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Peroxydisulfate (PDS) and peroxymonosulfate (PMS) could be efficiently activated by heat to generate reactive oxygen species (ROS) for the degradation of organic contaminants. However, defects including the inefficiency treatment and pH dependence of monooxidant process are prominent. In this study, synergy of heat and the PDS-PMS binary oxidant was studied for efficient triclosan (TCS) degradation and apply in rubber wastewater. Under different pH values, the degradation of TCS followed pseudo-first-order kinetics, the reaction rate constant (kobs) value of TCS in heat/PDS/PMS system increased from 1.8 to 4.4 fold and 6.8-49.1 fold when compared to heat/PDS system and heat/PMS system, respectively. Hydroxyl radicals (·OH), sulfate radicals (SO4·-) and singlet oxygen (1O2) were the major ROS for the degradation of TCS in heat/PDS/PMS system. In addition, the steady-state concentrations of ·OH/1O2 and SO4·-/·OH/1O2 increased under acidic conditions and alkaline conditions, respectively. It was concluded that the pH regulated the ROS for degradation of TCS in heat/PDS/PMS system significantly. Based on the analysis of degradation byproducts, it was inferred that the dechlorination, hydroxylation and ether bond breaking reactions occurred during the degradation of TCS. Moreover, the biological toxicity of the ten byproducts was lower than that of TCS was determined. Furthermore, the heat/PDS/PMS system is resistant to the influence of water substrates and can effectively improve the water quality of rubber wastewater. This study provides a novel perspective for efficient degradation of TCS independent of pH in the heat/PDS/PMS system and its application of rubber wastewater.
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Triclosan , Poluentes Químicos da Água , Oxidantes/química , Águas Residuárias , Espécies Reativas de Oxigênio , Borracha , Oxirredução , Poluentes Químicos da Água/química , Peróxidos/químicaRESUMO
Due to large specific surface area, abundant surface functional groups, and stable chemical structure, biochar has been widely used in many environmental fields, including the remediation of Cr pollution. Alternatively, electrochemically active organic matter (e-OM), which is prevalent in both natural environments and industrial wastewater, exerts an inevitable influence on the mechanisms underlying Cr(VI) removal by biochar. The synergistic interplay between biochar and e-OM in the context of Cr(VI) remediation remains to be fully elucidated. In this study, disodium anthraquinone-2,6-disulfonate (AQDS) was used as a model for e-OM, characterized by its quinone group's ability to either donate or accept electrons. We found that AQDS sped up the Cr(VI) removal process, but the enhancement effect decreased with the increase in pyrolysis temperature. With the addition of AQDS, the removal amount of Cr(VI) by BC300 and BC600 increased by 160.0% and 49.5%, respectively. AQDS could release more electrons trapped in the lower temperature biochar samples (BC300 and BC600) for Cr(VI) reduction. However, AQDS inhibited the Cr(VI) removal by BC900 due to the adsorption of AQDS on biochar surface. In the presence of the small molecule carbon source lactate, more AQDS was adsorbed onto the biochar surface. This led to an inhibition of the electron transfer between biochar and Cr(VI), resulting in an inhibitory effect. This study has elucidated the electron transfer mechanism involved in the removal of Cr(VI) by biochar, particularly in conjunction with e-OM. Furthermore, it would augment the efficacy of biochar in applications targeting the removal of heavy metals.
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Biochar can facilitate Cr(VI) bioreduction, but it is still undetermined which biochar property control this process. We observed that the apparent Cr(VI) bioreduction by Shewanella oneidensis MR-1 could be identified as a fast and a relatively slow processes. The fast-bioreduction rates (rf0) were 2-15 times higher than the slow-bioreduction rates (rs0). In this study, we investigated the kinetics and efficiency of biochar in promoting Cr(VI) reduction by S. oneidensis MR-1 in the neutral solution using a "dual-process model" (fast and slow processes), and analyzed the mechanisms of biochar concentration, conductivity, particle size and other properties on these two processes. The correlation analysis of these rate constants and biochar properties was carried out. The fast-bioreduction rates were associated with higher conductivity and smaller particle sizes of biochar, which facilitated the direct electron transfer from Shewanella oneidensis MR-1 to Cr(VI). The Cr(VI) slow-bioreduction rates (rs0) were mainly determined by the electron donating capability of biochar and independent of the cell concentration. Our results suggested that Cr(VI) bioreduction was mediated by both electron conductivity and redox potential of biochar. This result is instructive for biochar production. Manipulating biochar properties to control fast and slow Cr(VI) reduction may be helpful to effectively remove or detoxify Cr(VI) in the environment.
