Unique dissolved organic matter molecules and microbial communities in rhizosphere of three typical crop soils and their significant associations based on FT-ICR-MS and high-throughput sequencing analysis.

Using cucumber, maize, and ryegrass as model plants, the diversity and uniqueness of the molecular compositions of dissolved organic matter (DOM) and the structures of microbial communities in typical crop rhizosphere soils, as well as their associations, were investigated based on high-resolution mass spectrometry combined with high-throughput sequencing. The results showed that the rhizosphere contained 2200 organic molecules that were not identified in the non-rhizosphere soils, as characterized by FT-ICR-MS. The rhizosphere DOM molecules generally contained more N, S, and P heteroatoms, stronger hydrophilicity, and more refractory organic matter, representing high and complex chemical diversity characteristics. 16SrRNA sequencing results demonstrated that Proteobacteria, Actinomycetes and Firmicutes were the dominant flora in the soils. Plant species could significantly change the composition and relative abundance of rhizosphere microbial populations. The microbial community structures of rhizosphere and non-rhizosphere soils showed significant differences at both the phylum and class levels. Multiple interactions between the microorganisms and DOM compositions formed a complex network of relationships. There were strong and remarkable positive or negative couplings between different sizes and categories of DOM molecules and the specific microbial groups (P < 0.05, |R| ≥ 0.9) in the rhizosphere soils as shown by network profiles. The correlations between DOM molecules and microbial groups in rhizosphere soils had plant species specificity. The results above emphasized the relationship between the heterogeneity of DOM and the diversity of microbial communities, and explored the molecular mechanisms of the biochemical associations in typical plant rhizosphere soils, providing a foundation for in-depth understanding of plant-soil-microbe interactions.

Stability performance analysis of Fe based MOFs for peroxydisulfates activation to effectively degrade ciprofloxacin.

Fe-based metal-organic frameworks (MOFs) show high activity toward the activation of peroxodisulfate (PDS) for the removal of organic micropollutants (OMPs) in wastewater treatment. However, there is a phenomenon of Fe ion dissolution in the Fe-based MOFs' active PDS system, and the reasons and influencing factors that cause Fe ion dissolution are poorly understood. In this study, we synthesized four types of Fe-based MOFs and confirmed their crystal structure through characterization. All types of Fe-based MOFs were found to activate PDS and form sulfate radicals (SO4 -), which effectively remove OMPs in wastewater. During the process of Fe-based MOFs activating PDS for CIP removal, activated species, oxidant reagent, and pH negatively impact the stability performance of the MOFs' structure. The coordination bond between Fe atom and O atom can be attacked by water molecules, free radicals, and H+, causing damage to the crystal structure of MOFs. Additionally, Fe (II)-MOFs exhibit the best stability performance, due to the enhanced bond energy of the coordination bond in MOFs by the F ligands. This study summarizes the influencing factors of Fe-based MOFs' damage during PDS activation processes, providing new insights for the future development of Fe-based MOFs.

Unexpected Persistent Production of Reactive Oxygen Species during the Degradation of Black Phosphorous in the Darkness.

Few-layer black phosphorus (FLBP) is easily degraded under ambient conditions which is problem that hinders the application of FLBP, but its degradation mechanism is not yet well understood. In this work, we surprisingly found that persistent generation of reactive oxygen species (ROS) was involved in FLBP degradation even in the dark. The ROS generation patterns and mechanism were revealed by chemiluminescence (CL) and density functional theory (DFT). Meanwhile, rhodamine B (RhB) and methyl orange (MO) can also be removed by FLBP under dark conditions, which further shows the ROS generation during FLBP self-degradation. This work provides new insights into the FLBP self-degradation mechanism and opens opportunities to practically implement FLBP for green catalytic application.

Efficient photodegradation of PFOA using spherical BiOBr modified TiO2 via hole-remained oxidation mechanism.

