Raman spectra and conformations of the cis-unsaturated fatty-acid chains

Raman spectra of low (13°C) and high (16°C) m.p. crystals of oleic acid were recorded and the spectral differences were ascribed to different conformations around a pair of sp², CC axes, i.e. (skew, skew′) and (skew, skew). Crystalline modifications (m.p. 29°C and 29.5°C) of petroselinic acid were found for the first time; after spectral comparison with oleic acid conformations in those crystals were predicted to be (skew, skew′) and (skew, skew). Raman spectra of dioleoyl- and dipetroselinoyl-l-α-phosphatidylcholines were measured for different crystalline phases and the conformation was examined.The skeletal vibration bands of the polymethylene chains of cis- and trans-unsaturated fatty-acids were analysed by using the frequency-phase difference relationships of saturated fatty-acids. The ν₄ (stretching) vibrations were localised within each polymethylene chain and the bands of an acid CH₃(CH₂)_m?2CHCH(CH₂)_n?2COOH were explained in terms of the set of phase differences δ = kπ/m and kπ/n (k = 1, 2,..). A unique ν₄ vibration with δ = π/2m was also found. The ν₅ (bending) vibrations sometimes couple strongly with each other to form overall vibrations characterised by δ = kπ/(m + n).Implications of the cis-olefin group for the physical properties of phospholipid bilayers and the applicability of Raman spectroscopy in probing chain conformations were discussed.     

Seasonal and spatial variations of methane emissions from coastal marshes in the northern Yellow River estuary, China

Aims and methods

To evaluate the seasonal and spatial variations of methane (CH₄) emissions and understand the controlling factors, we measured CH₄ fluxes and their environmental variables for the first time by a static chamber technique in high Suaeda salsa marsh (HSM), middle S. salsa marsh (MSM), low S. salsa marsh (LSM) and bare flat (BF) in the northern Yellow River estuary throughout a year.

Results

CH₄ emissions from coastal marsh varied throughout different times of the day and significant differences were observed in some sampling periods (p?<?0.05). Over all sampling periods, CH₄ fluxes averaged between ?0.392 mgCH₄ m^?2?h^?1 and 0.495 mgCH₄ m^?2?h^?1, and emissions occurred during spring (0.008 mgCH₄ m^?2?h^?1) and autumn (0.068 mgCH₄ m^?2?h^?1) while sinks were observed during summer (?0.110 mgCH₄ m^?2?h^?1) and winter (?0.009 mgCH₄ m^?2?h^?1). CH₄ fluxes from the four marshes were not significantly different (p?>?0.05), and emissions occurred in LSM (0.026 mgCH₄ m^?2?h^?1) and BF (0.055 mgCH₄ m^?2?h^?1) while sinks were observed in HSM (?0.035 mgCH₄ m^?2?h^?1) and MSM (?0.022 mgCH₄ m^?2?h^?1). The annual average CH₄ flux from the intertidal zone was 0.002 mgCH₄ m^?2?h^?1, indicating that coastal marsh acted as a weak CH₄ source. Temporal variations of CH₄ emission were related to the interactions of abiotic factors (temperatures, soil moisture and salinity) and the variations of limited C and mineral N in sediments, while spatial variations were mainly affected by the vegetation composition at spatial scale.

Conclusions

This study observed a large spatial variation of CH₄ fluxes across the coastal marsh of the Yellow River estuary (CV?=?7856.25 %), suggesting that the need to increase the spatial replicates at fine scales before the regional CH₄ budget was evaluated precisely. With increasing exogenous nitrogen loading to the Yellow River estuary, the magnitude of CH₄ emission might be enhanced, which should also be paid more attentions as the annual CH₄ inventory was assessed accurately.     

Design and synthesis of cholecystokinin-4 dipeptide analogues with anxiolytic and anxiogenic activities

A new series of dipeptide analogues of the general formula Ph(CH₂) _n CO-NH(CH₂) _m CO-Trp-NH₂ (n = 1, 3–5; m = 1–3) was designed based on the structure of the endogenous tetrapeptide cholescystokinin-4 (CCK-4) and the topochemical Shemyakin-Ovchinnikov-Ivanov principle. The L-tryptophan derivatives exhibited anxiolytic properties and the D-tryptophan derivatives, anxiogenic properties. The dipeptide Ph(CH₂)₅CO-Gly-L-Trp-NH₂ (GB-115) with the activity in rats of 0.05–0.2 mg/kg after oral and intraperitoneal administration was chosen for further studies as a promising anxiolytic agent.     

