Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 106
Filtrar
Más filtros

Banco de datos
Tipo del documento
Intervalo de año de publicación
1.
Ecotoxicol Environ Saf ; 284: 116867, 2024 Oct 01.
Artículo en Inglés | MEDLINE | ID: mdl-39154501

RESUMEN

The loss of nitrogen in soil damages the environment. Clarifying the mechanism of ammonium nitrogen (NH4+-N) transport in soil and increasing the fixation of NH4+-N after N application are effective methods for improving N use efficiency. However, the main factors are not easily identified because of the complicated transport and retardation factors in different soils. This study employed machine learning (ML) to identify the main influencing factors that contribute to the retardation factor (Rf) of NH4+-N in soil. First, NH4+-N transport in the soil was investigated using column experiments and a transport model. The Rf (1.29 - 17.42) was calculated and used as a proxy for the efficacy of NH4+-N transport. Second, the physicochemical parameters of the soil were determined and screened using lasso and ridge regressions as inputs for the ML model. Third, six machine learning models were evaluated: Adaptive Boosting, Extreme Gradient Boosting (XGB), Random Forest, Gradient Boosting Regression, Multilayer Perceptron, and Support Vector Regression. The optimal ML model of the XGB model with a low mean absolute error (0.81), mean squared error (0.50), and high test r2 (0.97) was obtained by random sampling and five-fold cross-validation. Finally, SHapely Additive exPlanations, entropy-based feature importance, and permutation characteristic importance were used for global interpretation. The cation exchange capacity (CEC), total organic carbon (TOC), and Kaolin had the greatest effects on NH4+-N transport in the soil. The accumulated local effect offered a fundamental insight: When CEC > 6 cmol+ kg-1, and TOC > 40 g kg-1, the maximum resistance to NH4+-N transport within the soil was observed. This study provides a novel approach for predicting the impact of the soil environment on NH4+-N transport and guiding the establishment of an early-warning system of nutrient loss.


Asunto(s)
Compuestos de Amonio , Aprendizaje Automático , Nitrógeno , Suelo , Suelo/química , Compuestos de Amonio/análisis , Nitrógeno/análisis , Contaminantes del Suelo/análisis , Monitoreo del Ambiente/métodos
2.
Ecotoxicology ; 33(8): 839-848, 2024 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-38995498

RESUMEN

Mercury (Hg) is a persistent soil pollutant, and its toxicity can be evaluated using soil enzyme indicators. However, a thorough understanding of how the enzyme resists and remains resilient to Hg stress is essential, as it significantly impacts the accuracy of toxicity assessments. Therefore, it is worthwhile to understand the functional stability of urease in soil under Hg pollution. This study compares the effects of Hg at different concentrations and exposure times on soil urease. Results indicate that soil urease activity was enhanced in the first two hours under low levels of Hg pollution, decreased after six hours of acute Hg pollution, and reached its maximum reduction in 24 hours. The urease in fluvo-aquic soil, with higher soil organic matter showed higher resistance to Hg acute pollution than that in red soil. Over a longer aging process, soil urease activity gradually recovered with time. Hormesis effects were observed in red soil under high Hg stress after 30 days, showing the strong resilience of urease enzyme function to Hg pollution. The ecological dose, ED10, (the Hg concentration causing a 10% reduction in soil urease activity) ranged from 0.09 to 0.59 mg kg-1 under short-term exposure, and was lower than that under a longer aging process (0.28 to 2.71 mg kg-1). Further, aging reduced the Hg ecotoxicity due to decreased Hg availability and the resilience of soil urease activity. This indicates that the risk of Hg pollution estimated by soil urease as an indicator depends on exposure time and enzyme stability. These factors need consideration in heavy metal pollution assessments using soil enzymes.


