o-phenylenediamine Derived Fluorescent Carbon Quantum dots for Detection of Hg(II) in Environmental Water.

With the expansion of human activities, the consequent influx of mercury (Hg) into the food chain and the environment is seriously threatening human life. Herein, nitrogen and sulfur co-doped fluorescent carbon quantum dots (yCQDs) were prepared via a hydrothermal method using o-phenylenediamine (OPD) and taurine as precursors. The morphological characteristics as well as spectral features of yCQDs indicated that the photoluminescence mechanism should be the molecular state fluorophores of 2, 3-diaminophenothiazine (oxOPD), which is the oxide of OPD. The as-synthesized yCQDs exhibited sensitive recognition of Hg2+. According to the investigation in combination of UV-Vis absorption spectra, time-resolved fluorescence spectra and quantum chemical calculations, the abundant functional groups on the surface of yCQDs allowed Hg2+ to bind with yCQDs through various interactions, and the formed complexes significantly inhibited the absorption of excitation light, resulting in the static fluorescence quenching of yCQDs. The proposed yCQDs was utilized for Hg2+ sensing with the limit of detection calculated to be 4.50 × 10- 8 M. Furthermore, the recognition ability of yCQDs for Hg2+ was estimated in tap water, lake water and bottled water, and the results indicated that yCQDs have potential applications in monitoring Hg2+.

Selenomethionine protects the liver from dietary deoxynivalenol exposure via Nrf2/PPARγ-GPX4-ferroptosis pathway in mice.

Deoxynivalenol (DON) is a significant Fusarium toxin that has gained global attention due to its high frequency of contamination in food and feed. It was reported to have hepatotoxicity, immunotoxicity, and reproduction toxicity in organs. On the other hand, Selenomethionine (SeMet) was proven to have anti-oxidation, tissue repairing, immunity improvement, and antifungal mycotoxin infection functions. However, the molecular mechanism by which SeMet alleviates DON damage is not yet clear. C57BL/6 mice were randomly divided into three groups, Se-A and Se-A+DON were fed with a diet containing 0.2 mg/kg Se whereas Se-S+DON were fed with a diet of 1.0 mg/kg Se. After feeding for four weeks, the mice were gavaged for 21 days with DON (2.0 mg/kg BW) or ultrapure water once per day. In the present study, we showed that SeMet significantly decreased the lipid peroxidation product malondialdehyde, and increased activities of antioxidant enzymes superoxide dismutase and total antioxidant capacity after DON exposure. In addition, our investigation revealed that SeMet regulated pathways related to lipid synthesis and metabolisms, and effectively mitigated DON-induced liver damage. Moreover, we have discovered that SeMet downregulation of N-acylethanolamine and HexCer accumulation induced hepatic lipotoxicity. Further study showed that SeMet supplementation increased protein levels of glutathione peroxidase 4 (GPX4), peroxisome proliferator-activated receptor γ (PPARγ), nuclear erythroid 2-related factor 2 (Nrf2), and upregulated target proteins, indicating suppression of oxidative stress in the liver. Meanwhile, we found that SeMet significantly reduced the DON-induced protein abundances of Bcl2, Beclin1, LC3B and proteins related to ferroptosis (Lpcat3, and Slc3a2), and downregulation of Slc7a11. In conclusion, SeMet protected the liver from damage by enhancing the Nrf2/PPARγ-GPX4-ferroptosis pathway, inhibiting lipid accumulation and hepatic lipotoxicity. The findings of this study indicated that SeMet has a positive impact on liver health by improving antioxidant capacity and relieving lipotoxicity in toxin pollution.

S-nitrosylation of the transcription factor MYB30 facilitates nitric oxide-promoted seed germination in Arabidopsis.

