Overexpressing CYP81D11 enhances 2,4,6-trinitrotoluene tolerance and removal efficiency in Arabidopsis.

Phytoremediation is a promising technology for removing the high-toxic explosive 2,4,6-trinitrotoluene (TNT) pollutant from the environment. Mining dominant genes is the key research direction of this technology. Most previous studies have focused on the detoxification of TNT rather than plants' TNT tolerance. Here, we conducted a transcriptomic analysis of wild type Arabidopsis plants under TNT stress and found that the Arabidopsis cytochrome P450 gene CYP81D11 was significantly induced in TNT-treated plants. Under TNT stress, the root length was approximately 1.4 times longer in CYP81D11-overexpressing transgenic plants than in wild type plants. The half-removal time for TNT was much shorter in CYP81D11-overexpressing transgenic plants (1.1 days) than in wild type plants (t1/2 = 2.2 day). In addition, metabolic analysis showed no difference in metabolites in transgenic plants compared to wild type plants. These results suggest that the high TNT uptake rates of CYP81D11-overexpressing transgenic plants were most likely due to increased tolerance and biomass rather than TNT degradation. However, CYP81D11-overexpressing plants were not more tolerant to osmotic stresses, such as salt or drought. Taken together, our results indicate that CYP81D11 is a promising target for producing bioengineered plants with high TNT removing capability.

Metabolic activation of 2,4,6-trinitrotoluene; a case for ROS-induced cell damage.

The explosive compound 2,4,6-trinitrotoluene (TNT) is well known as a major component of munitions. In addition to its potential carcinogenicity and mutagenicity in humans, recent reports have highlighted TNT toxicities in diverse organisms due to its occurrence in the environment. These toxic effects have been linked to the intracellular metabolism of TNT, which is generally characterised by redox cycling and the generation of noxious reactive molecules. The reactive intermediates formed, such as nitroso and hydroxylamine compounds, also interact with oxygen molecules and cellular components to cause macromolecular damage and oxidative stress. The current review aims to highlight the crucial role of TNT metabolism in mediating TNT toxicity, via increased generation of reactive oxygen species. Cellular proliferation of reactive species results in depletion of cellular antioxidant enzymes, DNA and protein adduct formation, and oxidative stress. While TNT toxicity is well known, its ability to induce oxidative stress, resulting from its reductive activation, suggests that some of its toxic effects may be caused by its reactive metabolites. Hence, further research on TNT metabolism is imperative to elucidate TNT-induced toxicities.

Microecological characteristics of water bodies/sediments and microbial remediation strategies after 50 years of pollution exposure in ammunition destruction sites in China.

The effects of long-term ammunition pollution on microecological characteristics were analyzed to formulate microbial remediation strategies. Specifically, the response of enzyme systems, N/O stable isotopes, ion networks, and microbial community structure/function levels were analyzed in long-term (50 years) ammunition-contaminated water/sediments from a contamination site, and a compound bacterial agent capable of efficiently degrading trinitrotoluene (TNT) while tolerating many heavy metals was selected to remediate the ammunition-contaminated soil. The basic physical and chemical properties of the water/sediment (pH (up: 0.57-0.64), nitrate (up: 1.31-4.28 times), nitrite (up: 1.51-5.03 times), and ammonium (up: 7.06-70.93 times)) were changed significantly, and the significant differences in stable isotope ratios of N and O (nitrate nitrogen) confirmed the degradability of TNT by indigenous microorganisms exposed to long-term pollution. Heavy metals, such as Pb, Zn, Cu, Cd, Cs, and Sb, have synergistic toxic effects in ammunition-contaminated sites, and significantly decreased the microbial diversity and richness in the core pollution area. However, long-term exposure in the edge pollution area induced microorganisms to use TNT as a carbon and nitrogen sources for life activities and growth and development. The Bacteroidales microbial group was significantly inhibited by ammunition contamination, whereas microorganisms such as Proteobacteria, Acidobacteriota, and Comamonadaceae gradually adapted to this environmental stress by regulating their development and stress responses. Ammunition pollution significantly affected DNA replication and gene regulation in the microecological genetic networks and increased the risk to human health. Mg and K were significantly involved in the internal mechanism of microbial transport, enrichment, and metabolism of TNT. Nine strains of TNT-utilizing microbes were screened for efficient TNT degradation and tolerance to typical heavy metals (copper, zinc and lead) found in contaminated sites, and a compound bacterial agent prepared for effective repair of ammunition-contaminated soil significantly improved the soil ecological environment.

