A novel colormetric and light-up fluorescent sensor from flavonol derivative grafted cellulose for rapid and sensitive detection of Hg2+ and its applications in biological and environmental system.

Mercury ion (Hg2+) is one of harmful heavy metal ions that can accumulate inside the human organism and cause some health problems. In the article, a highly effective fluorescent probe named EC-T-PCBM was prepared by grafting flavonol derivatives onto ethyl cellulose for the specific recognition of Hg2+. EC-T-PCBM exhibited a remarkable fluorescence light-up response toward Hg2+ with excellent sensitivity. EC-T-PCBM possessed several prominent sensing properties for Hg2+, such as low detection limit (43.9 nM), short response time (5 min), and wide detection pH range (6-9). The response mechanism of EC-T-PCBM to Hg2+ has been verified through 1H NMR titration and DFT computation. Additionally, EC-T-PCBM not only can be used for accurately determining trace amount of Hg2+ in actual environmental water samples, but also can serve as a portable and rapid device by loading it on test strips for sensitive and selective visualization of Hg2+. More importantly, the confocal fluorescence imaging of onion cells suggested the favorable cell membrane permeability of EC-T-PCBM and its prominent ability to continuously monitor the enrichment from Hg2+ within fresh plant tissues.

A ratiometric fluorescent probe with a large Stokes shift for the detection of Hg2+ and its applications in environmental sample and living system analysis.

Toxic mercury ions (Hg2+) can cause serious environmental pollution and accumulate in living organisms via the food chain. Therefore, monitoring Hg2+ is crucial in ensuring the safety of ecosystems and organisms. In this work, a novel ratiometric fluorescent probe CMT (5-(4-(diphenylamino)phenyl)-1-(7-hydroxy-coumarin-3-yl)-4-pentene-1,3-dione) based on coumarin was developed for detecting Hg2+, which displayed obvious fluorescence changes, a low detection limit (2.24 × 10-7 M), good selectivity, and a large Stokes shift (255 nm). The CMT probe could detect Hg2+ in real environmental soil and water samples. Furthermore, the CMT probe enabled the naked-eye detection of Hg2+ using test paper experiments. CMT was also applied for fluorescence imaging in living zebrafish and plants. This work provides a highly efficient tool for monitoring Hg2+ in environmental samples and biological systems.

Microplastics derived from plastic mulch films and their carrier function effect on the environmental risk of pesticides.

Plastic film mulching can maintain soil water and heat conditions, promote plant growth and thus generate considerable economic benefits in agriculture. However, as they age, these plastics degrade and form microplastics (MPs). Additionally, pesticides are widely utilized to control organisms that harm plants, and they can ultimately enter and remain in the environment after use. Pesticides can also be sorbed by MPs, and the sorption kinetics and isotherms explain the three stages of pesticide sorption: rapid sorption, slow sorption and sorption equilibrium. In this process, hydrophobic and partition interactions, electrostatic interactions and valence bond interactions are the main sorption mechanisms. Additionally, small MPs, biodegradable MPs and aged conventional MPs often exhibit stronger pesticide sorption capacity. As environmental conditions change, especially in simulated biological media, pesticides can desorb from MPs. The utilization of pesticides by environmental microorganisms is the main factor controlling the degradation rate of pesticides in the presence of MPs. Pesticide sorption by MPs and size effects of MPs on pesticides are related to the internal exposure level of biological pesticides and changes in pesticide toxicity in the presence of MPs. Most studies have suggested that MPs exacerbate the toxicological effects of pesticides on sentinel species. Hence, the environmental risks of pesticides are altered by MPs and the carrier function of MPs. Based on this, research on the affinity between MPs and various pesticides should be systematically conducted. During agricultural production, pesticides should be cautiously selected and used plastic film to ensure human health and ecological security.

The combined effects of azoxystrobin and different aged polyethylene microplastics on earthworms (Eisenia fetida): A systematic evaluation based on oxidative damage and intestinal function.