The gaseous signaling molecule nitric oxide (NO) plays an important role in breaking seed dormancy. NO induces a decrease in abscisic acid (ABA) content by transcriptionally activating its catabolic enzyme, the ABA 8'-hydroxylase CYP707A2. However, the underlying mechanism of this process remains unclear. Here, we report that the transcription factor MYB30 plays a critical role in NO-induced seed germination in Arabidopsis (Arabidopsis thaliana). MYB30 loss-of-function attenuates NO-mediated seed dormancy breaking. MYB30 triggers a NO-induced decrease in ABA content during germination by directly promoting CYP707A2 expression. NO induces S-nitrosylation at Cys-49 of MYB30 and enhances its transcriptional activity. Conversely, the ABA receptors PYRABACTIN RESISTANCE1 (PYR1)/PYR1-LIKE (PYL)/REGULATORY COMPONENTS OF ABA RECEPTORS (RCAR) interact with MYB30 and repress its transcriptional activity. ABA promotes the interaction between PYL4 and MYB30, whereas S-nitrosylation releases the PYL4-mediated inhibition of MYB30 by interfering with the PYL4-MYB30 interaction. Genetic analysis showed that MYB30 functions downstream of PYLs during seed dormancy and germination in response to NO. Furthermore, MYB30 mutation significantly represses the reduced dormancy phenotype and the enhanced CYP707A2 expression of the pyr1 pyl1 pyl2 pyl4 quadruple mutant. Our findings reveal that S-nitrosylation of MYB30 precisely regulates the balance of seed dormancy and germination, providing insights into the underlying mechanism of NO-promoted seed germination.

Facile synthesis of S, N-co-doped carbon dots for bio-imaging, Fe3+ detection and DFT calculation.

Turning waste into wealth, herein, two highly fluorescent N and S co-doped carbon dots (N, S-CDs-A and N, S-CDs-B) were synthesized by the hydrothermal reaction of contaminant reactive red 2 (RR2) and L-cysteine or L-methionine, respectively. The detailed morphology and structure of N, S-CDs were characterized by XRD, Raman spectrum, FTIR spectra, TEM, HRTEM, AFM and XPS. The maximum fluorescent of N, S-CDs-A and N, S-CDs-B are 565 and 615 nm under different excitation wavelengths with moderate fluorescence intensity of 14.0 % and 6.3 %, respectively. The microstructure models of N, S-CDs-A and N, S-CDs-B, which were induced by FT-IR, XPS and element analysis, had been applied in DFT calculation. The result indicated that the doping of S and N is beneficial to obtain the red-shift of fluorescent spectra. Both N, S-CDs-A and N, S-CDs-B showed highly sensitive and selective to Fe3+. N, S-CDs-A can also detect Al3+ ion with high sensitivity and selectivity. Finally, N, S-CDs-B was successfully applied in cell imaging.

A hydrogen bonding based SERS method for direct label-free L-hydroxyproline detection.

The detection of non-protein nitrogen adulterants is a major challenge in dairy testing. As a marker molecule of animal hydrolyzed protein, the presence of non-edible L-hydroxyproline (L-Hyp) molecules can be used to identify low-quality milk containing components of animal hydrolyzed protein. However, it is still difficult to detect L-Hyp directly in milk. The Ag@COF-COOH substrate in this paper can be used to realize label-free L-Hyp sensitive detection based on the hydrogen bond transition mechanism. To explore the mechanism, the binding sites of hydrogen bond interaction have been verified experimentally and computationally, and the charge transfer process was also explained in terms of HOMO/LOMO energy level. In conclusion, the quantitative models for L-Hyp in an aqueous environment and in milk were developed. The limit of detection (LOD) of L-Hyp in an aqueous environment could reach 8.18 ng/mL, with R2 of 0.982. The linear range of quantitative detection in milk was 0.5-1000 µg/mL and the LOD was as low as 0.13 µg/mL. In this work, a hydrogen bond interaction based Surface-enhanced Raman spectroscopy (SERS) method for the label-free detection of L-Hyp was proposed, which complemented the application of SERS technology in the detection of dairy products.

MIW1 participates in ABA signaling through the regulation of MYB30 in Arabidopsis.

Seed germination and seedling establishment are critical biological processes, and their underlying molecular mechanisms have practical implications. The ABA signaling during seed germination and early seedling development is negatively regulated by transcription factor MYB30, but its interaction partners and downstream targets are not fully understood. In this study, we identified MIW1 (MYB30-interacting WD40 protein 1), a WD40 protein that could interact with MYB30 and promote its degradation. In the miw1 mutant, the MYB30 protein became more stable. MIW1 enhanced the ABA-mediated inhibition of postgerminative development. The miw1 mutants became hyposensitive to exogenous ABA, and this effect was suppressed by mutations in MYB30. Furthermore, we found that MYB30 negatively regulated the expression of the ABA receptor genes PYR1/PYL/RCARs. The changes in PYLs expression during early seedling development or under ABA treatment became more pronounced in the myb30 mutant. ChIP-qPCR analyses showed MYB30 could directly bind to the promoters of PYL11 and PYL12. Our study reveals that the WD40 protein MIW1 promotes the expression of PYLs by destabilizing MYB30, thus positively regulating the ABA signaling during postgermination in Arabidopsis.

