Diagnosis of Helicobacter pylori infection with the (13)C-urea breath test by means of GC-MS analysis

The diagnosis of Helicobacter pylori (H. pylori) infection by GC-MS detection of the (13)CO(2) enrichment in (13)C-urea breath test ((13)C-UBT) samples is reported. This study aimed to optimize the (13)C-UBT with regards to the diagnostic cut-off value, sampling time, and frequency. The H. pylori status of 103 dyspeptic patients was obtained by histological examination, the rapid urease test as well as with the GC-MS (13)C-UBT. Analytical and diagnostic accuracies were determined by comparison of the GC-MS (13)C-UBT results with that of the analytical and diagnostic gold standards, namely GC-isotope ratio MS (IRMS) and histology. The (13)CO(2) enrichment values obtained with GC-MS analysis, correlated favorably (r(2) = 0.993) with those obtained by GC-IRMS analysis. When compared to histology, the GC-MS (13)C-UBT had a diagnostic sensitivity of 92% and a specificity of 93%. The positive predictive value (PPV), negative predictive value (NPV), and accuracy were 95, 89, and 92%, respectively. It was concluded that SIM GC-MS is capable of analyzing nonradioactive (13)C-UBT samples, with a precision and accuracy sufficient to distinguish between H. pylori positive and negative patients.     

Toward the quantification of the 13CO2/12CO2 ratio in exhaled mouse breath with mid-infrared hollow waveguide gas sensors

Mouse sepsis models are used to gain insight into the complex processes involved with patients suffering from glucose metabolism disorders. Measuring the expiratory release of ¹³CO₂ after administering stable labeled ¹³C₆-glucose enables assessment of the in vivo integrity and functionality of key metabolic processes. In the present study, we demonstrate that Fourier transform infrared spectroscopy operating in the mid-infrared spectral regime (2–20 μm) combined with hollow waveguide gas sensing modules simultaneously serving as a miniaturized gas cell and as a waveguide are capable of quantitatively monitoring ¹³CO₂ enrichment levels in low volume mouse breath samples.     

Changes in the natural abundance of 13CO2/12CO2 in breath due to lipopolysacchride‐induced acute phase response

The natural abundance of carbon‐13 in blood proteins increases during the cachectic state and may be a biomarker for disease status. We hypothesized a corresponding drop in the relative abundance of ¹³C in breath CO₂. Using the lipopolysacchride (LPS)‐induced endotoxemia model of the acute cachectic state, we demonstrated that the acute phase response causes shifts in the stable isotopes of carbon in exhaled CO₂ (¹³CO₂/¹²CO₂ delta value) shortly after administration of LPS while glucocorticoid treatment does not. Mice were injected with LPS and stable isotopes of blood amino acids and carbon in exhaled CO₂ were monitored. An increase in the relative isotopic mass of serum alanine, proline and threonine was observed at 3 h after LPS injection. Breath delta values began dropping immediately after administration of LPS, and were 4–5 delta values lower than those of the control animals by 2.5 h after injection. A corresponding drop in delta value was not observed with dexamethasone treatment. Thus protein synthesis during the acute phase response probably caused the fractionation of stable isotopes observed in the plasma amino acids and in exhaled breath ¹³CO₂ delta values. The exhaled breath ¹³CO₂ delta value may be a valuable real‐time biomarker of cachexia associated with an acute phase response due to endotoxemia. Copyright © 2009 John Wiley & Sons, Ltd.     

Carbon Isotope Fractionation during the Formation of CO2 Hydrate and Equilibrium Pressures of 12CO2 and 13CO2 Hydrates

Knowledge of carbon isotope fractionation is needed in order to discuss the formation and dissociation of naturally occurring CO₂ hydrates. We investigated carbon isotope fractionation during CO₂ hydrate formation and measured the three-phase equilibria of ¹²CO₂–H₂O and ¹³CO₂–H₂O systems. From a crystal structure viewpoint, the difference in the Raman spectra of hydrate-bound ¹²CO₂ and ¹³CO₂ was revealed, although their unit cell size was similar. The δ¹³C of hydrate-bound CO₂ was lower than that of the residual CO₂ (1.0–1.5‰) in a formation temperature ranging between 226 K and 278 K. The results show that the small difference between equilibrium pressures of ~0.01 MPa in ¹²CO₂ and ¹³CO₂ hydrates causes carbon isotope fractionation of ~1‰. However, the difference between equilibrium pressures in the ¹²CO₂–H₂O and ¹³CO₂–H₂O systems was smaller than the standard uncertainties of measurement; more accurate pressure measurement is required for quantitative discussion.     