Pesticides and microplastics are common pollutants in soil environments, adversely affecting soil organisms. However, the combined toxicological effects of aged microplastics and pesticides on soil organisms are still unclear. In this study, we systematically studied the toxicological effects of azoxystrobin and four different aged polyethylene (PE) microplastics on earthworms (Eisenia fetida). The purpose was to evaluate the effects of aging microplastics on the toxicity of microplastics-pesticides combinations on earthworms. The results showed that different-aged PE microplastics promoted azoxystrobin accumulation in earthworms. Meanwhile, combined exposure to azoxystrobin and aged PE microplastics decreased the body weight of earthworms. Besides, both single and combined exposure to azoxystrobin and aged PE microplastics could lead to oxidative damage in earthworms. Further studies revealed that azoxystrobin and aged PE microplastics damage the intestinal structure and function of earthworms. Additionally, the combination of different aged PE microplastics and azoxystrobin was more toxic on earthworms than single exposures. The PE microplastics subjected to mechanical wear, ultraviolet radiation, and acid aging exhibited the strongest toxicity enhancement effects on earthworms. This high toxicity may be related to the modification of PE microplastics caused by aging. In summary, these results demonstrated the enhancing effects of aged PE microplastics on the toxicity of pesticides to earthworms. More importantly, aged PE microplastics exhibited stronger toxicity-enhancing effects in the early exposure stages. This study provides important data supporting the impact of different aged PE microplastics on the environmental risks of pesticides.

An ultrasensitive cellulose-based fluorescent sensor for Al3+ detection and its applications in plant tissue and food samples.

Fluorescent sensors available for metal ions detection have been extensively developed in recent years. However, developing an ultrasensitive fluorescent sensor for highly selectively detecting Al3+ based on cellulose remains a challenge. In this study, an ethylcellulose-based flavonol fluorescent sensor named EC-BHA was synthesized by the esterification of ethylcellulose (EC) with a new flavonol derivative 4-(2-(2,3-bis(ethoxymeothy)phenyl)-3-hydroxy-4-oxo-4-H-chromen-7-yl) benzoic acid (BHA). The fluorescence intensity of EC-BHA exhibited a 180-fold increase at 490 nm after binding with Al3+ and provided an ultralow detection limit of 13.0 nM. The sensor showed some exceptional sensing properties including a broad pH range (4-10), large Stokes shifts (190 nm), and a short response time (3 min). This sensor was successfully applied for determining trace Al3+ in food samples as well as in plant tissue. Moreover, the electrostatic spun film EBP was fabricated by blending EC-BHA with PS (polystyrene) via electrostatic spinning technique and utilized for selective detection of Al3+ as soon as possible.

Rotenone nanoparticles based on mesoporous silica to improve the stability, translocation and insecticidal activity of rotenone.

Nanotechnology has been widely applied for pesticide carriers, which is an important way to improve the utilization, stability, and sustained release of pesticides. Mesoporous silica nanoparticles (MSNs) are a nanomaterial with adjustable particle and pore sizes, with a high specific surface area and good biocompatibility. Rotenone is a non-systemic botanical insecticide that is easily degraded in the environment. We used a modified soft-template method to prepare MSNs, in which rotenone was loaded using the solvent evaporation method. The prepared rotenone nanopesticide based on mesoporous silica showed considerable drug loading rates of 33.2%. Moreover, the prepared rotenone nanoparticles showed improved photostability and sustained release behavior, which improved the translocation of rotenone in tomato plants. Finally, the rotenone nanoparticles displayed superior insecticidal activity compared to traditional preparations. In summary, the rotenone nanopesticide improved the persistence and utilization rates of rotenone. These findings are of significance in reducing pesticide usage, mitigating environmental pollution, and ensuring food safety.

A highly specific chalcone derivative grafted ethylcellulose fluorescent probe for rapid and sensitive detection of Al3+ in actual environmental and food samples.

Al3+ is commonly utilized in daily life, however, the excessive accumulation of Al3+ within organisms can result in severe health problems. Herein, a highly efficient fluorescent probe EC-HTC for Al3+ was synthesized through chemical modification of ethyl cellulose. This probe exhibited a significant fluorescence enhancement response to Al3+, and it interestingly also possessed an obvious aggregation-induced emission (AIE) effect. The detection limit of probe EC-HTC for Al3+ was as low as 0.23 µM, and its pH usage range was as wide as 5-10. The complexation ratio of EC-HTC with Al3+ was determined to be 1:1 based on Job's plot, which was further confirmed by 1H NMR titration and HRMS analysis. Moreover, the probe EC-HTC was successfully employed for the determination of Al3+ in environmental and food samples. In addition, the probe EC-HTC compositing PS (polystyrene) electrostatic spun fiber membranes EHP with high specific surface area were prepared to achieve the rapid and portable detection of Al3+.

