Insights into the long-term immobilization performances and mechanisms of CMC-Fe0/FeS with different sulfur sources for uranium under anoxic and oxic aging.

Nanoscale zerovalent iron (Fe0)-based materials have been demonstrated to be a effective method for the U(VI) removal. However, limited research has been conducted on the long-term immobilization efficiency and mechanism of Fe0-based materials for U(VI), which are essential for achieving safe handling and disposal of U(VI) on a large scale. In this study, the prepared carboxymethyl cellulose (CMC) and sulfurization dual stabilized Fe0 (CMC-Fe0/FeS) exhibited excellent long-term immobilization performances for U(VI) under both anoxic and oxic conditions, with the immobilization efficiencies were respectively reached over 98.0 % and 94.8 % after 180 days of aging. Most importantly, different from the immobilization mechanisms of the fresh CMC-Fe0/FeS for U(VI) (the adsorption effect of -COOH and -OH groups, coordination effect with sulfur species, as well as reduction effect of Fe0), the re-mobilized U(VI) were finally re-immobilized by the formed FeOOH and Fe3O4 on the aged CMC-Fe0/FeS. Under anoxic conditions, more Fe3O4 was produced, which may be the main reason for the long-term immobilization U(VI). Under oxic conditions, the production of Fe3O4 and FeOOH were relatively high, which both played significant roles in re-immobilizing U(VI) through surface complexation, reduction and incorporation effects.

Remediation of contaminated soils by biotechnology with nanomaterials: bio-behavior, applications, and perspectives.

Soil contamination caused by heavy metals and organic pollutants has drawn world-wide concern. Biotechnology has been applied for many years to the decontamination of soils polluted with organic and inorganic contaminants, and novel nanomaterials (NMs) has attracted much concern due to their high capacity for the removal/stabilization/degradation of pollutants. Recently, developing advanced biotechnology with NMs for the remediation of contaminated soils has become a hot research topic. Some researchers found that bioremediation efficiency of contaminated soils was enhanced by the addition of NMs, while others demonstrated that the toxicity of NMs to the organism negatively influenced the repair capacity of polluted soils. This paper reviews the application of biotechnology and NMs in soil remediation, and further provides a critical view of the effects of NMs on the phytoremediation and micro-remediation of contaminated soils. This review also discusses the future research needs for the combined application of biotechnology and NMs in soil remediation.

White rot fungi and advanced combined biotechnology with nanomaterials: promising tools for endocrine-disrupting compounds biotransformation.

Endocrine-disrupting compounds (EDCs) can interfere with endocrine systems and bio-accumulate through the food chain and even decrease biodiversity in contaminated areas. This review discusses a critical overview of recent research progress in the biotransformation of EDCs (including polychlorinated biphenyl and nonylphenol, and suspected EDCs such as heavy metals and sulfonamide antibiotics) by white rot fungi (WRF) based on techniques with an emphasis on summarizing and analyzing fungal molecular, metabolic and genetic mechanisms. Not only intracellular metabolism which seems to perform essential roles in the ability of WRF to transform EDCs, but also advanced applications are deeply discussed. This review mainly reveals the removal pathway of heavy metal and antibiotic pollutants because the single pollution almost did not exist in a real environment while the combined pollution has become more serious and close to people's life. The trends in WRF technology and its related advanced applications which use the combined technology, including biocatalysis of WRF and adsorption of nanomaterials, to degrade EDCs have also been introduced. Furthermore, challenges and future research needs EDCs biotransformation by WRF are also discussed. This research, referring to metabolic mechanisms and the combined technology of WRF with nanomaterials, undoubtedly contributes to the applications of biotechnology. This review will be of great benefit to an understanding of the trends in biotechnology for the removal of EDCs.

Stabilized Nanoscale Zerovalent Iron Mediated Cadmium Accumulation and Oxidative Damage of Boehmeria nivea (L.) Gaudich Cultivated in Cadmium Contaminated Sediments.

