Diurnal variation in n(2) fixation and photosynthesis by aquatic blue-green algae

Rates of ¹⁴CO₂ fixation, O₂ evolution, and N₂ fixation (acetylene reduction) by natural populations of blue-green algae recovered from Lake Mendota were measured at frequent intervals between sunrise and sunset. Photosynthesis and N₂ fixation were depressed during midday when light intensity was greatest. As the light intensity rose, most of the algal population migrated to deeper, light-limited waters where radiation damage would be diminished. As the relative rate of N₂ fixation compared to CO₂ fixation increases with depth, it is suggested that the algae maintain balanced growth by migrating vertically via buoyancy regulation. High concentrations of dissolved O₂ in lake water may inhibit N₂ fixation by enhancing photorespiration. Several factors such as photosynthetic rate, light intensity, dissolved O₂, species composition, and vertical and horizontal migration all affect observed rates of in situ N₂ fixation.     

O2 versus N2O respiration in a continuous microbial enrichment

Despite its ecological importance, essential aspects of microbial N₂O reduction—such as the effect of O₂ availability on the N₂O sink capacity of a community—remain unclear. We studied N₂O vs. aerobic respiration in a chemostat culture to explore (i) the extent to which simultaneous respiration of N₂O and O₂ can occur, (ii) the mechanism governing the competition for N₂O and O₂, and (iii) how the N₂O-reducing capacity of a community is affected by dynamic oxic/anoxic shifts such as those that may occur during nitrogen removal in wastewater treatment systems. Despite its prolonged growth and enrichment with N₂O as the sole electron acceptor, the culture readily switched to aerobic respiration upon exposure to O₂. When supplied simultaneously, N₂O reduction to N₂ was only detected when the O₂ concentration was limiting the respiration rate. The biomass yields per electron accepted during growth on N₂O are in agreement with our current knowledge of electron transport chain biochemistry in model denitrifiers like Paracoccus denitrificans. The culture’s affinity constant (K_S) for O₂ was found to be two orders of magnitude lower than the value for N₂O, explaining the preferential use of O₂ over N₂O under most environmentally relevant conditions.

     

SPATIAL SEGREGATION OF CO2 FIXATION IN TRICHODESMIUM SPP.: LINKAGE TO N2 FIXATION POTENTIAL1

The aggregate-forming, nonheterocystous, filamentous blue-green alga (cyanobacteria) Trichodesmium spp. is a widespread and important planktonic N₂ fixer and primary producer in tropical and subtropical oceans. It is unique among nonheterocystous genera because it conducts N₂ and CO₂ fixation (O₂ evolution) simultaneously; a notable achievement, because O₂ is a potent inhibitor of N₂ fixation. Spatial and temporal CO₂ fixation patterns were examined in trichomes and aggregates from natural and cultured populations, utilizing microautoradiographic detection of ¹⁴CO₂ incorporation. Parallel N₂ fixation (acetylene reduction) measurements were also made. Diel N₂ and CO₂ fixation patterns were similar, with co-optimization of both processes near midday. Microautoradiographs revealed several trichome-level ¹⁴CO₂ incorporation patterns: 1)uniform, heavy labeling, 2)uniform, light labeling, 3) heavier labeling in distal as opposed, to proximal regions, and 4) virtually no labeling throughout. Similar patterns were observed in natural and cultured populations. Given previous immunochemical findings that N₂ fixation potential is widespread in Trichodesmium spp. trichomes and aggregates, current results suggest a high degree of individuality, and possibly a “division of labor” in terms of CO₂ fixation, among trichomes comprising active N₂-fixing aggregates. Segregation of photosynthesis within and among trichomes facilitates simultaneous N₂ and CO₂ fixation in Trichodesmium spp. trichomes and aggregates.     

