Mass spectrometry in structural and stereochemical problems. CXVII.
Structural and stereochemical characteristics of aliphatic epoxyketones by mass spectrometry and deuterium labeling
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Structural and stereochemical characteristics of aliphatic epoxyketones by mass spectrometry and deuterium labeling
Field ionization for improvment of mass spectrometry
Steranes and triterpanes identification from Green River shale by capillary gas liquid chromatography and mass spectrometry
Apollo 11 fines and rocks analysis by chromatography, mass spectrometry and light and scanning electron microscopy
The concept of a Comprehensive 2-Dimensional Gas Chromatography coupled with Time-of-Flight Mass Spectrometry (GCxGC-TOWS) for the analysis of organic compounds has been proven with commercially available instrumentation (LECO Corp). The performance of a GCxGC instrument has been characterized in various stages using two independent breadboard systems. The GCxGC separation systems, including the thermal modulator, have been miniaturized to the size of a benchtop configuration. One breadboard system employs a Flame Ionization Detector (FID), whereas the second breadboard system employs a Time-of-Fight mass spectrometer (TOFWS) as a detection system.
Exopolymers from a diverse collection of marine and freshwater bacteria were characterized by pyrolysis-mass spectrometry (Py-MS). Py-MS provides spectra of pyrolysis fragments that are characteristic of the original material. Analysis of the spectra by multivariate statistical techniques (principal component and canonical variate analysis) separated these exopolymers into distinct groups. Py-MS clearly distinguished characteristic fragments, which may be derived from components responsible for functional differences between polymers. The importance of these distinctions and the relevance of pyrolysis information to exopolysaccharide function in aquatic bacteria is discussed.
Mass spectrometry of cyclic sulfites and carbonate esters, analyzing electron impact induced fragmentations and metastable ion characteristics based on deuterium labeling
Gas chromatography and mass spectrometry applied to porphyrin microanalysis, studying homologous porphyrin series in ancient sediments and oils
Ion-polar molecule collision time history plots and computer movies, calculating capture cross sections for mass spectrometry
Paper chromatography combination with dinitrophenyl amino acids mass spectrometry for analyzing purine and pyrimidine bases
The high temperature diffusion of trace elements in metals and alloys was investigated. Measurements were made by high sensitivity mass spectrometry in which individual atoms were detected, and quantitative data was obtained for zircaloy-2, 304 stainless steel, and tantalum. Additionally, a mass spectrometer was also an analytical tool for determining an allotropic phase change for stainless steel at 955 C, and a phase transition region between 772 C and 1072 C existing for zircaloy-2. Diffusion rates were measured in thin (0.001" (0.0025 cm) and 0.0005" (0.0013 cm)) ribbons which were designed as high temperature thermal ion sources, with the alkali metals as naturally occurring impurities. In the temperature and pressure regime where diffusion measurements were made, the solute atoms evaporated from the ribbon filaments when the impurities diffused to the surface, with a fraction of these impurity atoms ionized according to the Langmuir-Saha relation. The techniques developed can be applied to many other alloys important to space vehicles and supersonic transports; and, with appropriate modifications, to the diffusion of impurities in composites.
Remote group interactions after electron impact in 4-substituted cyclohexanones, investigating mass spectrometry in structural and stereochemical problems
An instrument that analyzes the chemical composition of biological particles in aerosol or hydrosol form was developed. Efforts were directed toward the acquisition of mass spectra from aerosols of biomolecules and bacteria. The filament ion source was installed on the particle analysis by mass spectrometry system. Modifications of the vacuum system improved the sensitivity of the mass spectrometer. After the modifications were incorporated, detailed mass spectra of simple compounds from the three major classes of biomolecules, proteins, nucleic acids, and carbohydrates were obtained. A method of generating bacterial aerosols was developed. The aerosols generated were collected and examined in the scanning electron microscope to insure that the bacteria delivered to the mass spectrometer were intact and free from debris.
The design, construction, and initial use of an ion microprobe to carry out secondary ion mass spectrometry (SIMS) of solid samples is reported. The system is composed of a differentially pumped custom-made UHV (Ultra High Vacuum) chamber, a quadrupole mass spectrometer and a telefocus A-DIDA ion gun with the capability of producing beams of Cesium, as well as inert and reactive gases. The computer control and acquisition of the data were designed and implemented using a personal computer with plug-in boards, and external circuitry built as required to suit the system needs. The software is being developed by using a FORTH-like language. Initial tests aimed at characterizing the system, as well as preliminary surface and depth-profiling studies are presently underway.
Carbonaceous meteorites are derived from asteroids, although specific parent bodies are generally unknown. However, on September 24, 2023, NASA’s Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer (OSIRIS-REx) mission delivered regolith from the carbonaceous B-type asteroid (101955) Bennu, enabling coordinated laboratory analysis of pristine samples, with a well characterized geological context, from an asteroid of known provenance. One of primary mission goals [1] was the identification and characterization of primordial organic matter present in the returned samples. We report results from the coordinated analyses of Bennu samples using UV fluorescence, two-step laser mass spectrometry (μ-L2MS) and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX).
A description is given of experiments which provide a verification of three features of Penning ionization mass spectrometry. One of these features is related to the ability to simplify a molecular fragmentation pattern and to intensify the molecular ion peak. Another feature is concerned with the ability to identify uniquely geometric isomers which are indistinguishable using high-energy electron impact methods. The third feature involves the ability to identify components in a mixture, which cannot be discerned using electron impact or chemical ionization methods alone. The investigation shows that Penning ionization is an efficient soft ionization technique which can be used to simplify mass spectra of pure compounds as well as mixtures.
Volatile ratios (primarily of H2O and CO2) in individual silicate melt (glass) inclusions in minerals have been analyzed using laser volatilization and mass spectrometry. A Nd-glass laser was used to produce 50-micrometer diameter pits in silicate melt inclusions. Released volatiles were analyzed directly with a computer-controlled quadrupole mass spectrometer. The detection limits for CO2 and H2O were on the order of 3 x 10(-14) and 3 x 10(-13) moles, respectively. The reproducibility for CO2/H2O was better than +/- 9%. The total range of volatile ratios from vitreous silicate glass inclusions contained in a suite of Galapagos lavas were: 0.018 to 1.193 for CO2/H2O; 0.002 to 0.758 for CO/H2O; 0 to 0.454 for CH4/H2O; and 0 to 0.432 for Ar/H2O. The mean CO2/H2O from the propagating rift (0.245 +/- 0.068) silicate glass inclusions is significantly lower than that of the actively failing rift (0.641 +/- 0.241); this difference probably reflects different degrees of degassing during magmatic histories for the two regions. Relatively undifferentiated failing rift magmas must have relatively short crustal residence times prior to eruption and, therefore, have not undergone significant degassing of CO2, as would appear to be the case for the more highly fractionated propagating rift magmas. The laser-mass spectrometric system described herein has the ability to act as a point-source probing device that can differentiate between the various volatile sites in minerals and rocks (as well as synthetic materials) on a micrometer scale.
Nitric oxide has been measured in situ between 38.4 and 29.8 km by a new technique, photoionization mass spectrometry. Data indicate a peak mixing ratio of 5.7 plus or minus 0.35 ppbv at 37.5 km and only 0.2 plus or minus 0.2 ppbv at 32.8 km with a sharp gradient in concentration between 33 and 34 km. Simultaneous in-situ measurements of the ozone concentration show no significant feature at that altitude. The rapid decrease in mixing ratio is not predicted by current theory.