Resonance Raman spectroscopy of chemically modified retinals: Assigning the carbon-methyl vibrations in the resonance Raman spectrum of rhodopsin

To assign the observed vibrationsl modes in the resonance Raman spectrum of the retinylidene chromophore of rhodopsin, we have studied chemically modified retinals. The series of analogs investigated are the n-butyl retinals substituted at C₉ and C₁₃. The results obtained for the 11-cis isomer have clearly assigned the CCH₃ vibrational frequencies observed in the spectrum of the retinylidene chromophore. The data show that the C₍₉₎CH₃ stretching vibration can be assigned to the vibrational mode observed in the 1017 cm^?1 region, and the vibration detected at 997 cm^?1 can be assigned to the C₍₁₃CH₃ vibration. The C₍₅₎CH₃ stretching mode does not contribute to the vibrations observed in this region. The splitting in the C_(n)CH₃ (n = 9, 13) vibration is characteristic of the 11-cis conformation. The results on the modified retinals do not support the hypothesis that the splitting arises from equilibrium mixtures of 11-cis, 12-s-cis and 11-cis, 12-s-trans in solution. Thus, this splitting cannot be used to determine whether the chromophore in rhodopsin is in a 12-s-cis or 12-s-trans conformation. However, our results demonstrate that there are other vibrational modes in the spectra which are sensitive to this conformational equilibrium and we use the presence of a strong ~ 1271 cm^?1 mode in bovine and squid rhodopsin spectra as an indication that the chromophore in these pigments is 11-cis, 12-s-trans.     

Carbon Dioxide and Methane Fluxes From Tree Stems,Coarse Woody Debris,and Soils in an Upland Temperate Forest

Forest soils and canopies are major components of ecosystem CO₂ and CH₄ fluxes. In contrast, less is known about coarse woody debris and living tree stems, both of which function as active surfaces for CO₂ and CH₄ fluxes. We measured CO₂ and CH₄ fluxes from soils, coarse woody debris, and tree stems over the growing season in an upland temperate forest. Soils were CO₂ sources (4.58 ± 2.46 µmol m^?2 s^?1, mean ± 1 SD) and net sinks of CH₄ (?2.17 ± 1.60 nmol m^?2 s^?1). Coarse woody debris was a CO₂ source (4.23 ± 3.42 µmol m^?2 s^?1) and net CH₄ sink, but with large uncertainty (?0.27 ± 1.04 nmol m^?2 s^?1) and with substantial differences depending on wood decay status. Stems were CO₂ sources (1.93 ± 1.63 µmol m^?2 s^?1), but also net CH₄ sources (up to 0.98 nmol m^?2 s^?1), with a mean of 0.11 ± 0.21 nmol m^?2 s^?1 and significant differences depending on tree species. Stems of N. sylvatica, F. grandifolia, and L. tulipifera consistently emitted CH₄, whereas stems of A. rubrum, B. lenta, and Q. spp. were intermittent sources. Coarse woody debris and stems accounted for 35% of total measured CO₂ fluxes, whereas CH₄ emissions from living stems offset net soil and CWD CH₄ uptake by 3.5%. Our results demonstrate the importance of CH₄ emissions from living stems in upland forests and the need to consider multiple forest components to understand and interpret ecosystem CO₂ and CH₄ dynamics.     