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Elétrons , Shewanella , Oxirredução , CromoRESUMO
In this study, ferrous composites (FexO4) were prepared by microreactor to activate peroxydisulfate (PDS) for the degradation of bisphenol A (BPA) with visible (Vis) light irradiation. X-ray diffraction (XRD), energy-dispersive spectrometry (EDS), X-ray photoelectron spectroscopy (XPS), and scanning electron microscope (SEM) were used to characterize the morphology and crystal phase of FeXO4. Photoluminescence (PL) spectroscopy combined with amperometric tests were used to determine the role of PDS on the performance of photocatalytic reaction. The main reactive species and intermediates for BPA removal were determined by electron paramagnetic resonance (EPR) measurement and quenching experiments. The result indicated that singlet state oxygen (1O2) contributed more to the BPA degradation than that of other reactive radicals (·OH, SO4·- and ·O2-); these reactive radicals and 1O2 formed by the reaction between photo-generated electrons (e-) and holes (h+) of FexO4 and PDS. During this process, the consumption of e- and h+ also improved their separation efficiency and thus enhanced the degradation of BPA. In addition, the photocatalytic activity of FexO4 in Vis/FexO4/PDS system was 3.2-fold and 6.6-fold higher than that of single FexO4 and PDS under Vis light, respectively. The Fe2+/Fe3+ cycle could effectively drive the photocatalytic activation of PDS through indirect electron transfer and the formation of reactive radicals. This work illustrated that the degradation of BPA was rapidly in Vis/FexO4/PDS system mainly through 1O2, which further improve our understanding on the efficient removal of organic contaminants in the environment.
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Oxigênio , Oxigênio Singlete , Luz , Fenóis/químicaRESUMO
Environmentally persistent free radicals (EPFRs) are considered as an emerging pollutant due to their potential environmental risks, but the distribution characteristics of particulate matters (PMs)-EPFRs from residential combustion source are poorly understood. In this study, biomass (corn straw, rice straw, pine and jujube wood) combustion was studied in lab-controlled experiments. More than 80% of PM-EPFRs were distributed in PMs with aerodynamic diameter (dae) ≤ 2.1 µm, and their concentration in fine PMs was about 10 times that in coarse PM (2.1 µm ≤ dae ≤ 10 µm). The detected EPFRs were carbon-centered free radicals adjacent to oxygen atoms or a mixture of oxygen- and carbon-centered radicals. The concentrations of EPFRs in coarse and fine PMs were positively correlated with char-EC, but the EPFRs in fine PMs exhibited a negative correlation with soot-EC (p < 0.05). The increase of PM-EPFRs signals with the increased dilution ratio during pine wood combustion was more significant than that from rice straw, which may be resulted from the interactions between the condensable volatiles and the transition metals. Our study provides useful information for better understanding the formation of combustion-derived PM-EPFRs, and will be instructive for its purposeful emissions control.
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Glioma is often referred to as one of the most dreadful central nervous system (CNS)-specific tumors with rapidly-proliferating cancerous glial cells, accounting for nearly half of the brain tumors at an annual incidence rate of 30-80 per a million population. Although glioma treatment remains a significant challenge for researchers and clinicians, the rapid development of nanomedicine provides tremendous opportunities for long-term glioma therapy. However, several obstacles impede the development of novel therapeutics, such as the very tight blood-brain barrier (BBB), undesirable hypoxia, and complex tumor microenvironment (TME). Several efforts have been dedicated to exploring various nanoformulations for improving BBB permeation and precise tumor ablation to address these challenges. Initially, this article briefly introduces glioma classification and various pathogenic factors. Further, currently available therapeutic approaches are illustrated in detail, including traditional chemotherapy, radiotherapy, and surgical practices. Then, different innovative treatment strategies, such as tumor-treating fields, gene therapy, immunotherapy, and phototherapy, are emphasized. In conclusion, we summarize the article with interesting perspectives, providing suggestions for future glioma diagnosis and therapy improvement.