Nanoparticles can be absorbed by plants, but their impacts on phytoremediation are not yet well understood. This study was carried out to determine the impacts of starch stabilized nanoscale zerovalent iron (S-nZVI) on the cadmium (Cd) accumulation and the oxidative stress in Boehmeria nivea (L.) Gaudich (ramie). Plants were cultivated in Cd-contaminated sediments amended with S-nZVI at 100, 500, and 1000 mg/kg, respectively. Results showed that S-nZVI promoted Cd accumulation in ramie seedlings. The subcellular distribution result showed that Cd content in cell wall of plants reduced, and its concentration in cell organelle and soluble fractions increased at S-nZVI treatments, indicating the promotion of Cd entering plant cells by S-nZVI. In addition, the 100 mg/kg S-nZVI alleviated the oxidative damage to ramie under Cd-stress, while 500 and 1000 mg/kg S-nZVI inhibited plant growth and aggravated the oxidative damage to plants. These findings demonstrate that nanoparticles at low concentration can improve the efficiency of phytoremediation. This study herein develops a promising novel technique by the combined use of nanotechnology and phytoremediation in the remediation of heavy metal contaminated sites.

Prospects for the clinical application of exosomal circular RNA in squamous cell carcinoma.

Squamous cell carcinoma (SCC) is a prevalent malignancy affecting multiple organs in the human body, including the oral cavity, esophagus, cervix, and skin. Given its significant incidence and mortality rates, researchers are actively seeking effective diagnostic and therapeutic strategies. In recent years, exosomes and their molecular cargo, particularly circular RNA (circRNA), have emerged as promising areas of investigation in SCC research. Exosomes are small vesicles released into the extracellular environment by cells that contain biomolecules that reflect the physiological state of the cell of origin. CircRNAs, known for their unique covalently closed loop structure and stability, have garnered special attention in oncology and are closely associated with tumorigenesis, progression, metastasis, and drug resistance. Interestingly, exosomal circRNAs have been identified as ideal biomarkers for noninvasive cancer diagnosis and prognosis assessment. This article reviews the progress in research on exosomal circRNAs, focusing on their expression patterns, functions, and potential applications as biomarkers in SCC, aiming to provide new insights and strategies for the diagnosis and treatment of SCC.

Activation of persulfate by biochar-supported sulfidized nanoscale zero-valent iron for degradation of ciprofloxacin in aqueous solution: process optimization and degradation pathway.

The pollution of antibiotics, specifically ciprofloxacin (CIP), has emerged as a significant issue in the aquatic environment. Advanced oxidation processes (AOPs) are capable of achieving stable and efficient removal of antibiotics from wastewater. In this work, biochar-supported sulfidized nanoscale zero-valent iron (S-nZVI/BC) was adopted to activate persulfate (PS) for the degradation of CIP. The impacts of different influencing factors such as S/Fe molar ratios, BC/S-nZVI mass ratios, PS concentration, S-nZVI/BC dosage, CIP concentration, initial pH, coexisting anions, and humic acid on CIP degradation efficiency were explored by batch experiments. The results demonstrated that the highest degradation ability of S-nZVI/BC was achieved when the S/Fe molar ratio was 0.07 and the BC/S-nZVI mass ratio was 1:1. Under the experimental conditions with 0.6 g/L S-nZVI/BC, 2 mmol/L PS, and 10 mg/L CIP, the degradation rate reached 97.45% after 90 min. The S-nZVI/BC + PS system showed significant degradation in the pH range from 3 to 9. The coexisting anions affected the CIP degradation efficiency in the following order: CO32- > NO3- > SO42- > Cl-. The radical quenching experiments and electron paramagnetic resonance (EPR) revealed that oxidative species, including SO4•-, HO•, •O2-, and 1O2, all contribute to the degradation of CIP, in which •O2- plays a particularly prominent role. Furthermore, the probable degradation pathway of CIP was explored according to the 12 degradation intermediates identified by LC-MS. This study provides a new idea for the activation method of PS and presents a new approach for the treatment of aqueous antibiotics with highly catalytic active nanomaterials.