Nitrogenase activity and root nodule metabolism in response to O2 and short-term N2 deprivation in dark-treated Frankia-Alnus incana plants

Inhibition of nitrogenase (EC 1.18.6.1) activity by O₂ has been suggested to be an early response to disturbance in carbon supply to root nodules in the Frankia‐Alnus incana symbiosis. Intact nodulated root systems of plants kept in prolonged darkness of 22 h were used to test responses to O₂ and short‐term N₂ deprivation (1 h in Ar:O₂). By using a Frankia lacking uptake hydrogenase it was possible to follow nitrogenase activity over time as H₂ evolution in a gas exchange system. Respiration was simultaneously recorded as CO₂ evolution. Dark‐treated plants had lower initial nitrogenase activity in N₂:O₂ (68% of controls), which declined further during a 1‐h period in the assay system in N₂:O₂ at 21 and 17% O₂, but not at 13% O₂. When dark‐treated plants were deprived of N₂ at 21 and 17% O₂ nitrogenase activity declined rapidly to 61 and 74%, respectively, after 20 min, compared with control plants continuously kept in their normal light regime. In contrast, there was no decline in dark‐treated plants at 13% O₂, and only a smaller and temporary decline in control plants at 21% O₂. When dark‐treated plants were kept at 21% O₂ during 45 min prior to N₂ deprivation at 17% O₂ the decline was abolished. This supports the idea that the decline in nitrogenase activity observed in N₂:O₂ at 21% O₂ and during N₂ deprivation was caused by O₂, which affected a sensitive nodule fraction. Nodule contents of the amino acids Gln and Cit decreased during N₂ deprivation, suggesting decreased assimilation of NH₄⁺. Contents of ATP and ADP in nodules were not affected by short‐term N₂ deprivation. ATP/ADP ratios were about 5 indicating a highly aerobic metabolism in the root nodule. We conclude that nitrogenase activity of Alnus plants exposed to prolonged darkness becomes more sensitive to inactivation by O₂. It seemed that dark‐treated plants could not adjust their nodule metabolism at higher perceived pO₂ and during cessation of NH₄⁺ production.     

Effect of growth and subsequent decomposition of blue-green algae on the transformation of iron and manganese in submerged soils

N₂-fixing blue-green algae (Cyanobacteria), besides enriching soils with N and organic carbon, may modify a number of chemical and electro-chemical properties of the soils resulting in a change in availability of some micronutrient elements. Keeping this in view, an experiment was conducted to study the effects of growth and subsequent decomposition of blue-green algae on changes in the different forms of Fe and Mn in four soils under submerged condition. A mixed algal culture containing Anabaena, Nostoc, Cylindrospermum, and Tolypothrix was used as inoculum. It was allowed to grow for 2 months, after which the soils were sequentially extracted with (i) M NH₄OAc (pH 7.0), (ii) M K₄P₂O₇, (iii) 0.1 M NH₂OH.HCl (pH 2.0), (iv) 0.2 M (NH₄)₂C₂O₄ (pH 3.0) and (v) 0.1 M ascorbic acid to obtain water-soluble plus exchangeable, organically bound, easily reducible, amorphous oxides-and crystalline oxides-bound forms of Fe and Mn, respectively, both during the growth as well as the subsequent in-situ decomposition of the algal biomass in soils. Iron and Mn in the extracts were estimated by atomic absorption spectrophotometry.The results showed that growth of blue-green algae in submerged rice soils caused a decrease in the NH₄OAc-extractable forms of Fe and Mn with concomitant increases in all the other four determined forms of the elements. Such decreases and/or increases in different forms of Fe and Mn in soils were explained as being due to release of O₂, addition of organic matter and liberation of extracellular organic compounds by the blue-green algae during their growth. The decomposition of algal biomass resulted in an increase in the NH₄OAc-, K₄P₂O₇- and (NH₄)₂C₂O₄-extractable forms of Fe and Mn with a simultaneous decrease in the NH₂OH · HCl- and ascorbic acid-extractable forms. Development of strong reducing conditions and formation of organic acids with chelating properties were suggested as being the cause of the above changes. The implication of these changes in the forms of Fe and Mn for the Fe and Mn nutrition of rice plants were discussed.     

