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Mass spectra of alkyl carbamates derived from primary, secondary, and teriary alcohols by use of deuterium labeling and high resolution mass spectroscopy
Mass spectral properties of alkoxycyclohexanol trimethylsilyl ethers and alkoxycyclohexyl trimethylsilanes, using deuterium labeling
Diagnostic criteria are obtained for the distinction of alpha, beta, gamma, and N-methyl isomers of the C3 and C4 aliphatic amino acids, using mass spectral analysis of the derivatives of these acids. The use of deuterium labeling has helped in the understanding of certain fragmentation pathways.
Electron-impact induced fragmentations of o-, m-, and p-hydroxyalkylphenones and their trimethylsilyl (TMS) ethers are studied by means of high-resolution mass spectrometry, metastable defocusing, and deuterium labeling of the TMS ether derivatives. A markedly increased methyl radical loss from the o-TMS ether is attributed to a proximity effect. Minor fragmentation was observed with m- and p-isomers. Significantly intense doubly-charged ions were formed from ketonic cleavage and by the loss of a TMS methyl radical. The sequence of fragmentation was found to depend on the size of the alkyl group attached to the ketone carbonyl.
Investigations of low molecular weight compounds of the organogenic elements on lunar samples are reviewed. The three general techniques of vacuum pyrolysis, acid hydrolysis, and crushing have been employed by most investigators. Vacuum pyrolysis of lunar fines produce a variety of gaseous species which are either: (1) indigenous, (2) solar wind products and/or (3) chemical reaction products of mineral phases found in the lunar samples. Acid hydrolysis of lunar fines using deuterium-labeled acids yields evidence for indigenous methane and ethane. Methane and ethane found in the lunar fines are largely derived from the solar wind with only trace amounts indigenous to the samples. Crushing experiments with lunar fines and breccias produce methane, ethane, hydrogen, nitrogen, hydrogen sulfide and the rare gases.
The results of a study of the ion-molecule reactions of N(+), N(2)(+), and HCN(+) with methane, acetylene, and ethylene are reported. These studies were performed using the FA-SIFT at the University of Canterbury. The reactions studied here are important to understanding the ion chemistry in Titan's atmosphere. N(+) and N(2)(+) are the primary ions formed by photo-ionization and electron impact in Titan's ionosphere and drive Titan's ion chemistry. It is therefore very important to know how these ions react with the principal trace neutral species in Titan's atmosphere: Methane, acetylene, and ethylene. While these reactions have been studied before the product channels have been difficult to define as several potential isobaric products make a definitive answer difficult. Mass overlap causes difficulties in making unambiguous species assignments in these systems. Two discriminators have been used in this study to resolve the mass overlap problem. They are deuterium labeling and also the differences in reactivities of each isobar with various neutral reactants. Several differences have been found from the products in previous work. The HCN(+) ion is important in both Titan's atmosphere and in the laboratory.
Characterizing structural ensembles of intrinsically disordered proteins (IDPs) and intrinsically disordered regions (IDRs) of proteins is essential for studying structure–function relationships. Due to the different neutron scattering lengths of hydrogen and deuterium, selective labeling and contrast matching in small-angle neutron scattering (SANS) becomes an effective tool to study dynamic structures of disordered systems. However, experimental timescales typically capture measurements averaged over multiple conformations, leaving complex SANS data for disentanglement. We hereby demonstrate an integrated method to elucidate the structural ensemble of a complex formed by two IDRs. We use data from both full contrast and contrast matching with residue-specific deuterium labeling SANS experiments, microsecond all-atom molecular dynamics (MD) simulations with four molecular mechanics force fields, and an autoencoder-based deep learning (DL) algorithm. From our combined approach, we show that selective deuteration provides additional information that helps characterize structural ensembles. We find that among the four force fields, a99SB-disp and CHARMM36m show the strongest agreement with SANS and NMR experiments. In addition, our DL algorithm not only complements conventional structural analysis methods but also successfully differentiates NMR and MD structures which are indistinguishable on the free energy surface. Finally, we present an ensemble that describes experimental SANS and NMR data better than MD ensembles generated by one single force field and reveal three clusters of distinct conformations. Our results demonstrate a new integrated approach for characterizing structural ensembles of IDPs.