Affecting factors and mechanism of removing antibiotics and antibiotic resistance genes by nano zero-valent iron (nZVI) and modified nZVI: A critical review.

Antibiotics and antibiotic resistance genetic pollution have become a global environmental and health concern recently, with frequent detection in various environmental media. Therefore, finding ways to control antibiotics and antibiotic resistance genes (ARGs) is urgently needed. Nano zero-valent iron (nZVI) has shown a positive effect on antibiotics degradation and restraining ARGs, making it a promising solution for controlling antibiotics and ARGs. However, given the current increasingly fragmented research focus and results, a comprehensive review is still lacking. In this work, we first introduce the origin and transmission of antibiotics and ARGs in various environmental media, and then discuss the affecting factors during the degradation of antibiotics and the control of ARGs by nZVI and modified nZVI, including pH, nZVI dose, and oxidant concentration, etc. Then, the mechanisms of antibiotic and ARGs removal promoted by nZVI are also summarized. In general, the mechanism of antibiotic degradation by nZVI mainly includes adsorption and reduction, while promoting the biodegradation of antibiotics by affecting the microbial community. nZVI can also be combined with persulfates to degrade antibiotics through advanced oxidation processes. For the control of ARGs, nZVI not only changes the microbial community structure, but also affects the proliferation of ARGs through affecting the fate of mobile genetic elements (MGEs). Finally, some new ideas on the application of nZVI in the treatment of antibiotic resistance are proposed. This paper provides a reference for research and application in this field.

High performance self-assembled sulfidized nanoscale zero-valent iron for the immobilization of cadmium in contaminated sediments: Optimization, microbial response, and mechanisms.

Sulfidized nanoscale zero-valent iron (S-nZVI) showed excellent removal capacity for cadmium (Cd) in aqueous phase. However, the remediation effects of S-nZVI on Cd-contaminated sediment and its interactions with microorganisms in relation to Cd fate remain unclear. The complexity of the external environment posed a challenge for Cd remediation. This study synthesized S-nZVI with different S and Fe precursors to investigate the effect of precursors and applied the optimal material to immobilize Cd in sediments. Characterization analysis revealed that the precursor affected the morphology, Fe0 crystallinity, and the degree of oxidation of the material. Incubation experiments demonstrated that the immobilization efficiency of Cd using S-nZVIFe3++S2- (S/Fe = 0.14) reached the peak value of 99.54%. 1% and 5% dosages of S-nZVI significantly reduced Cd concentration in the overlying water, DTPA-extractable Cd content, and exchangeable (EX) Cd speciation (P < 0.05). Cd leaching in sediment and total iron in the overlying water remained at low levels during 90 d of incubation. Notably, each treatment maintained a high Cd immobilization efficiency under different pH, water/sediment ratio, organic acid, and coexisting ion conditions. Sediment physicochemical properties, functional bacteria, and a range of adsorption, complexation and precipitation of CdS effects dominated Cd immobilization.

Activity and mechanism of vanadium sulfide for organic contaminants oxidation with peroxymonosulfate.

