Superstructured Carbon with Enhanced Kinetics for Zinc-Air Battery and Self-Powered Overall Water Splitting.

The present study proposes a novel engineering concept for the customization of functionality and construction of superstructure to fabricate 2D monolayered N-doped carbon superstructure electrocatalysts decorated with Co single atoms or Co2 P nanoparticles derived from 2D bimetallic ZnCo-ZIF superstructure precursors. The hierarchically porous carbon superstructure maximizes the exposure of accessible active sites, enhances electron/mass transport efficiency, and accelerates reaction kinetics simultaneously. Consequently, the Co single atoms embedded N-doped carbon superstructure (Co-NCS) exhibits remarkable catalytic activity toward oxygen reduction reaction, achieving a half-wave potential of 0.886 V versus RHE. Additionally, the Co2 P nanoparticles embedded N-doped carbon superstructure (Co2 P-NCS) demonstrates high activity for both oxygen evolution reaction and hydrogen evolution reaction, delivering low overpotentials of 292 mV at 10 mA cm-2 and 193 mV at 10 mA cm-2 respectively. Impressively, when employed in an assembled rechargeable Zn-air battery, the as-prepared 2D carbon superstructure electrocatalysts exhibit exceptional performance with a peak power density of 219 mW cm-2 and a minimal charge/discharge voltage gap of only 1.16 V at 100 mA cm-2 . Moreover, the cell voltage required to drive an overall water-splitting electrolyzer at a current density of 10 mA cm-2 is merely 1.69 V using these catalysts as electrodes.

Transcriptome Profiling, Physiological and Biochemical Analyses Reveal Comprehensive Insights in Cadmium Stress in Brassica carinata L.

With the constant progress of urbanization and industrialization, cadmium (Cd) has emerged as one of the heavy metals that pollute soil and water. The presence of Cd has a substantial negative impact on the growth and development of both animals and plants. The allotetraploid Brasscia. carinata, an oil crop in the biofuel industry, is known to produce seeds with a high percentage of erucic acid; it is also known for its disease resistance and widespread adaptability. However, there is limited knowledge regarding the tolerance of B. carinata to Cd and its physiological responses and gene expressions under exposure to Cd. Here, we observed that the tested B. carinata exhibited a strong tolerance to Cd (1 mmol/L CdCl2 solution) and exhibited a significant ability to accumulate Cd, particularly in its roots, with concentrations reaching up to 3000 mg/kg. Additionally, we found that the total oil content of B. carinata seeds harvested from the Cd-contaminated soil did not show a significant change, but there were noticeable alterations in certain constituents. The activities of antioxidant enzymes, including catalase (CAT), superoxide dismutase (SOD), peroxidase (POD), and ascorbate peroxidase (APX), were observed to significantly increase after treatment with different concentrations of CdCl2 solutions (0.25 mmol/L, 0.5 mmol/L, and 1 mmol/L CdCl2). This suggests that these antioxidant enzymes work together to enhance Cd tolerance. Comparative transcriptome analysis was conducted to identify differentially expressed genes (DEGs) in the shoots and roots of B. carinata when exposed to a 0.25 mmol/L CdCl2 solution for 7 days. A total of 631 DEGs were found in the shoots, while 271 DEGs were found in the roots. It was observed that these selected DEGs, which responded to Cd stress, also showed differential expression after exposure to PbCl2. This suggests that B. carinata may employ a similar molecular mechanism when tolerating these heavy metals. The functional annotation of the DEGs showed enrichment in the categories of 'inorganic ion transport and metabolism' and 'signal transduction mechanisms'. Additionally, the DEGs involved in 'tryptophan metabolism' and 'zeatin biosynthesis' pathways were found to be upregulated in both the shoots and roots of B. carinata, suggesting that the plant can enhance its tolerance to Cd by promoting the biosynthesis of plant hormones. These results highlight the strong Cd tolerance of B. carinata and its potential use as a Cd accumulator. Overall, our study provides valuable insights into the mechanisms underlying heavy metal tolerance in B. carinata.

