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1.
NMR Biomed ; 37(3): e5063, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-37871617

RESUMO

Recently, intravoxel incoherent motion (IVIM) diffusion-weighted imaging (DWI) has also been demonstrated as an imaging tool for applications in neurological and neurovascular diseases. However, the use of single-shot diffusion-weighted echo-planar imaging for IVIM DWI acquisition leads to suboptimal data quality: for instance, geometric distortion and deteriorated image quality at high spatial resolution. Although the recently commercialized multi-shot acquisition methods, such as multiplexed sensitivity encoding (MUSE), can attain high-resolution and high-quality DWI with signal-to-noise ratio (SNR) performance superior to that of the conventional parallel imaging method, the prolonged scan time associated with multi-shot acquisition is impractical for routine IVIM DWI. This study proposes an acquisition and reconstruction framework based on parametric-POCSMUSE to accelerate the four-shot IVIM DWI with 70% reduction of total scan time (13 min 8 s versus 4 min 8 s). First, the four-shot IVIM DWI scan with 17 b values was accelerated by acquiring only one segment per b value except for b values of 0 and 600 s/mm2 . Second, an IVIM-estimation scheme was integrated into the parametric-POCSMUSE to enable joint reconstruction of multi-b images from under-sampled four-shot IVIM DWI data. In vivo experiments on both healthy subjects and patients show that the proposed framework successfully produced multi-b DW images with significantly higher SNRs and lower reconstruction errors than did the conventional acceleration method based on parallel imaging. In addition, the IVIM quantitative maps estimated from the data produced by the proposed framework showed quality comparable to that of fully sampled MUSE-reconstructed images, suggesting that the proposed framework can enable highly accelerated multi-shot IVIM DWI without sacrificing data quality. In summary, the proposed framework can make multi-shot IVIM DWI feasible in a routine MRI examination, with reasonable scan time and improved geometric fidelity.


Assuntos
Alprostadil , Encéfalo , Humanos , Encéfalo/diagnóstico por imagem , Imagem de Difusão por Ressonância Magnética/métodos , Cabeça , Imageamento por Ressonância Magnética , Imagem Ecoplanar/métodos , Movimento (Física)
2.
Environ Sci Technol ; 2024 Sep 12.
Artigo em Inglês | MEDLINE | ID: mdl-39262330

RESUMO

Sulfidation of nanoscale zerovalent iron (nZVI) can enhance particle performance. However, the underlying mechanisms of nZVI sulfidation are poorly known. We studied the effects of Fe2+ on 24-h dynamics of nZVI sulfidation by HS- using a dosed S to Fe molar ratio of 0.2. This shows that in the absence of Fe2+, HS- rapidly adsorbed onto nZVI particles and reacted with surface iron oxide to form mackinawite and greigite (<0.5 h). As nZVI corrosion progressed, amorphous FeSx in solution deposited on nZVI, forming S-nZVI (0.5-24 h). However, in the initial presence of Fe2+, the rapid reaction between HS- and Fe2+ produced amorphous FeSx, which deposited on the nZVI and corroded the surface iron oxide layer (<0.25 h). This was followed by redeposition of colloidal iron (hydr)oxide on the particle surface (0.25-8 h) and deposition of residual FeSx (8-24 h) on S-nZVI. S loading on S-nZVI was 1 order of magnitude higher when Fe2+ was present. Surface characterization of the sulfidated particles by TEM-SAED, XPS, and XAFS verified the solution dynamics and demonstrated that S2- and S22-/Sn2- were the principal reduced S species on S-nZVI. This study provides a methodology to tune sulfur loading and S speciation on S-nZVI to suit remediation needs.

