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1.
Proc Natl Acad Sci U S A ; 121(23): e2319148121, 2024 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-38805285

RESUMO

Magnetotactic bacteria produce chains of nanoscopic iron minerals used for navigation, which can be preserved over geological timescales in the form of magnetofossils. Micrometer-sized magnetite crystals with unusual shapes suggesting a biologically controlled mineralization have been found in the geological record and termed giant magnetofossils. The biological origin and function of giant magnetofossils remains unclear, due to the lack of modern analogues to giant magnetofossils. Using distinctive Ptychographic nanotomography data of Precambrian (1.88 Ga) rocks, we recovered the morphology of micrometric cuboid grains of iron oxides embedded in an organic filamentous fossil to construct synthetic magnetosomes. Their morphology is different from that of previously found giant magnetofossils, but their occurrence in filamentous microfossils and micromagnetic simulations support the hypothesis that they could have functioned as a navigation aid, akin to modern magnetosomes.


Assuntos
Fósseis , Magnetossomos , Magnetossomos/química , Magnetossomos/metabolismo , Óxido Ferroso-Férrico/química , Sedimentos Geológicos/química
2.
Proc Natl Acad Sci U S A ; 119(31): e2203758119, 2022 08 02.
Artigo em Inglês | MEDLINE | ID: mdl-35901209

RESUMO

Biominerals are important archives of the presence of life and environmental processes in the geological record. However, ascribing a clear biogenic nature to minerals with nanometer-sized dimensions has proven challenging. Identifying hallmark features of biologically controlled mineralization is particularly important for the case of magnetite crystals, resembling those produced by magnetotactic bacteria (MTB), which have been used as evidence of early prokaryotic life on Earth and in meteorites. We show here that magnetite produced by MTB displays a clear coupled C-N signal that is absent in abiogenic and/or biomimetic (protein-mediated) nanometer-sized magnetite. We attribute the presence of this signal to intracrystalline organic components associated with proteins involved in magnetosome formation by MTB. These results demonstrate that we can assign a biogenic origin to nanometer-sized magnetite crystals, and potentially other biominerals of similar dimensions, using unique geochemical signatures directly measured at the nanoscale. This finding is significant for searching for the earliest presence of life in the Earth's geological record and prokaryotic life on other planets.


Assuntos
Óxido Ferroso-Férrico , Magnetossomos , Proteínas de Bactérias/metabolismo , Materiais Biomiméticos , Óxido Ferroso-Férrico/química , Bactérias Gram-Negativas/metabolismo , Magnetossomos/química
3.
Proc Natl Acad Sci U S A ; 119(28): e2204765119, 2022 07 12.
Artigo em Inglês | MEDLINE | ID: mdl-35787048

RESUMO

Life as we know it is homochiral, but the origins of biological homochirality on early Earth remain elusive. Shallow closed-basin lakes are a plausible prebiotic environment on early Earth, and most are expected to have significant sedimentary magnetite deposits. We hypothesize that ultraviolet (200- to 300-nm) irradiation of magnetite deposits could generate hydrated spin-polarized electrons sufficient to induce enantioselective prebiotic chemistry. Such electrons are potent reducing agents that drive reduction reactions where the spin polarization direction can enantioselectively alter the reaction kinetics. Our estimate of this chiral bias is based on the strong effective spin-orbit coupling observed in the chiral-induced spin selectivity (CISS) effect, as applied to energy differences in reduction reactions for different isomers. In the original CISS experiments, spin-selective electron transmission through a monolayer of double-strand DNA molecules is observed at room temperature-indicating a strong coupling between molecular chirality and electron spin. We propose that the chiral symmetry breaking due to the CISS effect, when applied to reduction chemistry, can induce enantioselective synthesis on the prebiotic Earth and thus facilitate the homochiral assembly of life's building blocks.


Assuntos
Elétrons , Óxido Ferroso-Férrico , DNA/química , Planeta Terra , Estereoisomerismo
4.
Proc Natl Acad Sci U S A ; 119(3)2022 01 18.
Artigo em Inglês | MEDLINE | ID: mdl-35012979

RESUMO

Animals use geomagnetic fields for navigational cues, yet the sensory mechanism underlying magnetic perception remains poorly understood. One idea is that geomagnetic fields are physically transduced by magnetite crystals contained inside specialized receptor cells, but evidence for intracellular, biogenic magnetite in eukaryotes is scant. Certain bacteria produce magnetite crystals inside intracellular compartments, representing the most ancient form of biomineralization known and having evolved prior to emergence of the crown group of eukaryotes, raising the question of whether magnetite biomineralization in eukaryotes and prokaryotes might share a common evolutionary history. Here, we discover that salmonid olfactory epithelium contains magnetite crystals arranged in compact clusters and determine that genes differentially expressed in magnetic olfactory cells, contrasted to nonmagnetic olfactory cells, share ancestry with an ancient prokaryote magnetite biomineralization system, consistent with exaptation for use in eukaryotic magnetoreception. We also show that 11 prokaryote biomineralization genes are universally present among a diverse set of eukaryote taxa and that nine of those genes are present within the Asgard clade of archaea Lokiarchaeota that affiliates with eukaryotes in phylogenomic analysis. Consistent with deep homology, we present an evolutionary genetics hypothesis for magnetite formation among eukaryotes to motivate convergent approaches for examining magnetite-based magnetoreception, molecular origins of matrix-associated biomineralization processes, and eukaryogenesis.