Toxicity effects of pesticides based on zebrafish (Danio rerio) models: Advances and perspectives.

Pesticides inevitably enter aquatic environments, posing potential risks to organisms. The common aquatic model organism, zebrafish (Danio rerio), are widely used to evaluate the toxicity of pesticides. In this review, we searched the Web of Science database for articles published between 2012 and 2022, using the keywords "pesticide", "zebrafish", and "toxicity", retrieving 618 publications. Furthermore, we described the main pathways by which pesticides enter aquatic environments and the fate of their residues in these environments. We systematically reviewed the toxicity effects of pesticides on zebrafish, including developmental toxicity, endocrine-disrupting effects, reproductive toxicity, neurotoxicity, immunotoxicity, and genotoxicity. Importantly, we summarized the latest research progress on the toxicity mechanism of pesticides to zebrafish based on omics technologies, including transcriptomics, metabolomics, and microbiomics. Finally, we discussed future research prospects, focusing on the combined exposure of multiple pollutants including pesticides, the risk of multigenerational exposure to pesticides, and the chronic toxicity of aquatic nanopesticides. This review provides essential data support for ecological risk assessments of pesticides in aquatic environments, and has implications for water management in the context of pesticide pollution.

Fluorescent probe for sensitive discrimination of GSH and Hcy/Cys with single-wavelength excitation in biological systems via different emission.

Biothiols (GSH, Hcy, Cys) are important active sulfur substances in biological systems and widely participate in various physiological processes. The three kinds of biothiols have similar chemical structures, including the sulfhydryl group (-SH) and an amino group (-NH2), so distinguishing two or more of them simultaneously is an important challenge. Herein, a nopinone-based fluorescent probe 3-(3-((4-nitrobenzoxadiazole vinyl) nopinyl difluoride (NF-NBD) was designed to distinguish GSH and Hcy/Cys by generating different fluorescence channels with a single excitation wavelength. The nitrobenzodioxazole (NBD) was introduced in the fluorescent probe by ether bounds that can quench fluorescence and selectively discriminate GSH and Hcy/Cys. After reacting with GSH and Hcy/Cys, NF-NBD exhibited strong fluorescence (green for GSH and yellow for Hcy/Cys). NF-NBD displayed a wide linear range, low detection limit, a rapid response time, and superior selectivity for biothiols. Furthermore, NF-NBD was applied to image and distinguish different biothiols in living cells and zebrafish via different fluorescence signals at a single excitation wavelength.

An efficient chitosan-naphthalimide fluorescent probe for simultaneous detection and adsorption of Hg2+ and its application in seafood, water and soil environments.

As a virulent heavy metal ion, Hg2+ will lead to a serious threat to ecosystem and human health. In this work, we reported a chitosan-naphthalimide fluorescent probe CS-NA-ITC for specific recognition and efficient adsorption of Hg2+. CS-NA-ITC showed no fluorescence in solution state, while the fluorescence intensity increased obviously at the presence of Hg2+, accompanied by the fluorescence color becomes from colorless to bright yellow. It displayed favorable properties like low detection limit (73 nM), extensive pH detection range (5-10) and excellent anti-interference ability. The binding pattern of CS-NA-ITC to Hg2+ was verified by Job's plot, XPS analysis and FT-IR test. In addition, CS-NA-ITC was utilized to recognition of Hg2+ in actual water and soil samples and seafood products. Furthermore, the CS-NA-ITC hydrogel could be employed as an efficient Hg2+ adsorbent with good reusability, which adsorption ability was enhanced compared to chitosan hydrogel.

A naphthalimide functionalized chitosan-based fluorescent probe for specific detection and efficient adsorption of Cu2.