Temporal trends in N2O flux dynamics in a Danish wetland – effects of plant‐mediated gas transport of N2O and O2 following changes in water level and soil mineral‐N availability

Temporal trends of N₂O fluxes across the soil–atmosphere interface were determined using continuous flux chamber measurements over an entire growing season of a subsurface aerating macrophyte (Phalaris arundinacea) in a nonmanaged Danish wetland. Observed N₂O fluxes were linked to changes in subsurface N₂O and O₂ concentrations, water level (WL), light intensity as well as mineral‐N availability. Weekly concentration profiles showed that seasonal variations in N₂O concentrations were directly linked to the position of the WL and O₂ availability at the capillary fringe above the WL. N₂O flux measurements showed surprisingly high temporal variability with marked changes in fluxes and shifts in flux directions from net source to net sink within hours associated with changing light conditions. Systematic diurnal shifts between net N₂O emission during day time and deposition during night time were observed when max subsurface N₂O concentrations were located below the root zone. Correlation (P < 0.001) between diurnal variations in O₂ concentrations and incoming photosynthetically active radiation highlighted the importance of plant‐driven subsoil aeration of the root zone and the associated controls on coupled nitrification/denitrification. Therefore, P. arundinacea played an important role in facilitating N₂O transport from the root zone to the atmosphere, and exclusion of the aboveground biomass in flux chamber measurements may lead to significant underestimations on net ecosystem N₂O emissions. Complex interactions between seasonal changes in O₂ and mineral‐N availability following near‐surface WL fluctuations in combination with plant‐mediated gas transport by P. arundinacea controlled the subsurface N₂O concentrations and gas transport mechanisms responsible for N₂O fluxes across the soil–atmosphere interface. Results demonstrate the necessity for addressing this high temporal variability and potential plant transport of N₂O in future studies of net N₂O exchange across the soil–atmosphere interface.     

Conversion of photosynthetic products in the light in CO2-free O2 and N2 in leaves of Zea mays L. and Phaseolus vulgaris L.

Summary After 10 min illumination of segments of bean (Phaseolus vulgaris L.) or maize (Zea mays L.) leaves in air with ¹⁴CO₂, the atmosphere was changed to CO₂-free O₂ or N₂ and conversion of photosynthetic products in the light was investigated. The experiments have shown that after the ¹⁴CO₂ assimilation period the bean leaves contain the pool of weakly fixed ¹⁴C (WF-¹⁴C) which is converted into stable products during the subsequent period of illumination in CO₂-free N₂. In O₂ atmosphere the WF-¹⁴C pool is initially the main source of CO₂ evolved. The marked decrease in radioactivity of sucrose and starch during illumination of bean leaves in O₂ atmosphere indicates that these compounds were also the source of CO₂ evolved in the light. The total amount of previously fixed ¹⁴C remained almost on the same level during illumination of maize leaves in N₂ as well as in O₂. However, oxygen changed the distribution of ¹⁴C in photosynthetic products, which is suggested to be the consequence of the photorespiration process in maize.Abbreviation WF-¹⁴C weakly fixed ¹⁴C     

TRANSFER OF N2 AND CO2 FIXATION PRODUCTS FROM ANABAENA OSCILLARIOIDES TO ASSOCIATED BACTERIA DURING INORGANIC CARBON SUFFICIENCY AND DEFICIENCY1

Transfer of N₂ and CO₂ fixation products from the bloom forming blue-green alga, Anabaena oscillarioides Bory, to attached and free swimming bacteria is common during active growth of the former. Incubation with ¹⁵N₂ and ¹⁴CO₂ followed by size fractionation filtration reveals that: i) magnitudes of fixed N and C excretion, relative to N₂ and CO₂ fixation, are dictated by dissolved inorganic carbon (DIC) availability for A. oscillarioides photosynthetic production, ii) associated bacteria exhibit preferences for recently fixed excreted N compounds, iii) bacterial utilization of excreted N is independent of ambient light conditions, and iv) lag times between N₂ fixation and detectable bacterial assimilation of excreted fixed N compounds are ca. 1–2 h. Both ¹⁴NH₄Cl dilution and Hg(NH₃)₂ Cl₂ precipitation techniques indicate that NH₃ is a major excretion product from A. oscillarioides, particularly during DIC limited growth. Active N and C excretion and transfer to associated bacteria are features of viable A. oscillarioides filaments. Hence, transfer of these metabolites reflects complex mutualistic, and possibly symbiotic associations rather than solely signaling senescence.     

