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Electronic metal-support interaction (EMSI) has attracted great attention in volatile organic compound (VOC) abatement. Herein, Pt@Co3O4 catalysts were prepared via a metal-organic framework (MOF) in situ growth approach to boost toluene degradation. The partial electron transfer from Co3O4 to Pt species was induced by the EMSI effect to generate the electron-rich Pt and Co3+ species. The electrophilic O2 molecules could be activated by picking up the electrons from electron-rich Pt species to form nucleophilic oxygen species, which is conducive to attack C-H bonds in toluene. The redox ability and surface oxygen species activity of catalysts were improved due to strong EMSI. As expected, the excellent toluene activity was achieved, meanwhile exhibiting satisfactory water resistance and long-term stability for toluene combustion. In situ diffuse reflectance infrared Fourier transform spectroscopy results elucidated that surface lattice oxygen species should deeply participate in toluene degradation, which could be efficiently replenished by gaseous oxygen. This work may provide a new idea for exploring the relationship between the electron transfer effect and efficient catalytic performance of VOCs.
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Reaction rate constants and products of 1-octen-3-one, 3-octen-2-one and 4-hexen-3-one with ozone were studied in a 100-L fluorinated ethylene propylene (FEP) Teflon film bag using absolute rate method at 298 ± 1 K and atmospheric pressure. The rate constants were (1.09 ± 0.12) × 10-17, (3.48 ± 0.36) × 10-17 and (5.70 ± 0.60) × 10-17 cm3/(moleculeâ sec), respectively. According to the obtained rate constants, the effects of carbonyl were discussed. The carbonyl group in ß position has a net withdrawing effect with respect to an olefinic bond, then causing the decline of rate constants. The quantum chemical calculation was used to explain the results of rate constants. The products of ozonolysis were mainly aldehydes, which have significant influence on the formation of SOA, and hence play an important role in the atmosphere. In this work, we detected the main products of reaction and proposed the reaction mechanism by combining the results of quantum chemical calculations. Atmospheric lifetime for three unsaturated ketones reacted with ozone was 36.4, 11.4 and 6.9 hr for 1-octen-3-one, 3-octen-2-one and 4-hexen-3-one, respectively.
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Atmósfera , Ozono , Presión Atmosférica , Cetonas , CinéticaRESUMEN
The contribution of volatile organic acids to chloride depletion still remains unclear under ambient conditions in the coast and inland. In this work, the heterogeneous reaction of HCOOH on the NaCl surface at a series of relative humidities (RHs) was investigated using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The formate was found to be formed on NaCl surface under dry and wet conditions, accompanied by the corresponding chloride depletion. The adsorbed HCOOH and the formation of formate on NaCl surface decreased with increasing RH below 30% RH. The adsorbed HCOOH decreased, while the formation of formate increased with enhanced RH at 45-70% RH. The variation in the formation of formate with RH suggests that chloride depletion may undergo similar changes. Additionally, the mechanism and kinetics for uptake of HCOOH on NaCl surface at various RHs were discussed and analyzed. Our results highlight the role of heterogeneous chemistry of volatile organic acid in the chloride depletion of NaCl in the coast and inland.
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Rate constants for the reactions of ozone with 1-octen-3-ol, 1-nonen-3-ol and 1-nonen-4-ol have been determined at 298±1K and atmospheric pressure for the first time. The experiments were performed in a 100-L FEP Teflon film bag using absolute rate method; the rate constants were (1.91±0.19)×10-17, (1.89±0.20)×10-17, and (0.83±0.08)×10-17cm3/(molecule·sec) for 1-octen-3-ol, 1-nonen-3-ol, and 1-nonen-4-ol, respectively. The rate constants have been compared with those of unsaturated alcohols structural homologs, and used to estimate the reaction reactivity. The electronegativity of carbon-carbon double bond was calculated by atomic charges analysis. The calculated results show that the electronic effect of the lone pair electrons of hydroxyl oxygen is the main cause of the difference in rate coefficient. According to the obtained rate constants, the atmospheric lifetimes of studied unsaturated alcohols were also estimated, which indicates that the reaction with ozone is an important loss pathway in the atmosphere, especially in polluted areas.
