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The 14C peak in AD 775 (M12) has been measured and confirmed globally in several studies since it was first measured in annual tree rings by Miyake et al. (2012). However, M12 data measurements in early- and latewood are limited. This paper presents the Δ14C values in early- and latewood from AD 762–776 Zelkova serrata tree rings from Bangu-dong, Ulsan, South Korea (35°33′N, 129°20′E). The results indicate no early rise in Δ14C values in the latewood of AD 774 in this sample located at mid-latitude. A comparison of the results of this and previous studies suggests latitude dependence (Büntgen et al. 2018); that is, the early rise of Δ14C in AD 774 was not observed at mid-latitudes in South Korea but was observed at high latitudes in Finland. The half-oxidation time of 14C was estimated from a detailed analysis of a small bomb peak in AD 1962. Based on the half-oxidation time, the Δ14C rise in the latewood, but not in the earlywood, of AD 774 in Finland, and the absence of a Δ14C rise in both the early- and latewood of AD 774 in South Korea, the 14C spike was estimated to have been produced from late April to mid-June in AD 774.
The oxidation behavior of the selective laser melting (SLM)–fabricated Inconel 718 was investigated through isothermal oxidation testing at 650 °C for 500 h and compared with that of the as-cast and as-forged specimens at the same testing conditions. The effect of microstructure and surface roughness on the oxidation behavior of the SLM-fabricated, as-cast, and as-forged Inconel 718 specimens was examined. The result shows that Inconel 718 fabricated by SLM with the unique layer structure exhibited a better resistance to the 500 h oxidation at 650 °C compared with as-cast and as-forged 718 with coarse dendritic structure and uniform equiaxed grain microstructure, respectively. The influence of the surface roughness on the long-time oxidation resistance of SLM specimens is not pronounced compared with that of as-cast and as-forged specimens. The tiny dendrites instead of grain boundaries are a major influencing factor for the oxidation process of SLM specimens. The surface roughness has more evident influence on the oxidation resistance of as-forged specimens than that of the as-cast ones subjected to the 500 h oxidation at 650 °C.
One of the commonly used analytical approaches for measuring oxygen isotope ratios δ18O of solids (organic and inorganic) is to pyrolyze the samples to gaseous phases and then send the gas into an isotope ratio mass spectrometer system. Solid samples for δ18O measurements are usually stored in silver cups because of its low reactivity towards oxygen and other oxidants. Samples in silver cups can be dropped directly into the carbon column of the pyrolysis furnace. However, the silver cups can tarnish and then be oxidized over a prolonged storage period. We find that while a small amount of silver oxides does not affect measurements with appreciable sample sizes, it can skew isotope results of small samples. We thus recommend careful storage of samples in silver cups to minimize oxidation, such as under an air-isolated condition, and avoiding prolonged storage for accurate δ18O measurements.
The aim of the present study was to investigate the effects of dietary Zn level on growth performance, Zn bioaccumulation, antioxidant capacity and innate immunity in juvenile mud crabs (Scylla paramamosain). Six semi-purified diets were formulated to contain dietary Zn levels of 44·5, 56·9, 68·5, 97·3, 155·6 or 254·7 mg/kg. Dietary Zn level significantly influenced percentage weight gain (PWG), with the highest observed in crabs fed the diet containing 97·3 mg/kg Zn. Tissue Zn concentrations significantly increased as dietary Zn levels increased from 44·5 to 254·7 mg/kg. Retention of Zn in hepatopancreas increased with dietary Zn levels up to 68·5 mg/kg and then significantly decreased. Moreover, inadequate dietary Zn (44·5 and 56·9 mg/kg) reduced antioxidation markers including total superoxide dismutase (SOD) and Cu/Zn SOD activities and total antioxidant level. Crabs fed the diet with 44·5 mg/kg Zn also showed significantly lower expression of genes involved in antioxidant status, such as Cu/Zn SOD, glutathione peroxidase, catalase and thioredoxin than those fed diets containing 68·5 and 97·3 mg/kg Zn. The highest activities of phenoloxidase and alkaline phosphatase were recorded in crabs fed the diets containing 68·5 and 97·3 mg/kg Zn. Expression levels of prophenoloxidase and toll-like receptor 2 were higher in crabs fed the 97·3 mg/kg Zn diet compared with crabs fed the other diets. Based on PWG alone, the optimal dietary Zn level was estimated to be 82·9 mg/kg, with 68·5 to 97·3 mg/kg recommended for maintaining optimal Zn bioaccumulation, oxidation resistance and innate immune response of juvenile mud crabs.