BcaSOD1 enhances cadmium tolerance in transgenic Arabidopsis by regulating the expression of genes related to heavy metal detoxification and arginine synthesis.

Cadmium (Cd), which is a nonessential heavy metal element for organisms, can have a severe impact on the growth and development of organisms that absorb excessive Cd. Studies have shown that Brassica carinata, a semiwild oil crop, has strong tolerance to various abiotic stresses, and RNA-seq has revealed that the B. carinata superoxide dismutase gene (BcaSOD1) likely responds to Cd stress. To elucidate the BcaSOD1 function involved in tolerance of Cd stress, we cloned the coding sequences of BcaSOD1 from a purple B. carinata accession and successfully transferred it into Arabidopsis thaliana. The subcellular localization results demonstrated that BcaSOD1 was primarily located in the plasma membrane, mitochondria and nucleus. Overexpression of BcaSOD1 in transgenic Arabidopsis (OE) effectively decreased the toxicity caused by Cd stress. Compared to the WT (wild type lines), the OE lines exhibited significantly increased activities of antioxidant enzymes (APX, CAT, POD, and SOD) after exposure to 2.5 mM CdCl2. The Cd content of underground (root) in the OE line was dominantly higher than that in the WT; however, the Cd content of aboveground (shoot) was comparable between the OE and WT types. Moreover, the qRT‒PCR results showed that several heavy metal detoxification-related genes (AtIREG2, AtMTP3, AtHMA3, and AtNAS4) were significantly upregulated in the roots of OE lines under Cd treatment, suggesting that these genes are likely involved in Cd absorption in the roots of OE lines. In addition, both comparable transcriptome and qRT-PCR analyses revealed that exogenous BcaSOD1 noticeably facilitates detoxification by stimulating the expression of two arginine (Arg) biosynthesis genes (AtGDH1 and AtGDH2) while inhibiting the expression of AtARGAH1, a negative regulator in biosynthesis of Arg. The Arg content was subsequently confirmed to be significantly enhanced in OE lines under Cd treatment, indicating that BcaSOD1 likely strengthened Cd tolerance by regulating the expression of Arg-related genes. This study demonstrates that BcaSOD1 can enhance Cd tolerance and reveals the molecular mechanism of this gene, providing valuable insights into the molecular mechanism of Cd tolerance in plants.

A highly efficient lanthanide coordination polymer luminescent material for the multi-task detection of environmental pollutants.

It is challenging to explore novel-structure lanthanide coordination polymers (Ln-CPs) for sensing environmental pollutants. Herein, we designed and synthesized an organic bridging linker 3-(carboxymethoxy)-1-(carboxymethyl) pyrazole-4-carboxylic acid (H3ccpc), and then successfully prepared and characterized a novel Ln-CP, namely [Tb2(ccpc)2(H2O)6]·1.5H2O (ccpcTb). Structural analysis indicates that ccpcTb exhibits a two-dimensional structure, in which Tb ions are in an eight-coordinated environment. The photoluminescence performance of ccpcTb was discussed in detail. The ccpcTb displays bright green luminescence and behaves as a multi-responsive luminescent sensor toward Fe3+ ions, Cr2O72- ions and 2,4,6-trinitrophenol with high selectivity and low detection limits. Furthermore, the possible luminescence sensing mechanisms have been addressed in detail. The luminescence quenching mechanism of sensing Fe3+ and Cr2O72- is attributed to the energy competitive absorption, while that of sensing TNP is due to the synergistic effect of energy competitive absorption and photo-induced electron transfer.

Integrative Physiological and Transcriptome Analysis Reveals the Mechanism of Cd Tolerance in Sinapis alba.