3.
Sensors (Basel) ; 24(16)2024 Aug 22.
Artigo em Inglês | MEDLINE | ID: mdl-39205136

RESUMO

Saccharides, being one of the fundamental molecules of life, play essential roles in the physiological and pathological functions of cells. However, their intricate structures pose challenges for detection. Nanopore technology, with its high sensitivity and capability for single-molecule-level analysis, has revolutionized the identification and structural analysis of saccharide molecules. This review focuses on recent advancements in nanopore technology for carbohydrate detection, presenting an array of methods that leverage the molecular complexity of saccharides. Biological nanopore techniques utilize specific protein binding or pore modifications to trigger typical resistive pulses, enabling the high-sensitivity detection of monosaccharides and oligosaccharides. In solid-state nanopore sensing, boronic acid modification and pH gating mechanisms are employed for the specific recognition and quantitative analysis of polysaccharides. The integration of artificial intelligence algorithms can further enhance the accuracy and reliability of analyses. Serving as a crucial tool in carbohydrate detection, we foresee significant potential in the application of nanopore technology for the detection of carbohydrate molecules in disease diagnosis, drug screening, and biosensing, fostering innovative progress in related research domains.


Assuntos
Técnicas Biossensoriais , Nanoporos , Técnicas Biossensoriais/métodos , Carboidratos/química , Carboidratos/análise , Humanos , Monossacarídeos/química , Monossacarídeos/análise
4.
Sensors (Basel) ; 24(7)2024 Mar 26.
Artigo em Inglês | MEDLINE | ID: mdl-38610321

RESUMO

The sensitivity and accuracy of nanopore sensors are severely hindered by the high noise associated with solid-state nanopores. To mitigate this issue, the deposition of organic polymer materials onto silicon nitride (SiNx) membranes has been effective in obtaining low-noise measurements. Nonetheless, the fabrication of nanopores sub-10 nm on thin polymer membranes remains a significant challenge. This work proposes a method for fabricating nanopores on polymethyl methacrylate (PMMA) membrane by the local high electrical field controlled breakdown, exploring the impact of voltage and current on the breakdown of PMMA membranes and discussing the mechanism underlying the breakdown voltage and current during the formation of nanopores. By improving the electric field application method, transient high electric fields that are one-seven times higher than the breakdown electric field can be utilized to fabricate nanopores. A comparative analysis was performed on the current noise levels of nanopores in PMMA-SiNx composite membranes and SiNx nanopores with a 5 nm diameter. The results demonstrated that the fast fabrication of nanopores on PMMA-SiNx membranes exhibited reduced current noise compared to SiNx nanopores. This finding provides evidence supporting the feasibility of utilizing this technology for efficiently fabricating low-noise nanopores on polymer composite membranes.

5.
Environ Sci Technol ; 57(49): 20951-20961, 2023 Dec 12.
Artigo em Inglês | MEDLINE | ID: mdl-38009568

RESUMO

Biogenic sulfidation of zero-valent iron (ZVI) using sulfate reducing bacteria (SRB) has shown enhanced dechlorination rates comparable to those produced by chemical sulfidation. However, controlling and sustaining biogenic sulfidation to enhance in situ dechlorination are poorly understood. Detailed interactions between SRB and ZVI were examined for 4 months in column experiments under enhanced biogenic sulfidation conditions. SRB proliferation and changes in ZVI surface properties were characterized along the flow paths. The results show that ZVI can stimulate SRB activity by removing excessive free sulfide (S2-), in addition to lowering reduction potential. ZVI also hinders downgradient movement of SRB via electrostatic repulsion, restricting SRB presence near the upgradient interface. Dissolved organic carbon (e.g., >2.2 mM) was essential for intense biogenic sulfidation in ZVI columns. The presence of SRB in the upgradient zone appeared to promote the formation of iron polysulfides. Biogenic FeSx deposition increased the S content on ZVI surfaces ∼3-fold, corresponding to 3-fold and 2-fold improvements in the trichloroethylene degradation rate and electron efficiency in batch tests. Elucidation of SRB and ZVI interactions enhances sustained sulfidation in ZVI permeable reactive barrier.


