RESUMO
Nasopharyngeal carcinoma (NPC), a malignant tumor distinctly characterized by ethnic and geographic distribution, is highly prevalent in Southern China and Southeast Asia. However, the molecular mechanisms of NPC have not been fully revealed at the proteomic level. In this study, 30 primary NPC samples and 22 normal nasopharyngeal epithelial tissues were collected for proteomics analysis, and a relatively complete proteomics landscape of NPC was depicted for the first time. By combining differential expression analysis, differential co-expression analysis, and network analysis, potential biomarkers and therapeutic targets were identified. Some identified targets were verified by biological experiments. We found that 17-AAG, a specific inhibitor of the identified target heat shock protein 90 (HSP90), could be a potential therapeutic drug for NPC. Finally, consensus clustering identified two NPC subtypes with specific molecular features. The subtypes and the related molecules were verified by an independent data set and may have different progression-free survival. The results of this study provide a comprehensive understanding of the proteomics molecular signatures of NPC and provide new perspectives and inspiration for prognostic determination and treatment of NPC.
Assuntos
Carcinoma , Neoplasias Nasofaríngeas , Humanos , Carcinoma Nasofaríngeo , Carcinoma/metabolismo , Neoplasias Nasofaríngeas/metabolismo , Proteômica/métodos , Biomarcadores Tumorais/genética , Biomarcadores Tumorais/metabolismoRESUMO
MOTIVATION: Side effects of drugs could cause severe health problems and the failure of drug development. Drug-target interactions are the basis for side effect production and are important for side effect prediction. However, the information on the known targets of drugs is incomplete. Furthermore, there could be also some missing data in the existing side effect profile of drugs. As a result, new methods are needed to deal with the missing features and missing labels in the problem of side effect prediction. RESULTS: We propose a novel computational method based on transductive matrix co-completion and leverage the low-rank structure in the side effects and drug-target data. Positive-unlabelled learning is incorporated into the model to handle the impact of unobserved data. We also introduce graph regularization to integrate the drug chemical information for side effect prediction. We collect the data on side effects, drug targets, drug-associated proteins and drug chemical structures to train our model and test its performance for side effect prediction. The experiment results show that our method outperforms several other state-of-the-art methods under different scenarios. The case study and additional analysis illustrate that the proposed method could not only predict the side effects of drugs but also could infer the missing targets of drugs. AVAILABILITY AND IMPLEMENTATION: The data and the code for the proposed method are available at https://github.com/LiangXujun/GTMCC. SUPPLEMENTARY INFORMATION: Supplementary data are available at Bioinformatics online.
Assuntos
Algoritmos , Efeitos Colaterais e Reações Adversas Relacionados a Medicamentos , Humanos , Desenvolvimento de Medicamentos , Interações Medicamentosas , Proteínas/químicaRESUMO
Microplastics (MPs)-derived dissolved organic matter (MPs-DOM) is becoming a non-negligible source of DOM pools in aquatic systems, but there is limited understanding about the photoreactivity of different MPs-DOM. Herein, MPs-DOM from polystyrene (PS), polyethylene terephthalate (PET), poly(butylene adipate-co-terephthalate) (PBAT), PE, and polypropylene (PP), representing aromatic, biodegradable, and aliphatic plastics, were prepared to examine their photoreactivity. Spectral and high-resolution mass spectrometry analyses revealed that PS/PET/PBAT-DOM contained more unsaturated aromatic components, whereas PE/PP-DOM was richer in saturated aliphatic components. Photodegradation experiments observed that unsaturated aromatic molecules were prone to be degraded compared to saturated aliphatic molecules, leading to a higher degradation of PS/PET/PBAT-DOM than PE/PP-DOM. PS/PET/PBAT-DOM was mainly degraded by hydroxyl (â¢OH) via attacking unsaturated aromatic structures, whereas PE/PP-DOM by singlet oxygen (1O2) through oxidizing aliphatic side chains. The [â¢OH]ss was 1.21-1.60 × 10-4 M in PS/PET/PBAT-DOM and 0.97-1.14 × 10-4 M in PE/PP-DOM, while the [1O2]ss was 0.90-1.35 × 10-12 and 0.33-0.44 × 10-12 M, respectively. This contributes to the stronger photoreactivity of PS/PET/PBAT-DOM with a higher unsaturated aromatic degree than PE/PP-DOM. The photodegradation of MPs-DOM reflected a decreasing tendency from aromatic-unsaturated molecules to aliphatic-saturated molecules. Special attention should be paid to the photoreactivity and environmental impacts associated with MPs-DOM containing highly unsaturated aromatic compounds.