Recently, pollution caused by the heavy metal Cd has seriously affected the environment and agricultural crops. While Sinapis alba is known for its edible and medicinal value, its tolerance to Cd and molecular response mechanism remain unknown. This study aimed to analyze the tolerance of S. alba to Cd and investigate its molecular response mechanism through transcriptomic and physiological indicators. To achieve this, S. alba seedlings were treated with different concentrations of CdCl2 (0.25 mmol/L, 0.5 mmol/L, and 1.0 mmol/L) for three days. Based on seedling performance, S. alba exhibited some tolerance to a low concentration of Cd stress (0.25 mmol/L CdCl2) and a strong Cd accumulation ability in its roots. The activities and contents of several antioxidant enzymes generally exhibited an increase under the treatment of 0.25 mmol/L CdCl2 but decreased under the treatment of higher CdCl2 concentrations. In particular, the proline (Pro) content was extremely elevated under the 0.25 and 0.5 mmol/L CdCl2 treatments but sharply declined under the 1.0 mmol/L CdCl2 treatment, suggesting that Pro is involved in the tolerance of S. alba to low concentration of Cd stress. In addition, RNA sequencing was utilized to analyze the gene expression profiles of S. alba exposed to Cd (under the treatment of 0.25 mmol/L CdCl2). The results indicate that roots were more susceptible to disturbance from Cd stress, as evidenced by the detection of 542 differentially expressed genes (DEGs) in roots compared to only 37 DEGs in leaves. GO and KEGG analyses found that the DEGs induced by Cd stress were primarily enriched in metabolic pathways, plant hormone signal transduction, and the biosynthesis of secondary metabolites. The key pathway hub genes were mainly associated with intracellular ion transport and cell wall synthesis. These findings suggest that S. alba is tolerant to a degree of Cd stress, but is also susceptible to the toxic effects of Cd. Furthermore, these results provide a theoretical basis for understanding Cd tolerance in S. alba.

Engineering highly dispersed AgI nanoparticles on hierarchical In2S3 hollow nanotube to construct Z-scheme heterojunction for efficient photodegradation of insecticide imidacloprid.

Increasing the exposure of active sites and improving the intrinsic activity are necessary considerations for designing a highly efficient photocatalyst. Herein, an In2S3/AgI stable Z-scheme heterojunction with highly dispersed AgI nanoparticles (NPs) is synthesized by the mild self-templated and in-situ ion exchange strategy. Impressively, the optimized In2S3/AgI-300 Z-scheme heterojunction exhibits superior photodegradation activity (0.020 min-1) for the decomposition of insecticide imidacloprid (IMD), which is extremely higher than that of pure In2S3 (0.002 min-1) and AgI (0.013 min-1). Importantly, the three-dimensional excitation-emission matrix (3D EEMs) fluorescence spectra, high-resolution mass spectrometry (HRMS), the photoelectrochemical tests, radical trapping experiment, and electron spin resonance (ESR) technique are performed to clarify the possible degradation pathway and mechanism of IMD by the In2S3/AgI-300 composite. The enhanced photocatalytic performance is attributed to the highly dispersed AgI NPs on hierarchical In2S3 hollow nanotube and the construction of In2S3/AgI Z-scheme heterojunction, which can not only increase active site exposure, but also improve its intrinsic activity, facilitating rapid charge transfer rate and excellent electron-hole pairs separation efficiency. Meanwhile, the practical application potential of the In2S3/AgI-300 composite is systematically investigated. This study opens a new insight for designing catalysts with high photocatalytic performance through a convenient approach.

The electronic structure and interfacial contact with metallic borophene of monolayer ScSX (X = I, Br, and Cl).

Two-dimensional (2D) semiconductors with excellent electronic and optical properties provide a great prospect for the fundamental research and application for the next-generation devices. Exploring the contact properties between 2D semiconductors and metal electrodes for improving the performance of nanodevices is of utmost importance. Motivated by the successful synthesis of bulk ScSI experimentally in a recent work [A. M. Ferrenti, M. A. Siegler, S. Gao, N. Ng and T. M. McQueen, Chem. Mater., 2022, 34, 12, 5443-5451], here we systematically investigate the intrinsic structural, electronic and optical properties of the novel monolayer ScSX (X = I, Br, and Cl) and their interfacial contact properties with the metal electrode of borophene using first-principles calculations. Interestingly, halogen X atoms with different electronegativities not only influence the intrinsic properties of monolayer ScSX, but also affect the interlayer coupling between monolayer ScSX and metallic borophene. The ScSI/borophene heterostructure forms a p-type Schottky contact, while both ScSBr/borophene and ScSCl/borophene heterostructures form a n-type Schottky contact. Moreover, our calculations demonstrate that strain engineering and applying an external electric field are effective strategies to regulate the Schottky barrier and contact types at the interface of ScSX/borophene. These findings provide a very promising path for designing tunable Schottky nanodevices with high-performance based on monolayer ScSX.