Assuntos
Biomineralização/genética , Óxido Ferroso-Férrico/química , Fenômenos Magnéticos , Animais , Evolução Biológica , Genômica , Magnetossomos/genética , Salmão
5.
Proc Natl Acad Sci U S A ; 119(6)2022 02 08.
Artigo em Inglês | MEDLINE | ID: mdl-35110403

RESUMO

Magnetosomes are lipid-bound organelles that direct the biomineralization of magnetic nanoparticles in magnetotactic bacteria. Magnetosome membranes are not uniform in size and can grow in a biomineralization-dependent manner. However, the underlying mechanisms of magnetosome membrane growth regulation remain unclear. Using cryoelectron tomography, we systematically examined mutants with defects at various stages of magnetosome formation to identify factors involved in controlling membrane growth. We found that a conserved serine protease, MamE, plays a key role in magnetosome membrane growth regulation. When the protease activity of MamE is disrupted, magnetosome membrane growth is restricted, which, in turn, limits the size of the magnetite particles. Consistent with this finding, the upstream regulators of MamE protease activity, MamO and MamM, are also required for magnetosome membrane growth. We then used a combination of candidate and comparative proteomics approaches to identify Mms6 and MamD as two MamE substrates. Mms6 does not appear to participate in magnetosome membrane growth. However, in the absence of MamD, magnetosome membranes grow to a larger size than the wild type. Furthermore, when the cleavage of MamD by MamE protease is blocked, magnetosome membrane growth and biomineralization are severely inhibited, phenocopying the MamE protease-inactive mutant. We therefore propose that the growth of magnetosome membranes is controlled by a protease-mediated switch through processing of MamD. Overall, our work shows that, like many eukaryotic systems, bacteria control the growth and size of biominerals by manipulating the physical properties of intracellular organelles.


Assuntos
Proteínas de Bactérias/metabolismo , Magnetossomos/metabolismo , Magnetospirillum/metabolismo , Organelas/metabolismo , Serina Proteases/metabolismo , Óxido Ferroso-Férrico/metabolismo , Proteólise , Proteômica/métodos , Serina Endopeptidases/metabolismo
6.
Proc Natl Acad Sci U S A ; 119(6)2022 02 08.
Artigo em Inglês | MEDLINE | ID: mdl-35101971

RESUMO

Metastatic osteosarcoma has a poor prognosis with a 2-y, event-free survival rate of ∼15 to 20%, highlighting the need for the advancement of efficacious therapeutics. Chimeric antigen receptor (CAR) T-cell therapy is a potent strategy for eliminating tumors by harnessing the immune system. However, clinical trials with CAR T cells in solid tumors have encountered significant challenges and have not yet demonstrated convincing evidence of efficacy for a large number of patients. A major bottleneck for the success of CAR T-cell therapy is our inability to monitor the accumulation of the CAR T cells in the tumor with clinical-imaging techniques. To address this, we developed a clinically translatable approach for labeling CAR T cells with iron oxide nanoparticles, which enabled the noninvasive detection of the iron-labeled T cells with magnetic resonance imaging (MRI), photoacoustic imaging (PAT), and magnetic particle imaging (MPI). Using a custom-made microfluidics device for T-cell labeling by mechanoporation, we achieved significant nanoparticle uptake in the CAR T cells, while preserving T-cell proliferation, viability, and function. Multimodal MRI, PAT, and MPI demonstrated homing of the T cells to osteosarcomas and off-target sites in animals administered with T cells labeled with the iron oxide nanoparticles, while T cells were not visualized in animals infused with unlabeled cells. This study details the successful labeling of CAR T cells with ferumoxytol, thereby paving the way for monitoring CAR T cells in solid tumors.