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Neoplasias Encefálicas , Glioma , Nanoestruturas , Humanos , Glioma/terapia , Glioma/tratamento farmacológico , Neoplasias Encefálicas/terapia , Neoplasias Encefálicas/tratamento farmacológico , Nanomedicina , Nanoestruturas/uso terapêutico , Barreira Hematoencefálica , Microambiente TumoralRESUMO
Achieving up-cycling and reusing of silver from the waste X-rays films is currently a huge challenge. Here, we designed a facile method that upcycles Ag+ extract efficiently from waste film into highly dispersed value-added biological Ag/AgO-AgCl nanoparticles (bio-Ag/AgO-AgCl NPs) using Bacillus thuringiensis-secreted extracellular polymeric substance without additional reductants and electron donors. The recovery efficiency of silver exceeded 99.8%. Surprisingly, the bio-Ag/AgO-AgCl NPs can well solve the bottleneck problem of slow Ag catalytic kinetics. When the amount of catalyst was 1.9 mg, the reduction efficiency and reduction rate of 10 ppm methyl orange were 97.9% and 7 min, and that of 30 ppm Congo red were 95.3% and 5 min respectively, which is superior to other chemically synthesized silver-base catalysts. This bioremediation methodology provides an effective and practical technical approach for precious metal remediation and sustainable energy development.
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Nanopartículas Metálicas , Prata , Bactérias , Catálise , Matriz Extracelular de Substâncias Poliméricas , Nanopartículas Metálicas/química , Substâncias Redutoras , Prata/químicaRESUMO
The conventional fluorescence analysis methods for disease identification are vulnerable to the restriction with false-positive. Here, a fluorescent switch with high efficiency and regeneration by the black phosphorus (BP) nanosheets-regulated was developed to overcome false-positive issue in the assay of ß-amyloid1-42 oligomers (Aß) process. The Aß was rapidly recognized using the fluorescent emitter-nitrogen-doped carbon nanodots (N-CDs) under the regulation of BP nanosheets, while the N-CDs alone cannot recognize Aß without the introduction of BP. The fluorescence analysis methods exhibited a wide sensing range of 0.25-15.0 ng/mL and a low detection limit of 83 pg/mL for Aß analysis, which was superior to the reported fluorescence analysis method. Further, BP nanosheets were recycled, demonstrating the fluorescent switch with highly efficient, stable, and regenerable. This provides a new idea for developing high-efficiency and high-precision fluorescence detection platform.
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Pontos Quânticos , Peptídeos beta-Amiloides , Carbono , Corantes Fluorescentes , Nitrogênio , Fragmentos de Peptídeos , FósforoRESUMO
BACKGROUND: Delirium affects up to 80% of patients in intensive care units (ICUs) and is associated with higher mortality, physical dependence, and health care costs. The 2018 pain, agitation, delirium, immobility, and sleep guideline recommended ABCDEF care bundle for delirium prevention and management. However, limited information is available regarding the adoption of the care bundle in ICUs in Mainland China. AIMS AND OBJECTIVES: To assess the current implementation of the ABCDEF care bundle for delirium prevention as reported by ICU nurses in Mainland China. DESIGN: A cross-sectional study was conducted. METHODS: A cross-sectional online survey using a validated questionnaire about the practices of the ABCDEF care bundle was conducted among 334 registered nurses in 167 ICUs of 65 cities in Mainland China. RESULTS: Almost 50% of the sampled ICU nurses were unaware of the ABCDEF care bundle, though 86.83% of the surveyed ICUs implemented pain assessments and 95.51% implemented sedation assessments. Nearly half (46.41%) of the surveyed ICUs performed routine spontaneous awaking trials, with 21.26% performing them daily. Spontaneous breathing trials were performed in 38.32% of the surveyed ICUs. Only 47% of the surveyed ICUs routinely monitored patients for delirium. About one-third (38.35%) of the surveyed ICUs were supported by specialist teams that implemented the mobilization programmes. Most ICUs restricted the duration of family visits per day (<0.5 hour: 61.67%; 0.5-2 hours: 23.65%; >2 hours: 3.29%) and only 28.14% of the surveyed ICUs employed dedicated staff to support the families. CONCLUSIONS: Although most of the surveyed ICUs implemented pain and sedation assessments, many of them did not implement structured delirium assessments. Early mobilization programmes and family participation should be encouraged. RELEVANCE TO CLINICAL PRACTICE: Promoting the uses of a reliable delirium assessment tool such as Confusion Assessment Method for Intensive Care Unit patients, building an early mobilization team, and engaging family caregivers in the care plan may contribute to improved patients' clinical outcomes.