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Alcoholes/química , Modelos Químicos , Ozono/química , Atmósfera/química , Presión Atmosférica , Radical Hidroxilo/química , CinéticaRESUMEN
Secondary organic aerosol (SOA) plays a pivotal role in visibility and radiative forcing, both of which are intrinsically linked to the refractive index (RI). While previous studies have focused on the RI of SOA from traditional formation processes, the effect of multiphase reactions on the RI has not been considered. Here, we investigate the effects of multiphase processes on the RI and light-extinction of m-xylene-derived SOA, a common type of anthropogenic SOA. We find that multiphase reactions in the presence of liquid water lead to the formation of oligomers from intermediate products such as glyoxal and methylglyoxal, resulting in a large enhancement in the RI and light-scattering of this SOA. These reactions will result in increases in light-scattering efficiency and direct radiative forcing of approximately 20%-90%. These findings improve our understanding of SOA optical properties and have significant implications for evaluating the impacts of SOA on the rapid formation of regional haze, global radiative balance, and climate change.
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Cambio Climático , Compuestos Orgánicos , Aerosoles , Glioxal , AguaRESUMEN
Heterogeneous reactions have a vital role in the atmosphere due to their significant effects on the evolution of atmospheric aerosols, which in turn contribute to air pollution. However, the mechanism and kinetics of these processes involving unsaturated organic acids, important types of volatile organic compounds, are still unclear. In this work, the heterogeneous uptake of two representative atmospheric unsaturated organic acids (acrylic acid and methacrylic acid) on mineral aerosols including α-Al2 O3 and CaCO3 are investigated using a Knudsen cell reactor and an inâ situ diffuse reflectance infrared Fourier transform spectrometry (DRIFTS) reactor. The corresponding reaction pathways are proposed from the DRIFTS analysis. In addition, the initial uptake coefficients of unsaturated organic acids and their heterogeneous fate are obtained for the first time. Our results suggest that heterogeneous reactions on α-Al2 O3 and CaCO3 can be important sinks for acrylic acid and methacrylic acid, as well as possible contributors to the organic coating found on atmospheric aerosols, especially in high-pollution events.
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Atmospheric aerosols are usually complex mixtures of inorganic and organic compounds. The hygroscopicity of mixed particles is closely related to their chemical composition and interactions between components, which is still poorly understood. In this study, the hygroscopic properties of submicron particles composed of NaCl and dicarboxylic acids including oxalic acid (OA), malonic acid (MA), and succinic acid (SA) with various mass ratios are investigated with a hygroscopicity tandem differential mobility analyzer (HTDMA) system. Both the Zdanovskii-Stokes-Robinson (ZSR) method and extended aerosol inorganics model (E-AIM) are applied to predict the water uptake behaviors of sodium chloride/dicarboxylic acid mixtures. For NaCl/OA mixed particles, the measured growth factors were significantly lower than predictions from the model methods, indicating a change in particle composition caused by chloride depletion. The hygroscopic growth of NaCl/MA particles was well described by E-AIM, and that of NaCl/SA particles was dependent upon mixing ratio. Compared with model predictions, it was determined that water uptake of the NaCl/OA mixture could be enhanced and could be closer to the predictions by addition of levoglucosan or malonic acid, which retained water even at low relative humidity (RH), leading to inhibition of HCl evaporation during dehydration. These results demonstrate that the coexisting hygroscopic species have a strong influence on the phase state of particles, thus affecting chemical interactions between inorganic and organic compounds as well as the overall hygroscopicity of mixed particles.
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The hygroscopic behaviors of atmospherically relevant multicomponent water soluble organic compounds (WSOCs) and their effects on ammonium sulfate (AS) and sodium chloride were investigated using a hygroscopicity tandem differential mobility analyzer (HTDMA) in the relative humidity (RH) range of 5%-90%. The measured hygroscopic growth was compared with predictions from the Extended-Aerosol Inorganics Model (E-AIM) and Zdanovskii-Stokes-Robinson (ZSR) method. The equal mass multicomponent WSOCs mixture containing levoglucosan, succinic acid, phthalic acid and humic acid showed gradual water uptake without obvious phase change over the whole RH range. It was found that the organic content played an important role in the water uptake of mixed particles. When organic content was dominant in the mixture (75%), the measured hygroscopic growth was higher than predictions from the E-AIM or ZSR relation, especially under high RH conditions. For mass fractions of organics not larger than 50%, the hygroscopic growth of mixtures was in good agreement with model predictions. The influence of interactions between inorganic and organic components on the hygroscopicity of mixed particles was related to the salt type and organic content. These results could contribute to understanding of the hygroscopic behaviors of multicomponent aerosol particles.