2,4,6-trinitrotoluene causes mitochondrial toxicity in Caenorhabditis elegans by affecting electron transport.

As a typical energetic compound widely used in military activities, 2,4,6-trinitrotoluene (TNT) has attracted great attention in recent years due to its heavy pollution and wide distribution in and around the training facilities, firing ranges, and demolition sites. However, the subcellular targets and the underlying toxic mechanism of TNT remain largely unknown. In this study, we explored the toxic effects of TNT biological reduction on the mitochondrial function and homeostasis in Caenorhabditis elegans (C. elegans). With short-term exposure of L4 larvae, 10-1000 ng/mL TNT reduced mitochondrial membrane potential and adenosine triphosphate (ATP) content, which was associated with decreased expression of specific mitochondrial complex involving gas-1 and mev-1 genes. Using fluorescence-labeled transgenic nematodes, we found that fluorescence expression of sod-3 (muls84) and gst-4 (dvls19) was increased, suggesting that TNT disrupted the mitochondrial antioxidant defense system. Furthermore, 10 ng/mL TNT exposure increased the expression of the autophagy-related gene pink-1 and activated mitochondrial unfolded protein response (mt UPR), which was indicated by the increased expression of mitochondrial stress activated transcription factor atfs-1, ubiquitin-like protein ubl-5, and homeobox protein dve-1. Our findings demonstrated that TNT biological reduction caused mitochondrial dysfunction and the development of mt UPR protective stress responses, and provided a basis for determining the potential risks of energetic compounds to living organisms.

Biotransformation of 2,4,6-Trinitrotoluene by a cocktail of native laccases from Pycnoporus sanguineus CS43 under oxygenic and non-oxygenic atmospheres.

2,4,6-Trinitrotoluene (TNT) is a highly toxic nitroaromatic explosive known for its environmental consequences, contaminating soil and groundwater throughout its life cycle, from production to disposal. Therefore, the urgency of developing innovative and ecological strategies to remedy the affected areas is recognized. This study reports, for the first time, the enzymatic biotransformation of TNT by a cocktail of native laccases from Pycnoporus sanguineus CS43. The laccases displayed efficient TNT conversion under both oxygenic and non-oxygenic conditions, achieving biotransformation rates of 80% and 87% within 48 h at a temperature of 60 °C and pH 7. Preliminary kinetic constants were calculated with the laccase cocktail, being a Vmax of 1.133 µM min-1 and 0.2984 µM min-1, and the Km values were 1586 µM and 458 µM, in an oxygenic and non-oxygenic atmosphere, respectively. High-performance liquid chromatography-mass spectrometry (HPLC/MS) confirmed the formation of amino dinitrotoluene isomers and hydroxylamine isomers as biotransformation products. In summary, this study suggests the potential application of laccases for the direct biotransformation of recalcitrant compounds like TNT, offering an environmentally friendly approach to address contamination issues.

New insights into xenobiotic tolerance of Antarctic bacteria: transcriptomic analysis of Pseudomonas sp. TNT3 during 2,4,6-trinitrotoluene biotransformation.