Assuntos
Espectrometria de Massas , Microplásticos , Espécies Reativas de Oxigênio , Microplásticos/química , Espécies Reativas de Oxigênio/química , Poluentes Químicos da Água/química , FotóliseRESUMO
The fate of ubiquitous microplastics (MPs) is largely influenced by dissolved organic matter (DOM) in aquatic environments, which has garnered significant attention. The reactivity of DOM is reported to be greatly regulated by molecular weights (MWs), yet little is known about the effects of different MW DOM on MP aging. Here, the aging behavior of polystyrene MPs (PSMPs) in the presence of different MW fulvic acids (FAs) and humic acids (HAs) was systematically investigated. Under ultraviolet (UV) illumination, O/C of PSMPs aged for 96 h surged from 0.008 to 0.146 in the lower MW FA (FA<1kDa) treatment, suggesting significant PSMP aging. However, FA exhibited a stronger effect on facilitating PSMP photoaging than HA, which can be attributed to the fact that FA<1kDa contains more quinone and phenolic moieties, demonstrating a higher redox capacity. Meanwhile, compared to other fractions, FA<1kDa was more actively involved in the increase of different reactive species yields by 50-290%, including â¢OH, which plays a key role in PSMP photoaging, and contributed to a 25% increase in electron-donating capacity (EDC). This study lays a theoretical foundation for a better understanding of the environmental fate of MPs.
Assuntos
Substâncias Húmicas , Microplásticos , Peso Molecular , Poluentes Químicos da Água/química , Raios Ultravioleta , BenzopiranosRESUMO
Microplastic-derived dissolved organic matter (MP-DOM) is an emerging carbon source in the environment. Interactions between MP-DOM and iron minerals alter the transformation of ferrihydrite (Fh) as well as the distribution and fate of MP-DOM. However, these interactions and their effects on both two components are not fully elucidated. In this study, we selected three types of MP-DOM as model substances and utilized Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and extended X-ray absorption fine structure (EXAFS) spectroscopy to characterize the structural features of DOMs and DOM-mineral complexes at the molecular and atomic levels. Our results suggest that carboxyl and hydroxyl groups in MP-DOM increased the Fe-O bond length by 0.02-0.03 Å through interacting with Fe atoms in the first shell, thereby inhibiting the transformation of Fh to hematite (Hm). The most significant inhibition of Fh transformation was found in PS-DOM, followed by PBAT-DOM and PE-DOM. MP-DOM components, such as phenolic compounds and condensed polycyclic aromatics (MW > 360 Da) with high oxygen content and high unsaturation, exhibited stronger mineral adsorption affinity. These findings provide a profound theoretical basis for accurately predicting the behavior and fate of iron minerals as well as MP-DOM in complex natural environments.
RESUMO
Climate warming causes permafrost thaw predicted to increase toxic methylmercury (MeHg) and greenhouse gas [i.e., methane (CH4), carbon dioxide (CO2), and nitrous oxide (N2O)] formation. A microcosm incubation study with Arctic tundra soil over 145 days demonstrates that N2O at 0.1 and 1 mM markedly inhibited microbial MeHg formation, methanogenesis, and sulfate reduction, while it slightly promoted CO2 production. Microbial community analyses indicate that N2O decreased the relative abundances of methanogenic archaea and microbial clades implicated in sulfate reduction and MeHg formation. Following depletion of N2O, both MeHg formation and sulfate reduction rapidly resumed, whereas CH4 production remained low, suggesting that N2O affected susceptible microbial guilds differently. MeHg formation strongly coincided with sulfate reduction, supporting prior reports linking sulfate-reducing bacteria to MeHg formation in the Arctic soil. This research highlights complex biogeochemical interactions in governing MeHg and CH4 formation and lays the foundation for future mechanistic studies for improved predictive understanding of MeHg and greenhouse gas fluxes from thawing permafrost ecosystems.