Assuntos
Neoplasias Ósseas , Óxido Ferroso-Férrico/farmacologia , Imunoterapia Adotiva , Imageamento por Ressonância Magnética , Nanopartículas/uso terapêutico , Neoplasias Experimentais , Osteossarcoma , Receptores de Antígenos Quiméricos/imunologia , Linfócitos T/imunologia , Animais , Neoplasias Ósseas/diagnóstico por imagem , Neoplasias Ósseas/imunologia , Neoplasias Ósseas/terapia , Camundongos , Neoplasias Experimentais/diagnóstico por imagem , Neoplasias Experimentais/imunologia , Neoplasias Experimentais/terapia , Osteossarcoma/diagnóstico por imagem , Osteossarcoma/imunologia , Osteossarcoma/terapia
7.
Nano Lett ; 24(15): 4588-4594, 2024 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-38587406

RESUMO

Effective thawing of cryopreserved samples requires rapid and uniform heating. This is achievable through nanowarming, an approach that heats magnetic nanoparticles by using alternating magnetic fields. Here we demonstrate the synthesis and surface modification of magnetic nanoclusters for efficient nanowarming. Magnetite (Fe3O4) nanoclusters with an optimal diameter of 58 nm exhibit a high specific absorption rate of 1499 W/g Fe under an alternating magnetic field at 43 kA/m and 413 kHz, more than twice that of commercial iron oxide cores used in prior nanowarming studies. Surface modification with a permeable resorcinol-formaldehyde resin (RFR) polymer layer significantly enhances their colloidal stability in complex cryoprotective solutions, while maintaining their excellent heating capacity. The Fe3O4@RFR nanoparticles achieved a high average heating rate of 175 °C/min in cryopreserved samples at a concentration of 10 mg Fe/mL and were successfully applied in nanowarming porcine iliac arteries, highlighting their potential for enhancing the efficacy of cryopreservation.


Assuntos
Calefação , Magnetismo , Suínos , Animais , Criopreservação , Óxido Ferroso-Férrico , Campos Magnéticos
8.
Small ; 20(6): e2305974, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-37771197

RESUMO

Iron oxide nanoparticles (IONPs) have garnered significant attention as a promising platform for reactive oxygen species (ROS)-dependent disease treatment, owing to their remarkable biocompatibility and Fenton catalytic activity. However, the low catalytic activity of IONPs is a major hurdle in their clinical translation. To overcome this challenge, IONPs of different compositions are examined for their Fenton reaction under pharmacologically relevant conditions. The results show that wüstite (FeO) nanoparticles exhibit higher catalytic activity than magnetite (Fe3 O4 ) or maghemite (γ-Fe2 O3 ) of matched size and coating, despite having a similar surface oxidation state. Further analyses suggest that the high catalytic activity of wüstite nanoparticles can be attributed to the presence of internal low-valence iron (Fe0 and Fe2+ ), which accelerates the recycling of surface Fe3+ to Fe2+ through intraparticle electron transport. Additionally, ultrasmall wüstite nanoparticles are generated by tuning the thermodecomposition-based nanocrystal synthesis, resulting in a Fenton reaction rate 5.3 times higher than that of ferumoxytol, an FDA-approved IONP. Compared with ferumoxytol, wüstite nanoparticles substantially increase the level of intracellular ROS in mouse mammary carcinoma cells. This study presents a novel mechanism and pivotal improvement for the development of highly efficient ROS-inducing nanozymes, thereby expanding the horizons for their therapeutic applications.


Assuntos
Óxido Ferroso-Férrico , Nanopartículas , Camundongos , Animais , Transporte de Elétrons , Espécies Reativas de Oxigênio , Compostos Férricos/química , Compostos Ferrosos
9.
Appl Environ Microbiol ; 90(2): e0145123, 2024 02 21.
Artigo em Inglês | MEDLINE | ID: mdl-38224621

RESUMO

Adding trace calcium peroxide and magnetite into a semi-continuous digester is a new method to effectively improve the anaerobic digestion of food waste. However, the microbial mechanism in this system has not been fully explored. Metaproteomics further revealed that the most active and significantly regulated genus u_p_Chloroflexi had formed a good cooperative relationship with Methanomicrobiales and Methanothrix in the system. u_p_Chloroflexi decomposed more organic compounds into CO2, acetate, amino acids, and other substances by alternating between short aerobic-anaerobic respiration. It perceived and adapted to the surrounding environment by producing biofilm, extracellular enzymes, and accelerating substrate transport, formed a respiratory barrier, and enhanced iron transport capacity by using highly expressed cytochrome C. The methanogens formed reactive oxygen species scavengers and reduced iron transport to prevent oxidative damage. This study provides new insight for improving the efficiency of anaerobic digestion of food waste and identifying key microorganisms and their regulated functional proteins in the calcium peroxide-magnetite digestion system.IMPORTANCEPrevious study has found that the combination of calcium peroxide and magnetite has a good promoting effect on the anaerobic digestion process of food waste. Through multiple omics approaches, information such as microbial population structure and changes in metabolites can be further analyzed. This study can help researchers gain a deeper understanding of the digestion pathway of food waste under the combined action of calcium peroxide and magnetite, further elucidate the impact mechanisms of calcium peroxide and magnetite at the microbial level, and provide theoretical guidance to improve the efficiency and stability of anaerobic digestion of food waste, as well as reduce operational costs. This research contributes to improving energy recovery efficiency, promoting sustainable management and development of food waste, and is of great significance to environmental protection.


