In situ electron paramagnetic resonance (EPR) study of surface oxygen species on Au/ZnO catalyst for low-temperature carbon monoxide oxidation

Some paramagnetic superoxide ions detectable by electron paramagnetic resonance (EPR) can be generated on Au/ZnO catalyst by oxygen adsorption at room temperature as well as at 553 K. In both the cases, the O-2(-) ions are present on the catalyst surface. The disappearance of the O-2(-) signal by the introduction of carbon monoxide over the catalyst surface implies that the O-2(-) ions are either the active oxygen species or the precursors of the active oxygen species. The CO3- species produced are also detected by EPR. (C) 2001 Elsevier Science B.V. All rights reserved.

Canopy carbon and oxygen isotope composition of 9-year-old hoop pine families in relation to seedling carbon isotope composition, growth, field growth performance, and canopy nitrogen concentration

Carbon isotope composition (delta C-13), oxygen isotope composition (delta O-18), and nitrogen concentration (N-mass) of branchlet tissue at two canopy positions were assessed for glasshouse seedlings and 9-year-old hoop pine (Araucaria cunninghamii Ait. ex D. Don) trees from 22 open-pollinated families grown in 5 blocks of a progeny test at a water-limited and nitrogen-deficient site in southeastern Queensland, Australia. Significant variations in canopy delta C-13, delta O-18, and N-mass existed among the 9-year-old hoop pine families, with a heritability estimate of 0.72 for branchlet delta C-13 from the upper inner canopy position. There was significant variation in canopy delta C-13 of glasshouse seedlings between canopy positions and among the families, with a heritability estimate of 0.66. The canopy delta C-13 was positively related to canopy N-mass only for the upper outer crown in the field (R = 0.62, p < 0.001). Phenotypic correlations existed between tree height and canopy delta C-13 (R = 0.37-0.41, p < 0.001). Strong correlations were found between family canopy delta C-13 at this site and those at a wetter site and between field canopy delta C-13 and glasshouse seedling delta C-13. The mechanisms of the variation in canopy delta C-13 are discussed in relation to canopy photosynthetic capacity as reflected in the N-mass and stomatal conductance as indexed by canopy delta O-18.

Globalisation and sustainability: environmental Kuznets curve and the WTO

Economic globalisation is seen by many as a driving force for global economic growth. Yet opinion is divided about the benefits of this process, as highlighted by the WTO meeting in Seattle in late 1999. Proponents of economic globalisation view it as a positive force for environmental improvement and as a major factor increasing the likelihood of sustainable development through its likely boost to global investment. These proponents mostly appeal to analysis based on the environmental Kuznets curve (EKC) to support their views about environmental improvement. But EKC-analysis has significant deficiencies. Furthermore, it is impossible to be confident that the process of economic globalisation will result in sustainable development, if 'weak conditions' only are satisfied. 'Strong conditions' probably need to be satisfied to achieve sustainable development, and given current global institutional arrangements, these are likely to be violated by the economic globalisation process. Global political action seems to be needed-to avert a deterioration in the global environment and to prevent unsustainability of development. This exposition demonstrates the limitations of EKC-analysis, identifies positive and negative effects of economic globalisation on pollution levels, and highlights connections between globalisation and the debate about whether strong or weak conditions are required for sustainable development. The article concludes with a short discussion of the position of WTO in relation to trade and the environment and the seemingly de facto endorsement of WTO of weak conditions for sustainable development. It suggests that WTO's relative neglect of environmental concerns is no longer politically tenable and needs to be reassessed in the light of recent developments in economic analysis. The skew of economic growth, e.g. in favour of developing countries, is shown to be extremely important from a global environmental perspective. (C) 2001 Elsevier Science B.V. All rights reserved.

Reduced Red Cell 2,3-Diphosphoglycerate Concentrations in Critical Illness without Decreased In Vivo P50