Photo-induced holes (h+) oxidation is an efficient approach for perfluorooctanoic acid (PFOA; C7F15COOH) removal. To maintain a high amount of h+ on the surface of photocatalysts participating in the PFOA photodegradation could be a critical issue. Herein, a highly efficient spherical BiOBr-modified nano-TiO2 (P25) was synthesised and used for PFOA photodegradation through direct oxidation with h+. A high number of h+ could be generated and remain on the surface of P25/BiOBr due to the appropriate position of the conduction band (CB) and valence band (VB) levels between P25 and BiOBr. Meanwhile, PFOA molecules were coordinated to the P25/BiOBr's surface via unidentate binding, being directly activated and oxidised by h+, resulting in a decomposition yield of 99.5% (100 mg/L) under simulated solar light irradiation within 100 min, at the initial pH condition (3.5). A stepwise photodegradation pathway was proposed due to the significant intermediates detected as the short-chain perfluorinated carboxylic acids (C2-C7). Reactive oxygen species (ROS) generation, scavenging and trapping analysis indicated that the direct oxidation on h+ followed PFOA degradation. In a real aqueous environment of Tangxun lake (adjusted pH 3.5), stable common anions and natural organic matter (NOM) would restrain the PFOA photodegradation. However, adding 10 mg/L of NO3- or HA could reduce the inhibition effect of PFOA photodegradation. These findings gave an alternative strategy to drive an h+ directly oxidation to treat PFOA contaminated water bodies.

Bioaccumulation and biotransformation of tetrabromoethylcyclohexane (TBECH) in maize (Zea mays L.): Stereoselective driving roles of plant biomacromolecules.

The bioaccumulation and biotransformation of tetrabromoethylcyclohexane (TBECH) in maize were investigated. Furthermore, the roles of plant biomacromolecules such as lipid transfer proteins (LTPs), CYP and GST enzymes in driving the biological processes of TBECH stereoisomers were explored. The uptake and translocation of TBECH in maize were diastereo- and enantio-selective. Isomerization from α- to δ-TBECH and ß- to γ-TBECH, and metabolites of debromination, hydroxylation and TBECH-GSH adducts were identified in maize roots. The gene expressions of LTPs, CYPs and GSTs were extensively changed in maize after exposure to technical TBECH. CYP and GST enzyme activities as well as GST31 and CYP71C3v2 gene expressions were selectively induced or inhibited by TBECH diastereomers over time. TBECH was able to dock into the active sites and bind with specific residues of the typical biomacromolecules ZmLTP1.6, GST31 and CYP71C3v2, indicating their roles in the bioaccumulation and metabolization of TBECH. Binding modes and affinities to biomacromolecules were significantly different between α- and ß-TBECH, which contributed to their stereo-selectivity. This study provided a deep understanding of the biological fate of TBECH, and revealed the driving molecular mechanisms of the selectivity of TBECH stereoisomers in plants.

Structure-Activity Relationship Investigation on Reaction Mechanism between Chlorinated Quinoid Carcinogens and Clinically-Used Aldoxime Nerve-Agent Antidote under Physiological Condition.

Pyridinium aldoximes are best-known therapeutic antidotes used for clinical treatment of poisonings by organophosphorus nerve-agents and pesticides. Recently, we found that pralidoxime (2-PAM, a currently clinically used nerve-agent antidote) could also detoxify tetrachloro-1,4-benzoquinone (TCBQ), which is a carcinogenic quinoid metabolite of the widely used wood preservative pentachlorophenol under normal physiological conditions, via an unusually mild and facile Beckmann fragmentation mechanism accompanied by radical homolysis. However, it is not clear whether the less-chlorinated benzoquinones (CnBQs, n ≤ 3) act similarly; if so, what is the structure-activity relationship? In this study, we found that (1) The stability of reaction intermediates produced by different CnBQs and 2-PAM was dependent not only on the position but also the degree of Cl-substitution on CnBQs, which can be divided into TCBQ- and DCBQ (dichloro-1,4-benzoquinone)-subgroup; (2) The pKa value of hydroxlated quinones (Cn-1BQ-OHs, the hydrolysis products of CnBQs), determined the stability of corresponding intermediates, that is, the decomposition rate of the intermediates depended on the acidity of Cn-1BQ-OHs; (3) The pKa value of the corresponding Cn-1BQ-OHs could also determine the reaction ratio of Beckmann fragmentation to radical homolysis in CnBQs/2-PAM. These new findings on the structure-activity relationship of the halogenated quinoid carcinogens detoxified by pyridinium aldoxime therapeutic agents via Beckmann fragmentation and radical homolysis reaction may have broad implications on future biomedical and environmental research.