The xenobiotic 2,4,6-trinitrotoluene (TNT) is a highly persistent environmental contaminant, whose biotransformation by microorganisms has attracted renewed attention. In previous research, we reported the discovery of Pseudomonas sp. TNT3, the first described Antarctic bacterium with the ability to biotransform TNT. Furthermore, through genomic analysis, we identified distinctive features in this isolate associated with the biotransformation of TNT and other xenobiotics. However, the metabolic pathways and genes active during TNT exposure in this bacterium remained unexplored. In the present transcriptomic study, we used RNA-sequencing to investigate gene expression changes in Pseudomonas sp. TNT3 exposed to 100 mg/L of TNT. The results showed differential expression of 194 genes (54 upregulated and 140 downregulated), mostly encoding hypothetical proteins. The most highly upregulated gene (> 1000-fold) encoded an azoreductase enzyme not previously described. Other significantly upregulated genes were associated with (nitro)aromatics detoxification, oxidative, thiol-specific, and nitrosative stress responses, and (nitro)aromatic xenobiotic tolerance via efflux pumps. Most of the downregulated genes were involved in the electron transport chain, pyrroloquinoline quinone (PQQ)-related alcohol oxidation, and motility. These findings highlight a complex cellular response to TNT exposure, with the azoreductase enzyme likely playing a crucial role in TNT biotransformation. Our study provides new insights into the molecular mechanisms of TNT biotransformation and aids in developing effective TNT bioremediation strategies. To the best of our knowledge, this report is the first transcriptomic response analysis of an Antarctic bacterium during TNT biotransformation.

Movement of TNT and RDX from composition B detonation residues in solution and sediment during runoff.

Energetics used in military exercises can potentially contaminate ground and surface waters. This study was conducted to evaluate the movement of Composition B, a formulation that includes TNT (2,4,6-trinitrotoluene), RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), and HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), in runoff. Mechanisms of transport we examined include movement of energetics dissolved in runoff, as particles and adsorbed to suspended sediment, and in infiltration. Rainfall simulations were conducted under controlled conditions with two rainfall rates (approximately 30 and 50 mm h-1), two soils with different infiltration capacities, and four energetic particle sizes (4.75-9.51 mm, 2.83-4.75 mm, 2-2.83 mm, and <2 mm). Particles remaining on the soil surface after rainfall were measured as well as energetics dissolved in runoff, in suspended sediment, and in infiltration. Greater concentrations of TNT than RDX and HMX were found dissolved in runoff due to its higher solubility and dissolution rates. We also found that particle transport in runoff increased with decrease in particle size. Smaller particle sizes also led to greater transport dissolved in solution. Relationships were found relating runoff and sediment yield to the transport of RDX and TNT. The results of this study allow improved prediction of Composition B transport in runoff and therefore its contamination potential.

Biotransformation of 2,4,6-trinitrotoluene by Diaphorobacter sp. strain DS2.

Diaphorobacter strain DS2 degrades 3-nitrotoluene and 2-nitrotoluene via ring oxidation with 3-nitrotoluene dioxygenase (3NTDO). In the current study, we hypothesized that 3NTDO might also be involved in the degradation of 2,4,6-trinitrotoluene (TNT), a major nitroaromatic explosive contaminant in soil and groundwater. Strain DS2 transforms TNT as a sole carbon and nitrogen source when grown on it. Ammonium chloride and succinate in the medium accelerated the TNT degradation rate. A resting cell experiment suggested that TNT does not compete with 3NT degradation (no negative impact of TNT on the reaction velocity for 3NT). Enzyme assay with 3NTDO did not exhibit TNT transformation activity. The above results confirmed that 3NTDO of DS2 is not responsible for TNT degradation. In the resting cell experiment, within 10 h, 4ADNT completely degraded. The degradation of 2ADNT was 97% at the same time. We hypothesized that 3NTDO involve in this reaction. Based on the DS2 genome, we proposed that the N-ethylmaleimide reductases (nemA) were involved in the initial reduction of the nitro group and aromatic ring of TNT. Our findings suggest that strain DS2 could be helpful for the removal of TNT from contaminated sites with or without any additional carbon and nitrogen source and with minimal accumulation of undesirable intermediates.

Preparation and study of straw porous biochar with aromatic ring structure for adsorption performance and mechanism toward TNT red water.