Spatial and temporal dynamics of diffusive methane emissions in the Okavango Delta,northern Botswana,Africa

Global warming is associated with the continued increase in the atmospheric concentrations of greenhouse gases; carbon dioxide, methane (CH₄) and nitrous oxide. Wetlands constitute the largest single natural source of atmospheric CH₄ in the world contributing between 100 and 231 Tg year^?1 to the total budget of 503–610 Tg year^?1, approximately 60 % of which is emitted from tropical wetlands. We conducted diffusive CH₄ emission measurements using static chambers in river channels, floodplains and lagoons in permanent and seasonal swamps in the Okavango Delta, Botswana. Diffusive CH₄ emission rates varied between 0.24 and 293 mg CH₄ m^?2 h^?1, with a mean (±SE) emission of 23.2 ± 2.2 mg CH₄ m^?2 h^?1 or 558 ± 53 mg CH₄ m^?2 day^?1. These emission rates lie within the range reported for other tropical wetlands. The emission rates were significantly higher (P < 0.007) in permanent than in seasonal swamps. River channels exhibited the highest average fluxes at 31.3 ± 5.4 mg CH₄ m^?2 h^?1 than in floodplains (20.4 ± 2.5 mg CH₄ m^?2 h^?1) and lagoons (16.9 ± 2.6 mg CH₄ m^?2 h^?1). Diffusive CH₄ emissions in the Delta were probably regulated by temperature since emissions were highest (20–300 mg CH₄ m^?2 h^?1) and lowest (0.2–3.0 mg m^?2 h^?1) during the warmer-rainy and cooler winter seasons, respectively. Surface water temperatures between December 2010 and January 2012 varied from 15.3 °C in winter to 33 °C in summer. Assuming mean inundation of 9,000 km², the Delta’s annual diffusive emission was estimated at 1.8 ± 0.2 Tg, accounting for 2.8 ± 0.3 % of the total CH₄ emission from global tropical wetlands.     

Irreversible Inhibition of Transglutaminases by Sulfonium Methylketones: Optimization of Specificity and Potency with w-Aminoacyl Spacers

Abstract

Sulfonium methylketones, of structure Cbz-Phe-NH(CH₂)_nCOCH₂S ⁺ (CH₃)₂, n < 2, are specific and potent inactivators of transglutaminases. The length of the -(CH₂)_n-spacer moiety, n = 1-5, is a critical determinant for both the specificity and potency of the inactivator. The dipeptidyl analog Cbz-Phe-Gly-(CH₂)_nS ⁺ (CH₃)₂, n = 1, is a more powerful inactivator of the thiol proteinase cathepsin B, k/K < 3 × 10⁵ M^?1 min^?1, than of transglutaminases, k_i(appl/K_i(appl < 1.5 × 10⁴ M^?1 min^?1. In contrast, the γ-aminobutyryl analog, n = 3, is a very potent transglutaminase inactivator with k_i(apP/ K_i(appl = 3.1 < 10⁶M^?1min^?1, but does not inactivate cathepsin B. In cell studies, the y-aminobutyryl and w-aminohexyl analogs inhibited the transglutaminase-mediated process of ionophore-induced cross-linked envelope formation by human malignant keratinocytes and the order of potency was related to that found for enzyme inhibition. The sulfonium methylketones, in equilibrium with the resonance stabilized ylides, are chemically inert towards glutathione under ambient conditions demonstrating the potential utility of this novel class of transglutaminase inhibitors for the study of enzyme inhibition in cellular environments.     

Structural features and bioactivities of the chitosan

Fourier transform infrared (FT-IR) spectroscopic studies (3500-600 cm⁻¹) showed some different bands of chitosan. The absorption at 3439 cm⁻¹ is stretching vibration of -OH and -NH₂ bonds, indicating the association of the hydrogen-bond between them. The bands at 1659, 1599 and 1321 cm⁻¹ are attributable to the peaks of stretching vibrations of amide I (ν_(CO)), II (δ_(N-H)), and the peak of stretching and bending vibrations of III (ν_(C-N)) (δ_(N-H)). The chitosan showed strong free radical scavenging activities. Pretreatment with chitosan significantly prevented the decrease of antioxidant enzymes activities and the increase of p-JNK at 3 h after renal ischemia and reduced renal tubular epithelial cell apoptosis.     