The aim of this study was to explore the application of deuterium (D) labeled glucose-D 7 as Raman-tag in Yarrowia lipolytica to assess triacyl glycerides (TAG) biosynthesis. Cells were grown in N depleted media in: (i) glucose in H 2 O (control), (ii) glucose-D 7 in H 2 O and (iii) glucose-D 7 in D 2 O, and the resulting biomass and lipids quantified. Infrared and Raman spectroscopies showed the incorporation of D with the presence of a C-D stretching bands in the silent region (1800–2600 cm -1 ) for cells grown in glucose-D 7 in H 2 O and glucose-D 7 in D 2 O as compared to the control. Fatty acid methyl ester analysis of cells grown in the three media showed significant differences in lipid profiles. Cells grown on glucose-D 7 in H 2 O and glucose-D 7 in D 2 O showed unequivocally D incorporation in fatty acids and TAG by mass spectrometry. Higher D incorporation was observed when cells were grown in D 2 O than H 2 O. Deuterium was also incorporated into the cell wall polysaccharides.
Mass spectrometry labelling technique - acid catalyzed deuterium and oxygen 18 exchange by gas-liquid chromatography
Here a mechanistic study was conducted on the catalytic conversion of ethanol over La 0.7 Sr 0.3 MnO 3–x perovskite catalysts in the presence and absence of water. The study sought insights into the path of C–C coupling toward acetone and crotonaldehyde and also into clarifying whether the lack of previous reports of C–C coupling over La 0.7 Sr 0.3 MnO 3–x (100) could be due to a “pressure gap”. Several types of experiments were performed at 400–800 K: flow experiments with a torr range reactant gas flown over La 0.7 Sr 0.3 MnO 3–x powders; ultra-high vacuum experiments with continuous gas exposures to a La 0.7 Sr 0.3 MnO 3–x (100) single-crystal sample; and torr range continuous gas exposures to a La 0.7 Sr 0.3 MnO 3–x (100) single-crystal sample. When ethanol and water were flown over La 0.7 Sr 0.3 MnO 3–x powders at 400–800 K, the products detected were ethene, acetaldehyde, acetone, crotonaldehyde, CO, CO 2 , and H 2 . Acetone was catalytically produced over both the La 0.7 Sr 0.3 MnO 3–x powder and the La 0.7 Sr 0.3 MnO 3–x (100) single-crystal sample at temperatures of 700–800 K when reaction conditions were on the order of 1 Torr of reactant gas and with an excess of water relative to ethanol (1 ethanol/9 water). Isotopic labeling with deuterium was used to gain insights into the C–C coupling reaction mechanism and paths in species with three and four carbons (C 3 and C 4 species). Additionally, steady-state isotopic transient kinetic analysis (SSITKA) experiments + simulations using carbon labeling of the ethanol feed were performed. Three mechanistic paths were considered for the C–C coupling step: the first two paths, A and B, involve coupling between two intermediates which are both in oxygen vacancies; and the third path, C, involves coupling between one intermediate in an oxygen vacancy and one intermediate outside of an oxygen vacancy. The results suggest that the dominant path to the C 3 product, acetone, depends on the conditions. The less active path (attributed to path A or B) occurs at 600–700 K and involves coupling between two irreversibly bound species. The more active path (attributed to path C) requires an excess of water, becomes dominant at 600–800 K, and involves coupling between one irreversibly bound species and one reversibly bound species. Based on these various observations from experiments and simulations, an elementary step is proposed for acetone formation involving a previously unreported C 4 transition state that is formed after aldol addition. Density functional theory calculations were performed based on this hypothesis, and it confirmed that this specific and previously unreported aldol addition path to acetone does exist and that this path consistent with the experimental data. In this path, C–C formation occurs to create a C 4 intermediate that is bound to an oxygen vacancy, then a hydrogen transfer with C–C bond breaking occurs that results in the production of the acetone molecule. The proposed mechanism is also consistent with the experimental observation that acetone formation has a greater than first-order dependence on the water vapor pressure.