Assuntos
Peróxidos , Eliminação de Resíduos , Anaerobiose , Alimentos , Perda e Desperdício de Alimentos , Óxido Ferroso-Férrico , Reatores Biológicos , Ferro , Metano , Esgotos , Digestão
10.
J Magn Reson Imaging ; 60(5): 2196-2204, 2024 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-38375996

RESUMO

BACKGROUND: Recently, dynamic contrast-enhanced (DCE) MRI with ferumoxytol as contrast agent has recently been introduced for the noninvasive assessment of placental structure and function throughout. However, it has not been demonstrated under pathological conditions. PURPOSE: To measure cotyledon-specific rhesus macaque maternal placental blood flow using ferumoxytol DCE MRI in a novel animal model for local placental injury. STUDY TYPE: Prospective animal model. SUBJECTS: Placental injections of Tisseel (three with 0.5 mL and two with 1.5 mL), monocyte chemoattractant protein 1 (three with 100 µg), and three with saline as controls were performed in a total of 11 rhesus macaque pregnancies at approximate gestational day (GD 101). DCE MRI scans were performed prior (GD 100) and after (GD 115 and GD 145) the injection (term = GD 165). FIELD STRENGTH/SEQUENCE: 3 T, T1-weighted spoiled gradient echo sequence (product sequence, DISCO). ASSESSMENT: Source images were inspected for motion artefacts from the mother or fetus. Placenta segmentation and DCE processing were performed for the dynamic image series to measure cotyledon specific volume, flow, and normalized flow. Overall placental histopathology was conducted for controls, Tisseel, and MCP-1 animals and regions of tissue infarctions and necrosis were documented. Visual inspections for potential necrotic tissue were conducted for the two Tisseelx3 animals. STATISTICAL TESTS: Wilcoxon rank sum test, significance level P < 0.05. RESULTS: No motion artefacts were observed. For the group treated with 1.5 mL of Tisseel, significantly lower cotyledon volume, flow, and normalized flow per cotyledon were observed for the third gestational time point of imaging (day ~145), with mean normalized flow of 0.53 minute-1. Preliminary histopathological analysis shows areas of tissue necrosis from a selected cotyledon in one Tisseel-treated (single dose) animal and both Tisseelx3 (triple dose) animals. DATA CONCLUSION: This study demonstrates the feasibility of cotyledon-specific functional analysis at multiple gestational time points and injury detection in a placental rhesus macaque model through ferumoxytol-enhanced DCE MRI. LEVEL OF EVIDENCE: NA TECHNICAL EFFICACY: Stage 2.


Assuntos
Meios de Contraste , Óxido Ferroso-Férrico , Macaca mulatta , Imageamento por Ressonância Magnética , Placenta , Animais , Feminino , Gravidez , Imageamento por Ressonância Magnética/métodos , Placenta/diagnóstico por imagem , Estudos Prospectivos , Processamento de Imagem Assistida por Computador/métodos
11.
Langmuir ; 40(24): 12792-12801, 2024 Jun 18.
Artigo em Inglês | MEDLINE | ID: mdl-38848468

RESUMO

Herein, we constructed the branch-shaped SiO2/nano GO (nGO)/Fe3O4/selenium quantum dots (QDs) (SeQDs) nanoparticles (SGF/SeQDs) embodying magnetism, fluorescence, and microwave stimulus response properties to enhance the performance of releasing drugs. The SGF/SeQDs composite was characterized by technologies including powder X-ray diffraction, transmission electron microscopy, infrared spectroscopy, etc. In the nanoparticles, the branch-shaped SiO2 provides a large specific surface area, nGO as the dielectric loss-style material promotes microwave-absorbing performance, and the Fe3O4 serves as a magnetic targeting agent and microwave absorber. Integrating nGO and Fe3O4 could further strengthen the microwave absorption of the entire composite; selenium features both fluorescence and anticancer effects. The synthesized nanoparticles as carriers exhibited a branch-like mesoporous sphere of ∼260 nm, a specific surface area of 258.57 m2 g-1, a saturation magnetization of 24.59 emu g-1, and good microwave thermal conversion performance that the temperature was elevated from 25 to 70 °C under microwave irradiation. These physical characteristics, including large pore volume (5.30 nm), high specific surface area, and fibrous morphology, are in favor of loading drugs. Meanwhile, the cumulative etoposide (VP16) loading rate of the nanoparticles reached to 21 wt % after 360 min. The noncovalent interaction between the VP16 and SGF/SeQDs was mainly the hydrogen-bonding effect during the loading process. Furthermore, the drug release rates at 180 min were up to 81.46, 61.92, and 56.84 wt % at pH 4, 5, and 7, respectively. At 25, 37, and 50 °C, the rates of drug release reach 25.40, 56.84, and 65.32 wt %, respectively. After microwave stimulation at pH 7, the rate of releasing drug increased distinctly from 56.84 to 71.74 wt % compared to that of nonmicrowave irradiation. Cytotoxicity tests manifested that the carrier had good biocompatibility. Therefore, the nanoparticles are looking forward to paving one platform for further applications in biomedicine and drug delivery systems.