Methanation of CO over nickel: Mechanism and kinetics at high H2/CO ratios

The CO methanation reaction over nickel was studied at low CO concentrations and at hydrogen pressures slightly above ambient pressure. The kinetics of this reaction is well described by a first-order expression with CO dissociation at the nickel surface as the rate-determining step. At very low CO concentrations, adsorption of CO molecules and H atoms compete for the sites at the surface, whereas the coverage of CO is close to unity at higher CO pressures. The ratio of the equilibrium constants for CO and H atom adsorption, K(CO)/K(H), was obtained from the rate of CO methanation at various CO concentrations. K(H) was determined independently from temperature programmed adsorption/desorption of hydrogen to be K(H) = 7.7 x 10(-4) (bar(-0.5)) exp[43 (kJ/mol)/RT] and hence the equilibrium constants for adsorption of CO molecules may be calculated to be K(CO) = 3 x 10(-7) (bar(-1)) exp[122 (kJ/mol)/RT]. Furthermore, the rate of dissociation of CO at the catalyst surface was determined to be 5 x 10(9) (s(-1)) exp[-96.7 (kJ/mol)/RT] assuming that 5% of the surface nickel atoms are active for CO dissociation. The results are compared to equilibrium and rate constants reported in the literature.     

Thermodynamics and kinetics of CO2, CO, and H+ binding to the metal centre of CO2 reduction catalysts

In our developing world, carbon dioxide has become one of the most abundant greenhouse gases in the atmosphere. It is a stable, inert, small molecule that continues to present significant challenges toward its chemical activation as a useful carbon end product. This tutorial review describes one approach to the reduction of carbon dioxide to carbon fuels, using cobalt and nickel molecular catalysts, with particular focus on studying the thermodynamics and kinetics of CO(2) binding to metal catalytic sites.     

Study of the pseudo-steady-state kinetics of CO2 hydrate formation and stability

This article describes a dynamic model for formation and stability of CO₂-hydrate on the interface of liquid CO₂(LCO₂) and ocean water at large depths. Experimental results indicate that a thin film of hydrate naturally forms on the interfaces between LCO₂ and water, and inhibits diffusion between the two phases. Experiments further shows that the flux of CO₂ through the hydrate film is dependent of the CO₂-concentration in the ambient sea water. The model proposed here explains these phenomena by introducing four major mechanisms; diffusion of water to the LCO₂-phase, formation of hydrate in the LCO₂-hydrate interface, decay of hydrate in the water-hydrate interface, and diffusion of CO₂ through the water phase. The model explains the CO₂ flux not by diffusion through the hydrate film, but suggest a mechanism of continuous hydrate formation and decay. The overall effect is a “moving,” pseudo-steady-state hydrate film due to transport of CO₂ through the film. The film velocity is dependent of liquid-liquid diffusivity parameters and reaction constant, and lacking experimental values of these parameters, an order–of-magnitude analysis is done by fitting the model to experimentally obtained data for the overall film velocity. The motivation for this work is to elucidate options for CO₂ depositions in deep oceans, of which liquid CO2 sequestration is believed to be one of the most feasible. Spreading of CO₂ from a liquid CO₂-lake and associated lowering of pH in the ecosystem surrounding the lake is of large concern. The work presented here concludes that diffusion of CO₂ in the ocean is largely reduced by the hydrate film and suggests that hydrate formation may alleviate some of the environmental concerns regarding deep ocean sequestration of liquid CO₂. © 1994 John Wiley & Sons, Inc.     

Unraveling the origin of band shapes in infrared spectra of N2O-12CO2 and 12CO2-13CO2 ice particles

Band structures in the region of strong infrared absorption bands for different N2O-12CO2 and 12CO2-13CO2 composite particles are investigated by combining quantum mechanical exciton calculations with systematic experimental investigations. The ice particles are generated by collisional cooling and characterized with rapid-scan infrared spectroscopy. The size of the particles lies between approximately 10 and 100 nm. The calculated spectra show excellent agreement with the experimental data. This work leads to a detailed understanding on a molecular level of shape effects in pure and statistically mixed particles as well as of the characteristic features observed for core-shell particles.     