We investigated whether red cell 2,3-diphosphoglycerate (2,3-DPG) concentrations are reduced in critical illness, whether acidaemia, hypophosphataemia or anaemia influence 2,3-DPG, and whether there is any net effect on in vivo P50. Twenty healthy, non-smoking, male volunteers were compared with 20 male intensive care patients with APACHE 2 scores > 20 on the preceding day. Those transfused in this time were excluded. Venous red cell 2,3-DPG concentrations were measured in both groups. In the patient group, routine multichannel biochemical profile and arterial blood gas analysis were also performed and in vivo P50 calculated. The mean 2,3-DPG concentration was significantly lower in the patient group than in the controls (4.2 +/-1.3 mmoll/l vs 4.9 +/-0.5 mmol/l, P=0.016). The patients were well oxygenated (lowest arterial PO2=75 mm Hg) and showed a tendency to acidaemia (median pH 7.37, range 7.06 to 7.48) and anaemia (median haemoglobin concentration 113 g/l, range 89 to 154 g/l). By linear regression of patient data, pH had a significant effect on 2,3-DPG concentrations (r=0.6, P=0.011). Haemoglobin and phosphate concentrations did not, but there were few abnormal phosphate values. There was no correlation between 2,3-DPG concentrations and in vivo P50 (r(2) less than or equal to 0.08). We conclude that 2,3-DPG concentrations were reduced in a broad group of critically ill patients. Although this would normally reduce the P50, the reduction was primarily linked with acidaemia, which increases the P50. Overall, there was no net effect on the P50 and thus no affinity-related decrease in tissue oxygenation.

Effect of water temperature and oxygen levels on the diving behavior of two freshwater turtles: Rheodytes leukops and Emydura macquarii

Rheodytes leukops is a bimodally respiring turtle that extracts oxygen from the water chiefly via two enlarged cloacal bursae that are lined with multi-branching papillae. The diving performance of R. leukops was compared to that of Emydura macquarii, a turtle with a limited ability to acquire aquatic oxygen. The diving performance of the turtles was compared under aquatic anoxia (0 mmHg), hypoxia (80 mmHg) and normoxia (155 mmHg) at 15, 23, and 30degreesC. When averaged across all temperatures the dive duration of R. leukops more than doubled from 22.4 +/- 7.65 min under anoxia to 49.8 +/- 19.29 min under normoxic conditions. In contrast, aquatic oxygen level had no effect on the dive duration of E. macquarii. Dive times for both species were significantly longer at the cooler temperature, and the longest dive recorded for each species was 538 min and 166 min for R. leukops and E. macquarii, respectively. Both species displayed a pattern of many short dives punctuated by occasional long dives irrespective of temperature or oxygen regime. Rheodytes leukops, on average, spent significantly less time (42 +/- 2 sec) at the surface per surfacing event than did E. macquarii (106 +/- 20 sec); however, surface times for both species were not related to either water temperature or oxygen level.

An in situ study of photosynthetic oxygen exchange and electron transport rate in the marine macroalga Ulva lactuca (Chlorophyta)

Direct comparisons between photosynthetic O-2 evolution rate and electron transport rate (ETR) were made in situ over 24 h using the benthic macroalga Ulva lactuca (Chlorophyta), growing and measured at a depth of 1.8 m, where the midday irradiance rose to 400-600 mumol photons m(-2) s(-1). O-2 exchange was measured with a 5-chamber data-logging apparatus and ETR with a submersible pulse amplitude modulated (PAM) fluorometer (Diving-PAM). Steady-state quantum yield ((Fm'-Ft)/Fm') decreased from 0.7 during the morning to 0.45 at midday, followed by some recovery in the late afternoon. At low to medium irradiances (0-300 mumol photons m(-2) s(-1)), there was a significant correlation between O-2 evolution and ETR, but at higher irradiances, ETR continued to increase steadily, while O-2 evolution tended towards an asymptote. However at high irradiance levels (600-1200 mumol photons m-(2) s(-1)) ETR was significantly lowered. Two methods of measuring ETR, based on either diel ambient light levels and fluorescence yields or rapid light curves, gave similar results at low to moderate irradiance levels. Nutrient enrichment (increases in [NO3-], [NH4+] and [HPO42-] of 5- to 15-fold over ambient concentrations) resulted in an increase, within hours, in photosynthetic rates measured by both ETR and O-2 evolution techniques. At low irradiances, approximately 6.5 to 8.2 electrons passed through PS II during the evolution of one molecule of O-2, i.e., up to twice the theoretical minimum number of four. However, in nutrient-enriched treatments this ratio dropped to 5.1. The results indicate that PAM fluorescence can be used as a good indication of the photosynthetic rate only at low to medium irradiances.