2,4,6-Trinitrotoluene (TNT) production processes generate a substantial amount of toxic wastewater. Therefore, it is crucial to identify efficient and sustainable methods for treating this wastewater. This paper explores the application of sustainable biomass-derived carbon produced from rice straw for the adsorption of 2,4,6-trinitrotoluene (TNT) red water. The rice straw-derived biochar (SBC) materials were synthesized by two-step reactions through hydrothermal carbonization and chemical activation with KOH. Characterization of the fabricated biochar was conducted using various techniques. Here, the chemical oxygen demand (COD) was used as an evaluation index for adsorption efficiency. The adsorption kinetics showed a good fit with the pseudo-second-order model, and the adsorption equilibrium was achieved in 30 min. The biochar's high surface area (1319 m2/g) and large pore volume (1.058 cm3/g) gave it a large adsorption capacity. The Langmuir model exhibited better correlation for equilibrium data analysis, with a maximum adsorption capacity of 173.9 mg/g at 298 K. The SBC was found to have a high removal effect over a wide pH range (from 1 to 13) and showed remarkable stability after undergoing five desorption-adsorption cycles using ethanol and acetone as eluent. The results provide a simple and low-cost method for the efficient treatment of TNT red water.

Oxygen-insensitive nitroreductase bacteria-mediated degradation of TNT and proteomic analysis.

2,4,6-trinitrotoluene (TNT) is a nitroaromatic compound that causes soil and groundwater pollution during manufacture, transportation, and use, posing significant environmental and safety hazards. In this study, a TNT-degrading strain, Bacillus cereus strain T4, was screened and isolated from TNT-contaminated soil to explore its degradation characteristics and proteomic response to TNT. The results showed that after inoculation with the bacteria for 4 h, the TNT degradation rate reached 100% and was transformed into 2-amino-4,6-dinitrotoluene (2-ADNT), 4-amino-2,6-dinitrotoluene (4-ADNT), 2,4-diamino-6-nitrotoluene (2,4-DANT), and 2,6-diamino-4-nitrotoluene (2,6-DANT), accompanied by the accumulation of nitrite and ammonium ions. Through proteomic sequencing, we identified 999 differentially expressed proteins (482 upregulated, 517 downregulated), mainly enriched in the pentose phosphate, glycolysis/gluconeogenesis, and amino acid metabolism pathways. In addition, the significant upregulation of nitroreductase and N-ethylmaleimide reductase was closely related to TNT denitration and confirmed that the strain T4 converted TNT into intermediate metabolites such as 2-ADNT and 4-ADNT. Therefore, Bacillus cereus strain T4 has the potential to degrade TNT and has a high tolerance to intermediate products, which may effectively degrade nitroaromatic pollutants such as TNT in situ remediation in combination with other bacterial communities.

A novel 3D-printed graphite/polylactic acid sensor for the electrochemical determination of 2,4,6-trinitrotoluene residues in environmental waters.

Here, lab-made graphite and polylactic acid (Gpt-PLA) biocomposite materials were used to additively manufacture electrodes via the fused deposition modeling (FDM) technique for subsequent determination of the explosive 2,4,6-trinitrotoluene (TNT, considered a persistent organic pollutant). The surface of the 3D-printed material was characterized by SEM and Raman, which revealed high roughness and the presence of defects in the graphite structure, which enhanced the electrochemical response of TNT. The 3D-printed Gpt-PLA electrode coupled to square wave voltammetry (SWV) showed suitable performance for fastly determining the explosive residues (around 7 s). Two reduction processes at around -0.22 V and -0.36 V were selected for TNT detection, with linear ranges between 1.0 and 10.0 µM. Moreover, detection limits of 0.52 and 0.66 µM were achieved for both reduction steps. The proposed method was applied to determine TNT in different environmental water samples (tap water, river water, and seawater) without a dilution step (direct analysis). Recovery values between 98 and 106% confirmed the accuracy of the analyses. Additionally, adequate selectivity was achieved even in the presence of other explosives commonly used by military agencies, metallic ions commonly found in water, and also some electroactive camouflage species. Such results indicate that the proposed device is promising to quantify TNT residues in environmental samples, a viable on-site analysis strategy.

