Is Pentane a Normal Constituent of Human Breath?

Breath analysis is a non-invasive method for investigation of the volatile compounds produced by humans. Pentane has often been taken as an indicator of lipid peroxidation. Our purpose in this study was to determine its normal concentration in the breath of healthy humans. Using a specific and sensitive gas chromatography-mass spectrometry technique pentane concentrations in breath were lower than 10 pmoles/1. The high levels of pentane found by some authors in healthy humans were probably due to the coelution of pentane with isoprene, a volatile hydrocarbon present in human breath.     

The effect of elevated atmospheric CO2 and drought on sources and sinks of isoprene in a temperate and tropical rainforest mesocosm

Isoprene is the most abundant volatile hydrocarbon emitted by many tree species and has a major impact on tropospheric chemistry, leading to formation of pollutants and enhancing the lifetime of methane, a powerful greenhouse gas. Reliable estimates of global isoprene emission from different ecosystems demand a clear understanding of the processes of both production and consumption. Although the biochemistry of isoprene production has been studied extensively and environmental controls over its emission are relatively well known, the study of isoprene consumption in soil has been largely neglected. Here, we present results on the production and consumption of isoprene studied by measuring the following different components: (1) leaf and soil and (2) at the whole ecosystem level in two distinct enclosed ultraviolet light‐depleted mesocosms at the Biosphere 2 facility: a cottonwood plantation with trees grown at ambient and elevated atmospheric CO₂ concentrations and a tropical rainforest, under well watered and drought conditions. Consumption of isoprene by soil was observed in both systems. The isoprene sink capacity of litter‐free soil of the agriforest stands showed no significant response to different CO₂ treatments, while isoprene production was strongly depressed by elevated atmospheric CO₂ concentrations. In both mesocosms, drought suppressed the sink capacity, but the full sink capacity of dry soil was recovered within a few hours upon rewetting. We conclude that soil uptake of atmospheric isoprene is likely to be modest but significant and needs to be taken into account for a comprehensive estimate of the global isoprene budget. More studies investigating the capacity of soils to uptake isoprene in natural conditions are clearly needed.     

Two independent biochemical pathways for isopentenyl diphosphate and isoprenoid biosynthesis in higher plants

In the early times of isoprenoid research, a single pathway was found for the formation of the C₅ monomer, isopentenyl diphosphate (IPP), and this acetate/mevalonate pathway was supposed to occur ubiquitously in all living organisms. Now, 40 years later, a totally different IPP biosynthesis route has been detected in eubacteria, green algae and higher plants. In this new pathway glyceraldehyde 3-phosphate (GAP) and pyruvate are precursors of isopentenyl diphosphate, but not acetyl-CoA and mevalonic acid. In green tissues of three higher plants it was shown that all chloroplastbound isoprenoids (β-carotene, phytyl chains of chlorophylls and nona-prenyl chain of plastoquinone-9) are formed via the GAP/pyruvate pathway, whereas the cytoplasmic sterols are formed via the acetate/mevalonate pathway. Also, isoprene, emitted by various plants at high light conditions by action of the plastid-bound isoprene synthase, is formed via the new GAP/pyruvate pathway. Thus, in higher plants, there exist two separate and biochemically different IPP biosynthesis pathways: (1) the novel alternative GAP/pyruvate pathway apparently bound to the plastidic compartment and (2) the classical cytoplasmic acetate/mevalonate pathway. This new GAP/pyruvate pathway for IPP formation allows a reasonable interpretation of previous odd results concerning the biosynthesis of chloroplast isoprenoids, which, so far, had mainly been interpreted assuming compartmentation differences. The novel GAP/pyruvate pathway for IPP formation in plastids appears as a heritage of their prokaryotic, endosymbiotic ancestors.     

Impact of inspired substance concentrations on the results of breath analysis in mechanically ventilated patients

Abstract

A well-defined relationship has to exist between substance concentrations in blood and in breath if blood-borne volatile organic compounds (VOCs) are to be used as breath markers of disease or health. In this study, the impact of inspired substances on this relationship was investigated systematically. VOCs were determined in inspired and expired air and in arterial and mixed venous blood of 46 mechanically ventilated patients by means of SPME, GC/MS. Mean inspired concentrations were 25% of expired concentrations for pentane, 7.5% for acetone, 0.7% for isoprene and 0.4% for isoflurane. Only if inspired concentrations were <5% did substance disappearance rates from blood and exhalation rates correlate well. Exhaled substance concentrations depended on venous and inspired concentrations. Patients with sepsis had higher n-pentane and lower acetone concentrations in mixed venous blood than patients without sepsis (2.27 (0.37–8.70) versus 0.65 (0.33–1.48) nmol L^?1 and 69 (22–99) versus 18 (6.7–56) µmol L^?1). n-Pentane and acetone concentrations in breath showed no differences between the patient groups, regardless whether or not expired concentrations were corrected for inspired concentrations. In mechanically ventilated patients, concentration profiles of volatile substances in breath may considerably deviate from profiles in blood depending on the relative amount of inspired concentrations. A simple correction for inspired substance concentrations was not possible. Hence, substances having inspired concentrations >5% of expired concentrations should not be used as breath markers in these patients without knowledge of concentrations in blood and breath.     

Structure of Isoprene Synthase Illuminates the Chemical Mechanism of Teragram Atmospheric Carbon Emission

The X-ray crystal structure of recombinant PcISPS (isoprene synthase from gray poplar hybrid Populus × canescens) has been determined at 2.7 Å resolution, and the structure of its complex with three Mg²⁺ and the unreactive substrate analogue dimethylallyl-S-thiolodiphosphate has been determined at 2.8 Å resolution. Analysis of these structures suggests that the generation of isoprene from substrate dimethylallyl diphosphate occurs via a syn-periplanar elimination mechanism in which the diphosphate-leaving group serves as a general base. This chemical mechanism is responsible for the annual atmospheric emission of 100 Tg of isoprene by terrestrial plant life. Importantly, the PcISPS structure promises to guide future protein engineering studies, potentially leading to hydrocarbon fuels and products that do not rely on traditional petrochemical sources.     

Seven new bibenzyls and a dihydrochalcone from Radula variabilis

Six new bibenzyls have been isolated from the liverwort, Radula variabilis and their structures have been established by chemical and spectral evidence. In addition, a new dihydrochalcone and a new bibenzy] have been isolated as their methyl ethers. Except for two of the bibenzyls, the present compounds have a unique seven-membered heterocyclic ring and they are the first members of a new group of natural product.