Two cases of bipolar psychosis presented a rapid manic switch following administration of tricyclic antidepressants. In both cases the oxidation capacity was genetically deficient. The role of oxidation deficit is discussed in the pathogenesis of switch process and preventive measures are considered.
BaxSr(1−x)TiO3 (BST) thin films were fabricated on a Ti substrate using micro-arc oxidation (MAO) in an aqueous solution with the addition of 0.6 M Ba(OH)2, 0.4 M Sr(OH)2, and 0.05 M EDTA. The morphology, composition, and electrical properties of BST films prepared under different processing times were characterized, and MAO growth characteristics of BST films were discussed. Results indicate that dielectric and ferroelectric properties of BST films are positively correlated with surface morphology dependent on MAO spark patterns. To obtain a smooth and compact film, the large spark stage should be avoided. During MAO processes, elements from the substrate and electrolyte solution migrate in opposite directions under an electric field, resulting in Ba, Sr, Ti, and O elements exhibiting a gradient distribution between the BST film and the Ti substrate. BST film prepared using MAO is composed of two layers: an outer loose layer and an inner dense layer. In addition, because of the position of discharge breakdown continually changing, the interface between the film and the substrate is uneven. As MAO processing time increases, BST film thickness increases and ferroelectric property improves. When processing time is 15 min, the residual polarization intensity (2Pr) of the BST film is about 4.9 μC/cm2.
Increasing clinical and experimental evidence accumulated during the past few decades supports an important role for dietary advanced glycation endproducts (AGE) in the pathogenesis of many chronic non-infectious diseases, such as type 2 diabetes, CVD and others, that are reaching epidemic proportions in the Western world. Although AGE are compounds widely recognised as generated in excess in the body in diabetic patients, the potential importance of exogenous AGE, mostly of dietary origin, has been largely ignored in the general nutrition audience. In the present review we aim to describe dietary AGE, their mechanisms of formation and absorption into the body as well as their main mechanisms of action. We will present in detail current evidence of their potential role in the development of several chronic non-infectious clinical conditions, some general suggestions on how to restrict them in the diet and evidence regarding the potential benefits of lowering their consumption.
Oxidation zones and mine wastes are metal-rich, near-surface environments, natural and man-made critical zones of ore deposits, respectively. They contain a number of minerals which, despite their metastability, occur consistently and in abundance. Field studies, presented as examples in this work, show that metastable minerals form not only directly from aqueous solutions, but also from more complex precursors, such as nanoparticles, gels, X-ray amorphous solids, or clusters. Initial precipitation of metastable phases and their conversion to stable phases is described by the Ostwald's step rule. Thermodynamic data show that there is a tendency, but no rule, that structurally more complex phases are also thermodynamically more stable. The Ostwald's step rule could then state that the initial metastable phases are structurally simple and easily assembled from aqueous solutions, nanoparticles, gels, disordered solids, or clusters. The structural similarity of the precursor and the forming phase is a kinetic factor favouring the crystallisation of the new phase. Calculation of saturation indices for mine drainage solutions show that they are mostly supersaturated with respect to the stable phases and the aqueous concentrations are sufficient to precipitate metastable minerals. In our fieldwork, we often encounter gelatinous substances with copper, manganese or tungsten that slowly convert to metastable oxysalt minerals. Another possibility is the crystallisation of various metastable minerals from solid, homogeneous ‘resins’ that are X-ray amorphous. Minerals typical for near-surface environments may be stabilised by their surface energy at high specific surface areas. For example, ferrihydrite is often described as a metastable phase but can be shown to be stable with respect to nanosised hematite.
