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1.
Exploring and evaluating the potential applications of two-dimensional graphene is an increasingly hot topic in graphene research. In this paper, by studying the adsorption of NO, N2O, and NO2 on pristine and silicon (Si)-doped graphene with density functional theory methods, we evaluated the possibility of using Si-doped graphene as a candidate to detect or reduce harmful nitrogen oxides. The results indicate that, while adsorption of the three molecules on pristine graphene is very weak, Si-doping enhances the interaction of these molecules with graphene sheet in various ways: (1) two NO molecules can be adsorbed on Si-doped graphene in a paired arrangement, while up to four NO2 molecules attach to the doped graphene with an average adsorption energy of −0.329 eV; (2) the N2O molecule can be reduced easily to the N2 molecule, leaving an O-atom on the Si-doped graphene. Moreover, we find that adsorption of NO and NO2 leads to large changes in the electronic properties of Si-doped graphene. On the basis of these results, Si-doped graphene can be expected to be a good sensor for NO and NO2 detection, as well as a metal-free catalyst for N2O reduction.  相似文献   

2.
Studying the interaction of some atmospheric gases (H2O, HCN, NH3, SO3 and H2S) with 3PT oligomers is important in the development of polymeric sensors for gas detection. In the present study, we studied the relaxed geometries, interaction energies, charge analysis, HOMO–LUMO orbital analysis, and UV–vis spectra of all interacted systems using first-principles density functional theory (DFT). All these analyses indicated the potential of polythiophene as an inexpensive polymeric sensor for the analytes mentioned. Interaction energy values of ?19.90, ?19.66, ?14.01, ?8.70, and ?4.76 kJ mol?1 were achieved for adsorption of SO3, H2O, NH3, HCN, and H2S on 3PT, respectively. Consequently, clarification of their physical parameters became the major focus of this study.  相似文献   

3.
Adsorption behavior of nitrous oxide (N2O) on pristine graphene (PG) and tetracyanoethylene (TCNE) modified PG surfaces is investigated using density functional theory. A number of initial adsorbate geometries are considered on both surfaces and the most stable ones are chosen upon calculation of the adsorption energies (Eads). N2O is found to adsorb in a weakly exoergic process (Eads?~??3.18 kJ mol?1) at the equilibrium distance of 3.52 Å on the PG surface. N2O adsorption can be greatly enhanced with the presence of a TCNE molecule (Eads?=??87.00 kJ mol?1). Mulliken charge analysis confirms that adsorption of N2O is not accompanied by distinct charge transfer from the surfaces to the molecule (? 0.001 │e│ for each case). Moreover, on the basis of calculated changes in the HOMO/LUMO energy gap, it is found that electronic properties of PG and TCNE modified PG are not sensitive toward adsorption of N2O, indicating that both surfaces are not good enough to introduce as an N2O detector. However, the considerable amount of Eads in TCNE modified PG can be a guide to the design of graphene-based adsorbents for N2O capture.  相似文献   