Asunto(s)
Ecotoxicología , Mercurio , Contaminantes del Suelo , Suelo , Ureasa , Ureasa/metabolismo , Mercurio/toxicidad , Contaminantes del Suelo/toxicidad , Suelo/química , Monitoreo del Ambiente
3.
J Environ Sci (China) ; 144: 137-147, 2024 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-38802225

RESUMEN

The pollution and ecological risks posed by arsenic (As) entering the soil are the major environmental challenges faced by human beings. Soil phosphatase can serve as a useful indicator for assessing As contamination under specific soil pH conditions. However, the study of phosphatase kinetics in long-term field As-contaminated soil remains unclear, presenting a significant obstacle to the monitoring and evaluation of As pollution and toxicity. The purpose of this study was to determine phosphatase activity and explore enzyme kinetics in soils subjected to long-term field As contamination. Results revealed that the soil phosphatase activity varied among the tested soil samples, depending on the concentrations of As. The relationship between total As, As fractions and phosphatase activity was found to be significant through negative exponential function fitting. Kinetic parameters, including maximum reaction velocity (Vmax), Michaelis constant (Km) and catalytic efficiency (Vmax/Km), ranged from 3.14 × 10-2-53.88 × 10-2 mmol/(L·hr), 0.61-7.92 mmol/L, and 0.46 × 10-2-11.20 × 10-2 hr-1, respectively. Vmax and Vmax/Km of phosphatase decreased with increasing As pollution, while Km was less affected. Interestingly, Vmax/Km showed a significant negative correlation with all As fractions and total As. The ecological doses (ED10) for the complete inhibition and partial inhibition models ranged from 0.22-70.33 mg/kg and 0.001-55.27 mg/kg, respectively, indicating that Vmax/Km can be used as an index for assessing As pollution in field-contaminated soil. This study demonstrated that the phosphatase kinetics parameters in the soil's pH system were better indicators than the optimal pH for evaluating the field ecotoxicity of As.


Asunto(s)
Arsénico , Monitoreo del Ambiente , Contaminantes del Suelo , Suelo , Contaminantes del Suelo/análisis , Arsénico/análisis , Suelo/química , Concentración de Iones de Hidrógeno , Monitoreo del Ambiente/métodos , Cinética , Monoéster Fosfórico Hidrolasas/metabolismo
4.
Environ Res ; 220: 115181, 2023 03 01.
Artículo en Inglés | MEDLINE | ID: mdl-36586710

RESUMEN

Arsenic-related functional genes are ubiquitous in microbes, and their distribution and abundance are influenced by edaphic factors. In arsenic-contaminated soils, soil arsenic content and pH determine the distribution of arsenic metabolizing microorganisms. In the uncontaminated natural ecosystems, however, it remains understudied for the key variable factor in determining the variation of bacterial assembly and mediating the arsenic biogeographical cycles. Here, we selected natural forest soils from southern and northern slopes along the altitudinal gradient of Taibai Mountain, China. The arsenic-related functional genes and soil bacterial community was examined using GeoChip 5.0 and high-throughput sequencing of 16S rRNA genes, respectively. It was found that arsenic-related functional genes were ubiquitous in tested forest soils. The gene arsB has the highest relative abundance, followed by arsC, aoxB, arrA, arsM, and arxA. The arsenic-related functional genes distribution on two slopes were decoupled from their corresponding bacterial community. Though there are higher abundance of bacterial communities on the northern slope than that on the southern slope, for arsenic-related functional genes, the abundance has the contrary trend which showing the more arsenic-related functional genes on the southern slope. In the top ten phyla, Proteobacteria and Actinobacteria were dominant phyla which affected the abundance of arsenic-related functional genes. Redundancy analysis and variance partitioning analysis indicated that soil pH, organic matter and altitude jointly determined the arsenic-related functional genes diversity in the two slopes of Taibai Mountain, and soil pH was a key factor. This indicates that the lower pH may shape more microbes with arsenic metabolic capacity. These findings suggested that soil pH plays a significant role in regulating the distribution of arsenic-related functional microorganisms, even for a forest ecosystem with an altitudinal gradient, and remind us the importance of pH in microbe mediated arsenic transformation.