Assuntos
Gases de Efeito Estufa , Compostos de Metilmercúrio , Solo , Compostos de Metilmercúrio/análise , Ecossistema , Gases de Efeito Estufa/análise , Óxido Nitroso/análise , Dióxido de Carbono/análise , Tundra , Metano/análise , Sulfatos/análise , Regiões ÁrticasRESUMO
Forkhead transcription factors bind a canonical consensus DNA motif, RYAAAYA (R = A/G, Y = C/T), as a monomer. However, the molecular mechanisms by which forkhead transcription factors bind DNA as a dimer are not well understood. In this study, we show that FOXO1 recognizes a palindromic DNA element DIV2, and mediates transcriptional regulation. The crystal structure of FOXO1/DIV2 reveals that the FOXO1 DNA binding domain (DBD) binds the DIV2 site as a homodimer. The wing1 region of FOXO1 mediates the dimerization, which enhances FOXO1 DNA binding affinity and complex stability. Further biochemical assays show that FOXO3, FOXM1 and FOXI1 also bind the DIV2 site as homodimer, while FOXC2 can only bind this site as a monomer. Our structural, biochemical and bioinformatics analyses not only provide a novel mechanism by which FOXO1 binds DNA as a homodimer, but also shed light on the target selection of forkhead transcription factors.
Assuntos
DNA/metabolismo , Proteína Forkhead Box O1/química , Proteína Forkhead Box O1/metabolismo , DNA/química , Fatores de Transcrição Forkhead/química , Fatores de Transcrição Forkhead/metabolismo , Células HEK293 , Humanos , Sequências Repetidas Invertidas , Modelos Moleculares , Ligação Proteica , Multimerização Proteica , Transcrição GênicaRESUMO
Oil pollution is causing deleterious damage to aquatic ecosystems and human health. The utilization of agricultural waste such as corn stalk (CS) to produce biosorbents has been considered an ecofriendly and efficient approach for removing oil. However, most previous studies focused on the modification of the whole CS, which is inefficient due to the heterogeneity of CS. In this study, corn stalk pith (CP), which has excellent amphipathic characteristics, was selected to prepare a high-efficiency oil sorbent by grafting dodecyl gallate (DG, a long-chain alkyl) onto CP surface lignin via laccase mediation. The modified biomass (DGCP) shows high hydrophobicity (water contact angle = 140.2°) and superoleophilicity (oil contact angle = 0°) and exhibits a high oil sorption capacity (46.43 g/g). In addition, DGCP has good stability and reusability for adsorbing oil from the aqueous phase. Kinetic and isotherm models and two-dimensional correlation spectroscopy integrated with FTIR analyses revealed that the main sorption mechanism involves the H-bond effect, hydrophobic effect and van der Waals force. This work provides an ecofriendly method to prepare oil sorbents and new insights into the mechanisms underlying the removal of spilled oil from wastewater.
Assuntos
Poluição por Petróleo , Poluentes Químicos da Água , Adsorção , Biomassa , Ecossistema , Humanos , Interações Hidrofóbicas e Hidrofílicas , Lacase , Lignina , Águas Residuárias , Água , Zea maysRESUMO
PURPOSE: Pancreatic adenocarcinoma (PAAD) is one of the most common causes of death among solid tumors, and its pathogenesis remains to be clarified. This study aims to elucidate the value of immune/stromal-related genes in the prognosis of PAAD through comprehensive bioinformatics analysis based on the immune microenvironment and validated in Chinese pancreatic cancer patients. METHODS: Gene expression profiles of pancreatic cancer patients were obtained from TCGA database. Differentially expressed genes (DEGs) were identified based on the ESTIMATE algorithm. Gene co-expression networks were constructed using WGCNA. In the key module, survival analysis was used to reveal the prognostic value. Subsequently, we performed functional enrichment analysis to construct a protein-protein interaction (PPI) network. The relationship between tumor immune infiltration and hub genes was analyzed by TIMER and CIBERSORT. Finally, it was validated in the GEO database and in tissues of Chinese pancreatic cancer patients. RESULTS: In the TCGA pancreatic cancer cohort, a low immune/stromal score was associated with a good prognosis. After bioinformatic analysis, 57 genes were identified to be significantly associated with pancreatic cancer prognosis. Among them, up-regulation of four genes (COL6A3, PLAU, MMP11 and MMP14) indicated poor prognosis and was associated with multiple immune cell infiltration. IHC results showed that PLAU protein levels from Chinese pancreatic cancer tissues were significantly higher than those from adjacent non-tumor tissues and were also associated with tumor TNM stage and lymph node metastasis. CONCLUSION: In conclusion, this study demonstrates that PLAU may serve as a new diagnostic and therapeutic target, which is highly expressed in Chinese pancreatic cancer tissues and associated with lymph node metastasis.