As one of the most abundant metal ions, Cu2+ has turned into a great threat to human health and the natural environment due to its widely utilized in various industries. In this paper, a chitosan-based fluorescent probe CTS-NA-HY for detection and adsorption of Cu2+ was rationally prepared. CTS-NA-HY exhibited a specific "turn off" fluorescence response to Cu2+ and the fluorescence color changed from bright yellow to colorless. It possessed satisfactory detection performance to Cu2+ including good selectivity and anti-interference, low detection limit (29 nM) and wide pH range (4-9). The detection mechanism was confirmed by Job's plot, X-ray photoelectron spectroscopy, FT-IR and 1H NMR analysis. Additionally, the probe CTS-NA-HY was capacity of determining Cu2+ in environmental water and soil samples. Besides, CTS-NA-HY-based hydrogel could also remove Cu2+ in aqueous solution effectively, which the ability of adsorption was greatly improved compared with original chitosan hydrogel.

Chlorothalonil induces obesity in mice by regulating host gut microbiota and bile acids metabolism via FXR pathways.

As the most commonly used organochlorine pesticide nowadays, chlorothalonil (CHI), is ubiquitous in a natural environment and poses many adverse effects to organisms. Unfortunately, the toxicity mechanisms of CHI have not been clarified yet. This study found that the CHI based on ADI level could induce obesity in mice. In addition, CHI could induce an imbalance in the gut microbiota of mice. Furthermore, the results of the antibiotic treatment and gut microbiota transplantation experiments showed that the CHI could induce obesity in mice in a gut microbiota-dependent manner. Based on the results of targeted metabolomics and gene expression analysis, CHI could disturb the bile acids (BAs) metabolism of mice, causing the inhibition of the signal response of BAs receptor FXR and leading to glycolipid metabolism disorders in liver and epiWAT of mice. The administration of FXR agonist GW4064 and CDCA could significantly improve the CHI-induced obesity in mice. In conclusion, CHI was found to induce obesity in mice by regulating the gut microbiota and BAs metabolism via the FXR signaling pathway. This study provides evidence linking the gut microbiota and pesticides exposure with the progression of obesity, demonstrating the key role of gut microbiota in the toxic effects of pesticides.

Transmembrane dimers of type 1 receptors sample alternate configurations: MD simulations using coarse grain Martini 3 versus AlphaFold2 Multimer.

Structures and dynamics of transmembrane (TM) receptor regions are key to understanding their signaling mechanism across membranes. Here we examine configurations of TM region dimers, assembled using the recent Martini 3 force field for coarse-grain (CG) molecular dynamics simulations. At first glance, our results show only a reasonable agreement with ab initio predictions using PREDDIMER and AlphaFold2 Multimer and with nuclear magnetic resonance (NMR)-derived structures. 5 of 11 CG TM structures are similar to the NMR structures (within <3.5 Å root-mean-square deviation [RMSD]) compared with 10 and 9 using PREDDIMER and AlphaFold2, respectively (with 8 structures of the later within 1.5 Å). Surprisingly, AlphaFold2 predictions are closer to NMR structures when the 2001 instead of 2020 database is used for training. The CG simulations reveal that alternative configurations of TM dimers readily interconvert with a predominant population. The implications for transmembrane signaling are discussed, including for the development of peptide-based pharmaceuticals.

A highly effective "naked eye" colorimetric and fluorimetric curcumin-based fluorescent sensor for specific and sensitive detection of H2O2in vivo and in vitro.