Asunto(s)
Arsénico , Ecosistema , Arsénico/metabolismo , Suelo/química , ARN Ribosómico 16S/genética , Bacterias/metabolismo , Bosques , Concentración de Iones de Hidrógeno , Microbiología del Suelo
5.
Phys Chem Chem Phys ; 24(5): 2717-2728, 2022 Feb 02.
Artículo en Inglés | MEDLINE | ID: mdl-35072681

RESUMEN

The multifunction of molecule-based devices is always achieved by improving their charge transport characteristics. These characteristics depend strongly on the energy levels of molecular semiconductors, which fundamentally govern the working principle and device performance. Therefore, an accurate measurement of these energy levels is crucial for evaluating the availability of the prepared materials and thus optimizing the device performance. Here, an easy-to-operate three-terminal hot electron transistor has been developed, which comprises a molecular optoelectronic device that records the charge transport. It achieves exceptional properties including the lowest unoccupied molecular orbit level, highest occupied molecular orbit level, higher energy states, and higher electronic bandgap. When compared with existing techniques such as cyclic voltammetry, inverse photoemission spectroscopy, and ultraviolet photoemission spectroscopy, the hot electron transistor provides in-situ characterization and categorizes the measured energy information as intrinsic properties of the molecular semiconductor. Furthermore, we provide an in-depth understanding of the fundamental device-physics, which provides promising guidance for performance optimization.

6.
Appl Microbiol Biotechnol ; 104(13): 5873-5887, 2020 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-32415321

RESUMEN

Microbial tolerance to phenolic pollutants is the key to their efficient biodegradation. However, the metabolic mechanisms that allow some microorganisms to adapt to high phenol concentrations remain unclear. In this study, to reveal the underlying mechanisms of how Burkholderia sp. adapt to high phenol concentrations, the strain's tolerance ability and time-course transcriptome in combination with cell phenotype were evaluated. Surprisingly, Burkholderia sp. still grew normally after a long adaptation to a relatively high phenol concentration (1500 mg/L) and exhibited some time-dependent changes compared to unstressed cells prior to the phenol addition. Time-course transcriptome analysis results revealed that the mechanism of adaptations to phenol was an evolutionary process that transitioned from tolerance to positive degradation through precise gene regulation at appropriate times. Specifically, basal stress gene expression was upregulated and contributed to phenol tolerance, which involved stress, DNA repair, membrane, efflux pump and antioxidant protein-coding genes, while a phenol degradation gene cluster was specifically induced. Interestingly, both the catechol and protocatechuate branches of the ß-ketoadipate pathway contributed to the early stage of phenol degradation, but only the catechol branch was used in the late stage. In addition, pathways involving flagella, chemotaxis, ATP-binding cassette transporters and two-component systems were positively associated with strain survival under phenolic stress. This study provides the first insights into the specific response of Burkholderia sp. to high phenol stress and shows potential for application in remediation of polluted environments. KEY POINTS: • Shock, DNA repair and antioxidant-related genes contributed to phenol tolerance. • ß-Ketoadipate pathway branches differed at different stages of phenol degradation. • Adaptation mechanisms transitioned from negative tolerance to positive degradation.


Asunto(s)
Adaptación Fisiológica/genética , Burkholderia/metabolismo , Fenoles/metabolismo , Biodegradación Ambiental , Burkholderia/genética , Burkholderia/crecimiento & desarrollo , Catecoles/metabolismo , Perfilación de la Expresión Génica , Regulación Bacteriana de la Expresión Génica , Genes Bacterianos/genética , Fenotipo , Estrés Fisiológico/genética
7.
Ecotoxicol Environ Saf ; 191: 110215, 2020 Mar 15.
Artículo en Inglés | MEDLINE | ID: mdl-31978765

RESUMEN

Information on the kinetic characteristics of soil enzymes under long-term arsenic (As) pollution in field soils is scarce. We investigated Michaelis-Menten kinetic properties of four soil enzymes including ß-glucosidase (BG), acid phosphatase (ACP), alkaline phosphatase (ALP), and dehydrogenase (DHA) in field soils contaminated by As resulting from long-term realgar mining activity. The kinetic parameters, namely the maximum reaction velocity (Vmax), enzyme-substrate affinity (Km) and catalytic efficiency (Vmax/Km) were calculated. Results revealed that the enzyme kinetic characteristics varied in soils and were significantly influenced by total nitrogen (N) and total As, which explained 31.8% and 30.7% of the variance in enzyme kinetics respectively. Enzyme pools (Vmax) and catalytic efficiency (Vmax/Km) of BG, ACP and DHA decreased with elevated As pollution, while the enzyme affinity for substrate (Km) was less affected. Redundancy analysis and stepwise regression suggested that the adverse influence of As on enzyme kinetics may offset or weakened by soil total N and soil organic matter (SOM). Concentration-response fitting revealed that the specific kinetic parameters expressed as the absolute enzyme kinetic parameters multiplied by normalized soil total N and SOM were more relevant than the absolute ones to soil total As. The arsenic ecological dose values that cause 10% decrease (ED10) in the specific enzyme kinetics were 20-49 mg kg-1, with a mean value of 35 mg kg-1, indicating a practical range of threshold for As contamination at field level. This study concluded that soil enzymes exhibited functional adaptation to long-term As stress mainly through the reduction of enzyme pools (Vmax) or maintenance of enzyme-substrate affinity (Km). Further, this study demonstrates that the specific enzyme kinetics are the better indicators of As ecotoxicity at field-scale compared with the absolute enzyme parameters.