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Delírio , Pacotes de Assistência ao Paciente , Cuidados Críticos , Estudos Transversais , Delírio/prevenção & controle , Humanos , Unidades de Terapia IntensivaRESUMO
The remediation of heavy metal is facing the great challenge of failing to achieve valuable transformation. Therefore, the development of a sustainable technology for heavy metal recycling and reuse is essential. The present study proposed a new way to convert Cr(VI) into value-added biological Cr2O3 nanoparticles (bio-Cr2O3 NPs) with B. megaterium-secreted tryptophan residues proteins (TPN). In this process, Cr(VI) was reduced extracellularly to Cr(III) by B. megaterium without additional reductant and electron donors. This study overcomes the difficulty of separation of NPs and biomass, and realizes the recovery of bio-Cr2O3 NPS from biomass. The conversing efficiency of bio-Cr2O3 NPs reached the highest level (96.56%) at the concentration of 10 ppm Cr(VI). In particular, bio-Cr2O3 NPs exhibited excellent catalytic activity for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in 1 M KOH, outperforming chemically synthesized Cr-base catalysts. Three-dimensional matrix fluorescence (EEM), verification of tryptophan reduction and computation chemistry fully confirmed that TPN was responsible for the bio-Cr2O3 NPs formation. This comprehensive approach to bioremediation, synthesis NPs and recovery, as well as application will open a window for sustainable energy development and heavy metal pollution remediation.
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Bacillus megaterium , Metais Pesados , Biodegradação Ambiental , Cromo/análiseRESUMO
Although bio-inspired designs for ultrasmall metal nanoparticles (NPs) are likely to play an important role in exploring future heterogeneous catalysis materials, synthesizing these structures while retaining surface activity and avoiding aggregation is challenging. Inspired by the Morchella with the spatially and well-organized porous structures, we proposed a biological strategy to yield NPs with ultrasmall and highly dispersed while maintaining high catalytic activity through surfactin self-assembly. Here, multifunctional Morchella-like biological pores (MBP) nanomaterials (~28 nm) with reduction and encapsulation has been synthesized by surfactin self-assembly, then, ultrasmall PtPd (~2.90 nm) and Pd NPs (~2.87 nm) with coordinated sizes and well-dispersed have been successfully reduced and encapsulated inside the MBP. Notably, the synthesis possesses distinct advantages such as mild reaction conditions, strong controllability, good biological compatibility, low-toxicity and environmental friendliness. The as-prepared MBP-encapsulated ultrasmall PtPd and Pd NPs (M@MBP NPs) exhibited excellent catalytic activity and toxicity resistance for the ethanol oxidation reaction (EOR) in KOH, due to the synergistic effect of MBP and ultrasmall metal NPs. The current density of PtPd@MBP and Pd@MBP NPs were 3.35 and 2.72 A mg-1, respectively. Such MBP synthesized and encapsulated nanoparticles open a new frontier for the design and preparation of NPs for various applications, such as catalysis, bioremediation and drug delivery.