Predictions of methane emission levels and categories based on milk fatty acid profiles from dairy cows

Milk fatty acid (MFA) have already been used to model methane (CH₄) emissions from dairy cows. However, the data sets used to develop these models covered limited variation in dietary conditions, reducing the robustness of the predictions. In this study, a data set containing 140 observations from nine experiments (41 Holstein cows) was used to develop models predicting CH₄ expressed as g/day, g/kg dry matter intake (DMI) and g/kg milk. The data set was divided into a training (n=112) and a test data set (n=28) for model development and validation, respectively. A generalized linear mixed model was fitted to the data using the marginal R²_(m) and the Akaike information criterion to evaluate the models. The coefficient of determination of validation (R²_(v)) for different models developed ranged between 0.18 and 0.41. Form the intake-related parameters, only inclusion of total DMI improved the prediction (R²_(v)=0.58). In addition, in an attempt to further explore the relationships between MFA and CH₄ emissions, the data set was split into three categories according to CH₄ emissions: LOW (lowest 25% CH₄ emissions); HIGH (highest 25% CH₄ emissions); and MEDIUM (50% remaining observations). An ANOVA revealed that concentrations of several MFA differed for observations in HIGH compared with observations in LOW. Furthermore, the Gini coefficient was used to describe the MFA distribution for groups of MFA in each CH₄ emission category. The relative distribution of the MFA, particularly of the odd- and branched-chain fatty acids and mono-unsaturated fatty acids of observations in category HIGH differed from those in the other categories. Finally, in an attempt to validate the potential of MFA to identify cases of high or low emissions, the observations were re-classified into HIGH, MEDIUM and LOW according to the proportion of each individual MFA. The proportion of observations correctly classified were recorded. This was done for each individual MFA and for the calculated Gini coefficients, finding that a maximum of 67% of observations were correctly classified as HIGH CH₄ (trans-12 C18:1) and a maximum of 58% of observations correctly classified as LOW CH₄ (cis-9 C17:1). Gini coefficients did not improve this classification. These results suggest that MFA are not yet reliable predictors of specific amounts of CH₄ emitted by a cow, while holding a modest potential to differentiate cases of high or low emissions.     

N2O and CH4 fluxes in undisturbed and burned holm oak, scots pine and pyrenean oak forests in central Spain

We investigated N₂O and CH₄ fluxes from soils of Quercus ilex, Quercus pyrenaica and Pinus sylvestris stands located in the surrounding area of Madrid (Spain). The fluxes were measured for 18?months from both mature stands and post fire stands using the static chamber technique. Simultaneously with gas fluxes, soil temperature, soil water content, soil C and soil N were measured in the stands. Nitrous oxide fluxes ranged from ?11.43 to 8.34?μg N₂O–N?m^?2?h^?1 in Q.ilex, ?7.74 to 13.52?μg N₂O–N?m^?2?h^?1 in Q. pyrenaica and ?28.17 to 21.89?μg N₂O–N?m^?2?h^?1 in P. sylvestris. Fluxes of CH₄ ranged from ?8.12 to 4.11?μg CH₄–C?m^?2?h^?1 in Q.ilex, ?7.74 to 3.0?μg CH₄–C m^?2?h^?1 in Q. pyrenaica and ?24.46 to 6.07?μg CH₄–C?m^?2?h^?1 in P. sylvestris. Seasonal differences were detected; N₂O fluxes being higher in wet months whereas N₂O fluxes declined in dry months. Net consumption of N₂O was related to low N availability, high soil C contents, high soil temperatures and low moisture content. Fire decreased N₂O fluxes in spring. N₂O emissions were closely correlated with previous day’s rainfall and soil moisture. Our ecosystems generally were a sink for methane in the dry season and a source of CH₄ during wet months. The available water in the soil influenced the observed seasonal trend. The burned sites showed higher CH₄ oxidation rates in Q. ilex, and lower rates in P. sylvestris. Overall, the data suggest that fire alters both N₂O and CH₄ fluxes. However, the magnitude of such variation depends on the site, soil characteristics and seasonal climatic conditions.     