Assuntos
Ferro , Poluentes Químicos da Água , Ferro/química , Poluentes Químicos da Água/química , Elétrons
6.
Sens Actuators B Chem ; 377: 133075, 2023 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-36467330

RESUMO

Since the outbreak of COVID-19 in the world, it has spread rapidly all over the world. Rapid and effective detection methods have been a focus of research. The SARS-CoV-2 N protein (NP) detection methods currently in use focus on specific recognition of antibodies, but the reagents are expensive and difficult to be produced. Here, aptamer-functionalized nanopipettes utilize the unique ion current rectification (ICR) of nanopipette to achieve rapid and highly sensitive detection of trace NP, and can significantly reduce the cost of NP detection. In the presence of NP, the surface charge at the tip of the nanopipette changes, which affects ion transport and changes the degree of rectification. Quantitative detection of NP is achieved through quantitative analysis. Relying on the high sensitivity of nanopipettes to charge fluctuations, this sensor platform achieves excellent sensing performance. The sensor platform exhibited a dynamic working range from 102-106 pg/mL with a detection limit of 73.204 pg/mL, which showed great potential as a tool for rapidly detecting SARS-CoV-2. As parallel and serial testing are widely used in the clinic to avoid missed diagnosis or misdiagnosis, we hope this platform can play a role in controlling the spread and prevention of COVID-19.

7.
Nano Lett ; 22(5): 2147-2154, 2022 03 09.
Artigo em Inglês | MEDLINE | ID: mdl-35041434

RESUMO

To be considered as a promising candidate for mimicking biological nanochannels, carbon nanotubes (CNTs) have been used to explore the mass transport phenomena in recent years. In this study, the single nucleotide transport phenomena are comparatively studied using individual CNTs with a length of ∼15 µm and diameters ranging from 1.5 to 2.5 nm. In the case of CNTs with a diameter of 1.57-1.98 nm, the current traces of nucleotide transport are independent with the metallicity of CNTs and consist of single peak current pulses, whereas extraordinary stepwise current signals are observed in CNT with a diameter of 2.33 nm. It suggests that there is only one molecule in the nanochannel at a time until the diameter of CNT increases to 2.33 nm. Furthermore, it also demonstrates that the single nucleotides can be identified statistically according to their current pulses, indicating the potential application of CNT-based sensors for nucleotides identification.


Assuntos
Nanotubos de Carbono , Nucleotídeos
8.
J Magn Reson Imaging ; 55(1): 126-137, 2022 01.
Artigo em Inglês | MEDLINE | ID: mdl-34169600

RESUMO

BACKGROUND: Single-shot diffusion-weighted imaging (ssDWI) has been shown useful for detecting active bowel inflammation in Crohn's disease (CD) without MRI contrast. However, ssDWI suffers from geometric distortion and low spatial resolution. PURPOSE: To compare conventional ssDWI with higher-resolution ssDWI (HR-ssDWI) and multi-shot DWI based on multiplexed sensitivity encoding (MUSE-DWI) for evaluating bowel inflammation in CD, using contrast-enhanced MR imaging (CE-MRI) as the reference standard. STUDY TYPE: Prospective. SUBJECTS: Eighty nine patients with histological diagnosis of CD from previous endoscopy (55 male/34 female, age: 17-69 years). FIELD STRENGTH/SEQUENCES: ssDWI (2.7 mm × 2.7 mm), HR-ssDWI (1.8 mm × 1.8 mm), MUSE-DWI (1.8 mm × 1.8 mm) based on echo-planar imaging, T2-weighted imaging, and CE-MRI sequences, all at 1.5 T. ASSESSMENT: Five raters independently evaluated the tissue texture conspicuity, geometry accuracy, minimization of artifacts, diagnostic confidence, and overall image quality using 5-point Likert scales. The diagnostic performance (sensitivity, specificity and accuracy) of each DWI sequences was assessed on per-bowel-segment basis. STATISTICAL TESTS: Inter-rater agreement for qualitative evaluation of each parameter was measured by the intra-class correlation coefficient (ICC). Paired Wilcoxon signed-rank tests were performed to evaluate the statistical significance of differences in qualitative scoring between DWI sequences. A P value <0.05 was considered to be statistically significant. RESULTS: Tissue texture conspicuity, geometric distortions, and overall image quality were significantly better for MUSE-DWI than for ssDWI and HR-ssDWI with good agreement among five raters (ICC: 0.70-0.89). HR-ssDWI showed significantly poorer performance to ssDWI and MUSE-DWI for all qualitative scores and had the worst diagnostic performance (sensitivity of 57.0% and accuracy of 87.3%, with 36 undiagnosable cases due to severe artifacts). MUSE-DWI showed significantly higher sensitivity (97.5% vs. 86.1%) and accuracy (98.9% vs. 95.1%) than ssDWI for detecting bowel inflammation. DATA CONCLUSION: MUSE-DWI was advantageous in assessing bowel inflammation in CD, resulting in improved spatial resolution and image quality. LEVEL OF EVIDENCE: 2 TECHNICAL EFFICACY STAGE: 2.


