Novel Insights into the Promoted Accumulation of Nitro-Polycyclic Aromatic Hydrocarbons in the Roots of Legume Plants.

Substituted polycyclic aromatic hydrocarbons (sub-PAHs) are receiving increased attention due to their high toxicity and ubiquitous presence. However, the accumulation behaviors of sub-PAHs in crop roots remain unclear. In this study, the accumulation mechanism of sub-PAHs in crop roots was systematically disclosed by hydroponic experiments from the perspectives of utilization, uptake, and elimination. The obtained results showed an interesting phenomenon that despite not having the strongest hydrophobicity among the five sub-PAHs, nitro-PAHs (including 9-nitroanthracene and 1-nitropyrene) displayed the strongest accumulation potential in the roots of legume plants, including mung bean and soybean. The nitrogen-deficient experiments, inhibitor experiments, and transcriptomics analysis reveal that nitro-PAHs could be utilized by legumes as a nitrogen source, thus being significantly absorbed by active transport, which relies on amino acid transporters driven by H+-ATPase. Molecular docking simulation further demonstrates that the nitro group is a significant determinant of interaction with an amino acid transporter. Moreover, the depuration experiments indicate that the nitro-PAHs may enter the root cells, further slowing their elimination rates and enhancing the accumulation potential in legume roots. Our results shed light on a previously unappreciated mechanism for root accumulation of sub-PAHs, which may affect their biogeochemical processes in soils.

Impact Mechanisms of Humic Acid on the Transmembrane Transport of Per- and Polyfluoroalkyl Substances in Wheat at the Subcellular Level: The Important Role of Slow-Type Anion Channels.

Per- and polyfluoroalkyl substances (PFASs) have potential to accumulate in crops and pose health risks to humans, but it is unclear how the widely present organic matters in soil, such as humic acid (HA), affect their uptake and translocation in plants. In this study, hydroponic experiments were conducted to systematically disclose the impacts of HA on the uptake, translocation, and transmembrane transport at the subcellular level of four PFASs, including perfluorooctane sulfonic acid, perfluorooctanoic acid, perfluorohexane sulfonic acid, and 6:2 chlorinated polyfluoroalkyl ether sulfonate in wheat (Triticum aestivum L.). The results of the uptake and depuration experiments indicated that HA depressed the adsorption and absorption of PFASs in wheat roots by reducing the bioavailability of PFASs, and HA did not affect the long-range transport of PFASs to be eliminated via the phloem of wheat. However, HA facilitated their transmembrane transport in wheat roots, while the contrary effect was observed in the shoots. The inhibitor experiments coupled with transcriptomics analysis uncover that the increased transmembrane transport of PFASs stimulated by HA is mainly driven by the slow-type anion channel pathways interacting with Ca2+-dependent protein kinases (Ca2+-CDPK-SLAC1). The promoted transmembrane transport of PFASs might cause adverse effects on the plant cell wall, which causes further concerns.

Magnetotransport property of oxygen-annealed Fe1+yTe thin films.

Fe-based superconductors are one of the current research focuses. FeTe is unique in the series of FeSe1-xTex, since it is nonsuperconducting near the FeTe side in the phase diagram in contrast to the presence of superconductivity in other region. However, FeTe thin films become superconducting after oxygen annealing and the mechanism remains elusive. Here, we report the temperature dependences of resistivity, Hall effect and magnetoresistance (MR) of a series of FeTe thin films with different amounts of excess Fe and oxygen. These properties show dramatic changes with excess Fe and oxygen incorporation. We found the Hall coefficients are positive for the oxygen-annealed samples, in contrast to the transition from positive to negative below 50 K for the vacuum-annealed samples. For all samples, both the resistivity and Hall coefficient show a dramatic drop, respectively, at around 50 K-75 K, implying coexistence of superconductivity and antiferromagnetic order for the oxygen-annealed samples. The vacuum-annealed samples show both positive and negative values of MR depending on temperature, while negative MR dominates for the oxygen-annealed samples. We also found that oxygen annealing reduces the excess Fe in FeTe, which has been neglected before. The results are discussed in terms of several contributions, and a comparison is made between the oxygen-annealed FeTe thin films and FeSe1-xTex. This work is helpful for shedding light on the understanding of oxygen-annealed FeTe thin films.

Investigating Long-Distance Transport of Perfluoroalkyl Acids in Wheat via a Split-Root Exposure Technique.