Recent Updates on Electrogenerated Hypervalent Iodine Derivatives and Their Applications as Mediators in Organic Electrosynthesis.

With the renaissance of chemical electrosynthesis in the last decade, the electrochemistry of hypervalent iodine compounds has picked up the pace and achieved significant improvements. By employing traceless electrons instead of stoichiometric oxidants as the alternative clean "reagents", many hypervalent iodine compounds were efficiently electro-synthesized via anodic oxidation methods and utilized as powerful redox mediators triggering valuable oxidative coupling reactions in a more sustainable way. This minireview gives an up-to-date overview of the recent advances during the past 3 years, encompassing enhanced electrosynthesis technologies, novel synthetic applications, and ideas for improving reaction sustainability.

Efficient detection for Nitrofurazone based on novel Ag2S QDs/g-C3N4 fluorescent probe.

In the paper, a novel fluorescent probe based on Ag2S QDs/g-C3N4 composite was synthesized by loading Ag2S quantum dots (Ag2S QDs) on the surface of g-C3N4 through in-situ synthesis method and developed to detect Nitrofurazone (NFZ) sensitively. The results showed that the linear detection range of Ag2S QDs/g-C3N4 to NFZ was 0-30 µM, with a low detection limit of 0.054 µM. The results of time-fluorescence-resolved spectroscopy and UV-vis absorption spectroscopy exhibited that the possible detection mechanism of Ag2S QDs/g-C3N4 to NFZ was proposed to be Internal Filtration Effect (IFE). Moreover, Multiwfn wavefunction analysis was employed to uncover the possible interaction between the Ag2S QDs/g-C3N4 and NFZ, thereby further revealing the fluorescence detection mechanism from the scale of atoms. Combining experiments and theoretical calculations, we proposed the sensing mechanism of the formation of non-fluorescent ground state complex linked by hydrogen bonds. This work indicated that the Ag2S QDs/g-C3N4 composite processed the ability to detect NFZ efficiently and sensitively.

Ionothermal synthesis of octahedral lanthanoid coordination networks exhibiting slow magnetization relaxation and efficient photoluminescence.

An ionothermal reaction of lanthanoid salts with tetraethyl-p-xylenediphosphonate (tepxdp) in ionic liquids, such as choline chloride and malonic acid, resulted in the formation of three novel lanthanoid-organic coordination networks with the formula [Ln(H2pxdp)1.5]n {Ln = Tb (1), Dy (2) and Ho(3) and H4pxdp = p-xylenediphosphonic acid}. The structures, photoluminescence and magnetic properties of the three compounds were investigated in detail. Single crystal X-ray diffraction analysis revealed that the three compounds are isostructural and the Ln3+ ions show an unusual six-coordinate environment with the {LnO6} octahedron. In these compounds, each {PO3C} tetrahedron is corner-shared with two {LnO6} octahedra and each {LnO6} octahedron is corner-shared with six {PO3C} tetrahedra, thus forming an inorganic layer in the crystallographic ab plane. The inorganic layers are further connected by a phenyl group, leading to a three-dimensional framework. Compound 1 exhibits the strong and characteristic emission of TbIII with an impressive quantum yield of 46.2%. Detailed magnetic analysis demonstrated that compound 2 displays a slow magnetic relaxation of magnetization with multiple relaxation mechanisms. The anisotropic energy barrier and the pre-exponential factor τ0 are 51.2 K and 3.9 × 10-7 s, respectively, in the presence of a direct-current field of 500 Oe. This work demonstrates a successful strategy to isolate octahedrally coordinated lanthanoid complexes through ionothermal synthesis to exhibit the single-ion-magnet-like behaviour and photoluminescence properties.