Here, this work presents the first application of isotopically labeled LLM-105 (2,6-diamino-3,5-dinitropyrazine-1-oxide) to investigate thermal decomposition pathways. Specially synthesized LLM-105 isotopologues were utilized to isolate the influence of labeled 15 NO 2 nitro groups on the formation of lightgas products. Simultaneous differential scanning calorimetry, thermo-gravimetric, and mass spectrometry measurements were employed to track the evolution of product gases, enabling the direct comparison of isotopically shifted species with unlabeled LLM-105. Key findings show that C 2 N 2 production is mainly dependent on nitrogen sources from either the amine groups or the pyrazine ring (i.e., not the nitro groups). The formation of NO, N 2 , and N 2 O all involves the nitro groups to some extent. NO (nitric oxide) was found to be the predominant gas species directly formed from the nitro group of LLM-105. In contrast, mixed nitrogen isotopologues of N 2 and N 2 O (i.e., 14 N 15 N and 15 NNO) formed more readily in comparison to their pure counterparts (i.e., 15 N 2 and 15 N 2 O). This indicates the amine and/or pyrazine groups of LLM-105, in addition to the nitro group, are involved in the decomposition pathways forming N 2 and N 2 O. In addition, our investigation led to the discovery of two previously unreported decomposition products (CHO and HNCO), which were confirmed through hydrogen labelling utilizing deuterium isotopes. These results provide detailed speciation trends of gaseous products during LLM-105 decomposition, offering new insights into reaction pathways. Experimental data reported here will support the development of a detailed chemical kinetics model for LLM-105, essential for the safe handling of high explosives.
Acetogenic bacteria represent a class of organisms capable of converting reducing equivalents and carbon dioxide into products with carbon–carbon bonds. Materials-based bio-electrochemical approaches are attractive for supplying biological organisms directly with grid-supplied electrons to convert carbon dioxide to value-added chemicals. Carbon nanotube-modified biocathodes have emerged as promising candidates for microbial electrosynthesis with high yields of carbon product formation, but a fundamental understanding of extracellular charge transfer at this electrode-biofilm interface is still lacking. Here, we utilize solid-state interfaces between semiconducting single-walled carbon nanotubes (s-SWCNT) and a model acetogenic bacterium for mechanistic studies of electro-catalytic CO 2 conversion to acetate. Studies of bacteria/s-SWCNT interactions in a transistor-based device suggest direct extracellular electron transfer (EET) at the bio-nano interface. Deuterium isotope labeling experiments confirmed that the availability of electrochemically produced H 2 as a redox mediator does not limit the efficiency of EET and CO 2 electro-reduction for C. ljungdahlii biofilms, suggesting the primary reducing equivalents are the electrons delivered across the electrode/bacterium interface or involvement of biological redox mediators. Additional isotope labeling studies demonstrate high Faradaic efficiency for CO 2 electro-reduction at the SWCNT/bacterium interface. These results provide important information about EET across the bacterium/material interface in a model biocathode.