Asunto(s)
Arsénico/toxicidad , Enzimas/química , Contaminantes del Suelo/toxicidad , Suelo/química , Arsénico/análisis , Arsenicales , Biomarcadores Ambientales/efectos de los fármacos , Cinética , Minería , Nitrógeno/análisis , Compuestos Orgánicos/análisis , Contaminantes del Suelo/análisis , Sulfuros/toxicidad
8.
J Am Chem Soc ; 141(21): 8516-8526, 2019 May 29.
Artículo en Inglés | MEDLINE | ID: mdl-31050410

RESUMEN

A method enabling the accurate and precise correlation between structures and properties is critical to the development of efficient electrocatalysts. To this end, we developed an integrated single-electrode method (ISM) that intimately couples electrochemical rotating disk electrodes, in situ/operando X-ray absorption fine structures, and aberration-corrected transmission electron microscopy on identical electrodes. This all-in-one method allows for the one-to-one, in situ/operando, and atomic-scale correlation between structures of electrocatalysts with their electrochemical reactivities, distinct from common methods that adopt multisamples separately for electrochemical and physical characterizations. Because the atomic step is one of the most fundamentally structural elements in electrocatalysts, we demonstrated the feasibility of ISM by exploring the roles of atomic steps in the reactivity of electrocatalysts. In situ and atomic-scale evidence shows that low-coordinated atomic steps not only generate reactive species at low potentials and strengthen surface contraction but also act as templates to disturb interfacial water networks and thus affect the reactivity of electrocatalysts. This template role interprets the long-standing puzzle regarding why high-index facets are active for the oxygen reduction reaction in acidic media. The ISM as a fundamentally new method for workflows should aid the study of many other electrocatalysts regarding their nature of active sites and operative mechanisms.

9.
Environ Res ; 179(Pt A): 108801, 2019 12.
Artículo en Inglés | MEDLINE | ID: mdl-31606617

RESUMEN

Although cost-effective, phytoremediation is too expensive when considering the large-scale pollution. Relative to harvesting the whole plant, it is more practicable to remove and dispose of senescent and dead leaves after phytoremediation. The phytoremediation efficiency of Festuca arundinacea for Cd was evaluated in this study, because over about 7% of the land area in China was contaminated with Cd. The accumulation, redistribution, and extraction of Cd were evaluated in different leaves of F. arundinacea intercropped with N-fixing species at different densities (Cicer arietinum L). The results showed that coordinate and malposed intercropping systems increased the dry weight of the senescent and dead leaves of F. arundinacea by 30-41% and 103-168% compared to the monoculture system, respectively. More Cd was redistributed to the senescent and dead leaves of F. arundinacea under both intercropping systems. Occupying only 22-30% of the total leaf biomass, senescent and dead leaves accumulated 74-88% of leaf Cd under different cultivation conditions. Relative to the monoculture system, intercropping decreased the amount of time needed to reduce soil Cd by 44-53%. The biomass production and Cd accumulation of F. arundinacea were higher in the malposed intercropping system, and it had higher remediation efficiency than the coordinate intercropping system. This study demonstrated that intercropping, especially malposed intercropping of F. arundinacea and C. arietinum L., is a practicable technology for leaf harvesting phytoremediation.