Assuntos
Portadores de Fármacos , Pontos Quânticos , Selênio , Dióxido de Silício , Dióxido de Silício/química , Portadores de Fármacos/química , Portadores de Fármacos/síntese química , Humanos , Pontos Quânticos/química , Pontos Quânticos/toxicidade , Selênio/química , Micro-Ondas , Liberação Controlada de Fármacos , Nanopartículas/química , Sobrevivência Celular/efeitos dos fármacos , Etoposídeo/química , Etoposídeo/farmacologia , Antineoplásicos/química , Antineoplásicos/farmacologia , Tamanho da Partícula , Propriedades de Superfície , Óxido Ferroso-Férrico/química
12.
Eur Radiol ; 34(11): 7197-7207, 2024 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-38713277

RESUMO

OBJECTIVES: Comprehensive evaluation of lower-extremity varicose veins (VVs) in patients with diabetes is crucial for treatment strategizing. The study aims to assess the feasibility of using ferumoxytol-enhanced MR venography (FE-MRV) for lower-extremity venous mapping and the detection of VVs in patients with diabetes. MATERIALS AND METHODS: As part of a phase II clinical trial of a generic brand of ferumoxytol, documented patients with diabetes were enrolled and underwent FE-MRV on a 3-Τ MRI system. Two observers assessed FE-MRV images for image quality, signal intensity ratio (SIR), perforator (PV) diameter, and luminal signal uniformity in deep-to-superficial venous networks with the assessment of intra- and inter-rater reliability. FE-MRV was used to detect lower-extremity VVs. RESULTS: Eleven patients underwent FE-MRV without adverse events. The average image quality, as scored by the two observers who assessed 275 venous segments, was 3.4 ± 0.6. Two observers strongly agreed on image quality (κ = 0.90) and SIR measurements (interclass correlation coefficient [ICC]: 0.72) and had good agreement on PV diameter (ICC: 0.64). FE-MRV revealed uniform luminal signals in deep and saphenous venous networks (0.13 ± 0.05 vs 0.08 ± 0.03). Below-knee segments exhibited a significantly higher heterogeneity index than above-knee (p = 0.039) segments. Superficial VVs were observed in 55% (12/22) of legs in 64% (7/11) of patients. Calf muscle VVs were present in 64% (14/22) of legs in 9 patients. CONCLUSION: FE-MRV safely and robustly mapped entire lower-extremity venous networks, enabling the detection and pre-treatment evaluation of both superficial, and deep VVs in patients with diabetes. CLINICAL RELEVANCE STATEMENT: Ferumoxytol-enhanced magnetic resonance venography offers a "one-stop" imaging strategy for the detection and pre-operative evaluation of both superficial and deep VVs in diabetic patients. KEY POINTS: Diabetic patients with VVs are at a higher risk of ulcer-related complications. FE-MRV allowed rapid and comprehensive visualization of the lower-limb venous networks and abdominopelvic veins in diabetic patients. This technique allowed for the detection of superficial and deep VVs in diabetic patients before the development of severe peripheral artery disease.


Assuntos
Meios de Contraste , Óxido Ferroso-Férrico , Extremidade Inferior , Angiografia por Ressonância Magnética , Varizes , Humanos , Varizes/diagnóstico por imagem , Masculino , Feminino , Pessoa de Meia-Idade , Angiografia por Ressonância Magnética/métodos , Extremidade Inferior/diagnóstico por imagem , Extremidade Inferior/irrigação sanguínea , Idoso , Adulto , Estudos de Viabilidade , Reprodutibilidade dos Testes , Flebografia/métodos
13.
Am J Hematol ; 99(6): 1077-1083, 2024 06.
Artigo em Inglês | MEDLINE | ID: mdl-38476079