Large amounts of perfluoroalkyl acids (PFAAs) have been introduced into the soil and accumulated by plants, posing potential risks to human health. It is imperative to investigate the accumulation and translocation of PFAAs within plants. Long-distance transport is an important pathway for PFAAs transferred from the plant leaves to the edible tissues through the phloem. However, it was previously difficult to assess the translocation potential of organic contamination in a short-term exposure period. The split-root experiment provides a solution to effectively uncover the long-distance translocation of PFAAs using a hydroponic experiment, which, in this study, was carried out in two 50 mL centrifuge tubes (A and B), of which centrifuge tube A had 50 mL of one-quarter strength Hoagland sterile nutrient solution, while centrifuge tube B had the same amount of nutrient concentration, and the target PFAAs (perfluorooctane sulfonic acid, PFOS, and perfluorooctane acid, PFOA) added at a given concentration. A whole wheat root was manually separated into two parts and inserted carefully into tubes A and B. The concentration of PFAAs in the roots, shoots of wheat, and solutions in tubes A and B were evaluated using LC-MS/MS, respectively, after being cultured in an incubator for 7 days and harvested. The results suggested that PFOA and PFOS experience a similar long-distance transport process through the phloem from the shoot to the root and could be released into the ambient environment. Thus, the split-root technique can be used to evaluate the long-distance transport of different chemicals.

Underlying Mechanisms for Low-Molecular-Weight Dissolved Organic Matter to Promote Translocation and Transformation of Chlorinated Polyfluoroalkyl Ether Sulfonate in Wheat.

Dissolved organic matter (DOM) such as fulvic acid (FA) and humic acid (HA) in soil considerably affects the fate of per- and polyfluoroalkyl substances (PFASs). However, the effect of DOM on their behavior in plants remains unclear. Herein, hydroponic experiments indicate that FA and HA reduce the accumulation of an emerging PFAS of high concern, 6:2 chlorinated polyfluoroalkyl ether sulfonate (6:2 Cl-PFESA), in wheat roots by reducing its bioavailability in the solution. Nevertheless, FA with low molecular weight (MW) promotes its absorption and translocation from the roots to the shoots by stimulating the activity and the related genes of the plasma membrane H+-ATPase, whereas high-MW HA shows the opposite effect. Moreover, in vivo and in vitro experiments indicate that 6:2 Cl-PFESA undergoes reductive dechlorination, which is regulated mainly using nitrate reductase and glutathione transferase. HA and FA, particularly the latter, promote the dechlorination of 6:2 Cl-PFESA in wheat by enhancing electron transfer efficiency and superoxide production. Transcriptomic analysis indicates that FA also stimulates catalytic activity, cation binding, and oxidoreductase activity, facilitating 6:2 Cl-PFESA transformation in wheat.

One-Step Genotyping Method in loxP-Based Conditional Knockout Mice Generated by CRISPR-Cas9 Technology.

With the development of CRISPR-Cas9 gene editing and in vitro fertilization (IVF) technology, we can now easily construct genetically modified mouse strains with indels, especially for loxP-based strategy. However, the general genotyping methods are time-consuming and unreliable given the loxP site is only 34 bp long. Here, based on the tetra primer-paired PCR amplification, we describe an efficient genotyping method which can simultaneously generate the internal control band, wild type (wt)-genotype band, and/or loxP-genotype band through one single PCR amplification. It is easy to interpret the mouse genotypes from the pattern of the bands. Further, the results could also help to exclude the possibility of minor cross-contamination, since the ratio between the bands' quantity in wt/wt, wt/loxP, and loxP/loxP mice are relatively constant, which makes the genotyping more reliable when it is performed in a large amount.

Theoretical and experimental insights into the mechanisms of C6/C6 PFPiA degradation by dielectric barrier discharge plasma.

As an emerging alternative legacy perfluoroalkyl substance, C6/C6 PFPiA (perfluoroalkyl phosphinic acids) has been detected in aquatic environments and causes potential risks to human health. The degradation mechanisms of C6/C6 PFPiA in a dielectric barrier discharge (DBD) plasma system were explored using validated experimental data and density functional theory (DFT) calculations. Approximately 94.5% of C6/C6 PFPiA was degraded by plasma treatment within 15 min at 18 kV. A relatively higher discharge voltage and alkaline conditions favored its degradation. C6/C6 PFPiA degradation was attributed to attacks of •OH, •O2-, and 1O2. Besides PFHxPA and C2 -C6 shorter-chain perfluorocarboxylic acids, several other major intermediates including C4/C6 PFPiA, C4/C4 PFPiA, and C3/C3 PFPiA were identified. According to DFT calculations, the potential energy surface was proposed for possible reactions during C6/C6 PFPiA degradation in the discharge plasma system. Integrating the identified intermediates and DFT results, C6/C6 PFPiA degradation was deduced to occur by stepwise losing CF2, free radical polymerization, and C-C bond cleavage. Furthermore, the DBD plasma treatment process decreased the toxicity of C6/C6 PFPiA to some extent. This study provides a comprehensive understanding of C6/C6 PFPiA degradation by plasma advanced oxidation.