Synthesis,physicochemical and biological evaluation of tacrine derivative labeled with technetium-99m and gallium-68 as a prospective diagnostic tool for early diagnosis of Alzheimer’s disease

Design, physicochemical and biological studies of novel radioconjugates for the early diagnosis of Alzheimer's disease, based on the newly synthesized tacrine derivatives were performed. Novel tacrine analogues were labeled with technetium-99m and gallium-68. For all obtained radioconjugates ([^99mTc]Tc-Hynic-(tricine)₂NH(CH₂)_ntacrine and [⁶⁸Ga]Ga-DOTA-NH(CH₂)₉tacrine, where n = 2–9 denotes the number of methylene groups CH₂) the studies of physicochemical properties (lipophilicity, stability in the presence of an excess of standard amino acids cysteine or histidine, human serum and in cerebrospinal fluid) were performed. For two selected radioconjugates [^99mTc]Tc-Hynic-(tricine)₂NH(CH₂)₉Tac and [⁶⁸Ga]Ga-DOTA-NH(CH₂)₉tacrine (characterized with the highest lipophilicity values) the biological tests (inhibition of cholinesterases action, molecular docking and biodistribution studies) have been performed. All novel radioconjugates showed high stability in biological solutions used. Both selected radioconjugates proved to be good inhibitors of cholinesterases and be able to cross the blood-brain barrier. Radioconjugates [^99mTc]Tc-Hynic-(tricine)₂NH(CH₂)₉tacrine and [⁶⁸Ga]Ga-DOTA-NH(CH₂)₉tacrine fulfil the conditions for application in nuclear medicine. Radiopharmaceutical [⁶⁸Ga]Ga-DOTA-NH(CH₂)₉tacrine, due to increased accuracy and improved sensitivity in PET imaging, may be better potential diagnostic tool for early diagnosis of Alzheimer’s disease.     

Influence of chain length on mono- versus di-alkylation in the reactivity of [Pt2(μ-S)2(PPh3)4] towards α,ω-dihalo-n-alkanes; a synthetic route to platinum(II) ω-haloalkylthiolate complexes

The reactions of [Pt₂(μ-S)₂(PPh₃)₄] with α,ω-dibromoalkanes Br(CH₂)_nBr (n = 4, 5, 6, 8, 12) gave mono-alkylated [Pt₂(μ-S){μ-S(CH₂)_nBr}(PPh₃)₄]⁺ and/or di-alkylated [Pt₂(μ-S(CH₂)_nS}(PPh₃)₄]²⁺ products, depending on the alkyl chain length and the reaction conditions. With longer chains (n = 8, 12), intramolecular di-alkylation does not proceed in refluxing methanol, with the mono-alkylated products [Pt₂(μ-S){μ-S(CH₂)_nBr}(PPh₃)₄]⁺ being the dominant products when excess alkylating agent is used. The bridged complex [{Pt₂(μ-S)₂(PPh₃)₄}₂{μ-(CH₂)₁₂}]²⁺ was accessible from the reaction of [Pt₂(μ-S)₂(PPh₃)₄] with 0.5 mol equivalents of Br(CH₂)₁₂Br. [Pt₂(μ-S){μ-S(CH₂)₄Br}(PPh₃)₄]⁺ can be cleanly isolated as its BPh₄⁻ salt, but undergoes facile intramolecular di-alkylation at −18 °C, giving the known species [Pt₂(μ-S(CH₂)₄S}(PPh₃)₄]²⁺. The reaction of I(CH₂)₆I with [Pt₂(μ-S)₂(PPh₃)₄] similarly gives [Pt₂(μ-S){μ-S(CH₂)₆I}(PPh₃)₄]⁺, which is fairly stable towards intramolecular di-alkylation once isolated. These reactions provide a facile route to ω-haloalkylthiolate complexes which are poorly defined in the literature. X-ray crystal structures of [Pt₂(μ-S){μ-S(CH₂)₅Br}(PPh₃)₄]BPh₄ and [Pt₂(μ-S(CH₂)₅S}(PPh₃)₄](BPh₄)₂ are reported, together with a study of these complexes by electrospray ionisation mass spectrometry. All complexes fragment by dissociation of PPh₃ ligands, and the bromoalkylthiolate complexes show additional fragment ions [Pt₂(μ-S){μ-S(CH₂)_n−2CHCH₂}(PPh₃)_m]⁺ (m = 2 or 3; m ≠ 4), most significant for n = 4, formed by elimination of HBr.     