H-1 NMR study of the states of water in equilibrium Poly(HEMA-co-THFMA) hydrogels

The spin-spin relaxation times, T-2, of hydrated samples of poly(hydroxymethyl methacrylate), PHEMA, poly(tetrahydrofurfuryl methacrylate),PTHFMA, and the,corresponding HEMA-THFMA copolymers have been examined to probe the states of,the imbibed water in these polymers. The decay in the transverse magnetization of water. in fully hydrated samples of PHEMA, PTHFMA, and copolymers of HEMA and THFMA was described by a multiexponential function. The short component of T-2 was interpreted as water molecules that were strongly interacting with the polymer chains. The intermediate component of T-2 was assigned to water residing in the porous structure of the samples. The long component of T-2 was believed to arise from water residing in the remnants of cracks formed in the polymer network during water sorption.

[18O]-Oxygen incorporation reveals novel pathways in spiroacetal biosynthesis by Bactrocera cacuminata and B. cucumis

The origins of the oxygen atoms in 1,7-dioxaspiro[5.5]undecane (1) and hydroxyspiroacetal (2) from Bactrocera cacuminata, and in 2,8-dimethyl-1,7-dioxaspiro[5.5]undecane (3) and hydroxyspiroacetal (4) from B. cucumis, have been investigated by incorporation studies from both [18O2]-dioxygen and [18O]-water. Combined GC-MS examination and high-field NMR analysis have demonstrated that all oxygen atoms in 1 and 2 from B. cacuminata are dioxygen derived, but in contrast, the spiroacetals 3 and 4 from B. cucumis incorporate one ring oxygen from water and one ring oxygen (and the hydroxyl oxygen in 4) from [18O2]-dioxygen. These results reveal not only the generality of monoxygenase mediation of spiroacetal formation in Bactrocera sp., but also an unexpected complexity in their biosynthesis. A general paradigm accommodating these and other observations is presented.

Effect of maternal epidural analgesia on fetal intrapartum oxygen saturation

The use of maternal epidural analgesia in labor may be associated with nonreassuring fetal heart rate (FHR) patterns. Fetal oxygen saturation (FSpO(2)) monitoring may improve assessment of fetal well-being during this time. Mean FSpO(2) values were compared over seven 5-minute epochs: 5 minutes prior to an epidural event (combined insertion of epidural/top-up epidural analgesia and infusion pump bolus), to 30 minutes following the event, including possible effects of maternal position and FHR pattern on FSpO(2) values. Mean FSpO(2) values were significantly different between the 5 minutes prior (49.5%) versus 16-20 minutes (44.3%, p

PFG-NMR measurements of the self-diffusion coefficients of water in equilibrium poly(HEMA-co-THFMA) hydrogels

The self-diffusion coefficients for water in a series of copolymers of 2-hydroxyethyl methacrylate, HEMA, and tetrahydrofurfuryl methacrylate, THFMA, swollen with water to their equilibrium states have been studied at 310 K using PFG-NMR. The self-diffusion coefficients calculated from the Stejskal-Tanner equation, D-obs, for all of the hydrated polymers were found to be dependent on the NMR storage time, as a result of spin exchange between the proton reservoirs of the water and the polymers, reaching an equilibrium plateau value at long storage times. The true values of the diffusion coefficients were calculated from the values of D-obs, in the plateau regions by applying a correction for the fraction of water protons present, obtained from the equilibrium water contents of the gels. The true self-diffusion coefficient for water in polyHEMA obtained at 310 K by this method was 5.5 x 10(-10) m(2) s(-1). For the copolymers containing 20% HEMA or more a single value of the self-diffusion coefficient was found, which was somewhat larger than the corresponding values obtained for the macroscopic diffusion coefficient from sorption measurements. For polyTHFMA and copolymers containing less than 20% HEMA, the PFG-NMR stimulated echo attenuation decay curves and the log-attenuation plots were characteristic of the presence of two diffusing water species. The self-diffusion coefficients of water in the equilibrium-hydrated copolymers were found to be dependent on the copolymer composition, decreasing with increasing THFMA content.

Exact theory of sedimentation equilibrium made useful

The exact description of the thermodynamics of solutions has been used to describe, without approximation, the distribution of all the components of an incompressible solution in a centrifuge cell at sedimentation equilibrium. Thermodynamic parameters describing the interactions between solute components of known molar mass can be obtained by direct analysis of the experimental data. Interpretation of the measured thermodynamic parameters in terms of molecular interactions requires that an arbitrary distinction be made between nonassociative forces, like hard-sphere volume-exclusion and mean-field electrostatic repulsion or attraction, and specific short-range forces of association that give rise to the formation of molecular aggregates. Provided the former can be accounted for adequately, the effects of the latter can be elucidated in the form of good estimates of the equilibrium constants for the reactions of aggregation.