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Contaminantes Atmosféricos/química , Modelos Químicos , Sales (Química)/química , Contaminantes Químicos del Agua/química , Aerosoles/química , Sulfato de Amonio/química , Cloruro de Sodio/química , HumectabilidadRESUMEN
Sodium nitrate is a main component of aging sea salt aerosol, and its phase behavior has been studied repeatedly with wide ranges observed in the efflorescence relative humidity (RH) in particular. Studies of the efflorescence dynamics of NaNO3 droplets deposited on a ZnSe substrate are reported, using an in situ Fourier transform infrared attenuated total reflection (FTIR-ATR) technique. The time-dependence of the infrared spectra of NaNO3 aerosols accompanying step changes in RH have been measured with high signal-to-noise ratio. From the IR difference spectra recorded, changes of the time-dependent absorption peak area of the O-H stretching band (ν-OH, â¼3400 cm(-1)) and the nitrate out-of-plane bending band (ν2-NO3(-), â¼836 cm(-1)) are obtained. From these measurements, changes in the IR signatures can be attributed to crystalline and solution phase nitrate ions, allowing the volume fraction of the solution droplets that have crystallized to be determined. Then, using these clear signatures of the volume fraction of droplets that have yet to crystallize, the homogeneous and heterogeneous nucleation kinetics can be studied from conventional measurements using a steady decline in RH. The nucleation rate measurements confirm that the rate of crystallization in sodium nitrate droplets is considerably less than in ammonium sulfate droplets at any particular degree of solute supersaturation, explaining the wide range of efflorescence RHs observed for sodium nitrate in previous studies. We demonstrate that studying nucleation kinetics using the FTIR-ATR approach has many advantages over brightfield imaging studies on smaller numbers of larger droplets or measurements made on single levitated particles.
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Atmósfera/química , Nitratos/química , Compuestos de Selenio/química , Compuestos de Zinc/química , Aerosoles , Sulfato de Amonio/química , Cristalización , Humedad , Relación Señal-Ruido , Espectroscopía Infrarroja por Transformada de Fourier , VolatilizaciónRESUMEN
Oxygen vacancy engineering in transition metal oxides is an effective strategy for improving catalytic performance. Herein, defect-enriched Mn2O3 catalysts were constructed by controlling the calcination temperature. The high content of oxygen vacancies and accompanying Mn4+ ions were generated in Mn2O3 catalysts calcined at low temperature, which could greatly improve the low-temperature reducibility and migration of surface oxygen species. DFT theoretical calculations further confirmed that molecular oxygen and toluene were easily adsorbed over defective α-Mn2O3 (222) facets with an energy of -0.29 and -0.48 eV, respectively, and corresponding OO bond length is stretched to 1.43 Å, resulting in the highly reactive oxygen species. Mn2O3-300 catalyst with abundant oxygen vacancies exhibited the highest specific reaction rate and lowest activation energy. Furthermore, the optimized catalyst possessed the outstanding stability, water tolerance and CO2 yield. In comparison with the fresh Mn2O3-300 catalyst, the physical structure and surface property of the used catalyst remained almost unchanged regardless of whether undergoing the stability test at consecutive catalytic runs as well as high temperature, and water resistance test. In situ DRIFTS spectra further elucidated that introducing the water vapor had little effect on the reaction intermediates, indicating the excellent durability of the defect-enriched catalyst.
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A novel nanocellulose/carbon dots hydrogel (NCH) was fabricated using cellulose nanofibrils (CN), carbon dots (CD) and zinc oxide (ZnO)/silver bromide (AgBr) nanocomposite, where CD enhanced amino group-induced adsorption of hexavalent chromium (Cr(VI)) and promoted the photocatalytic properties of ZnO/AgBr nanocomposite via the transfer of photogenerated electrons, resulting in enhanced efficiency in the removal of Cr(VI) from aqueous solution. The structure, morphology, and physicochemical properties of the prepared NCH were characterized, with the results of adsorption and photocatalysis experiments showing the maximum theoretical adsorption capacity of the NCH to be 315 mg/g, 219 times that of the ZnO/AgBr nanocomposite; the apparent removal rate constant of the NCH was 0.0319 min-1, 11.7 times that of the ZnO/AgBr nanocomposite. Furthermore, the removal performance of NCH was attributed to CD-enhanced synergistic adsorption and photocatalysis effects, supported by characterization and experimental results. This work provides insight into the design and fabrication of a novel adsorptive photocatalyst with CD-enhanced synergistic adsorption and photocatalysis effects for removing Cr(VI) from aqueous solution.