Delivery of N2 to bacteroids in simulated soybean nodule cells: consideration of gradients of concentration of dissolved N2 in cell walls,cytoplasm, and symbiosomes

Summary The previously published simulation of physiological functions occurring in infected cells of soybean nodules has been extended to include consideration of the diffusion of N₂ from the outside of a nodule to the nitrogen-fixing bacteroids, in relation to published values for the apparentK _m(N₂) for nitrogen fixation in the soybean nodule system. Nitrogen fixation is driven by bacteroid respiration, so increases in the average relative oxygenation (Y) of cytoplasmic leghaemoglobin lead to increased bacteroid respiration, increased nitrogen fixation, and greater differences in concentration of dissolved N₂ between the cell surface and the innermost bacteroids (d[N₂]). Over the range ofY considered, values for d[N₂] were from 5.2- to 6.2-fold greater than the corresponding values for d[O₂], because of facilitation of O₂ flux by cytoplasmic leghaemoglobin. Gradients of [N₂] within symbiosomes are small relative to cytoplasmic values and at the symbiosome surface [N₂] was greater than 0.4 mol/m³ at the greatest rates of nitrogen fixation calculated. Therefore, it is unlikely that values for [N₂] anywhere in the infected cell are low enough to affect rates of nitrogen fixation significantly, unless low external atmospheric N₂ pressures are used experimentally.Abbreviations Lb leghaemoglobin - LbO₂ oxyleghaemoglobin - [O₂], [N₂ concentrations of free, dissolved oxygen and nitrogen - Y fractional oxygenation of leghaemoglobin     

In situ 15N-N2O site preference and O2 concentration dynamics disclose the complexity of N2O production processes in agricultural soil

Arable soil continues to be the dominant anthropogenic source of nitrous oxide (N₂O) emissions owing to application of nitrogen (N) fertilizers and manures across the world. Using laboratory and in situ studies to elucidate the key factors controlling soil N₂O emissions remains challenging due to the potential importance of multiple complex processes. We examined soil surface N₂O fluxes in an arable soil, combined with in situ high-frequency measurements of soil matrix oxygen (O₂) and N₂O concentrations, in situ ¹⁵N labeling, and N₂O ¹⁵N site preference (SP). The in situ O₂ concentration and further microcosm visualized spatiotemporal distribution of O₂ both suggested that O₂ dynamics were the proximal determining factor to matrix N₂O concentration and fluxes due to quick O₂ depletion after N fertilization. Further SP analysis and in situ ¹⁵N labeling experiment revealed that the main source for N₂O emissions was bacterial denitrification during the hot-wet summer with lower soil O₂ concentration, while nitrification or fungal denitrification contributed about 50.0% to total emissions during the cold-dry winter with higher soil O₂ concentration. The robust positive correlation between O₂ concentration and SP values underpinned that the O₂ dynamics were the key factor to differentiate the composite processes of N₂O production in in situ structured soil. Our findings deciphered the complexity of N₂O production processes in real field conditions, and suggest that O₂ dynamics rather than stimulation of functional gene abundances play a key role in controlling soil N₂O production processes in undisturbed structure soils. Our results help to develop targeted N₂O mitigation measures and to improve process models for constraining global N₂O budget.     

Oxygen Isotope Fractionation during Photosynthesis in a Blue-Green and a Green Alga

Oxygen isotope fractionation (¹⁸O/¹⁶O) at the natural abundance level has been measured during photosynthesis of a blue-green and a green alga. When sufficient attention is paid to removal of contaminating air O₂ before and during the experiments, then the photosynthetic O₂ evolved, as compared to the water O₂, had an average difference of −0.36% for a blue-green alga and −0.80% for a green alga. These experiments suggest that there is no reason to invoke an inverse isotope effect in photosynthesis as part of the explanation for the ¹⁸O enrichment in atmospheric O₂ relative to O₂ in oceanic waters. In addition, in an indirect way, the experiments also support the argument that the bulk of O₂ evolved during photosynthesis comes from water. A 10% contribution of O₂ arising from CO₂ would have been detectable in the present work.     