Chirality of gold nanocluster affects its interaction with coagulation factor XII.

Probing the interaction of nanomaterials (NMs) with proteins is the basic step for biological safety assessment. Many physiochemical factors of NMs play important roles in binding with proteins as they determine the binding process. Among them, the chirality-related biological effects and nanotoxicology have not been fully understood. As NMs are mainly exposed to human circulatory system with intentional or unintentional exposure, understanding the interaction mechanism of plasma functional proteins with chiral NMs is of great importance. Herein, we show the interaction of chiral gold nanoclusters (AuNCs), L- and D-cysteine coated AuNC (i.e., L-AuNC and D-AuNC, respectively) with human coagulation factor XII (FXII, an important plasma zymogen initiating the inner coagulation system). D-AuNC exhibited weak binding affinity for FXII, induced FXII aggregation due to significant conformational change, which then activated the FXII for further cleavage. In contrast to D-AuNC, the binding affinity of L-AuNC for FXII was strong and their bioconjugate was quite stable without aggregation. L-AuNC induced the structural change and autoactivation of FXII to a lower extent. Moreover, the enzymatic activity of FXIIa (the activated form of FXII) was influenced upon incubation with L- AuNCs and D-AuNCs with different molecular mechanisms. The finding will expand the understanding of the nanobiological effects of chiral NMs and suggest the potential application in nanomedicine.

A feasible strategy to improve confident elemental composition determination of compounds in complex organic mixture such as natural organic matter by FTICR-MS without internal calibration.

Confident elemental composition determination of compounds in complex samples such as natural organic matter (NOM) by ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) is challenging due to the interference between multiple components in these samples during detection. Here the performance of Solarix 15T-FTICR-MS in terms of accurate relative natural isotope abundance (RIA) and mass measurements for elemental composition determination of compounds in complex samples such as NOM was systematically evaluated. The optimal sweep excitation power values ranging from 20% to 22% was found to significantly diminish the underestimation of RIA measurement for 13C1 peaks of NOM components by FTICR-MS. Random error was found to be one of the main sources for the RIA errors of 13C1 peaks with S/N ratios <25. The mean averaged RIA errors of less than 10% could be obtained by averaging the measured RIAs of each 13C1 peaks in five replicated runs. By adjusting the total ion abundance of NOM complex sample between 3.8-E7 and 1.4-E8 which was simultaneously similar to that of external calibrant during detection, mass errors of lower than 1 ppm for NOM components with m/z lower than 700 Da could be obtained without internal calibration. Meanwhile, a linear correlation between mass errors of ions in NOM complex sample and their m/z values could be obtained. The mass error deviation derived from the linearity was firstly used as new criterion to reduce the number of false formula candidates. A novel strategy of combination of high mass accuracy, high spectral accuracy, and mass error deviation for elemental composition determination of unknown compounds in complex sample such as NOM by FTICR-MS was proposed and applied for different complex samples. Compared to the traditional method, about one fold increasement in the number of the unique formula assignments for measured ions was obtained by using our strategy.

Advanced molecular-fingerprinting analysis of dissolved organic sulfur by electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry using optimal spray solvent.

Molecular level characterization of dissolved organic sulfur (DOS) by electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR MS) is necessary for further understanding of the role of DOS in the environment. Here, ESI spray solvent, a key parameter for ion production during ESI process, was investigated for its effect on the molecular characterization of DOS by ESI-FTICR MS. 100% MeOH as spray solvent was found for the first time to remarkably enhance the ionization efficiency of the majority of CHOS-molecules in NOM, which facilitated a total of 1473 CHOS-molecular formulas with one sulfur atom to be detected. The number of CHOS-molecular formulas obtained using 100%MeOH as spray solvent increased notably over 740 in comparison with those using 50% MeOH aqueous solution (731) or 50% ACN aqueous solution (653). Moreover, due to the enhancement of ionization efficiency of DOS during ESI processes, the tandem mass spectra of the NOM CHOS-molecules could be easily obtained using 100% MeOH as spray solvent, which were hardly obtained using 50% MeOH aqueous solution as spray solvent. The results of the tandem mass spectra suggested the first discovery of organosulfates or sulfonic acids in Suwannee River NOM sample. A simple method based on 100% MeOH as ESI spray solvent for advanced molecular characterization of DOS by ESI-FTICR MS was proposed and applied, and the results revealed more molecular information of DOS in sea DOM samples.