Al2O3@Ag composite structure as SERS substrate for sensitive detection of sodium thiocyanate.

Sodium thiocyanate (NaSCN) can be added to fresh milk to enhance the sterilization ability of the lactoperoxidase system (LP system) in milk, extending shelf life. However, excessive intake of NaSCN can be harmful to human health because it can prevent absorption of iodine leading to disease. Also NaSCN can be used as a marker to distinguish smokers from non-smokers. In this work, we successfully synthesized meatball-like Al2O3@Ag composite structures as surface-enhanced Raman scattering (SERS) substrates using a simple wet chemical method adapted to conventional laboratory conditions. The substrate exhibited strong SERS enhancement for NaSCN. Under the optimal experiment conditions, we obtained a detection limit of 0.28 µg L-1 and a quantification limit of 1 µg L-1, R2 = 0.992. Based on the analysis of the intensity of SERS characteristic peak, the substrate had good reproducibility and uniformity. In summary, the Al2O3@Ag composite structure achieved sensitive SERS detection of NaSCN. Combining the facile and low-cost methods, we believe that the SERS detection method developed in this work can be used as a potential candidate for biosensing applications in the future.

Effect of Zn2+ on emodin molecules studied by time-resolved fluorescence spectroscopy and quantum chemical calculations.

Emodin is a natural drug for treating neurodegenerative diseases and plays a vital role in the mitigation of nerve damage. Metal ions can modify the drug properties of emodin, where Zn2+ can synergize with the emodin molecule and enhance the drug effect of emodin. Besides, complex changes can be observed in the fluorescence intensity and fluorescence lifetime of the emodin molecule as the concentration of Zn2+ increases. Herein, the synergistic effects of ligand structural in Zn(II)-Emodin complexes and the electronic effects of metal elements on the antioxidant properties of the complexes are discussed in detail based on UV-vis absorption spectroscopy, fluorescence spectroscopy, time-correlated single photon counting (TCSPC) technique and quantum chemical calculations at the B3LYP/6-31G(d) level. The experimental results confirm that Zn2+ can coordinate with the hydroxyl groups on the emodin to make the molecule structure more rigid, thus inhibiting the non-radiative processes such as high-frequency vibrations of the emodin molecule in solution. The suppression of non-radiative processes leads to an increase in the average fluorescence lifetime of the emodin molecule, and finally results in the enhanced fluorescence intensity. The chemical softness of Zn(II)-Emodin is then confirmed to be higher than that of emodin by Gaussian calculations, indicating its higher chemical reactivity and lower stability. The stronger electron donating ability of Zn(II)-Emodin compared to emodin may explain the higher antioxidant activity of Zn(II)-Emodin, which gives it a stronger pharmacological activity. The results of this study show that emodin can well complex with Zn2+ to remove excess Zn2+ in human body and the resulting complex has better antioxidant properties, which helps to understand the role of Zn2+ in drug-metal coordination and provides guidance for the design of new drugs.

Boric acid-functionalized silver nanoparticles as SERS substrate for sensitive and rapid detection of fructose in artificial urine.

The accurate detection of fructose in human urine can help prevent and screen for diseases such as fructokinase deficiency and hereditary fructose intolerance. Surface-enhanced Raman spectroscopy (SERS) is an analytical technique with selectivity and high sensitivity, which has been widely applied to the detection of targets with complex backgrounds. In this work, 4-mercaptophenylboronic acid (4-MPBA) was modified on the surface of silver nanoparticles (AgNPs) under mild conditions to obtain a boronic acid-functionalized SERS substrate for the detection of fructose in artificial urine. The detection mechanism was based on the deboronization reaction of 4-MPBA on the surface of AgNPs, which was induced by fructose, and the Raman signal of the generated thiophenol (TP) molecules was significantly enhanced by the silver nanoparticles, with a linear increase in SERS peak intensity at 1570 cm-1. We achieved the detection limits of 0.084 µmol/L in water and 0.535 µmol/L in urine by this method. The relative standard deviation (RSD) in the recovery experiments of urine ranged from 1.01 % to 2.22 %, and the whole detection time was less than 10 min, which indicated that this method is highly reliable for fructose detection and has a good prospect in bioassay and clinical medicine.