Hydrogen peroxide (H2O2) is involved in many important tasks in normal cell metabolism and signaling. However, abnormal levels of H2O2 are associated with the occurrence of several diseases. Therefore, it is important to develop a new method for the detection of H2O2in vivo and in vitro. A turn-off sensor, 2,2-difluoro-4,6-bis(3-methoxy-4-((4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzyl)oxy)styryl)-2H-1,3,2-dioxaborine (DFCB), based on curcumin was developed for the detection of H2O2. The DFCB, an orange-emitting sensor, was constructed by employing 2,2-difluoro-4,6-bis(4-hydroxy-3-methoxystyryl)-2H-1,3,2-dioxaborine (DFC) as the main carrier, and 2-(4-bromomethylphenyl)-4,4,5,5-tetramethyl-1,3,2-doxaborolane as the recognition site. The recognition group on the DFCB sensor could be completely cleaved by H2O2 to generate the intermediate DFC, which would lead to a colorimetric change from bright orange to light blue accompanying by a significantly quenched fluorescence, which could be seen by the naked eye. This sensor exhibited a highly specific fluorescence response to H2O2, in preference to other relevant species, with an excellent anti-interference performance. The sensor DFCB also possessed some advantages including a wide pH response range (6-11), a broad linear range (0-300 µM), and a low detection limit (1.31 µM). The sensing mechanism of the DFCB sensor for H2O2 was verified by HRMS analysis, 1H-NMR titration and DFT calculations. In addition, the use of the DFCB sensor was compatible with the fluorescence imaging of H2O2 in living cells and zebrafish.

Basic helix-loop-helix pioneer factors interact with the histone octamer to invade nucleosomes and generate nucleosome-depleted regions.

Nucleosomes drastically limit transcription factor (TF) occupancy, while pioneer transcription factors (PFs) somehow circumvent this nucleosome barrier. In this study, we compare nucleosome binding of two conserved S. cerevisiae basic helix-loop-helix (bHLH) TFs, Cbf1 and Pho4. A cryo-EM structure of Cbf1 in complex with the nucleosome reveals that the Cbf1 HLH region can electrostatically interact with exposed histone residues within a partially unwrapped nucleosome. Single-molecule fluorescence studies show that the Cbf1 HLH region facilitates efficient nucleosome invasion by slowing its dissociation rate relative to DNA through interactions with histones, whereas the Pho4 HLH region does not. In vivo studies show that this enhanced binding provided by the Cbf1 HLH region enables nucleosome invasion and ensuing repositioning. These structural, single-molecule, and in vivo studies reveal the mechanistic basis of dissociation rate compensation by PFs and how this translates to facilitating chromatin opening inside cells.

A novel coumarin derivative-modified cellulose fluorescent probe for selective and sensitive detection of CN- in food samples.

In this work, a novel coumarin derivative-modified cellulose acetate (DCB-CA) was synthesized as a fluorescent probe for highly selective and sensitive determination of CN- in food samples. The DCB-CA was synthesized by using CA as a skeleton, and the coumarin derivative as the fluorophore. The DCB-CA obtained was characterized by different methods including FTIR, SEM, 1H-NMR, TGA and UV-vis spectroscopy. The DCB-CA exhibited a significant "turn-off" fluorescence response to CN-, accompanied by a distinct fluorescence color change from bright yellow to colorless. The detection limit of CN- using DCB-CA was calculated to be 5.8 × 10-7 M, which was much lower than the threshold limit of CN- recommended by the World Health Organization (1.9 × 10-6 M). Because of the favorable solubility and processability of the CA, the DCB-CA was easily processed into different fluorescent materials including fluorescent films and coatings. The fluorescent film obtained was also applied to the selective detection of CN-. Furthermore, the DCB-CA was successfully applied to determine CN- in food samples.

A new strategy to alleviate the obesity induced by endocrine disruptors-A unique lysine metabolic pathway of nanoselenium Siraitia grosvenorii to repair gut microbiota and resist obesity.

Obesity caused by endocrine disruptors (EDCs) has become a hot topic threatening human health. Recently, Nanoselenium Siraitia grosvenorii (NSG) has been shown to have potential health-modulating uses. Based on the results of 16S rRNA sequencing and metabolomics analysis, NSG has the unique function of improving gut microbiota and inhibiting obesity. Specifically, NSG can enhance gut microbiota diversity and change their composition. A significant positive correlation exists between the liver change in lysine and the high-importance dominant species ([Ruminococcus]_gnavus, Alistipes_finegoldii, etc.). NSG metabolites analysis showed that the lysine level increased by 44.45% and showed a significantly negatively correlated with (TG, TC, Leptin, etc.). Significantly, NSG reduces the degradation of lysine metabolism in the liver and inhibits fatty acid ß-oxidation. In addition, NSG decreased Acetyl-CoA levels by 24% and regulated the downregulation of TCA genes (CS, Ogdh, Fh1, and Mdh2) and the upregulation of ketone body production genes (BDH1). NSG may have a positive effect on obesity by reducing the participation of Acetyl-CoA in the TCA cycle pathway and enhancing the ketogenic conversion of Acetyl-CoA. In conclusion, the results of this study may provide a new dietary intervention strategy for preventing endocrine disruptor-induced obesity.