Transition metal sulfides have been demonstrated to be effective for peroxymonosulfate (PMS) activation towards wastewater treatment. However, the activity of vanadium sulfide (VS4) and the role of the chemical state of V have not been revealed. Here, three types of VS4 with various morphologies and chemical states of V were synthesized by using methanol (M-VS4, nanosphere composed of nanosheets), ethanol (E-VS4, sea urchin like nanosphere) and ultrapure water (U-VS4, compact nanosphere) as hydrothermal solvent, respectively, and used as heterogeneous catalysts to activate PMS for the degradation of refractory organic pollutants. The effects of PMS concentration, temperature, pH, inorganic ions, and humic acid (HA) on the degradation efficiency of VS4/PMS system were investigated systematically. The results indicated that the highest specific surface area and lowest ratio of V5+ enable E-VS4/PMS system possessed the highest performance in degrading tetracycline hydrochloride (TCH), in which 100% TCH was removed after operating 10 min (0.805 min-1) under a relatively low concentration of PMS (1 mM) and catalyst (100 mg/L). It also revealed that the system exhibited a typical radical process in TCH degradation, which could be attributed to the redox cycles between V5+, V4+ and V3+ in the presence of PMS to generate various radicals. This radical process enabled the E-VS4/PMS system with a high activity in wide reaction conditions and high mineralization ratios in degrading various refractory organic pollutants within 10 min. In addition, the E-VS4/PMS system exhibited favorable reusability and stability with very less V and S ions leaching, and showed excellent performance in real water purification.

Immobilization of cadmium in river sediments by different modified nanoscale zero-valent iron: performance, mechanisms, and Fe dissolution.

Modified nanoscale zero-valent iron (NZVI) exhibited great potential for the remediation of heavy metal contaminated river sediments, but its mechanisms and environmental risks are still unclear. This study systematically discussed the performance and the mechanisms of modified NZVI materials, i.e., sodium alginate-coated NZVI (SNZVI), rhamnolipid-coated NZVI (RNZVI), and graphene oxide-loaded NZVI (GNZVI), for the stabilization of Cd in sediment, with the exploration of their stability to Cd at various pH values and Fe dissolution rate. Compared with the control, the toxicity characteristic leaching procedure (TCLP) leachable Cd decreased by 52.66-96.28%, and the physiologically based extraction test (PBET) extractable Cd decreased by 44.68-70.21% after 56 days of incubation with the immobilization efficiency varying according to GNZVI > RNZVI > SNZVI > NZVI. Besides, the adsorption behavior of Cd on materials was fitted with the Freundlich model and classified as an endothermic, spontaneous, and chemical adsorption process. SEM-EDX, XRD, and FTIR results verified that the stabilization mechanisms of Cd were principally based on the adsorption, complexation of Cd2+ with secondary Fe minerals (including Fe2O3, γ-Fe2O3, and γ-FeOOH) and precipitation (Cd(OH)2). From the risk assessment results, it was observed that the materials were favorable for Cd stabilization at a pH range from 7 to 11, meanwhile, the leaching concentration of Fe in the overlying water was detected below the limit value. These findings pave the way to developing an effective strategy to remediate Cd contaminated river sediments.

Synergistically adsorbing and reducing Uranium from water by a novel nano zero-valent copper/MXene 0D/2D nanocomposite.

Proper disposal of uranium-containing waste is of utmost importance for safeguarding the environment and human health. In this study, we proposed a novel zero-dimensional (0D)/two-dimensional (2D) nanocomposite material, nZVC/Ti3C2, composed of nano zero-valent copper (nZVC) nanoparticles loaded onto Ti3C2 MXene nanoflakes, which was prepared using a simple in situ chemical reduction method. The uniform dispersion of 0D nZVC nanoparticles, with a size of approximately 5 nm, onto the 2D ultrathin Ti3C2 MXene effectively prevented agglomeration and corrosion of nZVC. This unique configuration provided numerous adsorption sites for UO22+and facilitated a fascinating charge channel for reducing adsorbed UO22+ into low-mobilized UO2 by nZVC. Under the synergistic effect of Ti3C2 MXene and nZVC, remarkable efficiency and selectivity of nZVC/Ti3C2 for U (VI) removal were demonstrated, which exhibited an exceptional adsorption capacity of up to 360 mg/g, coupled with a high removal efficiency of 97.5 % and rapid kinetics. Importantly, the presence of humic acid did not significantly affect the U (VI) removal efficiency of the composite because of the reduction effect of nZVC. The underlying mechanism of U (VI) removal was elucidated, revealing the involvement of reductive immobilization in the form of UO2 (as high as 73.6 %), inner-sphere surface complexation, and hydrolytic precipitation. This mechanism was dependent on the availability of active nZVC and the solution's pH. These findings highlight the potential of nZVC/Ti3C2 composites as efficient decontaminants for radioactive wastewater, thus contributing to advancements in environmental remediation endeavors.