4.
The adsorption processes of elemental lead on carbonaceous surfaces which adsorbed CO/CO2/NO flue gases were investigated to understand the effects of CO/CO2/NO on elemental lead adsorption on carbonaceous surfaces with density functional theory. All calculations including optimizations, energies, and frequencies were conducted at B3PW91 density functional theory level, utilizing SDD basis set for lead and 6-31G(d) Pople basis set for other atoms. The results indicate that CO, CO2, and NO can promote the adsorption of elemental lead on the carbonaceous surface, but probably compete for adsorption sites with elemental lead. The promotion effects on adsorption can be attributed to active sites on the carbonaceous surface rather than flue gas adsorption on the carbonaceous surface. In addition, the adsorption order of three kinds of flue gas on the carbonaceous surface is CO2?>?NO?>?CO?>?Pb on average. Furthermore, the enhancement order of three kinds of flue gas on the elemental lead adsorption on carbonaceous surfaces is CO-CS?>?CO2-CS?>?NO-CS?>?CS in general. In particular, atomic charge and adsorption energy have good linear relationship in the process of elemental lead adsorption.
Graphical Abstract Competitive adsorption between flue gas and elemental lead on carbonaceous surfaces.
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5.
The capacity of SX2 (X = F, Cl, and Br) to engage in different kinds of noncovalent bonds was investigated by ab initio calculations. SCl2 (SBr2) has two σ-holes upon extension of Cl (Br)?S bonds, and two σ-holes upon extension of S?Cl (Br) bonds. SF2 contains only two σ-holes upon extension of the F?S bond. Consequently, SCl2 and SBr2 form chalcogen and halogen bonds with the electron donor H2CO while SF2 forms only a chalcogen bond, i.e., no F···O halogen bond was found in the SF2:H2CO complex. The S···O chalcogen bond between SF2 and H2CO is the strongest, while the strongest halogen bond is Br···O between SBr2 and H2CO. The nature of these two types of noncovalent interaction was probed by a variety of methods, including molecular electrostatic potentials, QTAIM, energy decomposition, and electron density shift maps. Termolecular complexes X2S···H2CO···SX′2 (X = F, Cl, Br, and X′ = Cl, Br) were constructed to study the interplay between chalcogen bonds and halogen bonds. All these complexes contained S···O and Cl (Br)···O bonds, with longer intermolecular distances, smaller values of electron density, and more positive three-body interaction energies, indicating negative cooperativity between the chalcogen bond and the halogen bond. In addition, for all complexes studied, interactions involving chalcogen bonds were more favorable than those involving halogen bonds.
Graphical Abstract Molecular electrostatic potential and contour map of the Laplacian of the electron density in Cl2S···H2CO···SCl2 complex
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6.
Using density functional theory (DFT) and molecular dynamics (MD), we studied the interaction of a titanium atom with a half of a C60 fullerene (i.e., C30), formed from the corannulene structure with a pentagonal base. We considered atmospheric pressure and 300 K. We found that the most stable adsorption of the titanium atom on C30 occurs in the concave surface of the molecule. Afterward, we investigated the interaction of the system C30-titanium with carbon monoxide and carbon dioxide molecules, respectively. We found that each of these molecules is chemisorbed, with no dissociation. The value of the adsorption energy for the carbon monoxide molecule varies from ?0.897 to ?1.673 eV, and for the carbon dioxide molecule, it is between ?1.065 and ?1.274 eV. These values depend on the initial orientation of these molecules with respect to TiC30.
Graphical Abstract The TiC30 system chemisorbs CO or CO2?with no dissociation at atmospheric pressure and 300K
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7.
Barley seedlings were pre-treated with 1 and 5 μM H2O2 for 2 d and then supplied with water or 150 mM NaCl for 4 and 7 d. Exogenous H2O2 alone had no effect on the proline, malondialdehyde (MDA) and H2O2 contents, decreased catalase (CAT) activity and had no effect on peroxidase (POX) activity. Three new superoxide dismutase (SOD) isoenzymes appeared in the leaves as a result of 1 μM H2O2 treatment. NaCl enhanced CAT and POX activity. SOD activity and isoenzyme patterns were changed due to H2O2 pre-treatment, NaCl stress and leaf ageing. In pre-treated seedlings the rate of 14CO2 fixation was higher and MDA, H2O2 and proline contents were lower in comparison to the seedlings subjected directly to NaCl stress. Cl content in the leaves 4 and 7 d after NaCl supply increased considerably, but less in pre-treated plants. It was suggested that H2O2 metabolism is involved as a signal in the processes of barley salt tolerance.  相似文献   

8.
The aim of this study is to estimate emissions of greenhouse gases CO2, CH4 and N2O, and the effects of drainage and peat extraction on these processes, in Estonian transitional fens and ombrotrophic bogs. Closed-chamber-based sampling lasted from January to December 2009 in nine peatlands in Estonia, covering areas with different land-use practices: natural (four study sites), drained (six sites), abandoned peat mining (five sites) and active peat mining areas (five sites). Median values of soil CO2 efflux were 1,509, 1,921, 2,845 and 1,741 kg CO2-C ha?1 year?1 from natural, drained, abandoned and active mining areas, respectively. Emission of CH4-C (median values) was 85.2, 23.7, 0.07 and 0.12 kg ha?1 year?1, and N2O-N ?0.05, ?0.01, 0.18 and 0.19 kg ha?1 year?1, respectively. There were significantly higher emissions of CO2 and N2O from abandoned and active peat mining areas, whereas CH4 emissions were significantly higher in natural and drained areas. Significant Spearman rank correlation was found between soil temperature and CO2 flux at all sites, and CH4 flux with high water level at natural and drained areas. Significant increase in CH4 flux was detected for groundwater levels above 30 cm.  相似文献   

9.
Measurements of CO2 and H2O fluxes were carried out using two different techniques—eddy-covariance (EC) and open system gas exchange chamber (OC)—during two-years’ period (2003–2004) at three different grassland sites. OC measurements were made during fourteen measurement campaigns. We found good agreement between the OC and EC CO2 flux values (n = 63, r 2 = 0.5323, OC FCO2 = −0.6408+0.9508 EC FCO2). The OC FH2O values were consistently lower than those measured by the EC technique, probably caused by the air stream difference inside and outside the chamber. Adjusting flow rate within the chamber to the natural conditions would be necessary in future OC measurements. In comparison with EC, the OC proved to be a good tool for gas exchange measurements in grassland ecosystems.  相似文献   