RESUMO

Restless legs syndrome (RLS) is a neurological disorder that can have a profound effect on sleep and quality of life. Idiopathic RLS is associated with brain iron insufficiency despite normal peripheral iron stores. There is, however, a five- to six-fold increase in prevalence of RLS in patients with iron deficiency anemia (IDA). Several open-label trials have demonstrated symptomatic improvement in RLS following treatment of IDA using oral or intravenous iron supplementation. To date, there have been no randomized double-blind controlled trials of intravenous iron compared with oral iron for the treatment of RLS patients with IDA. In the current study, oral ferrous sulfate and ferumoxytol were compared for efficacy and speed of response for treatment of RLS occurring in patients with IDA. The planned recruitment for this study was 70 patients with RLS and IDA, to be randomly assigned 1:1 to oral or intravenous iron, using double-blind, double-dummy procedures. At Week 6, the primary outcomes of Clinical Global Impression-Improvement score and change from baseline in the International Restless Legs Syndrome Study Group rating scale score were assessed. Due to challenges, performing the clinical trial during the COVID-19 pandemic, final-week data were found missing for 30 patients. As a result, in order to maintain the prespecified statistical analysis, an additional 30 patients were recruited. Both IV and oral iron were associated with a marked improvement in RLS symptoms, with no statistically significant difference between treatment groups. No serious adverse events were observed in either treatment group.


Assuntos
Administração Intravenosa , Anemia Ferropriva , Compostos Ferrosos , Síndrome das Pernas Inquietas , Humanos , Síndrome das Pernas Inquietas/tratamento farmacológico , Anemia Ferropriva/tratamento farmacológico , Administração Oral , Método Duplo-Cego , Masculino , Feminino , Projetos Piloto , Pessoa de Meia-Idade , Compostos Ferrosos/administração & dosagem , Compostos Ferrosos/uso terapêutico , Compostos Ferrosos/efeitos adversos , Adulto , Idoso , Resultado do Tratamento , Óxido Ferroso-Férrico/administração & dosagem , Óxido Ferroso-Férrico/uso terapêutico , Óxido Ferroso-Férrico/efeitos adversos , Ferro/administração & dosagem , Ferro/uso terapêutico
14.
Environ Sci Technol ; 58(15): 6595-6604, 2024 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-38573735

RESUMO

Meaningful interpretation of U isotope measurements relies on unraveling the impact of reduction mechanisms on the isotopic fractionation. Here, the isotope fractionation of hexavalent U [U(VI)] was investigated during its reductive mineralization by magnetite to intermediate pentavalent U [U(V)] and ultimately tetravalent U [U(IV)]. As the reaction proceeded, the remaining aqueous phase U [containing U(VI) and U(V)] systematically carried light isotopes, whereas in the bicarbonate-extracted solution [containing U(VI) and U(V)], the δ238U values varied, especially when C/C0 approached 0. This variation was interpreted as reflecting the variable relative contribution of unreduced U(VI) (δ238U < 0‰) and bicarbonate-extractable U(V) (δ238U > 0‰). The solid remaining after bicarbonate extraction included unextractable U(V) and U(IV), for which the δ238U values consistently followed the same trend that started at 0.3-0.5‰ and decreased to ∼0‰. The impact of PIPES buffer on isotopic fractionation was attributed to the variable abundance of U(V) in the aqueous phase. A few extremely heavy bicarbonate-extracted δ238U values were due to mass-dependent fractionation resulting from several hypothesized mechanisms. The results suggest the preferential accumulation of the heavy isotope in the reduced species and the significant influence of U(V) on the overall isotopic fractionation, providing insight into the U isotope fractionation behavior during its abiotic reduction process.


Assuntos
Óxido Ferroso-Férrico , Urânio , Bicarbonatos , Isótopos , Fracionamento Químico
15.
Environ Sci Technol ; 58(40): 17756-17765, 2024 Oct 08.
Artigo em Inglês | MEDLINE | ID: mdl-39323212

RESUMO

Humic substances are organic substances prevalent in various natural environments, such as wetlands, which are globally important sources of methane (CH4) emissions. Extracellular electron transfer (EET)-mediated anaerobic oxidation of methane (AOM)-coupled with humic substances reduction plays an important role in the reduction of methane emissions from wetlands, where magnetite is prevalent. However, little is known about the magnetite-mediated EET mechanisms in AOM-coupled humic substances reduction. This study shows that magnetite promotes the reduction of the AOM-coupled humic substances model compound, anthraquinone-2,6-disulfonate (AQDS). 13CH4 labeling experiments further indicated that AOM-coupled AQDS reduction occurred, and acetate was an intermediate product of AOM. Moreover, 13CH313COONa labeling experiments showed that AOM-generated acetate can be continuously reduced to methane in a state of dynamic equilibrium. In the presence of magnetite, the EET capacity of the microbial community increased, and Methanosarcina played a key role in the AOM-coupled AQDS reduction. Pure culture experiments showed that Methanosarcina barkeri can independently perform AOM-coupled AQDS reduction and that magnetite increased its surface protein redox activity. The metatranscriptomic results indicated that magnetite increased the expression of membrane-bound proteins involved in energy metabolism and electron transfer in M. barkeri, thereby increasing the EET capacity. This phenomenon potentially elucidates the rationale as to why magnetite promoted AOM-coupled AQDS reduction.