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Nanocompuestos , Contaminantes Químicos del Agua , Óxido de Zinc , Carbono , Óxido de Zinc/química , Contaminantes Químicos del Agua/química , Adsorción , Hidrogeles , Cromo/química , Nanocompuestos/químicaRESUMEN
Hydrogel, a common carrier of photocatalyst that suffers from compromised catalytic efficiency, is still far from practical application. Herein, based on "computer chip-inspired design", a novel nanocellulose/carbon dots hydrogel (NCH) was fabricated as superior intensifier instead of common carrier of sodium titanate nanofibre (STN), where carbon dots (CDs) enhanced amino group-induced adsorption for Cr(VI), promoted photocatalytic properties of STN via transferring the photogenerated electron-hole pairs and improved amino group-induced desorption for reduced product (Cr(III)) via electrostatic repulsion, showing an efficiency of 1 + 1 > 2. Adsorption and photocatalysis experiments demonstrated superior removal performance of the NCH incorporating STN, as shown by theoretical maximum adsorption capacity of 425.74 mg/g and kinetic constant of 0.0374 min-1 in the photocatalytic process, which was nearly 6.6 and 7.3 times of STN. A series of experiments was conducted to confirm the novel mechanism of CDs-enhanced adsorption-photocatalysis-desorption synergy. This work not only provides new insights into the fabrication of a superior intensifier for nanosized photocatalyst, but also proposes one new mechanism of CDs-enhanced adsorption-photocatalysis-desorption synergy, which is helpful for designing and optimizing nanosized photocatalyst.
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Peroxyacetyl nitrate (PAN) is a typical secondary photochemical product in the atmospheric environment with significant adverse effects on human health and plant growth. In this study, PAN and other pollutants, as well as meteorological conditions were observed intensively from August to September in 2022 at a typical urban sampling site in Beijing, China. The mean and maximum PAN concentrations during the observation period were 1.00 ± 0.97 ppb and 4.84 ppb, respectively. Severe photochemical pollution occurred during the observation period, with the mean PAN concentration about 3.1 times higher than that during the clean period. There was a good positive correlation between O3 and PAN, and their correlation was higher during the O3 exposure period than that during the clean period. The simulated results by box-model coupled with the Master Chemical Mechanism (MCM v3.3.1) showed that the O3-related reactions were the largest sources of OH radicals during O3 exposure period, which was conducive to the co-contamination of PAN and O3. Acetaldehyde (CH3CHO) and methylglyoxal (MGLY) were the largest OVOCs precursors of peroxyacetyl radicals (PA), with the contributions to the total PA generated by OVOCs about 67 % - 83 % and 17 % - 30 %, respectively. The reduction of emissions from liquefied petroleum gas (LPG) and solvent usage has the highest reduction effect on PAN and O3, followed by the control of gasoline vehicle exhaust emissions. This study deepens the understanding of the PAN photochemistry in urban areas with high O3 background conditions and the impact of anthropogenic activities on the photochemical pollution. Meanwhile, the findings of this study highlight the necessity of strengthening anthropogenic emissions control to effectively reduce the co-contamination of PAN and O3 in Beijing in the future.
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Atmospheric trace metals are a key component of particulate matter and significantly influence the atmospheric process and human health. The dissolved fraction of trace metals represents their bioavailability and exhibits high chemical activity. However, the optimum measurement method for detecting the soluble fraction of trace metals is still undetermined. The impact of variations in pollution on the soluble fraction is largely unrevealed. Therefore, in this work, a one-month field observation was conducted in Central China and different extraction solvents were used to determine the proper measurement method for the soluble fraction of trace metals and investigate the variation pattern under different pollution conditions. The findings show that solvents with acidity near that of aerosol water can better reflect the actual soluble fraction of trace metals in fine particulate matter. The soluble fraction of trace metals tends to increase with pollution level increased, demonstrating unexpectedly high health risks and chemical activity under heavy haze conditions. Our results indicate that remediation and trace metal pollution control are urgently needed.