10.
In many coastal areas of South-East Asia, attempts have been made to revive coastal ecosystem by initiating projects that encourage planting of mangrove trees. Compared to the terrestrial trees, mangrove trees possess a higher carbon fixation capacity. It becomes a very significant option for clean development mechanism (CDM) program. However, a reliable method to estimate CO2 fixation capacity of mangrove trees has not been established. Acknowledging the above fact, we decided to set up an estimation method for the CDM program, using gas exchange analysis to estimate mangrove productivity, we put into consideration the net CO2 fixation of reforested Kandelia candel (5-, 10-, and 15-year-old stand). This was estimated by gas exchange analysis and growth curve analysis. In growth curve analysis, we drew a growth curve of a single stand using data of above- and below-ground biomass. In the gas exchange analysis, we calculated CO2 fixation capacity by (1) measuring respiration rate of each organ of stand and calculating respiratory CO2 emission from above- to below-ground biomass. (2) Measuring the single-leaf photosynthetic rate in response to light intensity and calculating the photosynthetic CO2 absorption. (3) We also developed a model for the diurnal changes in temperature, and monthly averages based on one-day estimation of CO2 absorption and emission, which we corrected by this model in order to estimate the net CO2 fixation capacity in response to temperature. Comparing the biomass accumulation of the two methods constructed for the same forest, the above-ground biomass accumulation of 10-year-old forest (34.3 ton ha−1 yr−1) estimated by gas exchange analysis was closely compared to those of growth curve analysis (26.6 ton ha−1 yr−1), suggesting that the gas exchange analysis was capable of estimating mangrove productivity. The validity of the estimated CO2 fixation capacity by the gas exchange analysis and the growth curve analysis was also discussed.  相似文献   

11.
Growth of the green algae Chlamydomonas reinhardtii and Chlorella sp. in batch cultures was investigated in a novel gas-tight photobioreactor, in which CO2, H2, and N2 were titrated into the gas phase to control medium pH, dissolved oxygen partial pressure, and headspace pressure, respectively. The exit gas from the reactor was circulated through a loop of tubing and re-introduced into the culture. CO2 uptake was estimated from the addition of CO2 as acidic titrant and O2 evolution was estimated from titration by H2, which was used to reduce O2 over a Pd catalyst. The photosynthetic quotient, PQ, was estimated as the ratio between O2 evolution and CO2 up-take rates. NH4 +, NO2 , or NO3 was the final cell density limiting nutrient. Cultures of both algae were, in general, characterised by a nitrogen sufficient growth phase followed by a nitrogen depleted phase in which starch was the major product. The estimated PQ values were dependent on the level of oxidation of the nitrogen source. The PQ was 1 with NH4 + as the nitrogen source and 1.3 when NO3 was the nitrogen source. In cultures grown on all nitrogen sources, the PQ value approached 1 when the nitrogen source was depleted and starch synthesis became dominant, to further increase towards 1.3 over a period of 3–4 days. This latter increase in PQ, which was indicative of production of reduced compounds like lipids, correlated with a simultaneous increase in the degree of reduction of the biomass. When using the titrations of CO2 and H2 into the reactor headspace to estimate the up-take of CO2, the production of O2, and the PQ, the rate of biomass production could be followed, the stoichiometrical composition of the produced algal biomass could be estimated, and different growth phases could be identified.  相似文献   