Assuntos
Adenocarcinoma , Neoplasias Pancreáticas , Adenocarcinoma/patologia , Biomarcadores Tumorais/genética , Biologia Computacional/métodos , Perfilação da Expressão Gênica/métodos , Regulação Neoplásica da Expressão Gênica , Humanos , Metástase Linfática , Neoplasias Pancreáticas/genética , Neoplasias Pancreáticas/patologia , Prognóstico , Microambiente Tumoral/genética , Neoplasias PancreáticasRESUMO
As a major entry point of mercury (Hg) to aquatic food webs, algae play an important role in taking up and transforming Hg species in aquatic ecosystems. However, little is known how and to what extent Hg reduction, uptake, and species transformations are mediated by algal cells and their exudates, algal organic matter (AOM), under either sunlit or dark conditions. Here, using Chlorella vulgaris (CV) as one of the most prevalent freshwater model algal species, we show that solar irradiation could enhance the reduction of mercuric Hg(II) to elemental Hg(0) by both CV cells and AOM. AOM reduced more Hg(II) than algal cells themselves due to cell surface adsorption and uptake of Hg(II) inside the cells under solar irradiation. Synchrotron radiation X-ray absorption near-edge spectroscopy (SR-XANES) analyses indicate that sunlight facilitated the transformation of Hg to less bioavailable species, such as ß-HgS and Hg-phytochelatins, compared to Hg(Cysteine)2-like species formed in algal cells in the dark. These findings highlight important functional roles and potential mechanisms of algae in Hg reduction and immobilization under varying lighting conditions and how these processes may modulate Hg cycling and bioavailability in the aquatic environment.
Assuntos
Chlorella vulgaris , Mercúrio , Compostos de Metilmercúrio , Transporte Biológico , Chlorella vulgaris/metabolismo , Ecossistema , Água Doce , Mercúrio/química , Compostos de Metilmercúrio/metabolismoRESUMO
Drug side effects are closely related to the success and failure of drug development. Here we present a novel machine learning method for side effect prediction. The proposed method treats side effect prediction as a multi-label learning problem and uses sparse structure learning to model the relationships between side effects. Additionally, the proposed method adopts the adaptive graph regularization strategy to explore the local structure in drug data and fuse multiple types of drug features. An alternating optimization algorithm is proposed to solve the optimization problem. We collected chemical structures and biological pathway features of drugs as the inputs of our method to predict drug side effects. The results of the cross-validation experiment showed that our method could significantly improve the prediction performance compared to the other state-of-the-art methods. Besides, our model is highly interpretable. It could learn the drug neighbourhood relationships, side effect relationships, and drug features related to side effects. We systematically validated the information extracted by the model with independent data. Some prediction results could also be supported by literature reports. The proposed method could be applied to integrate both chemical and biological data to predict side effects and helps improve drug safety.