Stabilization of cadmium in contaminated sediment based on a nanoremediation strategy: Environmental impacts and mechanisms.

Nanomaterials have great application potential for the remediation of heavy metal contaminated sediments, but their environmental impacts are still limited. Herein, graphene oxide-supported nanoscale zero-valent iron (GNZVI) was synthesized to explore its role in mediating the immobilization of cadmium (Cd) from contaminated river sediments, with the consideration of the potential impacts on sediment enzyme activities and bacterial community. Compared to NZVI and GO, GNZVI could more effectively promote the transformation of mobile Cd into stable speciation with a maximum residual percentage increasing by 64.82% after 56 days of treatment. The activities of urease, catalase and sucrase were gradually increased and stabilized with the prolongation of treatment time, indicating that the metabolic function of sediments was recovered. 16 S rRNA gene sequencing results confirmed that the application of GNZVI increased the abundance of some Fe(III)-reducing bacteria, further stimulating the bioavailability of organic matter. Additionally, the properties of GO were gradually changed via microbial reduction and finally showed similar properties to rGO. The critical role of rGO as an electrical conductor was to promote the electron transfer process of microbial Fe(III) mineral reduction, which redistributes part of the Fe(III) mineral-associated Cd to more stable secondary iron minerals, thereby further improving the stabilization efficiency of r-GNZVI for Cd.

Progress and challenges of metal-organic frameworks-based materials for SR-AOPs applications in water treatment.

As environmental problems become more and more severe, sulfate radical (SO4-) based advanced oxidation processes (SR-AOPs) are widely recognized for their high removal efficiency of recalcitrant organic pollutants in water. Metal-organic frameworks (MOFs) have attracted wide attention in SR-AOPs due to their outstanding properties (e.g. large surface area, ultra-high porosity, and diversity of material design, etc). Herein, we present an overview of the development and challenges in the synthesis of different types of MOFs, combination of MOFs with other materials (metal centers, conductors, cellulose, etc.) and the construction of catalysts with special structures (core-shell structures and hollow structures) as well as their applications in SR-AOPs for the degradation of organic pollutants. Several review papers have already mentioned the application of a branch of MOFs or simple composites of MOFs in SR-AOP, whereas the latest progresses on the application of MOFs-based materials to SR-AOPs was described rarely. Besides, the degradation mechanism of MOFs as catalysts has not been systematically discussed. To this end, the mechanisms of MOFs and MOF-based materials as catalysts to activate PMS/PS in different systems are analyzed, including radicals and non-radicals pathways. Meanwhile, considering that the research in this field is still in its infancy, a lot of improvements are still needed to effectively promote and implement this technology.

Degradation of sulfamethazine by biochar-supported bimetallic oxide/persulfate system in natural water: Performance and reaction mechanism.

The rapid development of aquaculture results in the increased concentrations and kinds of antibiotics in water environment, and the sharply growing antibiotic contamination has caused increasing concerns. Herein, an innovative sulfamethazine (SMT) removal approach was developed by activation of persulfate (PS) using biochar-based materials prepared by co-precipitation and pyrolysis: Fe-Mg oxide/biochar (FeMgO/BC). Experiments on the activation of PS by FeMgO/BC under different factors were carried out. The involved mechanism and degradation pathway were also studied. Notably, the SMT removal rate reached 99 % under the optimum reaction condition, while the TOC removal efficiency reached 77.9 %. PS was activated by FeMgO/BC and the dominated active radical was SO4•-. Fe2+ from FeMgO and the hydroxyl and carboxyl groups on the surface of biochar contributed to the production of SO4•-. The dehydrogenation, bond cracking and unsaturated bond addition process occurred in the degradation of SMT. Furthermore, FeMgO/BC exhibits excellent reusability and stability. Considering the outstanding actual water application performances and the weak biotoxicity, FeMgO/BC shows a promising potential in the removal of antibiotics under actual water conditions.