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Contaminantes Atmosféricos , Metales Pesados , Oligoelementos , Contaminantes Atmosféricos/análisis , China , Monitoreo del Ambiente/métodos , Humanos , Metales Pesados/análisis , Material Particulado/análisis , Solventes , Oligoelementos/análisisRESUMEN
The plant vacuolar H+-ATPase (V-ATPase) is a multisubunit complex. In addition to performing basic housekeeping functions, this complex is also involved in abiotic stress resistance in plants. In this study, a V-ATPase c`` subunit gene (ThVHAc``1) from Tamarix hispida Willd was cloned with a 534-bp ORF. Sequence analysis showed that the ThVHAc``1 protein contains four transmembrane helices and lacks a signal peptide. qRT-PCR results showed that ThVHAc``1 was primarily induced by treatments of NaCl, NaHCO3, PEG6000, CdCl2 or ABA in roots, stems and leaves of T. hispida. The expression pattern of ThVHAc``1 was significantly different from that of ThVHAc1 (a V-ATPase c subunit in T. hispida). Furthermore, the cell survival rates and density (OD600) results showed that the transgenic yeast overexpressing ThVHAc``1 exhibited increased tolerance to the above-mentioned abiotic stresses. In addition, the overexpression of ThVHAc``1 confers salt tolerance to transgenic Arabidopsis plants by improving the ROS content and decreasing the accumulation of O2- and H2O2. Similarly, the homologous transformation of the ThVHAc``1 gene into T. hispida also improved salt tolerance. Our results suggest that the ThVHAc``1 gene plays an important role in plant stress tolerance.
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Proteínas de Plantas/fisiología , Tolerancia a la Sal/genética , Tamaricaceae/fisiología , ATPasas de Translocación de Protón Vacuolares/fisiología , Regulación de la Expresión Génica de las Plantas , Peróxido de Hidrógeno , Proteínas de Plantas/genética , Plantas Modificadas Genéticamente/fisiología , Tamaricaceae/genética , ATPasas de Translocación de Protón Vacuolares/genéticaRESUMEN
O3 and alkenes are important reactants in the formation of SOA in the atmosphere. The intermediates and reaction mechanism of ozonation of alkene is an important topic in atmospheric chemistry. In this study, the low-temperature matrix isolation was used to capture the intermediates such as Primary ozonides (POZs), Criegee Intermediates (CIs), and Secondary ozonides (SOZs) generated from ozonation of 2-methyl-1-butene (2M1B) and 2-methyl-2-butene (2M2B). The results have been identified by the vacuum infrared spectroscopy and theoretical calculation. Our results show that during the ozonation of asymmetric alkenes, two kinds of CIs and more than two kinds of SOZs were generated due to the different decomposition modes of POZs. The infrared absorption peaks of (CH3)2COO and CH3CH2C(CH3)OO for O-O telescopic vibration was determined to be 889 cm-1 and 913 cm-1, respectively. Using the merged jet method, it was found that a large amount of HCHO was produced during the ozonation of 2M1B, and glyoxal and methylglyoxal were produced in the ozonation of 2M2B. Our findings highlight the importance of asymmetric alkene ozonolysis reactions in producing CIs, further improving the understanding of the generation of CIs from ozonation of alkenes.
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Alquenos/química , Modelos Químicos , Ozono/química , Atmósfera , Compuestos Heterocíclicos , Espectrofotometría Infrarroja , Espectroscopía Infrarroja por Transformada de FourierRESUMEN
Calcium sulfate is a major constituent of atmospheric sulfate, with a typical rod-like morphology ranging from several hundred nanometers to approximately two micrometers observed in field studies. However, the chemical formation mechanism is still not well known. In this study, the kinetics and mechanism for the formation and growth of rod-like calcium sulfate crystals through oxidation of SO2 by O3 on size-resolved CaCO3 at different relative humidity (RH) were investigated using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and scanning electron microscopy (SEM). We found that the concentration and formation rate of sulfate decreased with the increasing diameter of CaCO3 particles, and thus smaller particles could enhance the formation of sulfate due to more reactive sites on smaller particles. The rod-like calcium sulfate crystals were formed only at RH above 60% and in the presence of reactant gases through the heterogeneous pathway. The liquid-like water layer formed by promotion of high RH in the presence of reactant gases could facilitate the formation and aggregation of calcium sulfate hydrates and thus promote the formation and growth of rod-like calcium sulfate crystals. This study provides a possible mechanism for the formation and growth of rod-like calcium sulfate crystals existing in the atmosphere.