Assuntos
Doença de Crohn , Adolescente , Adulto , Idoso , Doença de Crohn/diagnóstico por imagem , Imagem de Difusão por Ressonância Magnética , Feminino , Humanos , Inflamação/diagnóstico por imagem , Imageamento por Ressonância Magnética , Masculino , Pessoa de Meia-Idade , Estudos Prospectivos , Adulto Jovem
9.
Analyst ; 146(2): 655-663, 2021 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-33206065

RESUMO

The formation of G-quadruplexes (G4) in human telomere and other important biological regions inhibits the replication and transcription of DNA, thereby influencing further cell proliferation. The investigation of G4 formation and unfolding is vital for understanding their modulation in biological processes and life science. Photo regulation is a facile and sensitive approach for monitoring the structures of biomacromolecules and material surface properties. The nanopore-based technique is also prevalent for label-free single-molecule characterization with high accuracy. This study provides a combination of solid-state nanopore technology with light-switch as a platform for the modulation of human telomere G4 formation and splitting under switchable light exposure. The introduction of molecular switch, namely azobenzene moiety at different positions of the DNA sequence influences the formation and stability of G4. Three azobenzenes immobilized on each of the G-quartet plane (hTelo-3azo-p) or four azobenzenes on the same plane (hTelo-4azo-4p) of the human telomere G4 sequence realized the reversible control of G4 folding/unfolding at the temporal scale upon photo regulation, and the formation and splitting of G4 with hTelo-4azo-4p is slower and not thorough compared to that with hTelo-3azo-p due to the coplanar steric hindrance. Moreover, the G4 formation recorded with the combined nanopore and photo-responsive approach was also characterized with fluorescence, and the variation in the fluorescence intensity of the NMM and G4 complex exhibited a different tendency under reverse light irradiation due to the distinct interactions of NMM with the azobenzene-modified G4. Our study demonstrated a controllable and sensitive way for the manipulation of G4 structures, which will be inspiring for the intervention of G4-related cell senescence, cancer diagnosis and drug exploration.


Assuntos
Quadruplex G , Nanoporos , Nanotecnologia/métodos , Telômero/química , Compostos Azo/química
10.
Environ Sci Technol ; 55(23): 16088-16098, 2021 12 07.
Artigo em Inglês | MEDLINE | ID: mdl-34787396