Effects of n(2) deficiency on transport and partitioning of C and N in a nodulated legume

Nodulated root systems of white lupin (Lupinus albus L. cv Ultra: Rhizobium strain WU425) were exposed to Ar:O₂ (80:20, v/v) or Ar:N₂:O₂ (70:10:20, v/v/v) and C and N partitioning were examined over a 9- or 10-day period in comparison with control plants with nodulated roots retained in air. Accumulation of N ceased in plants exposed to Ar:O₂ or was much reduced in plants exposed to Ar:N₂:O₂, but net C assimilation rates and profiles of C utilization remained similar to those of control N₂-fixing plants. There was, however, a proportional reduction in CO₂ evolution from nodulated roots of the Ar:O₂ treatment. Xylem N levels fell rapidly after application of Ar:O₂. C:N ratios of phloem sap of petioles and of stem base rose during the first day of Ar:O₂ treatment and then fell progressively back to levels close to that of control plants as leaf reserves of N became available for loading of phloem. Stem top phloem sap increased progressively in C:N ratio throughout Ar:O₂ treatment, presumably due to increasing shortage of xylem derived N for xylem to phloem exchange. Reexposure of Ar:O₂-treated nodulated root systems to air prompted a rapid recovery of N₂ fixation and restoration of plant N status. Rates of N₂ fixation in plants whose roots were exposed to a range of N₂ concentrations indicated an apparent K_m of 10% N₂ for the attached intact white lupin nodule.     

The action of two toxic quinones on Anacystis nidulans

Summary A study was made of the factors affecting the toxicity to the blue-green alga, Anacystis nidulans, of two quinones, 2,3-dichloro-1,4-naphthoquinone and 9,10-phenanthraquinone. These two substances, which are known to be far more toxic to blue-green algae than other quinones so far studied, were shown to differ considerably in their properties. For instance, the toxicity of 2,3-dichloro-1,4-naphthoquinone is increased by light, vitamin K₃ and H₂O₂, whilst vitamin K₁ has no effect. On the other hand, the toxicity of 9,10-phenanthraquinone is increased by vitamin K₃, decreased by vitamin K₁, whilst H₂O₂ and light have no effect. The toxicity of both substances is decreased by the extracellular materials of various blue-green algae.     

Amperometric method for determining nitrous oxide in denitrification and in nitrogenase-catalyzed nitrous oxide reduction

A conventional Clark-type O₂ probe was used to determine N₂O concentrations in suspensions. At a polarizing voltage of–0.95 V versus the reference Ag/AgCl electrode, the probe is almost half as sensitive for N₂O as for O₂, and the detection limit is less than 1 M N₂O. The probe can also be used to determine NO for which the suitable polarizing voltage is–0.7 V. The method was successfully applied for continuously recording dissimilatory formation or utilization of N₂O by intactAzospirillum brasilense Sp 7, NO production by extracts from this bacterium, and N₂O reduction catalyzed by nitrogenase in intactKlebsiella pneumoniae. It is concluded that the probe is useful for measuring N₂O or NO contents in bacterial suspensions when the O₂ level is zero or kept constant during the assays.     

The occurrence of the hydrogenase in some blue-green algae

Several blue-green algae were surveyed for the occurrence of the hydrogenase which was assayed by the oxyhydrogen or Knallgas reaction in the intact organisms. In aerobically grown cultures, the reaction was detectable in Anabaena cylindrica, Nostoc muscorum and in two Anabaena variabilis species, whereas virtually no activity was observed in Anacystis nidulans and Cyanophora paradoxa. In these latter two algae, the reaction was, however, found after growth under molecular hydrogen for several days, which drastically increased the activity levels with all the algae tested. In the nitrogen fixing species, the activity of the Knallgas reaction was enhanced when all combined nitrogen was omitted from the media. H₂ and hydrogenase could not significantly support the CO₂-fixation in photoreduction experiments with all blue-green algae investigated here. Hydrogenase was assayed by the dithionite and methyl viologen dependent evolution of hydrogen and was found to be present with essentially the same specific activity levels in preparations of both heterocysts and vegetative cells from Anabaena cylindrica. Na₂S₂O₄ as well as H₂ supported the C₂H₂-reduction of the isolated heterocysts. The H₂-dependent C₂H₂-reduction did not require the presence of oxygen but was strictly light-dependent where H₂ served as an electron donor to photosystem I of these cells. It is concluded that hydrogen can be utilized by two different pathways in blue-green algae.Abbreviations Chl chlrophyll - CP creatine phosphate - CP kinase creatine phosphokinase - DCMU N-(3,4-dichlorophenyl)N,N-dimethylurea     