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Nanopartículas Metálicas , Nanoestruturas , Preparações Farmacêuticas , Catálise , OxirreduçãoRESUMO
Metal-cyanide complexes are hazardous and toxic pollutants that can accumulate in organisms, and their natural degradation is difficult. These complexes are primarily present in alkaline wastewater effluents, and an effective technique for their removal must be developed. Herein, we have successfully synthesized a novel quaternary ammonium-functionalized Zr4+ metal-organic resin (MOR) (H16[Zr6O16(MPATP)4]Cl8·xH2O, MPATP = 2-((1-methylpyridin-1-ium-2-ylmethyl)amino)-terephthalic acid), which we refer to as MOR-2-QAS. With alkali resistance, high surface area, and high anion exchange capacity, it acts by introducing positively charged pyridine into the organic ligand. The experimental results indicate that MOR-2-QAS becomes rapidly attached and efficiently removes Pt(CN)42-, Pd(CN)42-, Co(CN)63-, and Fe(CN)63-. Valuable metals (Pt(II) and Pd(II)) can be effectively recovered from the simulated wastewater containing four-component cyanide complexes via the two-step elution process. The recovery efficiency of Pt(II) and Pd(II) was higher than 90.0% after three adsorption-desorption cycles. The adsorption mechanism, which proceeded via ionic association (ion-exchange) and complied with the minimum surface charge density experiential principle, was confirmed using density functional theory. This study provides ideas for developing efficient and stable MORs to enable the simultaneous removal of multiple metal-cyanide complexes and recovery of valuable metals.
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Mixed [C8bet]Br/[C4mim][NTf2] ionic liquids were used as a new extraction system to extract Pd(II) from multimetal-ion solutions. The separation factors K Pd/M (M: Cu, Fe, Ni, Zn, Co) are greater than 103. Thiourea was found to be an effective stripping agent. After three cycles, the recovery efficiency was higher than 91.0%. Direct electrodeposition of palladium from the mixed ionic liquid phase was also studied. The Pd(II) complex in [C8bet]Br/[C4mim][NTf2] system was studied by cyclic voltammetry at 348 K. The results indicate the existence of three types of Pd(II) complex in the [C8bet]Br/[C4mim][NTf2] system, leading to three reductive waves. The reduction of Pd(II) to Pd(0) in this system is irreversible. A uniform black coating was obtained by constant-potential deposition at -1.7 V on a nickel foil, confirmed to be palladium metal by energy-dispersive spectrometry, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy analyses. After three cycles of continuous extraction-electrodeposition, over 90.0% of palladium was recovered.
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In this study, soluble extracellular polymeric substances (s-EPS) secreted by Bacillus cereus (B. cereus) were studied as a novel, dual bio-functional corrosion and scale inhibiting material, in artificial seawater. Static tests showed that the scale inhibition efficiency (SI%) was close to 87.60% for CaCO3 at the concentration of 80â¯mg/L s-EPS. Electrochemical technique results showed that s-EPS inhibition efficiencies, in relation to 316L stainless steel (SS), and at the concentration of 40â¯mg/L, reached 91.05% at 10â¯d and 91.16% at 30â¯d, respectively. The high anti-scale and anti-corrosion performance of s-EPS was related to their chelating, adsorption, and biomineralization abilities. s-EPS integrated with metal ions on the SS surface, resulting in formation of a thin but dense biomineralized film, which exhibited lasting corrosion resistance. Meanwhile, s-EPS controlled the kinetic pathway of CaCO3 biomineralized nucleation and crystal growth, which inhibited CaCO3 crystal precipitation. This finding suggests that B. cereus s-EPS may offer a green, sustainable, and economic strategy for anti-corrosion and anti-scale application in industry.
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Bacillus cereus , Biofilmes , Corrosão , Água do Mar , Aço InoxidávelRESUMO
It is well known that microorganisms tend to form biofilms on metal surfaces to accelerate/decelerate corrosion and affect their service life. Bacillus subtilis was used to produce a dense biofilm on an AZ31B magnesium alloy surface. Corrosion behavior of the alloy with the B. subtilis biofilm was evaluated in artificial seawater. The results revealed that the biofilm hampered extracellular electron transfer significantly, which resulted in a decrease of icorr and increase of Rt clearly compared to the control group. Moreover, an ennoblement of Ecorr was detected under the condition of B. subtilis biofilm covering. Significant reduction of the corrosion was observed by using the cyclic polarization method. All of these prove that the existence of the B. subtilis biofilm effectively enhances the anti-corrosion performance of the AZ31B magnesium alloy. This result may enhance the usage of bio-interfaces for temporary corrosion control. In addition, a possible corrosion inhibition mechanism of B. subtilis on AZ31B magnesium alloy was proposed.