RESUMO

Sulfidated zero-valent iron (S-ZVI) enhances the degradation of chlorinated hydrocarbon (CHC) in contaminated groundwater. Despite numerous studies of S-ZVI, a versatile strategy to improve its dechlorination kinetics, electron efficiency (εe), and dechlorination capacity is still needed. Here, we used heteroatom incorporation of N(C) and S by ball-milling of microscale ZVI with melamine and sulfur via nitridation and sulfidation to synthesize S-N(C)-mZVIbm particles that contain reactive Fe-NX(C) and FeS species. Sulfidation and nitridation synergistically increased the trichloroethene (TCE) dechlorination rate, with reaction constants kSA of 2.98 × 10-2 L·h-1·m-2 by S-N(C)-mZVIbm, compared to 1.77 × 10-3 and 8.15 × 10-5 L·h-1·m-2 by S-mZVIbm and N(C)-mZVIbm, respectively. Data show that sulfidation suppressed the reductive dissociation of N(C) from S-N(C)-mZVIbm, which stabilized the reactive Fe-NX(C) and reserved electrons for TCE dechlorination. In addition to lowering H2 production, S-N(C)-mZVIbm dechlorinated TCE to less reduced products (e.g., acetylene), contributing to the material's higher εe and dechlorination capacity. This synergistic effect on TCE degradation can be extended to other recalcitrant CHCs (e.g., chloroform) in both deionized and groundwater. This multiheteroatom incorporation approach to optimize ZVI for groundwater remediation provides a basis for further advances in reactive material synthesis.


Assuntos
Água Subterrânea , Tricloroetileno , Poluentes Químicos da Água , Elétrons , Ferro , Cinética
11.
Environ Sci Technol ; 54(21): 13527-13537, 2020 11 03.
Artigo em Inglês | MEDLINE | ID: mdl-32985864

RESUMO

Dissolved organic matter (DOM) plays a significant role in the transport and transformation of pollutants in the aquatic environment. However, the experimental characterization of DOM has been limited mainly to bulk properties, and the molecular-level interactions among various components of DOM remain to be fully characterized. Here, we use molecular dynamics (MD) simulations to probe the structural properties of model DOM systems at atomic detail. The 200 ns simulations, validated by available experimental data, reveal processes and mechanisms by which chemical species (cations, peptides, lipids, lignin, carbohydrates, and some low-molecular-weight aliphatic and aromatic compounds) aggregate to form complex DOM. The DOM aggregates are dynamic, consisting of a hydrophobic core and amphiphilic exterior. The lipid tails and other hydrophobic fragments form the core, with hydrophilic and amphiphilic groups exposed to water, making DOM accessible to both polar and nonpolar species. Thus, the lipid component acts as a nucleator, whereas cations (especially Ca2+) connect the molecular fragments on the surface by coordinating with the O-containing functional groups of DOM. The structural details revealed here provide new insights including surface accessible atoms, overall assemblage, and interactions among the molecules of DOM for understanding the kinetics and mechanisms through which DOM interacts with metal and other contaminants.


Assuntos
Simulação de Dinâmica Molecular , Poluentes Químicos da Água , Cátions , Metais , Compostos Orgânicos , Água , Poluentes Químicos da Água/análise
12.
Environ Sci Technol ; 53(18): 10685-10694, 2019 Sep 17.
Artigo em Inglês | MEDLINE | ID: mdl-31415168

RESUMO

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 , Ligantes
13.
Langmuir ; 34(49): 14825-14833, 2018 12 11.
Artigo em Inglês | MEDLINE | ID: mdl-30021440

RESUMO

A versatile and highly sensitive strategy for nanopore detection of microcystin-LR (MC-LR) is proposed herein based on the aptamer and host-guest interactions by employing a gold nanoparticle (AuNP) probe. The aptamer of MC-LR and its complementary DNA (cDNA) are respectively immobilized on AuNPs with distinct sizes (5 nm AuNPs for the aptamer and 20 nm for the cDNA), and the constructed polymeric AuNP network via the hybridization of the aptamer and cDNA was disintegrated upon the addition of MC-LR. The specific interactions between the aptamer and MC-LR disrupt and release the cDNA-AuNPs that were then removed by centrifugation, leaving the MC-LR-aptamer-AuNP species in the supernatant for subsequent nanopore determination. By monitoring the current blockade of released MC-LR-aptamer-AuNPs using a specific tailored nanopore (10 and 20 nm in diameter, generated by current dielectric breakdown), we could deduce the presence of MC-LR, as the bulky NP network could not pass through a nanopore with a relatively smaller size. We realized the detection of MC-LR with a concentration as low as 0.1 nM; additionally, we have proved the specificity of the interaction between the aptamer and MC-LR by replacing MC-LR with other congener toxins (MC-RR and MC-YR), chlorophyll (a component abundantly coexists in water), and the mixture of the four.