Methionine, an essential sulphur-containing amino acid (SAA), plays an integral role in many metabolic processes. Evidence for the methionine requirements of adult dogs is limited, and we employed the indicator amino acid oxidation (IAAO) method to estimate dietary methionine requirements in Labrador retrievers (n 21). Using semi-purified diets, the mean requirement was 0·55 (95 % CI 0·41, 0·71) g/4184 kJ. In a subsequent parallel design study, three groups of adult Labrador retrievers (n 52) were fed semi-purified diets with 0·55 g/4184 kJ (test diet 1), 0·71 g/4184 kJ (test diet 2) or 1·37 g/4184 kJ (control diet) of methionine for 32 weeks to assess the long-term consequences of feeding. The total SAA content (2·68 g/4184 kJ) was maintained through dietary supplementation of cystine. Plasma methionine did not decrease in test group and increased significantly on test diet 1 in weeks 8 and 16 compared with control. Reducing dietary methionine did not have a significant effect on whole blood, plasma or urinary taurine or plasma N-terminal pro B-type natriuretic peptide. Significant effects in both test diets were observed for cholesterol, betaine and dimethylglycine. In conclusion, feeding methionine at the IAAO-estimated mean was sufficient to maintain plasma methionine over 32 weeks when total SAA was maintained. However, choline oxidation may have increased to support plasma methionine and have additional consequences for lipid metabolism. While the IAAO can be employed to assess essential amino acid requirements, such as methionine in the dog using semi-purified diets, further work is required to establish safe levels for commercial diet formats.
Ta–W co-alloying was realized by double glow plasma surface metallurgy technology, and their effects on high-temperature oxidation behavior of γ-TiAl were studied. Ta–W co-alloying coating was composed of a deposited layer and interdiffusion layer. The results of isothermal oxidation experiment indicated that a compact mixed oxide film of Ta and W was formed on the sample. The interdiffusion layer reduced the oxygen intrusion that improved the high-temperature oxidation resistance of γ-TiAl. The effects of Ta–W co-alloying on oxygen adsorption energy and electronic structure of γ-TiAl(111) were analyzed by first-principle calculation. The results showed that the optimal adsorption sites of O atoms changed from fcc-Al to hcp-Ti and hcp-Al, indicating that Ta–W co-alloying inhibited the diffusion of O. The electronic structure analysis of γ-TiAl(111) after Ta–W alloying indicated the affinity of Ti and O was inhibited, which resulted in decreased TiO2 in the oxide film.
Feed intake is controlled through a combination of long- and short-term mechanisms. Homeorhetic mechanisms allow adaptation to changes in physiological states in the long term, whereas homeostatic mechanisms are important to maintain physiological equilibrium in the short term. Feed intake is a function of meal size and meal frequency that are controlled by short-term mechanisms over the timeframe of minutes that are modulated by homeorhetic signals to adapt to changes in the physiological state. Control of feed intake by hepatic oxidation likely integrates these mechanisms. Signals from the liver are transmitted to brain feeding centers via vagal afferents and are affected by the hepatic oxidation of fuels. Because fuels oxidized in the liver are derived from both the diet and tissues, the liver is able to integrate long- and short-term controls. Whereas multiple signals are integrated in brain feeding centers to ultimately determine feeding behavior, the liver is likely a primary sensor of energy status.
A CoNiCrAlTaHfY/Co composite coating was prepared on the etched C/C composites by using duplex vapor phase surface alloying treatments, i.e., Co alloying and Co–Ni–Cr–Al–Ta–Hf–Y alloying. Microstructures and oxidation behavior of the coated C/C composites were analyzed by scanning electron microscopy, energy-dispersive spectroscopy, and X-ray diffraction. The result showed that the CoNiCrAlTaHfY/Co composite coating, 25 μm in thickness, was compact and composed of CrCoTa, AlCo2Ta, AlxCry, AlxNiy, and Co. The coating adhesion can be enhanced by microwave plasma chemical vapor deposition etching of matrix surface and adding a Co intermediate layer between the CoNiCrAlTaHfY top layer and C/C composites substrate. The honeycomb structure after etching was helpful to alloying element absorb and diffuse into substrate surface, and the composite coating continuation was improved by the Co buffer layer. After exposing in air for 180 min at 1000 °C, the bulk C/C composites volatilized while the loss rate of coated C/C composites was 0.82%, showing an improved oxidation resistance. Mixed oxides mainly containing Al2O3 and Cr2O3 were formed in the composite coating surface and protected the C/C composites from oxidation in air.