Assuntos
Efeitos Colaterais e Reações Adversas Relacionados a Medicamentos , Aprendizado de Máquina , Algoritmos , Desenvolvimento de Medicamentos , Humanos , Projetos de PesquisaRESUMO
BACKGROUND: Colon adenocarcinoma (COAD) is one of the most common malignant tumors and is diagnosed at an advanced stage with a poor prognosis worldwide. Pyroptosis is involved in the initiation and progression of tumors. This research focused on constructing a pyroptosis-related ceRNA network to generate a reliable risk model for risk prediction and immune infiltration analysis of COAD. METHODS: Transcriptome data, miRNA-sequencing data, and clinical information were downloaded from the TCGA database. First, differentially expressed mRNAs (DEmRNAs), miRNAs (DEmiRNAs), and lncRNAs (DElncRNAs) were identified to construct a pyroptosis-related ceRNA network. Second, a pyroptosis-related lncRNA risk model was developed applying univariate Cox regression analysis and least absolute shrinkage and selection operator method (LASSO) regression analysis. Kyoto Encyclopedia of Genes and Genomes (KEGG) and Gene Ontology (GO) enrichment analyses were utilized to functionally annotate RNAs contained in the ceRNA network. In addition, Kaplan-Meier analysis, receiver operating characteristic (ROC) curves, univariate and multivariate Cox regression, and nomogram were applied to validate this risk model. Finally, the relationship of this risk model with immune cells and immune checkpoint blockade (ICB)-related genes was analyzed. RESULTS: A total of 5373 DEmRNAs, 1159 DElncRNAs, and 355 DEmiRNAs were identified. A pyroptosis-related ceRNA regulatory network containing 132 lncRNAs, 7 miRNAs, and 5 mRNAs was constructed, and a ceRNA-based pyroptosis-related risk model including 11 lncRNAs was built. The tumor tissues were classified into high- and low-risk groups according to the median risk score. Kaplan-Meier analysis showed that the high-risk group had a shorter survival time; ROC analysis, independent prognostic analysis, and nomogram further indicated the risk model was a significant independent prognostic factor what had an excellent ability to predict patients' risk. Moreover, immune infiltration analysis indicated that the risk model was related to immune infiltration cells (i.e., B cell naïve, T cell follicular helper, macrophage M1) and ICB-related genes (i.e., PD-1, CTLA4, HAVCR2). CONCLUSIONS: This pyroptosis-related lncRNA risk model possessed good prognostic value, and the ability to predict the outcome of ICB immunotherapy in COAD.
Assuntos
Neoplasias do Colo , MicroRNAs , Doença Pulmonar Obstrutiva Crônica , RNA Longo não Codificante , Biomarcadores Tumorais/genética , Neoplasias do Colo/genética , Regulação Neoplásica da Expressão Gênica , Redes Reguladoras de Genes , Humanos , Imunidade , MicroRNAs/genética , Prognóstico , Doença Pulmonar Obstrutiva Crônica/genética , Piroptose , RNA Longo não Codificante/genética , RNA Mensageiro/genéticaRESUMO
BACKGROUND: Gelsolin-like capping actin protein (CapG) modulates actin dynamics and actin-based motility with a debatable role in tumorigenic progression. The motility-associated functions and potential molecular mechanisms of CapG in nasopharyngeal carcinoma (NPC) remain unclear. METHODS: CapG expression was detected by immunohistochemistry in a cohort of NPC tissue specimens and by Western blotting assay in a variety of NPC cell lines. Loss of function and gain of function of CapG in scratch wound-healing and transwell assays were performed. Inactivation of Rac1 and ROCK with the specific small molecular inhibitors was applied to evaluate CapG's role in NPC cell motility. GTP-bound Rac1 and phosphorylated-myosin light chain 2 (p-MLC2) were measured in the ectopic CapG overexpressing cells. Finally, CapG-related gene set enrichment analysis was conducted to figure out the significant CapG-associated pathways in NPC. RESULTS: CapG disclosed increased level in the poorly differentiated NPC tissues and highly metastatic cells. Knockdown of CapG reduced NPC cell migration and invasion in vitro, while ectopic CapG overexpression showed the opposite effect. Ectopic overexpression of CapG compensated for the cell motility loss caused by simultaneous inactivation of ROCK and Rac1 or inactivation of ROCK alone. GTP-bound Rac1 weakened, and p-MLC2 increased in the CapG overexpressing cells. Bioinformatics analysis validated a positive correlation of CapG with Rho motility signaling, while Rac1 motility pathway showed no significant relationship. CONCLUSIONS: The present findings highlight the contribution of CapG to NPC cell motility independent of ROCK and Rac1. CapG promotes NPC cell motility at least partly through MLC2 phosphorylation and contradicts with Rac1 activation.