Assuntos
Óxido Ferroso-Férrico , Substâncias Húmicas , Metano , Oxirredução , Metano/metabolismo , Anaerobiose , Transporte de Elétrons , Óxido Ferroso-Férrico/química
16.
Environ Sci Technol ; 58(1): 935-946, 2024 Jan 09.
Artigo em Inglês | MEDLINE | ID: mdl-38133817

RESUMO

Magnetite is a common mixed Fe(II,III) iron oxide in mineral deposits and the product of (anaerobic) iron corrosion. In various Earth systems, magnetite surfaces participate in surface-mediated redox reactions. The reactivity and redox properties of the magnetite surface depend on the surface speciation, which varies with environmental conditions. In this study, Kohn-Sham density functional theory (DFT + U method) was used to examine the stability and speciation of the prevalent magnetite crystal face {111} in a wide range of pH and Eh conditions. The simulations reveal that the oxidation state and speciation of the surface depend strongly on imposed redox conditions and, in general, may differ from those of the bulk state. Corresponding predominant phase diagrams for the surface speciation and structure were calculated from first principles. Furthermore, classical molecular dynamics simulations were conducted investigating the mobility of water near the magnetite surface. The obtained knowledge of the surface structure and oxidation state of iron is essential for modeling retention of redox-sensitive nuclides.


Assuntos
Óxido Ferroso-Férrico , Ferro , Óxido Ferroso-Férrico/química , Ferro/química , Oxirredução , Minerais , Água
17.
Environ Res ; 261: 119698, 2024 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-39074773

RESUMO

One of the few elements that can have negative health impacts in both conditions, when consumed in excess or insufficiency is fluoride. In current study, aluminium magnetite alginate composite (AMA) was fabricated and applied using batch adsorption of fluoride as well as by using statistical modelling. Heterogeneous surface as revealed from scanning electron micrograph, thermal stability shown by thermal studies, high surface area of 29.77 m2 g-1, pore volume 0.1987 cm3 g-1 with mesoporous structure having average pore radius of 133 Å shown by BET analysis, fare degree of magnetization from VSM analysis were the important features of this material. Screening experiments and batch trials were carried out to obtain optimum working conditions. pH of 3.0, dosage of 50 mg, interaction period of 60 min and concentration of 50 mg L-1 depicted maximum defluoridation efficacy of about 94%. The adsorption capacity was found to be 60.08 mg g-1 in accordance with Langmuir adsorption isotherm, while pseudo second order kinetics was followed. Overall effects of various factors on sorption process were optimized using response surface methodology (RSM). Regeneration potential of AMA has been demonstrated for 10 adsorption-desorption cycles, showing more than 60% efficiency in tenth cycle. The AMA composite shows E-factor value 0.004 depicting it is sustainable in environment. In short, this novel composite showed excellent morphological, magnetic, functional properties that led to enhanced adsorption efficiency in short span of time that can be regenerated and reused in multiple cycles.


Assuntos
Alginatos , Alumínio , Óxido Ferroso-Férrico , Fluoretos , Poluentes Químicos da Água , Purificação da Água , Alginatos/química , Fluoretos/química , Adsorção , Poluentes Químicos da Água/química , Purificação da Água/métodos , Alumínio/química , Óxido Ferroso-Férrico/química , Cinética , Porosidade
18.
Environ Res ; 249: 118471, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38354888

RESUMO

Nowadays, NOR-containing wastewater has placed huge pressure on global ecology. In this study, a chemically-modified chitosan-based polymer was cross-linked with magnetite to prepare a novel magnetic composite adsorbent named Fe3O4/CS-P(AM-SSS) for norfloxacin (NOR) removal. The preparation conditions were optimized by single factor experiments and response surface methodology. A series of characterization analyses were carried out on the morphology, structure, and properties of Fe3O4/CS-P(AM-SSS), verifying that Fe3O4/CS-P(AM-SSS) was successfully prepared. Batch adsorption experiments showed that NOR was efficiently removed by Fe3O4/CS-P(AM-SSS), with a broad pH applicability of 3-10, short adsorption equilibrium time of 60 min, maximum adsorption capacity of 268.79 mg/g, and high regeneration rate of 86% after eight adsorption-desorption cycles. Due to the three-dimensional network structure and abundant functional groups provided by modified chitosan polymer, the superior adsorption capability of Fe3O4/CS-P(AM-SSS) was achieved through electrostatic interaction, π-π stacking, hydrophobic interaction, and hydrogen bonding. Adsorption process was exothermic and well fitted by the pseudo-second-order kinetic model and the Langmuir isothermal model. The presence of cations had a slight inhibitory effect on NOR adsorption, while humic acid nearly had no effect. In model swine wastewater, 90.3% NOR was removed by Fe3O4/CS-P(AM-SSS). Therefore, with these superior characteristics, Fe3O4/CS-P(AM-SSS) was expected to be an ideal material for treating NOR-containing wastewater in the future.