Changes in methane oxidation activity and methanotrophic community composition in saline alkaline soils

The soil of the former Lake Texcoco is a saline alkaline environment where anthropogenic drainage in some areas has reduced salt content and pH. Potential methane (CH₄) consumption rates were measured in three soils of the former Lake Texcoco with different electrolytic conductivity (EC) and pH, i.e. Tex-S1 a >18 years drained soil (EC 0.7 dS m^?1, pH 8.5), Tex-S2 drained for ~10 years (EC 9.0 dS m^?1, pH 10.3) and the undrained Tex-S3 (EC 84.8 dS m^?1, pH 10.3). An arable soil from Alcholoya (EC 0.7 dS m^?1, pH 6.7), located nearby Lake Texcoco was used as control. Methane oxidation in the soil Tex-S1 (lowest EC and pH) was similar to that in the arable soil from Alcholoya (32.5 and 34.7 mg CH₄ kg^?1 dry soil day^?1, respectively). Meanwhile, in soils Tex-S2 and Tex-S3, the potential CH₄ oxidation rates were only 15.0 and 12.8 mg CH₄ kg^?1 dry soil day^?1, respectively. Differences in CH₄ oxidation were also related to changes in the methane-oxidizing communities in these soils. Sequence analysis of pmoA gene showed that soils differed in the identity and number of methanotrophic phylotypes. The Alcholoya soil and Tex-S1 contained phylotypes grouped within the upland soil cluster gamma and the Jasper Ridge, California JR-2 clade. In soil Tex-S3, a phylotype related to Methylomicrobium alcaliphilum was detected.     

The synthesis and characterization of mixed ligand Ru(II) complexes with dipyrido(2,3-a:3′,2′-j)phenazine (dpop′) and 2,3,5,6-tetra(2-pyridyl)-pyrazine (tppz)

The synthesis of the mixed ligand mono metallic [Ru(dpop′)(tppz)]²⁺ and bimetallic [(dpop′)Ru(tppz)Ru(dpop′)]⁴⁺ (dpop′ = dipyrido(2,3-a:3′,2′-j)phenazine; tppz = 2,3,5,6 tetra-(2-pyridyl)pyrazine) complexes is described. The [Ru(dpop′)(tppz)]²⁺ complex display an intense absorption at 518 nm which is assigned to a Ru(dπ) → dpop′ (π∗) MLCT transition, and at 447 nm which is assigned to a Ru(dπ) → tppz(π∗) MLCT transition. It undergoes emission at RT in CH₃CN with λ_em = 722 nm. The bimetallic [(dpop′)Ru(tppz)Ru(dpop′)]⁴⁺ complex shows a low energy absorption shoulder near 635 nm assigned to a Ru(dπ) → tppz(π∗) MLCT transition and an intense peak at 542 nm due to Ru(dπ) → dpop′ (π∗) MLCT transition. The bimetallic complex also emits at RT in CH₃CN with λ_em = 785 nm. Cyclic voltammetry shows reversible Ru^+2/+3 oxidations at 1.68 V for the monometallic complex and Ru^+2/+3 oxidation couples at +1.94 and +1.70 V for the bimetallic complex.     

Further properties of the polyamine oxidase of barley leaves

Polyamine analogues have been studied as potential inhibitors or substrates of barley leaf polyamine oxidase. NH₂(CH₂)₃NH(CH₂)₁₀NH₂ was particularly effective as an inhibitor of spermine oxidation at pH 4·5 (K_i = 5 × 10^?6 M). Methylglyoxal-bis(guanylhydrazone) inhibited spermine oxidation only slightly (K_i = 10^?4 M). Activity with the polyamine analogues as substrates was generally 10% or less of the activity with spermine. The K_m for oxygen was 3 × 10^?4 M. The K_m for spermine oxidation was independent of oxygen concentration. Using the N-methyl-2-benzothiazolone hydrazine reagent, 1-(3-aminopropyl)pyrroline was shown to be formed stoichiometrically by the enzyme on oxidation of spermine. The enzyme will not function as a dehydrogenase in the presence of oxygen with either potassium ferricyanide or dichlorophenolindophenol as electron acceptors. Activity in the leaves increased with age, up to 4 weeks. In the leaves of 11-week-old plants activity was lower than in leaves of 1-week-old plants. The enzyme was mainly associated with an easily-sedimented particulate fraction, and relatively small proportions were found in the cell wall or soluble fractions.     