Assuntos
Actinas , Neoplasias Nasofaríngeas , Humanos , Actinas/metabolismo , Carcinoma Nasofaríngeo/genética , Gelsolina/análise , Gelsolina/genética , Gelsolina/metabolismo , Linhagem Celular Tumoral , Movimento Celular/genética , Neoplasias Nasofaríngeas/genética , Guanosina Trifosfato , Regulação Neoplásica da Expressão Gênica , Proteínas dos Microfilamentos/metabolismo , Proteínas Nucleares/genéticaRESUMO
The FOXC family of transcription factors (FOXC1 and FOXC2) plays essential roles in the regulation of embryonic, ocular, and cardiac development. Mutations and abnormal expression of FOXC proteins are implicated in genetic diseases as well as cancer. In this study, we determined two crystal structures of the DNA-binding domain (DBD) of human FOXC2 protein, in complex with different DNA sites. The FOXC2-DBD adopts the winged-helix fold with helix H3 contributing to all the base specific contacts, while the N-terminus, wing 1, and the C-terminus of FOXC2-DBD all make additional contacts with the phosphate groups of DNA. Our structural, biochemical, and bioinformatics analyses allow us to revise the previously proposed DNA recognition mechanism and provide a model of DNA binding for the FOXC proteins. In addition, our structural analysis and accompanying biochemical assays provide a molecular basis for understanding disease-causing mutations in FOXC1 and FOXC2.
Assuntos
Proteínas de Ligação a DNA/química , DNA/química , Fatores de Transcrição Forkhead/química , DNA/genética , Proteínas de Ligação a DNA/genética , Fatores de Transcrição Forkhead/genética , Regulação da Expressão Gênica/genética , Humanos , Mutação , Conformação de Ácido Nucleico , Domínios Proteicos/genéticaRESUMO
Proteins of nuclear receptor subfamily 4 group A (NR4A), including NR4A1/NGFI-B, NR4A2/Nurr1, and NR4A3/NOR-1, are nuclear transcription factors that play important roles in metabolism, apoptosis, and proliferation. NR4A proteins recognize DNA response elements as monomers or dimers to regulate the transcription of a variety of genes involved in multiple biological processes. In this study, we determined two crystal structures of the NR4A2 DNA-binding domain (NR4A2-DBD) bound to two Nur-responsive elements: an inverted repeat and an everted repeat at 2.6-2.8 Å resolution. The structures revealed that two NR4A2-DBD molecules bind independently to the everted repeat, whereas two other NR4A2-DBD molecules form a novel dimer interface on the inverted repeat. Moreover, substitution of the interfacial residue valine 298 to lysine as well as mutation of DNA bases involved in the interactions abolished the dimerization. Overall, our structural, biochemical, and bioinformatics analyses provide a molecular basis for the binding of the NR4A2 protein dimers to NurREs and advance our understanding of the dimerization specificity of nuclear receptors.