Polyelectrolyte complexation plays an important role in materials science and biology. The internal structure of the resultant polyelectrolyte complex (PEC) phase dictates properties such as physical state, response to external stimuli, and dynamics. Small-angle scattering experiments with X-rays and neutrons have revealed structural similarities between PECs and semidilute solutions of neutral polymers, where the total scattering function exhibits an Ornstein–Zernike form. In spite of consensus among different theoretical predictions, the existence of positional correlations between polyanion and polycation charges has not been confirmed experimentally. Here, we present small-angle neutron scattering profiles where the polycation scattering length density is matched to that of the solvent to extract positional correlations among anionic monomers. The polyanion scattering functions exhibit a peak at the inverse polymer screening radius of Coulomb interactions, q* ≈ 0.2 Å –1 . This peak, attributed to Coulomb repulsions between the fragments of polyanions and their attractions to polycations, is even more pronounced in the calculated charge scattering function that quantifies positional correlations of all polymer charges within the PEC. Screening of electrostatic interactions by adding salt leads to the gradual disappearance of this correlation peak, and the scattering functions regain an Ornstein–Zernike form. Experimental scattering results are consistent with those calculated from the random phase approximation, a scaling analysis, and molecular simulations.
Tandem column gas-liquid chromatography labeling technique for mass spectrometry, noting ketones exchange and data on deutrium and oxygen compounds
To better understand the chemical species that gives rise to the 2165/cm (4.62 micron) "XCN" absorption feature seen towards embedded protostars such as W33A, we have performed laboratory studies using deuterium (H-2) isotopic labeling. We report the observation of a small but significant deuterium isotope shift for the "XCN" peak which demonstrates that the atomic motion(s) causing the "XCN" band in the laboratory samples must involve hydrogen. We also report the results of C-13, N-15 and O-18 labeling experiments that are consistent with previously reported values.
Abstract Daylength, a seasonal and latitudinal variable, exerts a substantial impact on plant growth. However, the relationship between daylength and growth is nonproportional, suggesting the existence of adaptive mechanisms. Thus, our study aimed to comprehensively investigate the adaptive strategies employed by plants in response to daylength variation. We grew false flax (Camelina sativa) plants, a model oilseed crop, under long-day (LD) and short-day (SD) conditions and used growth measurements, gas exchange measurements, and isotopic labeling techniques, including 13C, 14C, and 2H2O, to determine responses to different daylengths. Our findings revealed that daylength influences various growth parameters, photosynthetic physiology, carbon partitioning, metabolic fluxes, and metabolite levels. SD plants employed diverse mechanisms to compensate for reduced CO2 fixation in the shorter photoperiod. These mechanisms included enhanced photosynthetic rates and reduced respiration in the light (RL), leading to increased shoot investment. Additionally, SD plants exhibited reduced rates of the glucose 6-phosphate (G6P) shunt and greater partitioning of sugars into starch, thereby sustaining carbon availability during the longer night. Isotopic labeling results further demonstrated substantial alterations in the partitioning of amino acids and TCA cycle intermediates between rapidly and slowly turning over pools. Overall, the results point to multiple developmental, physiological, and metabolic ways in which plants adapt to different daylengths to maintain growth.
Multimaterial and Isotopically Labeled Specimen Fabrication via Material Extrusion Additive Manufacturing for Interlayer Diffusion Analysis
The doubly labeled water method for measuring total energy expenditure is subject to error from natural variations in the background 2H and 18O in body water. There is disagreement as to whether the variations in background abundances of the two stable isotopes covary and what relative doses of 2H and 18O minimize the impact of variation on the precision of the method. We have performed two studies to investigate the amount and covariance of the background variations. These were a study of urine collected weekly from eight subjects who remained in the Madison, WI locale for 6 wk and frequent urine samples from 14 subjects during round-trip travel to a locale > or = 500 miles from Madison, WI. Background variation in excess of analytical error was detected in six of the eight nontravelers, and covariance was demonstrated in four subjects. Background variation was detected in all 14 travelers, and covariance was demonstrated in 11 subjects. The median slopes of the regression lines of delta2H vs. delta18O were 6 and 7, respectively. Modeling indicated that 2H and 18O doses yielding a 6:1 ratio of final enrichments should minimize this error introduced to the doubly labeled water method.