Effects of the crystalline structure of Ga2O3 on the photocatalytic activity for CO production from CO2

Ga₂O₃ samples with different crystalline structures were prepared by calcination of a gallium nitrate powder around 800 K. Ga₂O₃ samples with mixed phases of γ and β showed high photocatalytic activity for CO production from CO₂ reduction with water, and the activity was even higher than that for an Ag-loaded β-Ga₂O_3. The photocatalytic activity increased with time. The increase was attributed to the appearance of GaOOH resulting from the interaction of Ga₂O₃ with water during the reaction as revealed by XRD and XPS analyses. In situ FT-IR measurements revealed that bicarbonates and bidentate carbonate species were adsorbed on GaOOH. Therefore, the increase of the photocatalytic activity with time would be derived from the formation of GaOOH phase on the γ-Ga₂O₃ and β-Ga₂O₃ sample.     

Influence of the cluster dimensionality on the binding behavior of CO and O2 on Au13

We present an ab initio density functional theory study of the binding behavior of CO and O(2) molecules to two- and three-dimensional isomers of Au(13) in order to investigate the potential catalytic activity of this cluster towards low-temperature CO oxidation. First, we scanned the potential energy surface of Au(13) and studied the effect of spin-orbit coupling on the relative stabilities of the 21 isomers we identified. While spin-orbit coupling increases the stability of the three-dimensional more than the two-dimensional isomers, the ground state structure at 0 K remains planar. Second, we systematically studied the binding of CO and O(2) molecules onto the planar and three-dimensional structures lowest in energy. We find that the isomer dimensionality has little effect on the binding of CO to Au(13). O(2), on the other hand, binds significantly to the three-dimensional isomer only. The simultaneous binding of multiple CO molecules decreases the binding energy per molecule. Still, the CO binding remains stronger than the O(2) binding. We did not find a synergetic effect due to the co-adsorption of both molecular species. On the three-dimensional isomer, we find O(2) dissociation to be exothermic with an dissociation barrier of 1.44 eV.     

Intrinsic adsorption properties of CO2 on 5A and 13X zeolite

Data for the adsorption of CO₂ on 5A (CaA) and 13X (NaX) zeolite are critically evaluated. In addition, fresh data for the adsorption of CO₂ on 13X zeolite is reported. Three intrinsic properties are examined: q _max , the saturation loading, K _H , the Henry constant, and (?ΔH) _q , the isosteric heat of sorption. Below a reduced temperature T _r , of 0.9, the q _max values for both 5A and 13X zeolites are similar to theoretical values that may be derived using zeolitic crystallographic properties and the sorbate density calculated using the Rackett equation. For the region 0.9 ≤ Tr ≤ 1.0, the calculated q _max values exceed the theoretical values similarly calculated, indicating that the molecules have a smaller molar volume than in a similar liquid phase. This is a similar result to that observed in ionic liquids. Linear regressed equations are derived for q _max for the region 0.9 ≤ Tr ≤ 1.25. The Henry constant values for 5A are remarkably consistent for the five studies examined, with a correlation coefficient, R, of 0.999 for the van’t Hoff equation, but for the seven studies examined in 13X the data is more disperse as indicated by a correlation coefficient R of 0.899 for the van’t Hoff equation. The values of (?ΔH) _q , the isosteric heat of sorption are in agreement with the literature. An explanation is advanced for the discrepancy between the higher heats of sorption values obtained calorimetrically from those obtained from isosteric adsorption studies. Finally, the fresh data is observed to fit the Toth model with regression coefficients of 0.999. However, the parameters obtained for the Toth equation by regression are significantly different from the intrinsic properties derived earlier, indicating the difficulty of deriving intrinsic parameters from isotherm fits.     

Adsorption dynamics and kinetics of CO2 on Fe/FeOx nanoclusters supported on HOPG

The adsorption dynamics and kinetics of CO₂ on FeO_x clusters have been studied using thermal desorption spectroscopy (TDS) and molecular beam scattering. According to AES data, even at good vacuum conditions, the vapor‐deposited Fe clusters oxidize readily. An ensemble of metallic and oxidized Fe clusters form. Three structures at 120 K, 160 K, and 500 K are seen in CO₂ TDS, which are assigned to physisorbed CO₂ and carbonate decomposition. The latter structure is only present for large Fe exposures, χ_Fe. The initial adsorption probabilities, S₀, decrease with increasing impact energy. S₀ increases with adsorption temperature, T_s, which is discussed in the framework of the capture‐zone model (CZM). Small effects of the cluster size on the initial adsorption probabilities, S₀, as well as its coverage dependence, S(Θ), have been seen. The coverage dependence of the adsorption probabilities obeys the Kisliuk precursor model, as predicted by the CZM. Copyright © 2008 John Wiley & Sons, Ltd.