14.
Environ Sci Technol ; 52(8): 4555-4564, 2018 04 17.
Artigo em Inglês | MEDLINE | ID: mdl-29569920

RESUMO

Molecular composition of the Arctic soil organic carbon (SOC) and its susceptibility to microbial degradation are uncertain due to heterogeneity and unknown SOC compositions. Using ultrahigh-resolution mass spectrometry, we determined the susceptibility and compositional changes of extractable dissolved organic matter (EDOM) in an anoxic warming incubation experiment (up to 122 days) with a tundra soil from Alaska (United States). EDOM was extracted with 10 mM NH4HCO3 from both the organic- and mineral-layer soils during incubation at both -2 and 8 °C. Based on their O:C and H:C ratios, EDOM molecular formulas were qualitatively grouped into nine biochemical classes of compounds, among which lignin-like compounds dominated both the organic and the mineral soils and were the most stable, whereas amino sugars, peptides, and carbohydrate-like compounds were the most biologically labile. These results corresponded with shifts in EDOM elemental composition in which the ratios of O:C and N:C decreased, while the average C content in EDOM, molecular mass, and aromaticity increased after 122 days of incubation. This research demonstrates that certain EDOM components, such as amino sugars, peptides, and carbohydrate-like compounds, are disproportionately more susceptible to microbial degradation than others in the soil, and these results should be considered in SOC degradation models to improve predictions of Arctic climate feedbacks.


Assuntos
Solo , Tundra , Alaska , Regiões Árticas , Carbono
15.
Environ Sci Technol ; 50(8): 4366-73, 2016 Apr 19.
Artigo em Inglês | MEDLINE | ID: mdl-27019098

RESUMO

Microbial methylation and demethylation are two competing processes controlling the net production and bioaccumulation of neurotoxic methylmercury (MeHg) in natural ecosystems. Although mercury (Hg) methylation by anaerobic microorganisms and demethylation by aerobic Hg-resistant bacteria have both been extensively studied, little attention has been given to MeHg degradation by anaerobic bacteria, particularly the iron-reducing bacterium Geobacter bemidjiensis Bem. Here we report, for the first time, that the strain G. bemidjiensis Bem can mediate a suite of Hg transformations, including Hg(II) reduction, Hg(0) oxidation, MeHg production and degradation under anoxic conditions. Results suggest that G. bemidjiensis utilizes a reductive demethylation pathway to degrade MeHg, with elemental Hg(0) as the major reaction product, possibly due to the presence of genes encoding homologues of an organomercurial lyase (MerB) and a mercuric reductase (MerA). In addition, the cells can strongly sorb Hg(II) and MeHg, reduce or oxidize Hg, resulting in both time and concentration-dependent Hg species transformations. Moderate concentrations (10-500 µM) of Hg-binding ligands such as cysteine enhance Hg(II) methylation but inhibit MeHg degradation. These findings indicate a cycle of Hg methylation and demethylation among anaerobic bacteria, thereby influencing net MeHg production in anoxic water and sediments.


Assuntos
Poluentes Ambientais/metabolismo , Geobacter/metabolismo , Mercúrio/metabolismo , Anaerobiose , Biodegradação Ambiental , Cisteína/química , Poluentes Ambientais/química , Ferro/metabolismo , Liases/metabolismo , Mercúrio/química , Metilação , Compostos de Metilmercúrio/metabolismo , Oxirredução , Oxirredutases/metabolismo
16.
Glob Chang Biol ; 21(2): 722-37, 2015 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-25308891