Synthesis,characterization, and electrocatalytic behaviour of hydrothermally grown nanostructured La2O3 and La2O3/K-complex

Rare earth metals play a conspicuous role in magnetic resonance imaging (MRI) for detecting cancerous cells. The alkali metal potassium is a neurotransmitter in the sodium–potassium pump in biomedical sciences. This unique property of rare earth metals and potassium drew our attention to carry forward this study. Therefore, in this work, previously synthesized potassium (K) complexes formed by the reflux of 4-N,N-dimethylaminobenzoic acid (DBA) and potassium hydroxide in methanol, and named [(μ2–4-N,N-dimethylaminobenzoate-κO)(μ2–4-N,N-dimethylaminobenzoic acid-κO)(4-N,N-dimethylaminobenzoic acid-κO) potassium(I) coordination polymer)] were treated hydrothermally with La₂O₃ nanomaterials to obtain a nanohybrid La₂O₃/K-complex. After that, the K-complex was analyzed using single-crystal X-ray diffraction and ¹H and ¹³C NMR spectroscopy. In addition, the structural and morphological properties of the as-prepared nanostructured La₂O₃/K-complex were also characterized, which involved an investigation using X-ray diffraction (XRD)spectroscopy, Fourier transform infrared (FTIR) spectroscopy, atomic force spectroscopy (AFM), transmission electron microscopy (TEM), and energy dispersive X-ray (EDX) analysis. After this, the electrochemical redox behaviour of the synthesized nanohybrid material was studied using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Therefore, the results from these studies revealed that the as-prepared material was a La₂O₃/K-complex that has a promising future role in sensing various analytes, as it showed effective electrocatalytic behaviour.     

N2 fixation in phototrophs: adaptation to a specialized way of life

Phototrophic diazotrophs include the photosynthetic green and purple bacteria, the heliobacteria, many cyanobacteria and the unusual chlorophyll-containing rhizobia that are found in the stem nodules of Aeschynomene spp. In this review, which concentrates on cyanobacteria, the interrelations between photosynthesis and N₂ fixation are discussed. Photosynthesis can, in theory, directly provide the ATP and reductant needed to support N₂ fixation but the link between these two processes is usually indirect, mediated through accumulated carbon reserves. In cyanobacteria, which possess an oxygenic photosynthesis, this serves to separate the O₂ that is produced by photosynthesis from the O₂-sensitive nitrogenase. However, in certain circumstances, oxygenic photosynthesis and N₂ fixation coexist. Under these conditions, respiratory consumption of photosynthetically generated O₂ may have an important role in minimizing O₂-damage to nitrogenase.     

Respiratory burst oxidase homologue‐dependent H2O2 and chloroplast H2O2 are essential for the maintenance of acquired thermotolerance during recovery after acclimation

Thermotolerance is improved by heat stress (HS) acclimation, and the thermotolerance level is “remembered” by plants. However, the underlying signalling mechanisms remain largely unknown. Here, we showed NADPH oxidase‐mediated H₂O₂ (NADPH‐H₂O₂), and chloroplast‐H₂O₂ promoted the sustained expression of HS‐responsive genes and programmed cell death (PCD) genes, respectively, during recovery after HS acclimation. When spraying the NADPH oxidase inhibitor, diphenylene iodonium, after HS acclimation, the NADPH‐H₂O₂ level significantly decreased, resulting in a decrease in the expression of HS‐responsive genes and the loss of maintenance of acquired thermotolerance (MAT). In contrast, compared with HS acclimation, NADPH‐H₂O₂ declined but chloroplast‐H₂O₂ further enhanced during recovery after HS over‐acclimation, resulting in the reduced expression of HS‐responsive genes and substantial production of PCD. Notably, the further inhibition of NADPH‐H₂O₂ after HS over‐acclimation also inhibited chloroplast‐H₂O₂, alleviating the severe PCD and surpassing the MAT of HS over‐acclimation treatment. Due to the change in subcellular H₂O₂ after HS acclimation, the tomato seedlings maintained a constant H₂O₂ level during recovery, resulting in stable and lower total H₂O₂ levels during a tester HS challenge conducted after recovery. We conclude that tomato seedlings increase their MAT by enhancing NADPH‐H₂O₂ content and controlling chloroplast‐H₂O₂ production during recovery, which enhances the expression of HS‐responsive genes and balances PCD levels, respectively.     