A fluorescent probe based on FRET effect between carbon nanodots and gold nanoparticles for sensitive detection of thiourea.

Illegal abuse results in the presence of thiourea (TU) in soil, wastewater, and even fruits, which is harmful for the environment and human health. It has urgent practical significance to design an efficient and reliable probe for TU detection. Herein, a sensitive fluorescent probe with off-on response for harmful TU was reported. The probe was designed with fluorescent carbon nanodots (CNDs) and gold nanoparticles (AuNPs) based on fluorescence resonance energy transfer (FRET) effect. Firstly, the CNDs were pre-combined with AuNPs and the fluorescence of CNDs was quenched due to the FRET effect. Upon addition of TU, the fluorescence of CNDs recovered due to the unbinding of CNDs and AuNPs, since the coordination interaction between TU and AuNPs is stronger than the electrostatic interaction among CNDs and AuNPs. Under the optimum parameters, a linear relationship was found between the relative fluorescence intensity of the probe and the concentration of TU in the range of 5.00 × 10-8-1.00 × 10-6 M (R2 = 0.9958), with the limit of detection (LOD) calculated to be 3.62 × 10-8 M. This proposed method is easy to operate and has excellent selectivity and sensitivity for TU, which can be effectively applied in environmental water and compound fruit-vegetable juice.

Sensitive determination of Norfloxacin in milk based on ß-cyclodextrin functionalized silver nanoparticles SERS substrate.

The norfloxacin (NFX) residue in milk will increase human resistance to drugs and pose a threat to public health. In this work, a highly sensitive method for detection of NFX was developed based on surface enhanced Raman spectroscopy (SERS) using ß-cyclodextrin functionalized silver nanoparticles (ß-CD-AgNPs) as substrate. The unique spatial size and hydrophilicity of ß-CD on the surface of AgNPs could selectively capture the target molecule (NFX) through some weak interactions, including hydrogen-bond interaction, electrostatic interaction, etc. The interactions were characterized by the UV-Vis absorption spectroscopy, fluorescence spectroscopy, Zeta potential and DLS. The Raman signal of NFX is largely enhanced when anchored by ß-CD on the surface of AgNPs due to SERS effect. Through a series of experiments and analysis, the limit of detection (LOD) in standard solution and spiked milk were calculated to be 3.214 pmol/L and 5.327 nmol/L. The correlation coefficients (R2) were 0.986 and 0.984, respectively. For milk sample determination of NFX, the recovery was 101.29% to 104.00% with the relative standard deviation (RSD) from 2.986% to 9.136%. To sum up, this developed SERS strategy is sensitive and specific to detect NFX in milk, it has practical application value and prospects.

Turning waste into wealth: facile and green synthesis of carbon nanodots from pollutants and applications to bioimaging.

In an effort to turn waste into wealth, Reactive Red 2 (RR2), a common and refractory organic pollutant in industrial wastewater, has been employed for the first time as a precursor to synthesize carbon nanodots (CNDs) by a facile, green and low-cost route, without utilization of any strong acids or other oxidizers. The detailed characterizations have confirmed that the synthesized CNDs exhibit good water dispersibility, with a mean particle size of 2.43 nm and thickness of 1-3 layers. Importantly, the excellent fluorescence properties and much reduced biotoxicity of the CNDs confer its potential applications in further biological imaging, which has been successfully verified in both in vitro (cell culture) and in vivo (zebrafish) model systems. Thus, it is demonstrated that the synthesized CNDs exhibit nice biocompatibility and fluorescence properties for bioimaging. This work not only provides a novel economical and environmentally friendly approach in recycling a chemical pollutant, but also greatly promotes the potential application of CNDs in biological imaging.