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Here, a heterogeneous Bacillus cereus (B. cereus) biofilm on the surface of 316 L stainless steel (SS) was observed. With electrochemical measurement and surface analysis, it was found that B. cereus biofilm could inhibit SS pitting corrosion, attributing to the blocking effect of bacterial biofilm on extracellular electron transfer (EET). Differential pulse voltammetry (DPV) and cyclic voltammetry (CV) results also showed that B. cereus biofilm clearly impeded the EET. The proposed mechanism for the decreased corrosion rates of SS involves the interactions of extracellular polymeric substance (EPS) with SS and biofilm formation blocking electron transfer, preventing the passive layer from destroying. After biofilm formation following initial attachment of cells and EPS, electron transfer between SS and the cathodic depolarizer (oxygen) was hindered.
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Bacillus cereus/química , Biofilmes/crescimento & desenvolvimento , Aço Inoxidável/química , Bacillus cereus/metabolismo , Aderência Bacteriana , Corrosão , Técnicas Eletroquímicas , Transporte de Elétrons , Elétrons , Espectroscopia de Infravermelho com Transformada de Fourier , Propriedades de SuperfícieRESUMO
In this paper, a novel adsorbent, Fe3O4@SiO2@PEI-NTDA, was first prepared by the immobilization of an amine and anhydride onto magnetic Fe3O4@SiO2 nanoparticles with polyethylenimine (PEI) and 1,4,5,8-naphthalenetetracarboxylic-dianhydride (NTDA) for the removal of heavy metal ions from aqueous solutions. The structure of Fe3O4@SiO2@PEI-NTDA was systematically investigated; the results confirmed that amine and anhydride groups were successfully covalently grafted onto the surface of Fe3O4@SiO2, which showed a homogenous core-shell structure with three layers of about 300 nm diameter (Fe3O4 core: 200 nm, nSiO2 layer: 20 nm, and PEI-NTDA layer: 20 nm). The adsorption performance of Fe3O4@SiO2@PEI-NTDA NPs was evaluated for single Pb2+ and coexisting Cd2+, Ni2+, Cu2+, and Zn2+ ions in an aqueous solution in a batch system. The amine and anhydride groups may have a synergistic effect on Pb2+ removal through electrostatic interactions and chelation; Fe3O4@SiO2@PEI-NTDA NPs exhibited preferable removal of Pb2+ with maximum adsorption capacity of 285.3 mg g-1 for Pb2+ at a solution pH of 6.0, adsorbent dosage of 0.5 g L-1, initial Pb2+ concentration of 200 mg L-1 and contact time of 3 h. The adsorption mechanism conformed well to the Langmuir isotherm model, and the adsorption kinetic data were found to fit the pseudo-second order model. Fe3O4@SiO2@PEI-NTDA NPs could be recovered easily from their dispersion by an external magnetic field and demonstrated good recyclability and reusability for at least 6 cycles with a high adsorption capacity above 204.5 mg g-1. The magnetic adsorbents showed high stability with a weight loss below 0.65% in the acid leaching treatment by 2 M HCl solution for 144 h. This study indicates that Fe3O4@SiO2@PEI-NTDA NPs are new promising adsorbents for the effective removal of Pb2+ in wastewater treatment.
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Bacteria biofilm formation on metals is well-known, while biofilm architecture varies under different conditions. To date, few studies have determined the possible contribution to corrosion of titanium made by biofilm architecture. We investigated the interaction between the oral Streptococcus sanguis biofilm architecture and its influence on titanium corrosion in enriched artificial saliva using electrochemical methods and microscopic study. Patchy biofilms were observed on titanium surface after being immersed in solution containing S. sanguis. The thickness and size of the patchy biofilms increased with an increase of immersion time. The extensive pits were clearly observed by scanning electron microscopy, showing that adsorption of S. sanguis on titanium promoted the localized corrosion. The electrochemical results indicated that the corrosion rates were clearly accelerated in the presence of S. sanguis. The low icorr and high Rt in the first 48 h indicated that a typical passive behavior still remained. Our study showed that the pitting corrosion of titanium was mainly attributed to the formation of a self-catalytic corrosion cell by the co-effect of patchy biofilm and organic acid secreted by S. sanguis.