We investigated whether non-digestible saccharide fermentation-derived hydrogen molecules (H2) in rat colon could improve the in vivo reduction–oxidation (redox) balance via regeneration of α-tocopherol, by assessing their effect on hydroxyl radicals, the α-tocopherol concentration and the redox balance. In Expt 1, a Fenton reaction with phenylalanine (0 or 1·37 mmol/l of H2) was conducted. In Expt 2, rats received intraperitoneally maize oil containing phorone (400 mg/kg) 7 d after drinking ad libitum water containing 0 or 4 % fructo-oligosaccharides (FOS) (groups CP and FP, respectively). In Expt 3, rats unable to synthesise ascorbic acid drank ad libitum for 14 d water with 240 mg ascorbic acid/l (group AC), 20 mg of ascorbic acid/l (group DC) or 20 mg of ascorbic acid/l and 4 % FOS (group DCF). In the Fenton reaction, H2 reduced tyrosine produced from phenylalanine to 72 % when platinum was added and to 92 % when platinum was excluded. In Expt 2, liver glutathione was depleted by administration of phorone to rats. However, compared with CP, no change in the m-tyrosine concentration in the liver of FP was detected. In Expt 3, net H2 excretion was higher in DCF than in the other rats after 3 d of the experiment. Furthermore, the concentrations of H2 and α-tocopherol and the redox glutathione ratio in perirenal adipose tissue of rats were significantly higher in DCF than in DC. To summarise, in rat colon, fermentation-derived H2 further shifted the redox balance towards a more reducing status in perirenal adipose tissue through increased regeneration of α-tocopherol.
Multifunctional biopolymer-based materials are promising candidates for next generation regenerative biomaterials. Understanding the degradation behavior of biomaterials is vital for ensuring biological safety, as well as for better control of degradation properties based on rational design of a material’s physical and chemical characteristics. In this study, we decipher the degradation of a hydrogel prepared from gelatin and lysine diisocyanate ethyl ester (LDI) using in vitro models, which simulate hydrolytic, oxidative and enzymatic degradation (collagenase). Gravimetrical, morphological, mechanical and chemical properties were evaluated. Notably, the hydrogels were relatively resistant to hydrolytic degradation, but degraded rapidly within 21 days (>95% mass loss) under oxidative and collagenase degradation. Oxidative and collagenase degradation rapidly decreased the storage and loss modulus of the hydrogels, and slightly increased their viscous component (tan δ). For each degradation condition, the results suggest different possible degradation pathways associated to the gelatin polypeptide backbone, urea linkages and ester groups. The primary degradation mechanisms for the investigated gelatin based hydrogels are oxidative and enzymatic in nature. The relative hydrolytic stability of the hydrogels should ensure minimal degradation during storage and handling prior to application in surgical theatres.
Mössbauer instruments were included on the Mars Exploration Rover (MER) Mission to determine the mineralogic composition, diversity, and oxidation state of Fe-bearing igneous materials and alteration products. A total of 16 Fe-bearing phases (consistent with bulk-sample chemistry) were identified, including Fe associated with rock-forming minerals (olivine, pyroxene, magnetite, ilmenite, and chromite), Fe3+-bearing oxyhydroxides (nanophase ferric oxide, hematite, and goethite), sulfates (jarosite and an unassigned Fe3+ sulfate phase), and Fe2+ carbonate. Igneous rock types ranged from basalts to ultramafic rocks at Gusev crater. Jarosite-hematite bedrock was pervasive at Meridiani Planum, and concretions winnowed from the outcrop were mineralogically hematite. Because their structures contain hydroxyl, goethite, and jarosite provide mineralogic evidence for aqueous processes on Mars, and jarosite and Fe3+ sulfate are evidence for acid-sulfate processes at both Gusev crater and Meridiani Planum. A population of rocks on the Meridiani Planum outcrop was identified as iron and stony meteorites by the presence of Fe metal (kamacite) and the sulfide troilite. The MER mission demonstrates that Mössbauer spectrometers landed on any Fe-bearing planetary surface provide first-order information on igneous provinces, alteration state, and alteration style and provide well-constrained criteria for sample selection on planetary sample-return missions including planets, moons, and asteroids.
New instruments and approaches have revolutionized the analysis of stable isotopologues – especially for methane – which is changing our understanding of the biotic versus abiotic formation of carbon compounds in the subsurface. This chapter highlights recent developments in analytical approaches, and it synthesizes recent results regarding the biotic versus abiotic origins of carbon compounds in the subsurface.