Explosives removal and quantification using porous adsorbents based on poly(2-oxazoline)s with various degree of functionalization.

Polymeric porous adsorbents are reported for removal of explosives, namely picric acid, 1,3,5-trinitro-1,3,5-triazinane (RDX), and pentaerythritol tetranitrate (PETN) and their subsequent quantification using direct analysis with ambient plasma mass spectrometry. The adsorbents are obtained by functionalization of short-chain poly(2-oxazoline)s with methyl ester side chains using 4-(aminomethyl)pyridine with a degree of functionalization equal to 0, 5, 10, and 20%. The subsequent step consist of cross-linking using a high internal phase emulsion procedure by further side-chain amidation with diethylenetriamine as crosslinker. Picric acid, RDX, and PETN were chosen as the model compounds as they belong to three different groups of explosives, in particular nitroaromatics, nitroamines, and nitrate esters, respectively. The adsorption isotherms, kinetics, as well as the influence of pH and temperature on the adsorption process was investigated. The porous adsorbents showed the highest maximum adsorption capacity towards picric acid, reaching 334 mg g-1, while PETN (80 mg g-1) and RDX (17.4 mg g-1) were less efficiently adsorbed. Subsequent quantification of the adsorbed explosives is performed by a specially designed ambient mass spectrometry setup equipped with a thermal heater. The obtained limits of detection were found to be 20-times improved compared to direct analysis of analyte solutions. The effectiveness of the proposed analytical setup is confirmed by successful quantification of the explosives in river water samples. The research clearly shows that functional porous adsorbents coupled directly with ambient mass spectrometry can be used for rapid quantification of explosives, which can be, e.g., used for tracking illegal manufacturing sites of these compounds.

Effects of exposure to the explosive and environmental pollutant 2,4,6-trinitrotoluene on ovarian follicle development in rats.

Although 2,4,6-trinitrotoluene (TNT) is a dangerous carcinogen in environmental pollution, information on the reproductive effects of TNT explosive contamination is limited. To explore the possible ovarian effects, TNT explosive-exposed rat models were established, and Wistar female rats were exposed to low and high TNT (40 g and 80 g, air and internal) explosives. After a month of exposure, the estrous cycle, ovarian histopathology, and follicle counting were conducted. Serum hormones follicle-stimulating hormone (FSH), luteinizing hormone (LH), anti-Müllerian hormone (AMH), progesterone, testosterone, and estradiol were detected, and the mRNA and protein expression of steroidogenic enzymes were measured. The results showed that the diestrus phase duration was significantly (P < 0.05) increased in the high TNT-exposed groups. In addition, the proportions of preantral follicles were significantly (P < 0.05) decreased in the high TNT-exposed groups, as well as the proportions of atretic follicles. The serum estradiol levels were significantly (P < 0.05) increased, and the follicle-stimulating hormone and luteinizing hormone levels were significantly (P < 0.05) decreased in the high TNT-exposed groups. The mRNA levels of steroidogenic acute regulatory protein (Star), cytochrome P450 cholesterol side chain cleavage (Cyp11a1, Cyp17a1 and Cyp19a1), hydroxysteroid dehydrogenase 3b (Hsd3b) and steroidogenic factor-1 (SF-1) were significantly (P < 0.05) increased in the TNT-exposed groups. The protein levels of Star, Cyp11a1 and Hsd3b were increased (P < 0.05) in the TNT-exposed groups. These results indicate that the exposure of rats to TNT explosive can subsequently affect ovarian follicle development, suggesting that the mechanism may involve disrupting steroidogenesis.

Interaction, Insensitivity and Thermal Conductivity of CL-20/TNT-Based Polymer-Bonded Explosives through Molecular Dynamics Simulation.