Assuntos
Quitosana , Óxido Ferroso-Férrico , Norfloxacino , Poluentes Químicos da Água , Norfloxacino/química , Adsorção , Poluentes Químicos da Água/química , Poluentes Químicos da Água/análise , Concentração de Íons de Hidrogênio , Óxido Ferroso-Férrico/química , Quitosana/química , Antibacterianos/química , Águas Residuárias/química , Polímeros/química , Cinética
19.
Environ Res ; 255: 119132, 2024 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-38735380

RESUMO

The anaerobic digestion (AD) process has become significant for its capability to convert organic wastewater into biogas, a valuable energy source. Excessive acetic acid accumulation in the anaerobic digester can inhibit methanogens, ultimately leading to the deterioration of process performance. Herein, the effect of magnetite particles (MP) as an enhancer on the methanogenic degradation of highly-concentrated acetate (6 g COD/L) was examined through long-term sequential AD batch tests. Bioreactors with (AM) and without (AO) MP were compared. AO experienced inhibition and its methane production rate (qm) converged to 0.45 L CH4/g VSS/d after 10 sequential batches (AO10, the 10th batch in a series of the sequential batch tests conducted using bioreactors without MP addition). In contrast, AM achieved 3-425% higher qm through the sequential batches, indicating that MP could counteract the inhibition caused by the highly-concentrated acetate. MP addition to inhibited bioreactors (AO10) successfully restored them, achieving qm of 1.53 L CH4/g VSS/d, 3.4 times increase from AO10 after 8 days lag time, validating its potential as a recovery strategy for inhibited digesters with acetate accumulation. AM exhibited higher microbial populations (1.8-3.8 times) and intracellular activity (9.3 times) compared to AO. MP enriched Methanosaeta, Peptoclostridium, Paraclostridium, OPB41, and genes related to direct interspecies electron transfer and acetate oxidation, potentially driving the improvement of qm through MP-mediated methanogenesis. These findings demonstrated the potential of MP supplementation as an effective strategy to accelerate acetate-utilizing methanogenesis and restore an inhibited anaerobic digester with high acetate accumulation.


Assuntos
Ácido Acético , Reatores Biológicos , Metano , Anaerobiose , Metano/metabolismo , Reatores Biológicos/microbiologia , Ácido Acético/metabolismo , Óxido Ferroso-Férrico/metabolismo , Eliminação de Resíduos Líquidos/métodos
20.
Environ Res ; 251(Pt 2): 118740, 2024 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-38521356

RESUMO

Magnetite mining is a significant contributor to land deterioration as well as HM-based soil contamination. The characteristics of magnetite mine tailing were examined in the present study, in addition to the positive and sustainable restoration strategy with Bougainvillaea glabra under the influence of Thiobacillus ferroxidance. The traits of test soil analysis findings demonstrated that the majority of the parameters exceeded the allowable limits (For instance: HMs such as Cr, Cu, Zn, Pb, Fe, and Co were found to be 208 ± 2.3, 131.43 ± 1.6, 185.41 ± 3.3, 312 ± 5.11, 956 ± 5.3, and 26.89 ± 2.43 mg kg-1 respectively). T. ferroxidance exhibited impressive HMs tolerance for as much as 800 g mL-1 concentrations of Cr, Cu, Zn, Pb, Fe, and Co. To prevent HMs toxic effects, the HMs contents in test soil were decreased by diluting with normal soil in the ratios of Ex-3 and Ex-2. A typical greenhouse study was carried out to assess the phytoremediation ability of B. glabra across six setups for experiments (Ex-1 to Ex-6). According to the findings of this research, the HMs tolerant T. ferroxidance from Ex-3 and Ex-2 had an outstanding impact on the growth, biomolecules level (such as chlorophylls: 65.84 & 41.1 mg g-1, proteins: 165.1 & 151.1 mg g-1, as well as carbohydrates: 227.4 & 159.3 mg g-1) as well as phytoremediation potential of B. glabra on magnetite mine soil. These findings indicated that a mixture of B. glabra as well as T. ferroxidance might serve as a valuable sustainable agent for removing HMs from contaminated soil.


Assuntos
Biodegradação Ambiental , Mineração , Poluentes do Solo , Poluentes do Solo/análise , Poluentes do Solo/metabolismo , Óxido Ferroso-Férrico/química , Solo/química , Metais Pesados/análise , Metais Pesados/metabolismo , Bacillaceae/metabolismo
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