Insights into the impacts of dissolved organic matter of different origins on bioaccumulation and translocation of per- and polyfluoroalkyl substances (PFASs) in wheat.

Per- and polyfluoroalkyl substances (PFASs) have been found to be widely present in soil. Dissolved organic matter (DOM) in soil are supposed to greatly affect the bioavailability of PFASs in soil. Herein, hydroponic experiments were conducted to understand the impacts of two kinds of typical DOM, bovine serum albumin (BSA) and humic acid (HA), on the uptake and translocation of legacy PFASs and their emerging alternatives, perfluorooctane sulfonic acid (PFOS), perfluorooctane acid (PFOA), perfluorohexane sulfonic (PFHxS) and 6:2 chlorinated polyfluoroalkyl ether sulfonate (6:2 Cl-PFESA) in wheat (Triticum aestivum L.). The results indicated that both HA and BSA significantly inhibited the bioaccumulation and translocation of PFASs in the roots and shoots of wheat, and the impacts of BSA were greater than HA. This difference was explained by the greater binding affinities of the four PFASs with BSA than with HA, as evidenced by the equilibrium dialysis and isothermal titration calorimetry (ITC) analyses. It was noting that inhibition impacts of the BSA-HA mixture (1:1) were lower than BSA alone. The results of Fourier transform infrared (FT-IR) spectroscopy and excitation-emission matrix (EEM) fluorescence spectroscopy suggested that HA could bind with the fluorescent tryptophan residues in BSA greatly, competing the binding sites with PFASs and forming a cover on the surface of BSA. As a result, the binding of PFASs with BSA-HA complex was much lower than that with BSA, but close to HA. The results of this study shed light on the impacts of DOM in soil on the bioaccumulation and translocation of PFASs in plants.

Efficient decolorization of Methylene Blue catalyzed by MgFe-layered double hydroxides in the presence of hydrogen peroxide.

MgFe-layered double hydroxides (LDHs) were prepared by co-precipitation method with the ratios of [Mg2+]/[Fe3+] varied in the range of 2:1-6:1, and occupied as heterogeneous catalysts for the degradation of Methylene Blue (MB) in the Fenton process. MgFe-LDH prepared with the ratio of [Mg2+]/[Fe3+] at 3:1 was verified to be of high purity. The Fenton-like process catalyzed by MgFe-LDH performed excellently, and more than 97% degradation of MB was obtained with 0.5 mmol/L H2O2 and 0.50 g/L MgFe-LDH at initial pH 2 at room temperature. The occurrence of hydroxyl radicals (·OH) was detected and the mechanism was proposed. MgFe-LDH is of excellent catalytic activity and good reusability.

The promoted dissolution of copper oxide nanoparticles by dissolved humic acid: Copper complexation over particle dispersion.

Humic substances are the dominant dissolved organic matter fraction in the aqueous phase of environmental media. They would inevitably react with chemicals released into the environment. The influence of dissolved humic acid (DHA) on the dissolution and dispersion of copper oxide nanoparticles (CuO NPs, 50 nm, 49.57 mg L-1) was therefore investigated in the present study. In addition to dispersing CuO NPs and reducing the size of the aggregates, the amount of released Cu from CuO NPs was found to increase over time with increasing concentrations of DHA, 96% of which was present as organic complexes after 72 h. At DHA concentrations exceeding 16.09 mg C L-1, the complexation coefficients of DHA with Cu and the adsorptivity of CuO NPs to DHA were both reduced due to increased homo-conjugation of DHA as promoted by negative charge-assisted H-bond. Although the adsorption capacity of DHA kept increasing up to 57.07 mg C L-1, the hydrodynamic diameter and ζ-potential were similar and the percentages of total released Cu continued to increase linearly to 4.92% at higher levels of DHA (30.13-57.07 mg C L-1). Thereupon, DHA promoted the dissolution of CuO NPs in a concentration-dependent fashion. The driving force was complexation of Cu by DHA, rather than the balancing between the exposed and the covered surface area of the CuO NPs due to DHA adsorption. Our findings facilitate understanding the underlying mechanisms on how DHA impacts the CuO NPs environmental behavior (or fate) as well as on their kinetics.

Lanthanide-doped mesoporous MCM-41 nanoparticles as a novel optical-magnetic multifunctional nanobioprobe.