12.
We studied the temporal sequence of changes in the photosynthetic CO2/H2O gas exchange intensity, as well as leaf water status, contents of soluble carbohydrates, starch, proline, pigments, and MDA, in maize seedlings (Zea mays L., cv. Luchistaya) under adaptation to increasing water deficit. The duration of drought was 2, 3, 5, and 6 days. Withholding water from maize plants caused gradual increase in the intensity of water deficit: from mild (2 or 3 days) to moderate (5 days) and nearly severe (6 days) water stress. After 6 days, relative leaf water content decreased by 19.8% as compared to the control. On the second day after the onset of drought, slight reduction in the photosynthetic CO2/H2O gas exchange intensity of the treated plants was observed. After 6 days, photosynthesis and transpiration of leaves synchronously reduced almost threefold due to stomatal closure. The progressive soil drought had substantial impact on the carbohydrate metabolism. After 2 days of water deficit, the content of reducing sugars and sucrose increased slightly, whereas after 6 days, it increased ten and four times, respectively. After 2, 3, and 5 days of drought, the starch content declined slightly; however, under severe drought (6 days), it increased by 30% as compared to the control. Simultaneously with the increase in the content of soluble sugars, proline content increased significantly and it was the highest on the sixth day of drought. At all stages of water deficit, the proline content increased more significantly than the content of reducing carbohydrates and sucrose. Under increasing water deficit (5 and 6 days), the content of MDA was found to rise. At the initial drought stage (2 or 3 days) and under severe water deficit (6 days), no significant changes in the pigment content were observed. Thus, at the initial stages of progressive drought, in the leaves of this maize cultivar, a decline in photosynthetic activity proceeded simultaneously with accumulation of reducing sugars, sucrose, and proline. The results obtained showed that, at the first stages of adaptation of maize seedlings to drought, the changes in carbohydrate and proline metabolism have been observed, which have increased upon further plant dehydration.  相似文献   

13.
A computational study of metal difluorides (MF2; M = Ca to Zn) and their interactions with carbon dioxide and water molecules was performed. The structural parameter values obtained and the results of AIM analysis and energy decomposition analysis indicated that the Ca–F bond is weaker and less ionic than the bonds in the transition metal difluorides. A deformation density plot revealed the stablizing influence of the Jahn–Teller effect in nonlinear MF2 molecules (e.g., where M= Sc, Ti, Cr). An anaysis of the metal K-edge peaks of the difluorides showed that shifts in the edge energy were due to the combined effects of the ionicity, effective nuclear charge, and the spin state of the metal. The interactions of CO2 with ScF2 (Scc3 geometry) and TiF2 (Tic2 geometry) caused CO2 to shift from its usual linear geometry to a bent geometry (η2(C=O) binding mode), while it retained its linear geometry (η1(O) binding mode) when it interacted with the other metal difluorides. Energy decomposition analysis showed that, among the various geometries considered, the Scc3 and Tic2 geometries possessed the highest interaction energies and orbital interaction energies. Heavier transition metal difluorides showed stronger affinities for H2O, whereas the lighter transition metal (Sc and Ti) difluorides preferred CO2. Overall, the results of this study suggest that fluorides of lighter transition metals with partially filled d orbitals (e.g., Sc and Ti) could be used for CO2 capture under moist conditions.
Graphical abstract Interaction of metal difluorides with carbon dioxide and water
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14.
Heavy water (H218O) has been used to label DNA of soil microorganisms in stable isotope probing experiments, yet no measurements have been reported for the 18O content of DNA from soil incubated with heavy water. Here we present the first measurements of atom% 18O for DNA extracted from soil incubated with the addition of H218O. Four experiments were conducted to test how the atom% 18O of DNA, extracted from Ponderosa Pine forest soil incubated with heavy water, was affected by the following variables: (1) time, (2) nutrients, (3) soil moisture, and (4) atom% 18O of added H2O. In the time series experiment, the atom% 18O of DNA increased linearly (R 2 = 0.994, p < 0.01) over the first 72 h of incubation. In the nutrient addition experiment, there was a positive correlation (R 2 = 0.991, p = 0.006) between the log10 of the amount of tryptic soy broth, a complex nutrient broth, added to soil and the log10 of the atom% 18O of DNA. For the experiment where soil moisture was manipulated, the atom% 18O of DNA increased with higher soil moisture until soil moisture reached 30%, above which 18O enrichment of DNA declined as soils became more saturated. When the atom% 18O for H2O added was varied, there was a positive linear relationship between the atom% 18O of the added water and the atom% 18O of the DNA. Results indicate that quantification of 18O incorporated into DNA from H218O has potential to be used as a proxy for microbial growth in soil.  相似文献   

15.
Our previous results have demonstrated that both nitric oxide (NO) and hydrogen peroxide (H2O2) are involved in the promotion of adventitious root development in marigold (Tagetes erecta L.). However, not much is known about the intricate molecular network of adventitious root development triggered by NO and H2O2. In this study, the involvement of calcium (Ca2+) and calmodulin (CaM) in NO- and H2O2-induced adventitious rooting in marigold was investigated. Exogenous Ca2+ was capable of promoting adventitious rooting, with a maximal biological response at 50 μM CaCl2. Ca2+ chelators and CaM antagonists prevented NO- and H2O2-induced adventitious rooting, indicating that both endogenous Ca2+ and CaM may play crucial roles in the adventitious rooting induced by NO and H2O2. NO and H2O2 treatments increased the endogenous content of Ca2+ and CaM, suggesting that NO and H2O2 enhanced adventitious rooting by stimulating the endogenous Ca2+ and CaM levels. Moreover, treatment with Ca2+ enhanced the endogenous levels of NO and H2O2. Additionally, Ca2+ might be involved as an upstream signaling molecule for CaM during NO- and H2O2-induced rooting. Altogether, the results suggest that both Ca2+ and CaM are two downstream signaling molecules in adventitious rooting induced by NO and H2O2.  相似文献   