Asunto(s)
Biodegradación Ambiental , Cadmio , Cicer , Festuca , Contaminantes del Suelo , China , Hojas de la Planta , Suelo
10.
Appl Microbiol Biotechnol ; 103(2): 747-760, 2019 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-30362077

RESUMEN

Bacterial laccases have received considerable attention because of several advantages associated with the higher environmental stability of these enzymes compared with fungal laccases. In this study, a laccase-like gene from Burkholderia cepacia BNS was successfully cloned. This gene was found to encode a mature protein of 279 amino acids that exhibited laccase activity in dimer form. The mature protein was found to contain approximately 4 mol of copper per monomer, and the metal ion-binding sites were predicted. BC_lacL gene transcription levels were analyzed by qRT-PCR to study expression patterns in the presence of different putative inducers (copper ions, guaiacol, veratryl alcohol, vanillin, coniferaldehyde, p-coumaric acid, sinapic acid, and ferulic acid). Copper ions had a positive effect on both transcription levels and intracellular laccase activity. Interestingly, upon induction with sinapic acid, BC_lacL gene transcription was lower than in the presence of copper ions, but laccase activity was highest under these conditions. The BC_lacL protein expressed in Escherichia coli exhibited a specific activity of 7.81 U/mg with 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) as the substrate and 12.3 U/mg with 2,6-dimethoxyphenol (2,6-DMP) as the substrate after purification through Ni-affinity chromatography. The optimal activity and kinetic parameters of the recombinant BC_lacL protein were observed (kcat/Km = 3.96 s-1 µM-1) at a pH of 4.0 at 55 °C for ABTS oxidization and (kcat/Km = 11.6 s-1 µM-1) at a pH of 10.0 at 75 °C for 2,6-DMP oxidization. The protein exhibited high stability in an alkaline environment, with a half-life of more than 12 h. The same results were obtained via decolorization of eight dyes. Hence, this laccase-like enzyme may have potential industrial applications.


Asunto(s)
Burkholderia cepacia/enzimología , Burkholderia cepacia/genética , Escherichia coli/metabolismo , Perfilación de la Expresión Génica , Expresión Génica , Lacasa/biosíntesis , Lacasa/genética , Sitios de Unión , Clonación Molecular , Coenzimas/análisis , Cobre/análisis , Activadores de Enzimas/análisis , Escherichia coli/genética , Cinética , Lacasa/química , Modelos Moleculares , Conformación Proteica , Multimerización de Proteína , Reacción en Cadena en Tiempo Real de la Polimerasa , Temperatura
11.
Arch Environ Contam Toxicol ; 76(1): 87-101, 2019 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-30443666

RESUMEN

PM2.5 samples (particles with aerodynamic diameter < 2.5 µm) were collected along the Guang-Shen expressway around the Qingming Festival, one of the most congested periods in China, which started from April 2-4, in 2016. Twenty-five trace elements and 16 priority polycyclic aromatic hydrocarbons (PAHs) of the samples were analyzed. Their major sources at different periods were identified. The concentrations of PAHs distinctly increased with growing traffic flow 2 days before the Qingming Festival (March 31th and April 1st), decreased gradually on the first 2 days of the 3-day festival (April 2nd and 3rd) and rose again on the last day (April 4th). The proportion changing of higher molecular weight containing 5- and 6-ring PAHs (HMW PAHs) closely related to the traffic flow variation were consistent with the concentration variation of PAHs during the experimental period. Indicators of gasoline/diesel engines emission, i.e., Mo, Co, Mn, and Pb showed similar concentration variation with PAHs. The concentrations of trace elements, mainly derived from wear instead of combustion process, such as Cu, Zn, Ti, and Sb, raised significantly during the rainy days. Incremental lifetime cancer risk (ILCR) values were calculated to evaluate the health risk caused by PAH around the Qingming Festival. The ILCR values increased by 3-10 times 2 days before and on the last day of the festival comparing with other days, as a result of traffic related sources, including engine emission and wearing of tires. It concluded by recommending the necessity of traffic diversion to alleviate the health risk to drivers and nearby residents during important festivals.