Synergistic removal of copper and tetracycline from aqueous solution by steam-activated bamboo-derived biochar.

Steam-activated biochar (SBC) was prepared and showed excellent performance for synergistic removal of Cu2+ and tetracycline (TC). The adsorption capacity of SBC and mutual effect of TC and Cu2+ were investigated via single and binary system and the adsorption isotherm. The adsorption capacity of TC was significantly enhanced when it coexisted with Cu2+. Likewise, increased amounts of Cu2+ were adsorbed in the presence of TC. The presence of NaCl exerted a negative influence on the adsorption of Cu2+, while the inhibitory effect of salinity on TC was neutralized by bridge enhancement in the binary system. Bridge enhancement and site competition were involved in the synergistic removal of TC and Cu2+. Considering the stable application in simulated and real water samples, SBC showed great potential for synergistic removal of antibiotics and heavy metals.

Biochar facilitated the phytoremediation of cadmium contaminated sediments: Metal behavior, plant toxicity, and microbial activity.

Cadmium (Cd) contamination in river sediments becomes increasingly serious, and phytoremediation has been used to remediate Cd contaminated sediments, but the remediation efficiency needs to be improved. In this study, tea waste derived biochar (TB) was used to facilitate the phytoremediation of Cd contaminated sediments. Results showed that TB at 100, 500 and 1000 mg kg-1 increased Cd accumulation and translocation in ramie seedlings by changing Cd speciation in sediments and altering the subcellular distribution of Cd in plant cells. TB at low contents alleviated Cd induced toxicity in ramie seedlings by promoting plant growth and mitigating the oxidative stress. In addition, the activities of urease-, phosphatase-, and catalase-producing microbes in the Cd contaminated sediments were promoted by the application of TB. These findings demonstrated that biochar at low concentrations could improve the phytoremediation efficiency and mitigating Cd-induced toxicity to plants and microbes in Cd contaminated sediments. This study herein provides a novel technological application of waste biomass in controlling and mitigating risks of heavy metals.

Cr(VI) removal from aqueous solution using biochar modified with Mg/Al-layered double hydroxide intercalated with ethylenediaminetetraacetic acid.

In this study, the bamboo biomass loaded with ethylenediaminetetraacetic acid (EDTA) intercalated Mg/Al-layered double hydroxides (LDH) was calcined to obtain a novel nano-adsorbent (BC@EDTA-LDH), and BC@EDTA-LDH was used to remove hexavalent chromium (Cr(VI)) in aqueous solutions. The results showed that the interaction between LDH and Cr(VI) on biochar played a dominant part in adsorption. The LDH of Cr(VI) intercalation was successfully reconstructed after adsorption. Fourier transform infrared spectra and X-ray diffraction results confirmed the reconstruction of Mg/Al-LDH. LDH had sustained release effect on the solution. As the pH values increased, the electrostatic repulsion between Cr2O72- and OH- increased, and there existed competition for adsorption sites. The maximum adsorption capacity of Cr(VI) was 38 mg/g. The data was well-fitted with pseudo second-order model and Langmuir-Freundlich model. BC@EDTA-LDH showed a high adsorption capacity and was potentially suitable for removing heavy metals in wastewater.

Adsorption behavior of engineered carbons and carbon nanomaterials for metal endocrine disruptors: Experiments and theoretical calculation.