Microwave-Assisted Synthesis of Hollow Microspheres with Multicomponent Nanocores for Heavy-Metal Removal and Magnetic Sensing.

The primary advantage of a hollow structure is the likelihood of introducing diverse components in a single particle to achieve multiple missions. Herein, hollow microspheres with multicomponent nanocores (HMMNs) have been prepared based on a template-free strategy via a microwave-assisted hydrothermal treatment of Chlorella. The resulting HMMNs retain the near-spherical hollow morphology and functional groups of the cell wall of Chlorella, obviating the need for templates and chemical modification. The elements (iron, cobalt, calcium, magnesium, chlorine, and phosphorus) naturally present within the Chlorella cells react to form hydroxyapatite/chlorapatite and magnetic nanocores without the need for exogenous chemical reagents. The performances of HMMNs for cadmium ion (Cd2+) removal and antibiotic detection are explored. HMMNs exhibit relatively high adsorbance of Cd2+ (1035.8 mmol/kg) and can be easily recovered by application of an external magnetic field. Ion exchange with Ca2+ and Mg2+ is shown to be the main mechanism of Cd2+ elimination. In addition, HMMNs are a suitable carrier for the construction of a magnetic immunosensor, as demonstrated by the successful development of such an immunosensor with acceptable analytical performance for the detection of neomycin in milk samples. The versatile applications of HMMNs result from their multicomponent nanocores, hollow structure, and the functional groups on their shell. This work not only offers a simple and eco-friendly strategy for the fabrication of novel HMMNs but also provides a valuable advanced material for contaminant detection and heavy-metal removal.

Formation of Nanosilver from Silver Sulfide Nanoparticles in Natural Waters by Photoinduced Fe(II, III) Redox Cycling.

Nanosilver (nAg) has been repeatedly demonstrated to end up as silver sulfide nanoparticles (Ag2SNPs), but little is known about the potential transformations of Ag2SNPs in natural environments that are very important for comprehensive assessments of nAg risks to human and environmental health. Here we show that Ag2SNPs can release tiny amounts of silver ion via cation exchange reactions between Ag(I) and Fe(III) in the dark, while in the light dramatic dissolution of Ag2SNP occurs, which is mainly attributed to the Ag2SNP oxidation by the hydroxyl radical formed during the reduction of Fe(III) to Fe(II) in water under sunlit conditions. However, silver ions are subsequently reduced to nAg in the light due to the strong reducing power of Fe(II). Thus, the formation of nAg from Ag2SNPs in the presence of Fe(III) under light conditions proceeds through a two-step reaction mechanism, the photoinduced and Fe(III)-dependent dissolution of Ag2SNPs, followed by the reduction of silver ions to nAg by Fe(II). The formation of nAg from Ag2SNPs is also validated in environmental waters under light conditions. It is thus concluded that photoinduced Fe(III)/Fe(II) redox cycling can drive the formation of nAg from Ag2SNPs in natural waters. These findings suggest that the previous consensus about the stability of Ag2SNPs in aquatic environments should be reconsidered.

Ion Accumulation Time Dependent Molecular Characterization of Natural Organic Matter Using Electrospray Ionization-Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

Natural organic matter (NOM) is a complex organic mixture and plays a crucial role in environmental processes. By using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS), detailed molecular information on NOM could be achieved. In this paper, ion accumulation time (IAT), a key parameter of FTICR-MS for complex mixture detection, was the focus, and its effect on the molecular characterization of NOM by FTICR-MS was systematically investigated. A notable feature of selective detection of NOM molecules by FTICR-MS with different IAT was observed. Most of the polar molecules with high O/C ratio (O/C ratio >0.5) could be easily detected by FTICR-MS with a short IAT, but extending IAT led to the ion intensities of these molecules decreasing or even disappearing. Meanwhile, a large number of unsaturated and aromatic molecules with low O/C ratio (O/C ratio <0.6) and low polarity, all of which could not be observed with a short IAT, were remarkably detected by extending IAT. Results also revealed that the unsaturated and aromatic molecules, which could only be observed by extending the IAT, were not generated by the fragmentation of molecules in NOM or from the dissociation of NOM aggregations but originally existed in NOM samples. The selective detection of NOM molecules caused by IAT extension was possibly attributed to their different polarity and different stability in the collision cell. On the basis of these results, a novel strategy of combining mass spectrometric data of NOM obtained with different IAT by FTICR-MS was proposed. With this strategy, more than 4715 CHO-molecular formulas were assigned, where about 2000 more formulas were obtained in comparison with using a short IAT (2733 CHO-molecular formulas identified) solely. The strategy is simple and robust and can be used as an alternative method to obtain more molecular information on NOM in the environment.