The Earth is a powerful organic chemist, transforming vast quantities of carbon through complex processes, leading to diverse suites of products that include the fossil fuels upon which modern societies depend. When exploring how the Earth operates as an organic chemist, it is tempting to turn to how organic reactions are traditionally studied in chemistry labs. While highly informative, especially in terms of insights gained into reaction mechanisms, this approach can also be a source of frustration, as many of the reactants and conditions employed in chemistry labs have few or no parallels to geologic processes. The primary goal of this chapter is to provide examples of predicting thermodynamic influences and using the predictions to design experiments that reveal the mechanisms of how reactions occur at the elevated temperatures and pressures encountered in the Earth. This work is ongoing, and we hope this chapter will inspire numerous and diverse experimental and theoretical advances in hydrothermal organic geochemistry.
Finishing late-maturing bulls on grass may alter the antioxidant/prooxidant balance leading to beef with higher susceptibility to lipid oxidation and a lower colour stability compared to bulls finished on cereal concentrates. In this context, lipid oxidation and colour stability of beef from late-maturing bulls finished on pasture, with or without concentrate supplements, or indoors on concentrate was assessed. Charolais or Limousin sired bulls (n = 48) were assigned to four production systems: (1) pasture only (P), (2) pasture plus 25% dietary DM intake as barley-based concentrate (PC25), (3) pasture plus 50% dietary DM intake as barley-based concentrate (PC50) or (4) a barley-based concentrate ration (C). Following slaughter and postmortem ageing, M. Longissimus thoracis et lumborum was subjected to simulated retail display (4°C, 1000 lux for 12 h out of 24 h) for 3, 7, 10 and 14 days in modified atmosphere packs (O2 : CO2; 80 : 20). Lipid oxidation was determined using the 2-thiobarbituric acid-reactive substances assay; α-tocopherol was determined by HPLC; fatty acid methyl esters were determined using Gas Chromatography. Using a randomised complete block design, treatment means were compared by either ANOVA or repeated measures ANOVA using the MIXED procedure of SAS. Total polyunsaturated fatty acid (PUFA) concentrations were not affected by treatment, n-3 PUFAs were higher (P < 0.001) and the ratio of n-6 to n-3 PUFAs was lower (P < 0.001) in muscle from P, PC25 and PC50 compared to C. α-Tocopherol concentration was higher in muscle from P compared to PC50 and C bulls (P = 0.001) and decreased (P < 0.001) in all samples by day 14. Lipid oxidation was higher in muscle from C compared to P bulls on day 10 and day 14 of storage (P < 0.01). Finishing on pasture without supplementation did not affect beef colour stability and led to lower lipid oxidation, possibly due to the higher α-tocopherol concentration compared to concentrate finished beef.
Body weight control is thought to be improved when physical activity and energy intake are both high (high energy turnover (ET)). The aim of the present study was to investigate the short-term impact of ET on fat balance during zero energy balance (EB), energetic restriction (ER) and overfeeding (OF). In a randomised crossover study, nine healthy men (BMI: 23·0 (SD 2·1) kg/m2, 26·6 (SD 3·5) years) passed 3 × 3 d in a metabolic chamber: three levels of ET (low, medium and high; physical activity level = 1·3−1·4, 1·5−1·6 and 1·7−1·8) were performed at zero EB, ER and OF (100, 75 and 125 % of individual energy requirement). Different levels of ET were obtained by walking (4 km/h) on a treadmill (0, 165 and 330 min). Twenty-four-hour macronutrient oxidation and relative macronutrient balance (oxidation relative to intake) was calculated, and NEFA, 24-h insulin and catecholamine secretion were analysed as determinants of fat oxidation. During EB and OF, 24-h fat oxidation increased with higher ET. This resulted in a higher relative fat balance at medium ET (EB: +17 %, OF: +14 %) and high ET (EB: +23 %, OF: +17 %) compared with low ET (all P < 0·05). In contrast, ER led to a stimulation of 24-h fat oxidation irrespective of ET (no differences in relative fat balance between ET levels, P > 0·05). In conclusion, under highly controlled conditions, a higher ET improved relative fat balance in young healthy men during OF and EB compared with a sedentary state.