NMR-based metabolomics approach to assess the ecotoxicity of prothioconazole on the earthworm (Eisenia fetida) in soil.

Prothioconazole (PTC) is a widely used agricultural fungicide. In recent years, studies have confirmed that it exerts adverse effects on various species, including aquatic organisms, mammals, and reptiles. However, the toxicological effects of PTC on soil organisms are poorly understood. Here, we investigated the toxic effects, via oxidative stress and metabolic responses, of PTC on earthworms (Eisenia fetida). PTC exposure can induce significant changes in oxidative stress indicators, including the activities of superoxide dismutase (SOD) and catalase (CAT) and the content of glutathione (GSH), which in turn affect the oxidative defense system of earthworms. In addition, metabolomics revealed that PTC exposure caused significant changes in the metabolic profiles of earthworms. The relative abundances of 16 and 21 metabolites involved in amino acids, intermediates of the tricarboxylic acid (TCA) cycle and energy metabolism were significantly altered after 7 and 14 days of PTC exposure, respectively. Particularly, Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway analysis showed that multiple different metabolic pathways could be disturbed after 7 and 14 days of PTC exposure. Importantly, these alterations in oxidative stress and metabolic responses in earthworms reveal that the effects of PTC on earthworms were time dependent, and vary with exposure time. In conclusion, this study highlights that the effects of PTC on soil organisms are of serious concern.

The nucleosome unwrapping free energy landscape defines distinct regions of transcription factor accessibility and kinetics.

Transcription factors (TF) require access to target sites within nucleosomes to initiate transcription. The target site position within the nucleosome significantly influences TF occupancy, but how is not quantitatively understood. Using ensemble and single-molecule fluorescence measurements, we investigated the targeting and occupancy of the transcription factor, Gal4, at different positions within the nucleosome. We observe a dramatic decrease in TF occupancy to sites extending past 30 base pairs (bp) into the nucleosome which cannot be explained by changes in the TF dissociation rate or binding site orientation. Instead, the nucleosome unwrapping free energy landscape is the primary determinant of Gal4 occupancy by reducing the Gal4 binding rate. The unwrapping free energy landscape defines two distinct regions of accessibility and kinetics with a boundary at 30 bp into the nucleosome where the inner region is over 100-fold less accessible. The Gal4 binding rate in the inner region no longer depends on its concentration because it is limited by the nucleosome unwrapping rate, while the frequency of nucleosome rewrapping decreases because Gal4 exchanges multiple times before the nucleosome rewraps. Our findings highlight the importance of the nucleosome unwrapping free energy landscape on TF occupancy and dynamics that ultimately influences transcription initiation.

An efficient tetrahydroquinazolin-2-amine derivative-grafted cellulose fluorescent probe for detection of Cu2+ and Zn2.

Cu2+ and Zn2+ play crucial roles in many physiological processes, and their disorder will cause harm to human health. An efficient difunctional fluorescent probe CMC-GE-PQA for simultaneous detection of Cu2+ and Zn2+ was synthesized based on carboxymethyl cellulose. The probe CMC-GE-PQA exhibited a moderate blue fluorescence color. Interestingly, this probe showed a distinct fluorescence enhancement response toward Zn2+, while it displayed a significant fluorescence quenching response toward Cu2+. The detection limits of CMC-GE-PQA for Cu2+ and Zn2+ were calculated as low as 5.0 × 10-8 M and 1.0 × 10-7 M, respectively. The detection mechanisms of CMC-GE-PQA for Cu2+ and Zn2+ were fully verified by Job's plot, X-ray photoelectron spectroscopy analysis. The probe CMC-GE-PQA was applied to determine the trace amounts of Cu2+ and Zn2+ in environmental water samples. In addition, the probe CMC-GE-PQA-based fluorescent film and hydrogel were manufactured to achieve the portable detection of Cu2+ and Zn2+.