16.
Tropical peatlands release significant quantities of greenhouse gases to the atmosphere, yet the relative contributions of heterotrophic and autotrophic respiration to net CO2 fluxes remains sparsely quantified. We used a combination of in situ trenching and vegetation removal in ex situ pots to quantify root-derived CO2 under two plant functional types within a mixed species forest. Trenching significantly reduced surface CO2 flux, indicating that approximately two-thirds of the released CO2 was derived from roots. In contrast, ex situ vegetation removal in pots indicated that root-derived CO2 accounted for 27% of the total CO2 flux for Campnosperma panamensis, a broadleaved evergreen tree, and 49% for Raphia taedigera, a canopy palm. The results show that root-derived CO2 is a major contribution to net CO2 emissions in tropical peatlands, and that the magnitude of the emissions is affected by plant species composition. This is important in the context of land use change driving alterations in vegetation cover.  相似文献   

17.
18.
The Arrhenius kinetic parameters of dissociation reactions and reactions of CF3CH2I with radicals like H, O, and OH are determined using highly accurate first principles calculations. Thermophysical properties like molar heat capacity (Cp), thermal stability index, and the bond dissociation energies are also determined for the CF3CH2I molecule under the PBE/DNP formalism. Since, there are no theoretical study or experimental investigation reports available regarding the dissociation reactions of CF3CH2I and reactions of this molecule with the H and OH radical, a parallel comparative analysis is done with similar iodoalkanes to ascertain the precision of the results obtained. The atmospheric lifetime of 0.54 years is obtained for this molecule.  相似文献   

19.
The spatial variation of soil greenhouse gas fluxes (GHG; carbon dioxide—CO2, methane—CH4 and nitrous oxide—N2O) remains poorly understood in highly complex ecosystems such as tropical forests. We used 240 individual flux measurements of these three GHGs from different soil types, at three topographical positions and in two extreme hydric conditions in the tropical forests of the Guiana Shield (French Guiana, South America) to (1) test the effect of topographical positions on GHG fluxes and (2) identify the soil characteristics driving flux variation in these nutrient-poor tropical soils. Surprisingly, none of the three GHG flux rates differed with topographical position. CO2 effluxes covaried with soil pH, soil water content (SWC), available nitrogen and total phosphorus. The CH4 fluxes were best explained by variation in SWC, with soils acting as a sink under drier conditions and as a source under wetter conditions. Unexpectedly, our study areas were generally sinks for N2O and N2O fluxes were partly explained by total phosphorus and available nitrogen concentrations. This first study describing the spatial variation of soil fluxes of the three main GHGs measured simultaneously in forests of the Guiana Shield lays the foundation for specific studies of the processes underlying the observed patterns.  相似文献   

20.
Plant growth, photosynthetic parameters, chloroplast ultrastructure, and the ascorbate-glutathione cycle system in chloroplasts of self-grafted and rootstock-grafted cucumber leaves were investigated. Grafted plants were grown hydroponically and were exposed to 0, 50, and 100 mM NaCl concentrations for 10 days. Under NaCl stress, the hydrogen peroxide (H2O2) content in cucumber chloroplasts increased, the chloroplast ultrastructure was damaged, and the gas stomatal conductance, intercellular CO2 concentration, as well as shoot dry weight, plant height, stem diameter, leaf area, and leaf relative water content were inhibited, whereas these changes were less severe in rootstock-grafted plants. The activities of ascorbate peroxidase (APX; EC 1.11.1.11), glutathione reductase (GR; EC 1.6.4.2), and dehydroascorbate reductase (DHAR EC 1.8.5.1) were higher in the chloroplasts of rootstock-grafted plants compared with those of self-grafted plants under 50 and 100 mM NaCl. Similar trends were shown in leaf net CO2 assimilation rate and transpiration rate, as well as reduced glutathione content under 100 mM NaCl. Results suggest that rootstock grafting enhances the H2O2-scavenging capacity of the ascorbate–glutathione cycle in cucumber chloroplasts under NaCl stress, thereby protecting the chloroplast structure and improving the photosynthetic performance of cucumber leaves. As a result, cucumber growth is promoted.  相似文献   

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