Assuntos
DNA/química , Membro 2 do Grupo A da Subfamília 4 de Receptores Nucleares/química , Receptores X de Retinoides/química , Motivos de Aminoácidos , Apoptose , Núcleo Celular/química , Proliferação de Células , Dimerização , Escherichia coli , Humanos , Lisina/química , Mutação , Ligação Proteica , Mapeamento de Interação de Proteínas , Transcrição Gênica , Valina/químicaRESUMO
Microbial production of the neurotoxin methylmercury (MeHg) is a significant health and environmental concern, as it can bioaccumulate and biomagnify in the food web. A chalkophore or a copper-binding compound, termed methanobactin (MB), has been shown to form strong complexes with mercury [as Hg(II)] and also enables some methanotrophs to degrade MeHg. It is unknown, however, if Hg(II) binding with MB can also impede Hg(II) methylation by other microbes. Contrary to expectations, MB produced by the methanotroph Methylosinus trichosporium OB3b (OB3b-MB) enhanced the rate and efficiency of Hg(II) methylation more than that observed with thiol compounds (such as cysteine) by the mercury-methylating bacteria Desulfovibrio desulfuricans ND132 and Geobacter sulfurreducens PCA. Compared to no-MB controls, OB3b-MB decreased the rates of Hg(II) sorption and internalization, but increased methylation by 5- to 7-fold, suggesting that Hg(II) complexation with OB3b-MB facilitated exchange and internal transfer of Hg(II) to the HgcAB proteins required for methylation. Conversely, addition of excess amounts of OB3b-MB or a different form of MB from Methylocystis strain SB2 (SB2-MB) inhibited Hg(II) methylation, likely due to greater binding of Hg(II). Collectively, our results underscore the complex roles of microbial exogenous metal-scavenging compounds in controlling net production and bioaccumulation of MeHg in the environment.IMPORTANCE Some anaerobic microorganisms convert inorganic mercury (Hg) into the neurotoxin methylmercury, which can bioaccumulate and biomagnify in the food web. While the genetic basis of microbial mercury methylation is known, factors that control net methylmercury production in the environment are still poorly understood. Here, it is shown that mercury methylation can be substantially enhanced by one form of an exogenous copper-binding compound (methanobactin) produced by some methanotrophs, but not by another. This novel finding illustrates that complex interactions exist between microbes and that these interactions can potentially affect the net production of methylmercury in situ.
Assuntos
Desulfovibrio desulfuricans/metabolismo , Poluentes Ambientais/metabolismo , Geobacter/metabolismo , Imidazóis/metabolismo , Mercúrio/metabolismo , Methylosinus trichosporium/metabolismo , Oligopeptídeos/metabolismo , MetilaçãoRESUMO
Mercury (Hg) isotope exchange is a common process in biogeochemical transformations of Hg in the environment, but it is unclear whether and at what rates dissolved elemental Hg(0)aq may exchange with divalent Hg(II) bound to various organic and inorganic ligands in water. Using enriched stable isotopes, we investigated the rates and dynamics of isotope exchange between 202Hg(0)aq and 201Hg(II) bound to organic and inorganic ligands with varying chemical structures and binding affinities. Time-dependent exchange reactions were followed by isotope compositional changes using both inductively coupled plasma mass spectrometry and Zeeman cold vapor atomic absorption spectrometry. Rapid, spontaneous isotope exchange (<1 h) was observed between 202Hg(0)aq and 201Hg(II) bound to chloride (Cl-), ethylenediaminetetraacetate (EDTA), and thiols, such as cysteine (CYS), glutathione (GSH), and 2,3-dimercaptopropanesulfonic acid (DMPS) at a thiol ligand-to-Hg(II) molar ratio of 1:1. Without external reductants or oxidants, the exchange resulted in transfer of two electrons and redistribution of Hg isotopes bound to the ligand but no net changes of chemical species in the system. However, an increase in the ligand-to-Hg(II) ratio decreased the exchange rates due to the formation of 2:1 or higher thiol:Hg(II) chelated complexes, but had no effects on exchange rates with 201Hg(II) bound to EDTA or Cl-. The exchange between 202Hg(0)aq and 201Hg(II) bound to dissolved organic matter (DOM) showed an initially rapid followed by a slower exchange rate, likely resulting from Hg(II) complexation with both low- and high-affinity binding functional groups on DOM (e.g., carboxylates vs bidentate thiolates). These results demonstrate that Hg(0)aq readily exchanges with Hg(II) bound to various ligands and highlight the importance of considering exchange reactions in experimental enriched Hg isotope tracer studies or in natural abundance Hg isotope studies in environmental matrices.
