the formation and properties of the carbonate apatites obtained. Interaction of apatite with a Mn²⁺-containing aqueous solution reveals that the molar uptake of Mn²⁺ by the apatite is higher than the Ca²⁺ released by it. Ligand-field and electron paramagnetic resonance spectroscopy results show that in Mn²⁺-doped Cd₅(PO₄)₃Cl, Mn²⁺ replaces Ca²⁺ in the apatite lattice, but in precipitated carbonate apatite it is in an MnO phase. The conclusion that Mn²⁺ in precipitated carbonate apatites is not incorporated in the apatite crystal is discussed in the light of the size differences between Mn²⁺ and Ca²⁺.     

Synthesis and unusual electron paramagnetic resonance spectrum of metastable nanoclusters of ZnO semiconductor crystallites

Metastable nanoclusters of ZnO semiconductor crystallites, 20 to 30 nm diameter, are synthesized by a reconstructive decomposition of a polymer precursor of dispersed Zn2+ cations in poly vinyl alcohol (PVA) polymer molecules. They have EPR (electron paramagnetic resonance) spectrum of distinct excitonic features. Multiple EPR bands appear in prominent intensities in oxygen vacancies VO+ and singly ionized Oi- and Zn(i)+ interstitials. A paramagnetic VO+ vacancy derives from usual diamagnetic O2- vacancy of VO++ (behaves as if doubly charged compared to the lattice) by addition of one electron. The results demonstrate the existence of a surface-interface or surface barrier layer in free-carrier depletion at the crystallite surface in the clusters and its effects on the Oi- and Zn(i)+ ionization states (determine green photoluminescence). Both VO+ and Zn(i)+ are curable by a thermal annealing in O2 gas. A cured sample of equilibrium structure achieved by heating at approximately 550 degrees C has a single EPR in Oi- at g = 1.990. The results are useful in understanding their correlation with EPR and optical properties in ZnO semiconductors and devices.     

Photoluminescence, thermally stimulated luminescence and electron paramagnetic resonance of europium-ion doped strontium pyrophosphate

Europium-ion doped strontium pyrophosphate was prepared via a chemical precipitation method to investigate the fluorescence of europium ions, the phosphate radical ions formed upon gamma-ray irradiation and their role in the thermally stimulated luminescence (TSL) of this compound. Fluorescence spectra revealed that europium ions were present in divalent as well as trivalent oxidation states. The measurements of fluorescence life time indicated that Eu³⁺ ions existed in two different types of environments in the lattice. Gamma irradiated europium-ion doped Sr₂P₂O₇ showed the presence of two thermo-luminescence glow peaks at 465 and 565 K; however, no glow was observed in the undoped sample. Electron paramagnetic resonance (EPR) studies of europium-ion doped samples showed signals from Mn²⁺ ions (present as impurity) prior to and after gamma irradiation. Upon gamma irradiation, signals originating from PO₂²⁻, PO₃²⁻ and O₂⁻ radical ions were observed in the undoped and doped samples. In the gamma irradiated europium-ion doped samples, additional low-field EPR signals, attributed to Eu²⁺ ions, were observed. By correlating the TSL and EPR results on europium-ion doped Sr₂P₂O₇, the mechanism for the glow peak at 565 K was identified.