RESUMO

Arctic permafrost ecosystems store ~50% of global belowground carbon (C) that is vulnerable to increased microbial degradation with warmer active layer temperatures and thawing of the near surface permafrost. We used anoxic laboratory incubations to estimate anaerobic CO2 production and methanogenesis in active layer (organic and mineral soil horizons) and permafrost samples from center, ridge and trough positions of water-saturated low-centered polygon in Barrow Environmental Observatory, Barrow AK, USA. Methane (CH4 ) and CO2 production rates and concentrations were determined at -2, +4, or +8 °C for 60 day incubation period. Temporal dynamics of CO2 production and methanogenesis at -2 °C showed evidence of fundamentally different mechanisms of substrate limitation and inhibited microbial growth at soil water freezing points compared to warmer temperatures. Nonlinear regression better modeled the initial rates and estimates of Q10 values for CO2 that showed higher sensitivity in the organic-rich soils of polygon center and trough than the relatively drier ridge soils. Methanogenesis generally exhibited a lag phase in the mineral soils that was significantly longer at -2 °C in all horizons. Such discontinuity in CH4 production between -2 °C and the elevated temperatures (+4 and +8 °C) indicated the insufficient representation of methanogenesis on the basis of Q10 values estimated from both linear and nonlinear models. Production rates for both CH4 and CO2 were substantially higher in organic horizons (20% to 40% wt. C) at all temperatures relative to mineral horizons (<20% wt. C). Permafrost horizon (~12% wt. C) produced ~5-fold less CO2 than the active layer and negligible CH4 . High concentrations of initial exchangeable Fe(II) and increasing accumulation rates signified the role of iron as terminal electron acceptors for anaerobic C degradation in the mineral horizons.


Assuntos
Dióxido de Carbono/metabolismo , Mudança Climática , Metano/metabolismo , Pergelissolo/química , Pergelissolo/microbiologia , Alaska , Anaerobiose , Carbono/metabolismo , Temperatura
17.
Environ Sci Technol ; 49(20): 12105-11, 2015 Oct 20.
Artigo em Inglês | MEDLINE | ID: mdl-26389816

RESUMO

The impact of mercury (Hg) on human and ecological health has been known for decades. Although a treaty signed in 2013 by 147 nations regulates future large-scale mercury emissions, legacy Hg contamination exists worldwide and small-scale releases will continue. The fate of elemental mercury, Hg(0), lost to the subsurface and its potential chemical transformation that can lead to changes in speciation and mobility are poorly understood. Here, we show that Hg(0) beads interact with soil or manganese oxide solids and X-ray spectroscopic analysis indicates that the soluble mercury coatings are HgO. Dissolution studies show that, after reacting with a composite soil, >20 times more Hg is released into water from the coated beads than from a pure liquid mercury bead. An even larger, >700 times, release occurs from coated Hg(0) beads that have been reacted with manganese oxide, suggesting that manganese oxides are involved in the transformation of the Hg(0) beads and creation of the soluble mercury coatings. Although the coatings may inhibit Hg(0) evaporation, the high solubility of the coatings can enhance Hg(II) migration away from the Hg(0)-spill site and result in potential changes in mercury speciation in the soil and increased mercury mobility.


Assuntos
Compostos de Mercúrio/química , Mercúrio/química , Óxidos/química , Poluentes do Solo/química , Compostos de Manganês/química , Mercúrio/análise , Solo/química , Poluentes do Solo/análise , Solubilidade , Água/química , Espectroscopia por Absorção de Raios X
18.
Biophys J ; 107(2): 393-400, 2014 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-25028881

RESUMO

The functional efficacy of colocalized, linked protein domains is dependent on linker flexibility and system compaction. However, the detailed characterization of these properties in aqueous solution presents an enduring challenge. Here, we employ a novel, to our knowledge, combination of complementary techniques, including small-angle neutron scattering, neutron spin-echo spectroscopy, and all-atom molecular dynamics and coarse-grained simulation, to identify and characterize in detail the structure and dynamics of a compact form of mercuric ion reductase (MerA), an enzyme central to bacterial mercury resistance. MerA possesses metallochaperone-like N-terminal domains (NmerA) tethered to its catalytic core domain by linkers. The NmerA domains are found to interact principally through electrostatic interactions with the core, leashed by the linkers so as to subdiffuse on the surface over an area close to the core C-terminal Hg(II)-binding cysteines. How this compact, dynamical arrangement may facilitate delivery of Hg(II) from NmerA to the core domain is discussed.