A ratiometric fluorescent sensor based on g-CNQDs@Zn-MOF for the sensitive detection of riboflavin via FRET.

A novel ratiometric fluorescent sensor based on Förster resonance energy transfer (FRET) platform was designed for riboflavin (RF) detection. The graphitic carbon nitrides quantum dots - Zn-MOF composite (g-CNQDs@Zn-MOF) was used as the fluorescent probe. In the FRET system, g-CNQDs@Zn-MOF and RF acted as donor and acceptor, respectively. The probe exhibited high sensitivity and good selectivity to RF, and had been successfully used for the detection of RF in milk and vitamin B2 tablets. The detection limit of the sensor was 15 nM. The strategy expanded the application of MOF in sensing filed and provided a new method for the detection of RF.

Recent Synthetic Applications of the Hypervalent Iodine(III) Reagents in Visible-Light-Induced Photoredox Catalysis.

The synergistic combination of visible-light-induced photoredox catalysis with hypervalent iodine(III) reagents (HIRs) represents a particularly important achievement in the field of hypervalent iodine chemistry, and numerous notable organic transformations were achieved in a mild and environmentally benign fashion. This account intends to summarize recent synthetic applications of HIRs in visible-light-induced photoredox catalysis, and they are organized in terms of the photochemical roles of HIRs played in reactions.

Converting Waste Polyethylene into ZnCCo3 and ZnCNi3 by a One-Step Thermal Reduction Process.

Plastic products have brought us great convenience in our daily life and work. But in the meantime, waste plastics have become solid pollutants in the environment due to its poor degradability. The resource utilization of waste plastic can decrease environmental pollution. Here, a thermal reduction method for the conversion of waste polyethylene to ZnCCo3 and ZnCNi3 in a stainless-steel autoclave under mild conditions has been reported. X-ray powder diffraction patterns indicate that the obtained samples are anti-perovskite-structured ternary carbides (ZnCCo3 and ZnCNi3) with good crystallinity. Moreover, the formation mechanism of ternary carbides has been briefly discussed. This method can be developed into an effective method for disposal of other waste plastics.

Cobalt and copper pyridylmethylphosphonates with two- and three-dimensional structures and field-induced magnetic transitions.

Two novel metal pyridylmethylphosphonates, namely, [Co(4-pmp)] (1) and [Cu(4-pmp)(H2O)] (2), (4-pmpH2 = 4-pyridylmethylphosphonic acid), have been hydrothermally synthesized and characterized by X-ray diffraction, infrared spectroscopy, elemental analysis, and thermogravimetric analysis. In compound 1, each {PO3C} tetrahedron is corner-shared with three {CoNO3} tetrahedra and vice versa, thus forming a one-dimensional (1-D) inorganic chain along the a axis containing 8-membered rings of [(Co-O-P-O)2]. The inorganic chains are further connected by a 4-pmp(2-) ligand, generating a 2-D layered structure. Compound 2 displays a three-dimensional (3-D) framework structure, in which the inorganic layers are pillared by the pyridyl groups of the ligand, generating a 3-D pillared-layered structure. The magnetic properties of 1 and 2 have been studied. Compounds 1 and 2 behave as metamagnets at low temperature. The critical fields are about 70 kOe for 1 and 47 kOe for 2 at 1.8 K.

Ionothermal synthesis, crystal structure, topology and catalytic properties of heterometallic coordination polymers constructed from N-(phosphonomethyl) iminodiacetic acid.

Reactions of rare earth chlorides, N-(phosphonomethyl)iminodiacetic acid (H(4)pmida) and ferrous oxalate dihydrate under ionothermal conditions result in four new isostructural 3d-4f heterometal coordination polymers, [LnFe(III)Fe(6)(Hpmida)(6)]·2H(2)O {Ln = Eu (1), Dy (2), Ho (3) and Y (4)}. All compounds were characterized by infrared spectroscopy, elemental analysis, thermogravimetric analysis, and X-ray diffraction. The compounds feature a very interesting three dimensional (3-D) structure built up from a secondary building unit, [Fe(2)(Hpmida)(2)](2-) and possess a new topology type and complicated unique tilings. The catalytic properties of compounds 1-4 were investigated showing that these types of compounds are heterogeneous catalysts in the Knöevenagel condensation with high selectivity.