To research and develop potential multifunctional nanoprobes for biological application, lanthanide-doped MCM-41 (Ln-MCM-41, Ln = Gd/Eu) silica nanoparticles with excellent pore structure and optical-magnetic properties were synthesized via a facile and economical sol-gel method. The microstructure and pore distribution of Ln-MCM-41 nanoparticles were obviously affected by the Ln-doping. As the Ln/Si mole ratio increased, the specific surface area and total pore volume of Ln-MCM-41 nanoparticles rapidly decreased. However, the Ln-MCM-41 nanoparticles still retained the typical well-ordered mesoporous structure, and exhibited excellent drug release behavior. Moreover, the drug release rate of Ln-MCM-41 was remarkably pH-dependent and increased gradually upon decreasing pH. Additionally, these nanoparticles also exhibit considerable photoluminescence properties, living cells photoluminescence imaging in vitro, and paramagnetism behavior at room temperature due to the Ln3+-ions doping. Our research shows the possibility of our Ln-MCM-41 nanoparticles as multifunctional nanoprobes for application in bioseparation, bioimaging, and drug delivery.

Tannic acid promotes ion release of copper oxide nanoparticles: Impacts from solution pH change and complexation reactions.

The increasing number of applications in which copper oxide nanoparticles (CuO NPs) are used, may lead to potential release of CuO NPs into the environment. However, the impact of natural organic matters on the behavior and fate of CuO NPs in aquatic media is still largely unknown. In this study, the dissolution and aggregation of CuO NPs under the exposure of tannic acid (TA) were monitored over a period of 72 h, with a focus on assessing the contributions of solution pH changes and complexation reactions. Results showed that the total amount of Cu2+ released from CuO NPs increased in the presence of TA especially at the highest TA concentration of 73.5 µmol/L. Although TA was observed to wrap around the CuO NPs, the aggregation of CuO NPs was not strongly influenced by TA and by the solution pH as investigated in this study. The kinetics of Cu2+ release were fitted using the modified pseudo second-order model and the rate of dissolution was assessed to be highest at TA = 14.7 µmol/L. At pH = 4, the increased H+ concentration was responsible for increased Cu2+ release, whereas the complexation reaction between Cu2+ and TA dominated at pH = 7. These findings suggested that the effects of TA on the dissolution of CuO NPs were a combination of solution pH change and complexation reaction, the relative fractions of which also depended on the solution pH. Additionally, the percentage of Cu2+ released from the CuO NPs was found to increase upon decreasing concentrations of CuO NPs. Our work helps to further understand how and to which extent natural organic matters affect the behavior and fate of CuO NPs.

Syntheses of 4-(Heteroaryl)cyclohexanones via Palladium-Catalyzed Ester α-Arylation and Decarboxylation.

An alternative synthesis of 4-(heteroaryl)cyclohexanones is described featuring a palladium-catalyzed ester α-arylation followed by decarboxylation. The substrate scope is broad with a wide range of heteroaryl halides. In particular, the reaction robustness is demonstrated by the synthesis of >10 g of 4-(pyrazin-2-yl)cyclohexanone with 85% overall yield.

Mineralized collagen coatings formed by electrochemical deposition.

Understanding and controlling the process of electrochemical deposition (ECD) of a mineralized collagen coating on metallic orthopedic implants is important for engineering highly bioactive coatings. In this work, the influence of different ECD parameters was investigated. The results showed that the mineralization degree of the coatings increased with deposition time, voltage potential and H2O2 addition, while chitosan addition led to weakening of mineralization, heavy mineralization resulted in a porous coating morphology. Furthermore, two typical coatings, dense and porous, were analyzed to investigate their microstructure and evaluated for their cytocompatibility; the dense coating showed better osteoblast adhesion and proliferation. Based on our understanding of how the different coating parameters influenced the coating, we proposed an ECD process in which the pH gradient near the cathode and the collagen isoelectric point were suggested to play crucial roles in controlling the mineralization and morphology of the coatings. The proposed ECD process may offer a guide for controlled deposition of a desired bioactive coating.

Effect of PEG amount in amorphous calcium phosphate on its crystallized products.

Biphasic alpha-tricalcium phosphate/beta-tricalcium phosphate (alpha/beta-TCP) with a designed phase ratio is thought to have controllable dissolution-reprecipitation behavior that is significant in the repair and regeneration of bone. Amorphous calcium phosphate (ACP) was selected as a precursor to prepare biphasic alpha/beta-TCP. The influence of polyethylene glycol (PEG) content in ACP on its crystallization, or on the phase ratio of the resulting biphasic TCP, was investigated. ACP was synthesized by the reaction of Ca(NO(3))(2) with (NH(4))(2)HPO(4) using PEG as an additive. Depending on the amount of PEG addition, resulting ACP could be crystallized to alpha-TCP, beta-TCP or biphasic alpha/beta-TCP after heat-treatment at 800 degrees C, showing that PEG addition is a critical factor to tailor the phase ratio of biphasic alpha/beta-TCP. One reason for the influence of PEG is that ACP with different PEG content could have two types of unit structures that tend to form alpha-TCP and beta-TCP after crystallization.