Assuntos
Oxirredutases/química , Sequência de Aminoácidos , Domínio Catalítico , Dados de Sequência Molecular , Difração de Nêutrons , Oxirredutases/metabolismo , Ligação Proteica , Espalhamento a Baixo Ângulo , Eletricidade Estática
19.
Environ Sci Technol ; 48(20): 11969-76, 2014 Oct 21.
Artigo em Inglês | MEDLINE | ID: mdl-25268220

RESUMO

G. sulfurreducens PCA cells have been shown to reduce, sorb, and methylate Hg(II) species, but it is unclear whether this organism can oxidize and methylate dissolved elemental Hg(0) as shown for Desulfovibrio desulfuricans ND132. Using Hg(II) and Hg(0) separately as Hg sources in washed cell assays in phosphate buffered saline (pH 7.4), we report how cell-mediated Hg reduction and oxidation compete or synergize with sorption, thus affecting the production of toxic methylmercury by PCA cells. Methylation is found to be positively correlated to Hg sorption (r = 0.73) but negatively correlated to Hg reduction (r = -0.62). These reactions depend on the Hg and cell concentrations or the ratio of Hg to cellular thiols (-SH). Oxidation and methylation of Hg(0) are favored at relatively low Hg to cell-SH molar ratios (e.g., <1). Increasing Hg to cell ratios from 0.25 × 10(-19) to 25 × 10(-19) moles-Hg/cell (equivalent to Hg/cell-SH of 0.71 to 71) shifts the major reaction from oxidation to reduction. In the absence of five outer membrane c-type cytochromes, mutant ΔomcBESTZ also shows decreases in Hg reduction and increases in methylation. However, the presence of competing thiol-binding ions such as Zn(2+) leads to increased Hg reduction and decreased methylation. These results suggest that the coupled cell-Hg sorption and redox transformations are important in controlling the rates of Hg uptake and methylation by G. sulfurreducens PCA in anoxic environments.


Assuntos
Geobacter/metabolismo , Mercúrio/metabolismo , Compostos de Metilmercúrio/metabolismo , Adsorção , Anaerobiose , Grupo dos Citocromos c/genética , Grupo dos Citocromos c/metabolismo , Geobacter/efeitos dos fármacos , Geobacter/genética , Mercúrio/química , Metilação , Oxirredução , Compostos de Sulfidrila/metabolismo , Zinco/metabolismo
20.
J Chem Phys ; 140(9): 094305, 2014 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-24606359

RESUMO

The complex scaled multiconfigurational time-dependent Hartree-Fock method (CMCTDHF also called the complex scaled multiconfigurational linear response method) is used to study the doubly excited He 2s(2) Feshbach resonance energy and lifetime. Various even-tempered Gaussian basis set/complete active space (CAS) combinations are examined. The results are compared with the complex scaled full configuration interaction (FCI) [P. R. Zdanska and N. Moiseyev, J. Chem. Phys. 123, 194105 (2005)], complex-scaled equation-of-motion coupled-cluster method with single and double substitutions [K. B. Bravaya, D. Z. Zuev, E. Epifanovsky, and A. I. Krylov, J. Chem. Phys. 138, 124106 (2013)], and exact numerical calculations [Y. K. Ho, Phys. Rev. A 23, 2137 (1981); E. Lindroth, Phys. Rev. A 49, 4473 (1994); A. Bürgers, D. Wintgren, and J.-M. Ross, J. Phys. B 28, 3163 (1995); and N. Elander, S. Levin, and E. Yarevsky, Phys. Rev. A 67, 062508 (2003)]. It is shown that CMCTDHF is able to provide highly accurate resonance parameters with a fairly small size of basis set and CAS, where the computational resources required are much less than the complex scaled FCI method and exact numerical results.

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