Asunto(s)
Contaminantes Atmosféricos/análisis , Monitoreo del Ambiente/métodos , Vacaciones y Feriados , Hidrocarburos Policíclicos Aromáticos/análisis , Oligoelementos/análisis , Emisiones de Vehículos/análisis , China
12.
J Environ Manage ; 241: 235-242, 2019 Jul 01.
Artículo en Inglés | MEDLINE | ID: mdl-31005001

RESUMEN

The influence of combined red and blue light on the capacity of Eucalyptus globulus to phytoremediate a metal-polluted soil was evaluated in this study. Five combinations of blue and red light (0%, 10%, 25%, 50% and 100% blue) at the same intensity were used to treat E. globulus, and its biomass generation, metal uptake and water absorption in phytoremediation under different light treatments were assessed. The plant produced significantly more biomass under blue light, regardless of the ratio, than under single red or white light. The highest biomass was generated under the light ratio of B10R90. In addition, light combination influenced the metal concentrations in different plant tissues. The highest concentrations of Cd and Cu in roots appeared under the light ratio of B0. All metals in plant shoots achieved their highest concentrations under the light ratio of B100, except Pb. Comparing with control, red and blue light combined in varying proportions increased the efficiency remove Cd, Pb and Cu by 50.6-65.6, 71.1-88.7 and 28.9-70.6%, respectively,. The leachate volume under blue and red light combinations was 46.7-66.0% less than control with the combination of B10R90 mitigating the most metal loss. Light sources with different spectra combinations can enhance the phytoremediation efficiency of Eucalyptus globulus and alleviate leaching risk at the same time.


Asunto(s)
Eucalyptus , Metales Pesados , Contaminantes del Suelo , Biodegradación Ambiental , Suelo
13.
Bull Environ Contam Toxicol ; 102(6): 887-891, 2019 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-30976836

RESUMEN

A long term experiment was conducted to verify the phytoremediation effect of large biomass plants and to seek the balance between remediation effect and economy. Eucalyptus globulus were planted with rotation periods of respectively 3, 6 and 9 years to examine the effect on soil remediation. Biomass and concentrations of Cd, Pb and Cu in E. globulus were measured after each harvest. The economic value of the plant was estimated. Results showed E3 (9th year uprooted) had the best soil remediation effect and economic benefit. Therefore, soil remediation and economy were best balanced when E. globulus were not cut.


Asunto(s)
Eucalyptus/metabolismo , Contaminantes del Suelo/metabolismo , Suelo/química , Biodegradación Ambiental , Biomasa , Cadmio/análisis , Cadmio/química , Cadmio/metabolismo , Cobre/análisis , Cobre/química , Cobre/metabolismo , Eucalyptus/crecimiento & desarrollo , Plomo/análisis , Plomo/química , Plomo/metabolismo , Contaminantes del Suelo/análisis , Factores de Tiempo
14.
Bull Environ Contam Toxicol ; 102(3): 413-418, 2019 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-30603769

RESUMEN

Guiyu is known as one of the largest e-waste disposal and recycling sites in China, which suffers greatly from heavy metal pollution. By evaluating the concentrations and distribution of 21 metal elements with Principal Component Analyses (PCA), five principal components were identified, which accounted for 70.4% of the information of the initial data matrix, including one e-waste recycling source, two geological sources, one source of human activities and one ocean aerosol source. Among them, the source of human activities cannot be detailed only by PCA. By using Pb isotope, the unexplained source was judged as battery sludge. Combining 21 metallic and metalloid element datasets with Pb isotope concentrations is more accurate and effective to identify uncertain sources in soil.


Asunto(s)
Residuos Electrónicos , Monitoreo del Ambiente/métodos , Plomo/análisis , Metales Pesados/análisis , Contaminantes del Suelo/análisis , Suelo/química , China , Isótopos/análisis , Análisis de Componente Principal , Reciclaje
15.
Angew Chem Int Ed Engl ; 58(12): 3829-3833, 2019 Mar 18.
Artículo en Inglés | MEDLINE | ID: mdl-30689285

RESUMEN

Photoresponsive molecular systems are essential for molecular optoelectronic devices, but most molecular building blocks are non-photoresponsive. Employed here is a photoinduced proton transfer (PIPT) strategy to control charge transport through single-molecule azulene junctions with visible light under ambient conditions, which leads to a reversible and controllable photoresponsive molecular device based on non-photoresponsive molecules and a photoacid. Also demonstrated is the application of PIPT in two single-molecule AND gate and OR gate devices with electrical signal as outputs.