Demonstration of Controlled Hydrogen Release Using Rh@GQDs during Hydrolysis of NH3BH3.

Achieving the controlled release of H2 through an effective approach still faces many challenges. Herein, high-quality graphene quantum dots (GQDs) are synthesized from a new precursor, 1,2,4-trihydroxy benzene, and a multifunctional platform of Rh@GQDs is further developed for the controlled H2 evolution upon the hydrolysis of NH3BH3 (AB). More importantly, the designing concepts of multistep and stepless speed controls have been introduced in the domains of both H2 evolution for the first time. Through a novel designing protocol, the rate of H2 evolution can be freely regulated and constantly varied on demand by means of chelation between Zn2+ and ethylene diamine tetraacetic acid (EDTA). The density functional theory calculation indicates that Zn2+ has the priority to be adsorbed onto Rh(100) due to its larger adsorption energy (107.98 kcal·mol-1) than that of AB (36.36 kcal·mol-1). A controlling mechanism is presented such that Zn2+ will cover the active sites of the nanocatalyst to prevent the H2 evolution, and EDTA can chelate Zn2+ to reactivate the nanocatalyst for the production of H2, greatly facilitating use of this strategy in other catalytic reactions. Moreover, it is demonstrated that the protocol is equally valid for diverse hydrogen storage materials. Therefore, this work not only establishes whole new concepts for the controlled production of H2 but also explains their mechanism, thus remarkably advancing the utilization of H2 energy and significantly enlightening the controlled process of catalysis.

Surface Coatings via the Assembly of Metal-Monophenolic Networks.

Mussel-inspired surface modification has received significant interest in recent years because of its simplicity and versatility. The deposition systems are still mainly limited to molecules with catechol chemical structures. In this paper, we report a novel deposition system based on a monophenol, vanillic acid (4-hydroxy-3-methoxybenzoic acid), to fabricate metal-phenolic network coatings on various substrates. The results of the water contact angle and zeta potential reveal that the modified polypropylene microfiltration membrane is underwater superhydrophobic and positively charged, showing applications in oil/water separation and dye removal. Furthermore, the single-face modified Janus membrane is promising in switchable oil/water separation. The results demonstrate a novel example of the metal-monophenolic deposition system, which expands the toolbox of surface coatings and facilitates the understanding of the deposition of phenols.

Synthesis of graphene quantum dot-stabilized gold nanoparticles and their application.

Herein, we report an in situ synthesis of graphene quantum dots (GQDs), which have been synthesized from only starch and water and stabilize AuNPs in water. The construction of six gold nanocomposites, i.e. AuNPs 1-6, with sizes ranging from 13.4 nm to 32.6 nm, was accomplished by only mixing the GQDs and chloroauric acid in different amounts without any additional reductants and surfactants. HRTEM has confirmed that the AuNPs have been stabilized by the GQDs, and a core/shell AuNPs@GQD structure has formed. In addition, the as-synthesized AuNPs show excellent catalytic performance in the reduction of 4-nitrophenol, a pertinacious pollutant occurring in industrial wastewater.

[Factors affecting residual sludge reducing by anaerobic hydrolysis-acidification and aerobic oxidation process of A1/A2/O bio-treatment system].

Hydrolysis-acidification and aerobic oxidation process could realize sludge reducing without those strengthening conditions such as high temperature, high pressure, strong oxidant or alkali which may destroy the cell structure of microorganisms, so it has good maneuverability and is economical. The purpose of sludge reducing system is mainly to degrade the pollutants in it ant its reducing effect is related to organic loading, HRT and temperature, etc. In the A1/A2/O bio-treatment system dealing with alkali minimization and dyeing-printing wastewater, residual sludge can be reduced effectively by recycling sludge to A1 segment. It proved that sludge could be reduced effectively and treated water could reach the grade I standard of GB8978-96 for long time operation of the system, when the volume loading of A1 (COD) was 2.54 kg x (m3 x d)(-1), the HRT of A1 was 7.56 h and the temperature of the system was 25 degrees C - 40 degrees C. The sludge reducing could be realized through recycling to A1 segment, and the N, P released from the broken bacteria cell could compensate the shortage of N and P of alkali minimization and dyeing-printing wastewater, and then the cost of adding the nutrition of N and P to the system could be reduced greatly.