Adsorption behaviors and mechanisms of metal endocrine disruptors (Pb2+, Cd2+, and Hg2+) by pyrogenic carbonaceous materials including engineered carbons (biochar and activated carbon) and carbon nanomaterials (multi-walled carbon nanotubes and graphene oxide) have been investigated by experimental and density functional theory (DFT) studies. The adsorption isotherms of metal endocrine disruptors on carbonaceous materials were better fitted by Langmuir models. The adsorption capacities were in the order as follows: GO > BC600 > BC300 > CNT > AC for Pb2+, GO > BC300 > AC > BC600 > CNT for Cd2+, and GO > BC300 ≥ AC > CNT > BC600 for Hg2+, respectively. The DFT-computed binding energy (kcal/mol) of different oxygen-containing functional groups with metal endocrine disruptors followed the orders: (ⅰ) CMCOCPb (-136.70) > CM-COO--Pb (-91.58) > CMCOPb (-33.57) > CMOHPb (-4.69), (ⅱ) CM-COO--Cd (-45.91) > CMCOCCd (-4.49) > CMOHCd (-3.68) > CMCOCd (1.08), (ⅲ) CM-COO--Hg (-25.51) > CMCOCHg (-3.58) > CMOHHg (-0.63) > CMCOHg (0.23). And COC has the highest binding energy for Pb2+, whereas COC has much lower binding energy for Cd2+ and Hg2+. Comprehensively considering DFT calculations, competitive adsorption results and the cost analysis, this work may provide insights into the design of selective adsorbent for specific contaminant.

Insights into the effect of chemical treatment on the physicochemical characteristics and adsorption behavior of pig manure-derived biochars.

Chemical treatment could improve the adsorption performance of biochars (BC). In order to deal with Pb(II) pollution, four types of biochars including unmodified, acid-treated, alkali-treated, and magnetic-treated pig manure-derived biochars (PBCs) were prepared. The effect of chemical treatment on the physical property, chemical composition, and the adsorption behavior of biochars was compared. Magnetic and alkali treatment improved pore volume and specific surface areas, and the adsorption capacity and rates were enhanced. In contrast, the adsorption capacity of acid-treated BC decreased due to the significant decrease of ash content. The magnetic samples displayed the satisfactory absorption performance, which could achieve 99.8% removal efficiency within 15 min at a Pb(II) concentration of 50 mg/L. Considering its properties of excellent adsorption performance, fast reaction rate, and convenient recovery by an external magnetic field, magnetic biochar based on pig manure may provide an effective way to remove heavy metals and decrease the pig manure solid waste.

Electrochemical Aptasensor Based on Sulfur-Nitrogen Codoped Ordered Mesoporous Carbon and Thymine-Hg2+-Thymine Mismatch Structure for Hg2+ Detection.

A renewable electrochemical aptasensor was proposed for super-sensitive determination of Hg2+. The novel aptasensor, based on sulfur-nitrogen codoped ordered mesoporous carbon (SN-OMC) and thymine-Hg2+-thymine (T-Hg2+-T) mismatch structure, used ferrocene as signal molecules to achieve the conversion of current signals. In the absence of Hg2+, the thiol-modified T-rich probe 1 spontaneously formed a hairpin structure by base pairing. After being hybridized with the ferrocene-labeled probe 2 in the presence of Hg2+, the hairpin structure of probe 1 was opened due to the preferential formation of the T-Hg2+-T mismatch structure, and the ferrocene signal molecules approached the modified electrode surface. SN-OMC with high specific surface area and ample active sites acted as a signal amplification element in electrochemical sensing. The sensitive determination of Hg2+ can be actualized by analyzing the relationship between the change of oxidation current caused by ferrocene signal molecules and the Hg2+ concentrations. The aptasensor had a fine linear correlation in the range of 0.001-1000 nM with a detection limit of 0.45 pM. The aptasensor also displayed a good response in real sample detection and provided a promising possibility for in situ detection.