16.
Angew Chem Int Ed Engl ; 58(52): 18987-18993, 2019 Dec 19.
Artículo en Inglés | MEDLINE | ID: mdl-31617293

RESUMEN

Together with the more intuitive and commonly recognized conductance mechanisms of charge-hopping and tunneling, quantum-interference (QI) phenomena have been identified as important factors affecting charge transport through molecules. Consequently, establishing simple and flexible molecular-design strategies to understand, control, and exploit QI in molecular junctions poses an exciting challenge. Here we demonstrate that destructive quantum interference (DQI) in meta-substituted phenylene ethylene-type oligomers (m-OPE) can be tuned by changing the position and conformation of methoxy (OMe) substituents at the central phenylene ring. These substituents play the role of molecular-scale taps, which can be switched on or off to control the current flow through a molecule. Our experimental results conclusively verify recently postulated magic-ratio and orbital-product rules, and highlight a novel chemical design strategy for tuning and gating DQI features to create single-molecule devices with desirable electronic functions.

17.
Ecotoxicol Environ Saf ; 148: 721-728, 2018 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-29175755

RESUMEN

Arsenic (As) is an inhibitor of phosphatase, however, in the complex soil system, the substrate concentration effect and the mechanism of As inhibition of soil alkaline phosphatase (ALP) and its kinetics has not been adequately studied. In this work, we investigated soil ALP activity in response to As pollution at different substrate concentrations in various types of soils and explored the inhibition mechanism using the enzyme kinetics. The results showed that As inhibition of soil ALP activity was substrate concentration-dependent. Increasing substrate concentration decreased inhibition rate, suggesting reduced toxicity. This dependency was due to the competitive inhibition mechanism of As to soil ALP. The kinetic parameters, maximum reaction velocity (Vmax) and Michaelis constant (Km) in unpolluted soils were 0.012-0.267mMh-1 and 1.34-3.79mM respectively. The competitive inhibition constant (Kic) was 0.17-0.70mM, which was lower than Km, suggesting higher enzyme affinity for As than for substrate. The ecological doses, ED10 and ED50 (concentration of As that results in 10% and 50% inhibition on enzyme parameter) for inhibition of catalytic efficiency (Vmax/Km) were lower than those for inhibition of enzyme activity at different substrate concentrations. This suggests that the integrated kinetic parameter, catalytic efficiency is substrate concentration independent and more sensitive to As than ALP activity. Thus, catalytic efficiency was proposed as a more reliable indicator than ALP activity for risk assessment of As pollution.


Asunto(s)
Fosfatasa Alcalina/antagonistas & inhibidores , Arsénico/análisis , Contaminantes del Suelo/análisis , Suelo/química , Arsénico/toxicidad , Biocatálisis , Relación Dosis-Respuesta a Droga , Cinética , Modelos Teóricos , Organofosfatos/química , Suelo/normas , Contaminantes del Suelo/toxicidad , Especificidad por Sustrato
18.
Ecotoxicol Environ Saf ; 147: 266-274, 2018 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-28850809

RESUMEN

Soil phosphatase, which plays an important role in phosphorus cycling, is strongly inhibited by Arsenic (As). However, the inhibition mechanism in kinetics is not adequately investigated. In this study, we investigated the kinetic characteristics of soil acid phosphatase (ACP) in 14 soils with varied properties, and also explored how kinetic properties of soil ACP changed with different spiked As concentrations. The results showed that the Michaelis constant (Km) and maximum reaction velocity (Vmax) values of soil ACP ranged from 1.18 to 3.77mM and 0.025-0.133mMh-1 in uncontaminated soils. The kinetic parameters of soil ACP in different soils changed differently with As contamination. The Km remained unchanged and Vmax decreased with increase of As concentration in most acid and neutral soils, indicating a noncompetitive inhibition mechanism. However, in alkaline soils, the Km increased linearly and Vmax decreased with increase of As concentration, indicating a mixed inhibition mechanism that include competitive and noncompetitive. The competitive inhibition constant (Kic) and noncompetitive inhibition constant (Kiu) varied among soils and ranged from 0.38 to 3.65mM and 0.84-7.43mM respectively. The inhibitory effect of As on soil ACP was mostly affected by soil organic matter and cation exchange capacity. Those factors influenced the combination of As with enzyme, which resulted in a difference of As toxicity to soil ACP. Catalytic efficiency (Vmax/Km) of soil ACP was a sensitive kinetic parameter to assess the ecological risks of soil As contamination.