Binders mixed with explosives to form polymer-bonded explosives (PBXs) can reduce the sensitivity of the base explosive by improving interfacial interactions. The interface formed between the binder and matrix explosive also affects the thermal conductivity. Low thermal conductivity may result in localized heat concentration inside the PBXs, causing the detonation of the explosive. To investigate the binder-explosive interfacial interactions and thermal conductivity, PBXs with polyurethane as the binder and 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane/2,4,6-trinitrotoluene (CL-20/TNT) co-crystal as the matrix explosive were investigated through molecular dynamics (MD) simulations and reverse non-equilibrium molecular dynamics (rNEMD) simulation. The analysis of the pair correlation function revealed that there are hydrogen bonding interactions between Estane5703 and CL-20/TNT. The length of the trigger bonds was adopted as a theoretical criterion of sensitivity, and the effect of polymer binders on the sensibility of PBXs was correlated by analyzing the interfacial trigger bonds and internal trigger bonds of PBXs for the first time. The results indicated that the decrease in sensitivity of CL-20/TNT mainly comes from the CL-20/TNT contact with Estane5703. Therefore, the sensitivity of CL-20/TNT-based PBXs can be further reduced by increasing the contact area between CL-20/TNT and Estane5703. The thermal conductivity of PBXs composed of Estane5703 and CL-20/TNT (0 0 1), (0 1 0) and (1 0 0) crystal planes, respectively, were calculated through rNEMD simulations, and the results showed that only the addition of Estane5703 to the (1 0 0) crystal plane can improve the thermal conductivity of PBX100.

(1-(4-(5-Phenyl-1,3,4-oxadiazol-2-yl)phenyl)-1H-1,2,3-triazol-4-yl)-methylenyls α,ω-Bisfunctionalized 3- and 4-PEG: Synthesis and Photophysical Studies.

Two new azaheterocycle-based bolas, such as (1-(4-(5-phenyl-1,3,4-oxadiazol-2-yl)phenyl)-1H-1,2,3-triazol-4-yl)-methylenyls α,ω-bisfunctionalized PEGs, were prepared via Cu-catalyzed click reaction between 2-(4-azidophenyl)-5-(aryl)-oxadiazole-1,3,4 and terminal ethynyls derived from PEG-3 and PEG-4. Due to the presence of two heteroaromatic cores and a PEG linker, these bola molecules are considered as promising fluorescent chemosensors for electron-deficient species. As a result of a well-pronounced "turn-off" fluorescence response towards common nitro-explosive components, such as 2,4-dinitrotoluene (DNT) and 2,4,6-trinitrotoluene (TNT), hard-to-detect pentaerythritol tetranitrate (PETN), as well as Hg2+ cation was observed.

Biological 2,4,6-trinitrotoluene removal by extended aeration activated sludge: optimization using artificial neural network.

Serious health issues can result from exposure to the nitrogenous pollutant like 2,4,6-trinitrotoluene (TNT), which is emitted into the environment by the munitions and military industries, as well as from TNT-contaminated wastewater. The TNT removal by extended aeration activated sludge (EAAS) was optimized in the current study using artificial neural network modeling. In order to achieve the best removal efficiency, 500 mg/L of chemical oxygen demand (COD), 4 and 6 h of hydraulic retention time (HRT), and 1-30 mg/L of TNT were used in this study. The kinetics of TNT removal by the EAAS system were described by the calculation of the kinetic coefficients K, Ks, Kd, max, MLSS, MLVSS, F/M, and SVI. Adaptive neuro fuzzy inference system (ANFIS) and genetic algorithms (GA) were used to optimize the data obtained through TNT elimination. ANFIS approach was used to analyze and interpret the given data, and its accuracy was around 97.93%. The most effective removal efficiency was determined using the GA method. Under ideal circumstances (10 mg/L TNT concentration and 6 h), the TNT removal effectiveness of the EAAS system was 84.25%. Our findings demonstrated that the artificial neural network system (ANFIS)-based EAAS optimization could enhance the effectiveness of TNT removal. Additionally, it can be claimed that the enhanced EAAS system has the ability to extract wastewaters with larger concentrations of TNT as compared to earlier experiments.