Assuntos
Mercúrio , Isótopos , Ligantes , Isótopos de Mercúrio , Compostos de SulfidrilaRESUMO
Plants can play important roles in overcoming selenium (Se) deficiency and Se toxicity in various regions of the world. Selenite (SeIV), selenate (SeVI), as well as Se nanoparticles (SeNPs) naturally formed through reduction of SeIV, are the three main Se species in the environment. The bioaccumulation and transformation of these Se species in plants still need more understanding. The aims of this study are to investigate the phytotoxicity, accumulation, and transformation of SeIV, SeVI and SeNPs in garlic, a relatively Se accumulative plant. The spatial distribution of Se in the roots were imaged using synchrotron radiation micro-focused X-ray fluorescence (SR-µXRF). The chemical forms of Se in different plant tissues were analyzed using synchrotron radiation X-ray absorption spectroscopy (SR-XAS). The results demonstrate that 1) SeNPs which has the lowest phytotoxicity is stable in water, but prone to be converted to organic Se species, such as C-Se-C (MeSeCys) upon uptake by root. 2) SeIV is prone to concentrate in the root and incorporated into C-Se-C (MeSeCys) and C-Se-R (SeCys) bonding forms; 3) SeVI with the lowest transformation probability to organic Se species has the highest phytotoxicity to plant, and is much easier to translocate from root to leaf than SeNPs and SeIV. The present work provides insights into potential impact of SeNPs, selenite and selenate on aquatic-plant ecosystems, and is beneficial for systematically understanding the Se accumulation and transformation in food chain.
Assuntos
Alho/metabolismo , Nanopartículas/metabolismo , Ácido Selênico/farmacocinética , Ácido Selenioso/farmacocinética , Selênio/farmacocinética , Selenito de Sódio/farmacocinética , Bioacumulação , Transporte Biológico , Biotransformação , Alho/efeitos dos fármacos , Hidroponia , Nanopartículas/toxicidade , Folhas de Planta/metabolismo , Raízes de Plantas/metabolismo , Ácido Selênico/toxicidade , Ácido Selenioso/toxicidade , Selênio/toxicidade , Selenito de Sódio/toxicidade , Espectroscopia por Absorção de Raios XRESUMO
The kinetics of mercuric ion (Hg2+) binding with heterogeneous naturally dissolved organic matter (DOM) has been hypothesized to result from competitive interactions among different organic ligands and functional groups of DOM for Hg2+. However, an experimental protocol is lacking to determine Hg2+ binding with various competitive ligands and DOM, their binding strengths, and their dynamic exchange reactions. In this study, a stepwise reduction approach using ascorbic acid (AA) and stannous tin [Sn(II)] was devised to differentiate Hg(II) species in the presence of two major functional groups in DOM: the carboxylate-bound Hg(II) is reducible by both AA and Sn(II), whereas the thiolate-bound Hg(II) is reducible only by Sn(II). Using this operational approach, the relative binding strength of Hg2+ with selected organic ligands was found in the order dimercaptopropanesulfonate (DMPS) > glutathione (GSH) > penicillamine (PEN) > cysteine (CYS) > ethylenediaminetetraacetate > citrate, acetate, and glycine at the ligand-to-Hg molar ratio < 2. Dynamic, competitive ligand exchanges for Hg2+ from weak carboxylate to strong thiolate functional groups were observed among these ligands and within DOM, and the reaction depended on the relative binding strength and abundance of thiols and carboxylates, as well as reaction time. These results provide additional insights into dynamic exchange reactions of Hg2+ within multicompositional DOM in controlling the transformation and bioavailability of Hg(II) in natural aquatic environments.
Assuntos
Mercúrio , Poluentes Químicos da Água , Ligação Competitiva , Cinética , LigantesRESUMO
The antagonistic effect between mercury (Hg) and selenium (Se) is conclusively established in animals and human beings in the past decades. However, the underlying mechanisms of the interactions between Hg and Se in plants, as well as the metabolism of Hg-Se compounds in crops are still far from being understood. The botanic metallomics of Hg and Se mainly focuses on the translocation, transformation, and metabolism of Hg and Se in the environmental and botanic systems employing metallomics methods. An adequate understanding of the biological behavior of Hg and Se in plant is beneficial for sequestration of Hg and Se in soil-plant systems with high Hg and Se contamination. It can also provide a molecular mechanistic basis for Se supplementation in Se-deficient areas. Here, the key developments in current understanding of Hg and Se interactions in plants are reviewed. The metabolism and antagonism of Hg and Se in various plants, as well as the advanced analytical methods commonly used in this field, are summarized and discussed. As suggested, plant Hg and Se uptake, metabolism, and antagonism can be taken into account for detoxification and remediation strategies for the reduction of Hg and Se in the food chain.