Plant-mediated CH4 transport and C gas dynamics quantified in-situ in a Phalaris arundinacea-dominant wetland

Northern peatland methane (CH₄) budgets are important for global CH₄ emissions. This study aims to determine the ecosystem CH₄ budget and specifically to quantify the importance of Phalaris arundinacea by using different chamber techniques in a temperate wetland. Annually, roughly 70?±?35% of ecosystem CH₄ emissions were plant-mediated, but data show no evidence of significant diurnal variations related to convective gas flow regardless of season or plant growth stages. Therefore, despite a high percentage of arenchyma, P. arundinacea-mediated CH₄ transport is interpreted to be predominantly passive. Thus, diurnal variations are less important in contrast to wetland vascular plants facilitating convective gas flow. Despite of plant-dominant CH₄ transport, net CH₄ fluxes were low (–?0.005–0.016 μmol m^?2 s^?1) and annually less than 1% of the annual C-CO₂ assimilation. This is considered a result of an effective root zone oxygenation resulting in increased CH₄ oxidation in the rhizosphere at high water levels. This study shows that although CH₄, having a global warming potential 25 times greater than CO₂, is emitted from this P. arundinacea wetland, less than 9% of the C sequestered counterbalances the CH₄ emissions to the atmosphere. It is concluded that P. arundinacea-dominant wetlands are an attractive C-sequestration ecosystem.     

Trace gas flux and the influence of short-term soil water and temperature dynamics in Australian sheep grazed pastures of differing productivity

Temperate pastures are often managed with P fertilizers and N₂-fixing legumes to maintain and increase pasture productivity which may lead to greater nitrous oxide (N₂O) emissions and reduced methane (CH₄) uptake. However, the diel and inter-daily variation in N₂O and CH₄ flux in pastures is poorly understood, especially in relation to key environmental drivers. We investigated the effect of pasture productivity, rainfall, and changing soil moisture and temperature upon short-term soil N₂O and CH₄ flux dynamics during spring in sheep grazed pasture systems in southeastern Australia. N₂O and CH₄ flux was measured continuously in a High P (23 kg P ha^?1 yr^?1) and No P pasture treatment and in a sheep camp area in a Low P (4 kg P ha^?1 yr^?1) pasture for a four week period in spring 2005 using an automated trace gas system. Although pasture productivity was three-fold greater in the High P than No P treatment, mean CH₄ uptake was similar (?6.3?±?SE 0.3 to ?8.6?±?0.4 μg C m^?2 hr^?1) as were mean N₂O emissions (6.5 to 7.9?±?0.8 μg N m^?2 hr^?1), although N₂O flux in the No P pasture did not respond to changing soil water conditions. N₂O emissions were greatest in the Low P sheep camp (12.4 μg?±?1.1 N m^?2 hr^?1) where there were also net CH₄ emissions of 5.2?±?0.5 μg C m^?2 hr^?1. There were significant, but weak, relationships between soil water and N₂O emissions, but not between soil water and CH₄ flux. The diel temperature cycle strongly influenced CH₄ and N₂O emissions, but this was often masked by the confounding covariate effects of changing soil water content. There were no consistently significant differences in soil mineral N or gross N transformation rates, however, measurements of substrate induced respiration (SIR) indicated that soil microbial processes in the highly productive pasture are more N limited than P limited after >20 years of P fertilizer addition. Increased productivity, through P fertilizer and legume management, did not significantly increase N₂O emissions, or reduce CH₄ uptake, during this 4 week measurement period, but the lack of an N₂O response to rainfall in the No P pasture suggests this may be evident over a longer measurement period. This study also suggests that small compacted and nutrient enriched areas of grazed pastures may contribute greatly to the overall N₂O and CH₄ trace gas balance.     