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Heterogeneous reactions of SO2 and O3 with CaCO3 particles were investigated at a series of relative humidity (RH, 1% to 90%) and 298K using a diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The uptake coefficients of SO2 on CaCO3 at different RHs were obtained for the first time. Our results proved that high RH could substantially promote the formation of sulfate, for which the highest concentration (80% RH and reaction time of 200min) and highest formation rate in stable stage (85% RH) were 14 times and 43 times that at 1% RH, respectively. The surface products, increment of concentration and formation rate of sulfate changed with RH which were due to the surface adsorbed water (SAW) on the particles. SAW could increase the reactive sites on the particles and thus accelerate the conversion of SO2 into sulfite, and sulfite could be oxidized rapidly. Liquid-like water layers formed on the particle surface could enhance the ion mobility and promote the aggregation of CaSO4 hydrates, which could expose more reactive sites and result in additional adsorption of SO2. Piecewise equations of uptake coefficient with RH were given and could be referred by model simulation. The results are of importance in understanding the explosive growth of sulfate during severe haze episodes accompanied with high RH.
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Dehydration-responsive element-binding (DREB) transcription factors are important abiotic stress tolerance related genes, and some reports on the roles of DREB have primarily addressed herbal plants. To explore the abiotic stress tolerance role of DREB (ThDREB) from Tamarix hispida, a ThDREB gene with a complete ORF of 783 bp that encodes a 28.74 kDa protein with 260 amino acids, was isolated and functionally annotated. ThDREB expression was highly induced by NaCl, PEG, NaHCO3 and CdCl2 treatments, and the highest expression level (369.2-fold of control) was found for the roots that were under NaCl stress for 6 h. The tobacco plants that were transformed by ThDREB were conferred with higher germination rates, fresh weights and root lengths than the wild type (WT) tobacco plants under NaCl and mannitol treatments. The total chlorophyll content (tcc), superoxide dismutase (SOD) and peroxidase (POD) activities were also higher in the transgenic lines in comparison with the WT, and the malondialdehyde (MDA) and H2O2 content, electrolyte leakage (EL) rate and ROS as tracked by staining were generated to a lesser degree in ThDREB transgenic plants than in the WT under NaCl and mannitol stress. Furthermore, the transient overexpression analysis of ThDREB in T. hispida also improved plant salt and drought tolerance in comparison with the empty vector-transformed lines. Our results indicated that ThDREB expression could effectively improve tolerance to salt and drought stress by enhancing the antioxidase activity that keeps the ROS at a low accumulation level and makes them easy to scavenge.
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Sequías , Nicotiana/genética , Proteínas de Plantas/genética , Plantas Tolerantes a la Sal/genética , Estrés Fisiológico/genética , Tamaricaceae/genética , Arabidopsis/genética , Arabidopsis/fisiología , Cloruro de Cadmio/farmacología , Clorofila/metabolismo , Regulación de la Expresión Génica de las Plantas/efectos de los fármacos , Germinación/efectos de los fármacos , Peróxido de Hidrógeno/metabolismo , Malondialdehído/metabolismo , Peroxidasa/metabolismo , Filogenia , Proteínas de Plantas/biosíntesis , Proteínas de Plantas/metabolismo , Plantas Modificadas Genéticamente , Polietilenglicoles/farmacología , Plantas Tolerantes a la Sal/efectos de los fármacos , Plantas Tolerantes a la Sal/enzimología , Plantas Tolerantes a la Sal/metabolismo , Bicarbonato de Sodio/farmacología , Cloruro de Sodio/farmacología , Superóxido Dismutasa/metabolismo , Tamaricaceae/efectos de los fármacos , Tamaricaceae/enzimología , Tamaricaceae/metabolismo , Nicotiana/efectos de los fármacos , Nicotiana/enzimología , Nicotiana/metabolismoRESUMEN
Heterogeneous reactions are thought to play a significant role in the formation of haze, especially in wintertime, which suggests that temperature may affect the heterogeneous formation of organic aerosols. As the most-abundant carboxylic acid in the Earth's atmosphere, we chose acetic acid to study the effect of temperature on its heterogeneous reaction with α-Al2 O3 between 248 and 298â K. The products were characterized by inâ situ DRIFTS, which indicated that lowering the temperature slowed the formation of acetate, but promoted the formation of crystalline acetic acid. Moreover, low temperatures promoted a different reaction mechanism to that at room temperature. Owing to the formation of chain structures at low temperatures, crystalline acetic acid molecules covered the surface active sites on α-Al2 O3 , thereby inhibiting the formation of acetate. However, crystalline acetic acid reacted with α-Al2 O3 itself in a sequential manner. Furthermore, the reactive uptake coefficients, active energies, and acetic acid lifetimes at different temperatures were investigated.