Chirality in Distorted Square Planar Pd(O,N)2 Compounds

Salicylidenimine palladium(II) complexes trans‐Pd(O,N)₂ adopt step and bowl arrangements. A stereochemical analysis subdivides 52 compounds into 41 step and 11 bowl types. Step complexes with chiral N‐substituents and all the bowl complexes induce chiral distortions in the square planar system, resulting in Δ/Λ configuration of the Pd(O,N)₂ unit. In complexes 1 , 2 , 3 , 4 , 5 , 6 with enantiomerically pure N‐substituents ligand chirality entails a specific square chirality and only one diastereomer assembles in the lattice. Dimeric Pd(O,N)₂ complexes with bridging N‐substituents in trans‐arrangement are inherently chiral. For dimers 7 , 8 , 9 , 10 , 11 different chirality patterns for the Pd(O,N)₂ square are observed. The crystals contain racemates of enantiomers. In complex 12 two independent molecules form a tight pair. The (R_C) configuration of the ligand induces the same Δ chirality in the Pd(O,N)₂ units of both molecules with varying square chirality due to the different crystallographic location of the independent molecules. In complexes 13 and 14 atrop isomerism induces specific configurations in the Pd(O,N)₂ bowl systems. The square chirality is largest for complex 15 [(Diop)Rh(PPh₃)Cl)], a catalyst for enantioselective hydrogenation. In the lattice of 15 two diastereomers with the same (R_C,R_C) configuration in the ligand Diop but opposite Δ and Λ square configurations co‐crystallize, a rare phenomenon in stereochemistry. Chirality 25:663–667, 2013. © 2013 Wiley Periodicals, Inc.     

Contribution of plants to N 2 O emissions in soil-winter wheat ecosystem: pot and field experiments

Outdoor pot and field experiments were conducted to assess the role of growing plants in agricultural ecosystem N₂O emissions. N₂O emissions from plants were quantified as the difference in soil-crop system N₂O emissions before and immediately after cutting plants during the main growth stages in 2001–02 and 2002–03 winter wheat seasons. Emissions of N₂O from plants depended on biomass within the same plant developmental status. Field results indicated that the seasonal contribution of N₂O emissions from plants to ecosystem fluxes averaged 25%, ranging from 10% at wheat tillering to 62% at the heading stage. The fluxes of N₂O emissions from plants varied between 0.3 and 3.9 mg N₂O-N m⁻² day⁻¹ and its seasonal amount was equivalent to 0.23% of plant N released as N₂O. A N₂O emission coefficient (N₂O_E, mg N₂O-N g⁻¹ C day⁻¹), defined as N₂O-N emission in milligrams from per gram carbon of plant dry matter within a day, was represented by a 5-fold variation ranging from 0.021 to 0.004 mg N₂O-N g C⁻¹ day⁻¹. A linear relationship (y=0.4611x+0.0015, r ²=0.9352, p < 0.001) between N₂O_E (y) and plant dark respiration rate (x, mg CO₂-C g C⁻¹ day⁻¹) suggested that in the absence of photosynthesis, some N₂O production in plant N assimilation was associated with plant respiration. Although this study could not show whether N₂O was produced or transferred by winter wheat plants, these results indicated an important role for higher plant in N₂O exchange. Identifying its potential contribution is critical for understanding agricultural ecosystem N₂O sources.