Photolytic CO-substitution reaction of organoiron thiocarboxylate derivatives CpFe(CO)2SCOR (R=alkyl, aryl) with diphosphines (Ph2P(CH2)nPPh2) (n=1-6): X-ray crystal structure of [CpFe(dppm)SCO(3,5-(NO2)2C6H3)]

The photolytic CO-substitution reaction of the organoiron thiocarboxylate complexes CpFe(CO)₂SCOR (R=CH₃, 2-CH₃C₆H₄, 2-NO₂C₆H₄, 4-NO₂C₆H₄, 3,5-(NO₂)₂C₆H₃) with diphosphines (Ph₂P(CH₂)_nPPh₂) [n=1 (dppm), n=2 (dppe), n=3 (dpppr), n=4 (dppb), n=5 (dppp), n=6 (dpph)] at room temperature using 1:2 (metal-ligand) molar ratio afforded exclusively the disubstituted complexes CpFe(Ph₂P(CH₂)_nPPh₂)SCOR when n=1, 2 and 3 and the monosubstituted analogs CpFe(CO)(Ph₂P(CH₂)_nPPh₂)SCOR when n=4, 5 and 6. This reaction was found to be strongly influenced by the backbone length of the diphosphine ligand, the nature of the R group of the thiocarboxylate moiety and the metal-ligand molar ratios. The crystal structure of CpFe(dppm)SCO(3,5-(NO₂)₂C₆H₃) was determined.     

Oxygen effects on methane production and oxidation in humid tropical forest soils

We investigated the effects of oxygen (O₂) concentration on methane (CH₄) production and oxidation in two humid tropical forests that differ in long‐term, time‐averaged soil O₂ concentrations. We identified sources and sinks of CH₄ through the analysis of soil gas concentrations, surface emissions, and carbon isotope measurements. Isotope mass balance models were used to calculate the fraction of CH₄ oxidized in situ. Complementary laboratory experiments were conducted to determine the effects of O₂ concentration on gross and net rates of methanogenesis. Field and laboratory experiments indicated that high levels of CH₄ production occurred in soils that contained between 9±1.1% and 19±0.2% O₂. For example, we observed CH₄ concentrations in excess of 3% in soils with 9±1.1% O₂. CH₄ emissions from the lower O₂ sites were high (22–101 nmol CH₄ m^?2 s^?1), and were equal in magnitude to CH₄ emissions from natural wetlands. During peak periods of CH₄ efflux, carbon dioxide (CO₂) emissions became enriched in ¹³C because of high methanogenic activity. Gross CH₄ production was probably greater than flux measurements indicated, as isotope mass balance calculations suggested that 48–78% of the CH₄ produced was oxidized prior to atmospheric egress. O₂ availability influenced CH₄ oxidation more strongly than methanogenesis. Gross CH₄ production was relatively insensitive to O₂ concentrations in laboratory experiments. In contrast, methanotrophic bacteria oxidized a greater fraction of total CH₄ production with increasing O₂ concentration, shifting the δ¹³C composition of CH₄ to values that were more positive. Isotopic measurements suggested that CO₂ was an important source of carbon for methanogenesis in humid forests. The δ¹³C value of methanogenesis was between ?84‰ and ?98‰, which is well within the range of CH₄ produced from CO₂ reduction, and considerably more depleted in ¹³C than CH₄ formed from acetate.     

Reactions of methylcobalamin with tin and lead compounds

Reactions of CH₃[Co] with (CH₃)_nM^(4?n)+ (n = 2, 3; M = Sn, Pb) at concentrations high enough to detect (CH₃)₄M in the head space (yields 7.08×10^?5?2.06×10^?5%), indicate that dismutation is the major route of production. Similarly, kinetic reactions at lower concentrations show that no demethylation of CH₃[Co] by (CH₃)₃M⁺ (M = Sn, Pb) occurs after 60 days. From the methylation of SnCl₂ by CH₃[Co] at pD 1.0 and under aerobic conditions, the following hydrolysis species were observed in the 400 MHz ¹H NMR spectrum: CH₃- Sn(OH)Cl₂·2H₂O (63.6%), [CH₃Sn(OH)(H₂O)₄]²⁺ (17.6%) and CH₃Sn(OH)₂Cl·nH₂O (18.8%). No methylation products were observed from similar reactions with Pb(II) salts.