Donor/acceptor nanoparticle pair-based singlet oxygen channeling homogenous chemiluminescence immunoassay for quantitative determination of bisphenol A.

Bisphenol A (BPA) is widely used in consumer products such as plastic bottles and food containers. It has become a ubiquitous environmental contaminant and poses a serious risk to human health. A rapid, sensitive, and high-throughput method for detecting BPA is therefore desirable. Herein, a donor/acceptor nanoparticle pair-based singlet oxygen channeling chemiluminescence homogenous immunoassay is developed for the determination of BPA. The donor nanoparticles were modified with phthalocyanine as a photosensitizer and were then coated with streptavidin. The acceptor nanoparticles were doped with thioxene derivatives and Eu(III) as a chemiluminescence emitter and then coated with anti-BPA antibody. Under light irradiation, oxygen near the donor surface transforms to singlet oxygen (1O2), which migrates to the acceptor and reacts with it, generating luminescence. Because 1O2 has a very short lifetime, luminescence is generated only when the donor and acceptor are in close proximity. This occurs when they are brought together by the antigen/antibody and streptavidin/biotin reaction. Based on this singlet oxygen channeling mechanism, a competitive homogenous chemiluminescence immunoassay for BPA was developed on 384 microplates. The assay exhibited linear detection over the range 10-1000 ng/mL and a limit of detection of 2.9 ng/mL. The intra- and inter-assay precisions were both below 5.1 %. The average recoveries of three spiked samples in tap and river water samples were in the range 95.5-121.0 %, in agreement with values obtained using high-performance liquid chromatography. The homogeneous assay is rapid, low cost, sensitive, and allows high-throughput, so is well suited for screening large numbers of environmental samples. Graphical abstract Principle of the singlet oxygen channeling homogenous chemiluminescence competitive immunoassay based on nanoparticle pairs for determination of BPA.

Comprehensive characterization of natural organic matter by MALDI- and ESI-Fourier transform ion cyclotron resonance mass spectrometry.

Natural organic matter (NOM) is a complex and non-uniform mixture of organic compounds which plays an important role in environmental processes. Due to the complexity, it is challenging to obtain fully detailed structural information about NOM. Although Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) has been demonstrated to be a powerful tool for providing molecular information about NOM, multiple ionization methods are needed for comprehensive characterization of NOM at the molecular level considering the ionizing selectivity of different ionization methods. This paper reports the first use of matrix assisted laser desorption/ionization (MALDI) method coupled with FT-ICR-MS for molecular characterization of NOM within a mass range of 200-800 Da. The mass spectral data obtained by MALDI were systematically compared with data generated by electrospray ionization (ESI). It showed that complementary molecular information about NOM which could not be detected by ESI, were provided by MALDI. More unsaturated and aromatic constituents of NOM with lower O/C ratio (O/C ratio<0.5) were preferentially ionized in MALDI negative mode, whereas more polar constituents of NOM with higher O/C ratio were preferentially ionized in ESI negative mode. Molecular anions of NOM appearing at even m/z in MALDI negative ion mode were detected. The results show that NOM molecules with aromatic structures, moderate O/C ratio (0.7>O/C ratio>0.25) and lower H/C ratio were liable to form molecular anions at even m/z, whereas those with higher H/C ratio are more likely to form deprotonated ions at odd m/z. It is speculated that almost half of the NOM molecules identified by MALDI may be aromatic or condensed aromatic compounds with special groups which are liable to absorb electron from other molecules to generate free radical anions during MALDI ionization.