Solid medium for the direct isolation of bacterial colonies growing with polycyclic aromatic hydrocarbons or 2,4,6-trinitrotoluene (TNT).

Isolation of hydrocarbon-degrading bacteria is a key step for the study of microbiological diversity, metabolic pathways, and bioremediation. However current strategies lack simplicity and versatility. We developed an easy method for the screening and isolation of bacterial colonies capable of degrading hydrocarbons, such as diesel or polycyclic aromatic hydrocarbons (PAHs), as well as the pollutant explosive, 2,4,6-trinitrotoluene (TNT). The method uses a two-layer solid medium, with a layer of M9 medium, and a second layer containing the carbon source deposited through the evaporation of ethanol. Using this medium we grew hydrocarbon-degrading strains, as well as TNT-degrading isolates. We were able to isolate PAHs-degrading bacterial colonies directly from diesel-polluted soils. As a proof of concept, we used this method to isolate a phenanthrene-degrading bacteria, identified as Acinetobacter sp. and determined its ability to biodegrade this hydrocarbon.

Plasmonic Coupling of Au Nanoclusters on a Flexible MXene/Graphene Oxide Fiber for Ultrasensitive SERS Sensing.

High sensitivity, good signal repeatability, and facile fabrication of flexible surface enhanced Raman scattering (SERS) substrates are common pursuits of researchers for the detection of probe molecules in a complex environment. However, fragile adhesion between the noble-metal nanoparticles and substrate material, low selectivity, and complex fabrication process on a large scale limit SERS technology for wide-ranging applications. Herein, we propose a scalable and cost-effective strategy to a fabricate sensitive and mechanically stable flexible Ti3C2Tx MXene@graphene oxide/Au nanoclusters (MG/AuNCs) fiber SERS substrate from wet spinning and subsequent in situ reduction processes. The use of MG fiber provides good flexibility (114 MPa) and charge transfer enhancement (chemical mechanism, CM) for a SERS sensor and allows further in situ growth of AuNCs on its surface to build highly sensitive hot spots (electromagnetic mechanism, EM), promoting the durability and SERS performance of the substrate in complex environments. Therefore, the formed flexible MG/AuNCs-1 fiber exhibits a low detection limit of 1 × 10-11 M with a 2.01 × 109 enhancement factor (EFexp), signal repeatability (RSD = 9.80%), and time retention (remains 75% after 90 days of storage) for R6G molecules. Furthermore, the l-cysteine-modified MG/AuNCs-1 fiber realized the trace and selective detection of trinitrotoluene (TNT) molecules (0.1 µM) via Meisenheimer complex formation, even by sampling the TNT molecules at a fingerprint or sample bag. These findings fill the gap in the large-scale fabrication of high-performance 2D materials/precious-metal particle composite SERS substrates, with the expectation of pushing flexible SERS sensors toward wider applications.

Enhanced removal of warfare agent tri-nitro-toluene by a Methylophaga-dominated microbiome.

Historical exposure of the marine environment to 2,4,6-trinitrotoluene (TNT) happened due to the dumping of left-over munitions. Despite significant research on TNT decontamination, the potential of marine microbiome for TNT degradation remains only little explored. In this study, TNT degradation experiments were conducted with sediment located near the World War I munition dumpsite - Paardenmarkt in the Belgian part of North Sea. A slow removal was observed using TNT as sole source of C and N, which could be enhanced by adding methanol. Degradation was reflected in nitro-reduced metabolites and microbial growth. 16S Illumina sequencing analysis revealed several enriched genera that used TNT as a sole source of C and N - Colwellia, Thalossospira, and Methylophaga. Addition of methanol resulted in increased abundance of Methylophaga, which corresponded to the rapid removal of TNT. Methanol enhanced the degradation by providing additional energy and establishing syntrophic association between methanol-utilizing and TNT-utilizing bacteria.