Six new 3d-4f heterometallic coordination polymers constructed from pyrazole-bridged Cu(II)Ln(III) dinuclear units.

Reactions of lanthanide chlorides, copper hydroxycarbonate and 3,5-pyrazole dicarboxylic acid (H3pdc) under hydrothermal conditions result in six new 3d-4f heterometallic coordination polymers with two types of structures. Compounds [CuLn2(pdc)2(Hpdc)(H2O)4]·2H2O (Ln = Tb (1), Dy (2), Er (3), and Y (4) exhibit a layered porous structure, made up of Cu(II)Ln(III) di-nuclear units which are connected by protonated Hpdc(2-) ligand, while the others [Cu3Ln4(pdc)6(H2O)8] (Ln = Eu (5), Gd (6)) display a three-dimensional (3-D) framework structure, in which six Cu(II)Ln(III) di-nuclear units are cross-linked by two coordinated lanthanide atoms. The catalytic properties of 3 are investigated showing its activity and recyclability in the reaction of cyclopropanation of styrene.

Metal monophosphonates M{(2-C5H4NO)CH2PO3}(H2O)2 (M = Co, Ni, Mn, Cd): synthesis, structure, and magnetism.

Four isostructural metal monophosphonates, M{(2-C(5)H(4)NO)CH(2)PO(3)}(H(2)O)(2) with M = Co (1), Ni (2), Mn (3), and Cd (4), were synthesized and structurally characterized. These compounds show a double-chain structure in which the M(2)(µ-O)(2) dimers are connected by O-P-O bridges. The magnetic responses of 1-3 were investigated over a wide range of magnetic fields (up to 10 T) and temperatures (down to 50 mK). Except for 4, which is weakly diamagnetic from 2 K to room temperature, the dominant magnetic interactions are antiferromagnetic. Isothermal magnetic field sweeps at 50 mK provide signatures in the magnetic responses that are associated with antiferromagnetic to field-induced fully polarized (magnetically saturated) transitions. Analysis of the magnetic data indicates that 1 and 2 form magnetic dimer-like clusters with weak dimer-dimer interactions present. Contrastingly, the magnetic interactions present in 3 are significantly weaker, so a definitive description of the magnetism of this compound is elusive.

[Amino-(iminio)meth-yl]phospho-nate.

The title compound, CH(5)N(2)O(3)P, exists as a zwitterion. The N atom of the imino group is protonated and the phospho-nic acid group is deprotonated. The mol-ecular geometry about the central C atom of this zwitterionic species was found to be strictly planar with the sum of the three angles about C being precisely 360°. In the crystal, the mol-ecules are inter-linked by O-H⋯O and N-H⋯O hydrogen-bonding inter-actions, forming a three-dimensional supra-molecular network structure.

Tuning the field-induced magnetic transition in a layered cobalt phosphonate by reversible dehydration-hydration process.

A layered cobalt phosphonate, Co(2-pmp)(H(2)O)(2) (1) (2-pmpH(2) = 2-pyridylmethylphosphonic acid) is reported, which provides the first example of metamagnetic cobalt system that shows reversible changes in both structures and magnetic behaviors upon dehydration-hydration process.

Poly[[diaqua-hemi-µ(4)-oxalato-µ(2)-oxalato-praseodymium(III)] monohydrate].

In the title complex, {[Pr(C(2)O(4))(1.5)(H(2)O)(2)]·H(2)O}(n), the Pr(III) ion, which lies on a crystallographic inversion centre, is coordinated by seven O atoms from four oxalate ligands and two O atoms from two water ligands; further Pr-O coordination from tetra-dentate oxalate ligands forms a three-dimensional structure. The compound crystallized as a monohydrate, the water mol-ecule occupying space in small voids and being secured by O-H⋯O hydrogen bonding as an acceptor from ligand water H atoms and as a donor to oxalate O-acceptor sites.