Asunto(s)
Fosfatasa Ácida/antagonistas & inhibidores , Arsénico/toxicidad , Monitoreo del Ambiente/métodos , Contaminantes del Suelo/toxicidad , Suelo/química , China , Concentración de Iones de Hidrógeno , Cinética , Modelos Teóricos , Fósforo/análisis , Suelo/normas
19.
Ecotoxicol Environ Saf ; 160: 308-315, 2018 Sep 30.
Artículo en Inglés | MEDLINE | ID: mdl-29857235

RESUMEN

As a toxic metalloid element, arsenic (As) derived from human activities can pose hazardous risks to soil and water. The bioavailability of arsenic is influenced by its behavior, in particular its adsorption-desorption in the soil environment. The maximum adsorption amount (Qmax) calculated from Langmuir equation is an important parameter to estimate the adsorption capacity of adsorbents. However, the soil is a more complicated system compared with specific adsorbents. Thus, in this study, we tried to find a more reasonable parameter (Qmax*) to evaluate the adsorption capacity of soils. Eighteen Chinese soil samples with different pH were used for adsorption-desorption experiments. The maximum As(V) adsorption capacity calculated through Langmuir fitting for 18 samples were ranged from 50.25 (S13) to 312.50 (S4) mg kg-1. Besides, Qmax was highly related with soil pH. Using the difference value of adsorption amount and desorption amount to indicate the amount of non-electrostatic adsorption of As(V) onto soils, calculated the maximum adsorption amount of non-electrostatic adsorption (Qmax*). The average Qmax* of acidic and neutral soils was 162.18 mg kg-1 whereas that for alkaline soils it was only 79.52 mg kg-1. The result from multiple linear regression analysis showed Qmax* was strongly influenced by Feox and clay contents. Furthermore, hysteresis index (HI) in the As(V) desorption varied from 0.83 (S13) to 1.82 (S6). The results further indicated the risk of secondary pollution originating from the desorption process cannot be ignored.


Asunto(s)
Arsénico/química , Contaminantes del Suelo/química , Suelo/química , Adsorción , Silicatos de Aluminio/química , Arcilla , Compuestos Férricos/química , Concentración de Iones de Hidrógeno
20.
Ecotoxicol Environ Saf ; 161: 78-84, 2018 10.
Artículo en Inglés | MEDLINE | ID: mdl-29859411

RESUMEN

The toxicity of heavy metals (HMs) to soil enzymes is directly influenced by the status of the enzyme (free vs. immobilized on minerals) and the duration of exposure. However, little information is available on the interaction effect of HMs, mineral, and exposure time on soil enzyme activities. We investigated the interaction mechanism of alkaline phosphatase (ALP) with minerals (montmorillonite and goethite) and the response of free and immobilized ALP to cadmium (Cd) toxicity under different exposure times. The adsorption isotherms of ALP on both minerals were L-type. The maximum adsorption capacity of goethite for ALP was 3.96 times than montmorillonite, although both had similar adsorption constant (K). Goethite showed a greater inhibitory effect on ALP activity than montmorillonite. The toxicity of Cd to free- and goethite-ALP was enhanced with increasing exposure time, indicating a time-dependent inhibition. However, Cd toxicity to montmorillonite-ALP was not affected by the exposure time. The inhibition of Cd to soil enzyme activity is influenced by the properties of mineral complexes and the duration of exposure. A further understanding of the time pattern of HMs toxicity is helpful for accurately assessing the hazards of HMs to soil enzyme activity.


Asunto(s)
Fosfatasa Alcalina/metabolismo , Bentonita/química , Cadmio/toxicidad , Compuestos de Hierro/química , Minerales/química , Contaminantes del Suelo/toxicidad , Suelo/química , Adsorción , Cadmio/química , Metales Pesados/química , Metales Pesados/toxicidad
SELECCIÓN DE REFERENCIAS
DETALLE DE LA BÚSQUEDA