ABSTRACT
Buprofezin (BUP) is an insect growth regulator widely used in agriculture to control hemipteran pests, particularly the melon aphid, Aphis gossypii, due to its efficiency and low toxicity. Although approved by the Chinese government, its maximum residue limit (MRL) in food is strictly regulated, and conventional techniques for detecting BUP have several limitations. Our study reports successful BUP detection using a supramolecular fluorescent probe DP@ALB, constructed with chalcone-based fluorescent dye DP and albumin as the host. The probe offers advantages such as low cost, visual signal output with high fluorescence color variation, rapid response, and high sensitivity. Additionally, portable test strips enable convenient on-site BUP detection and simplifying field monitoring of spiked real samples. The study achieves precise qualitative and quantitative BUP analysis in grape fruit, groundwater, and soil with satisfactory recoveries. Further, the biological applicability of sensor for the in vitro detection of BUP in L929 living cells was demonstrated. This research breakthrough overcomes the limitations of traditional analytical methods, offering an efficient and reliable approach for food and environmental monitoring and pesticide residue detection.
ABSTRACT
The development of a fluorescent probe for pyriproxyfen (PPF) is crucial due to its potential threat to human health. However, the chemical inertness and low solubility of PPF present significant challenges for the detection of PPF in aqueous solutions using fluorescent probes. Herein, we have originally proposed a complex based on 2-(4-(dimethylamino)phenyl)-3-hydroxy-6,7-dimethoxy-4 H-chromen-4-one (HOF) and serum albumin (SA) as a dual-mode fluorescent probe, HOF@SA. This probe utilizes an indicator displacement assay (IDA) to release the dye HOF from the probe at low PPF concentrations (< 10 µM) and embeds the free dye HOF into the micelle of PPF at high concentrations (> 10 µM). This results in dual-mode fluorescent response characteristics for PPF: a turn-off response at low concentrations and a ratiometric response at high concentrations. An investigation of sensing behavior of HOF@SA for PPF detection exhibits rapid response (< 60 s), high sensitivity (LOD â¼4.7 ppb), high selectivity, and excellent visual detection capability (from cyan to yellow). Moreover, with the aid of a portable device, this method enables to analyze PPF in environmental and food samples. These results promote the advancement of a fluorescent probe approach for PPF analysis in environment and food.
Subject(s)
Fluorescent Dyes , Food Contamination , Pyridines , Fluorescent Dyes/chemistry , Pyridines/chemistry , Pyridines/analysis , Food Contamination/analysis , Serum Albumin/analysis , Spectrometry, Fluorescence/methods , Limit of Detection , Environmental Monitoring/methodsABSTRACT
A novel ratiometric analytical method based on a quantum dot (QD)-integrated supramolecular sensing system successfully achieves the portable on-site detection of nitroxynil.
ABSTRACT
Facile evaluation of formation kinetics of key intermediate is crucial for a comprehensive understanding of electrochemical ammonia oxidation reaction (AOR) mechanisms and the design of efficient electrocatalysts. Currently, elucidating the formation kinetics of key intermediate associated with rate-determining step is still challenging. Herein, 4-phtalamide-N-(4'-methylcoumarin) naphthalimide (CF) is developed as a molecular probe to detect N2H4 intermediate during AOR via electrochemiluminescence (ECL) and further investigated the formation kinetics of N2H4 on Pt catalysts with different crystal planes. CF probe can selectively react with N2H4 to release ECL substance luminol. Thus, N2H4 intermediate as a key intermediate can be sensitively and selectively detected by ECL during AOR. For the first time, Pt(100) facet is discovered to exhibit faster N2H4 formation kinetics than Pt(111) facet, which is further confirmed by Density functional theory calculation and the finite element simulation. The AOR mechanism under the framework of Gerischer and Mauerer is further validated by examining N2H4 formation kinetics during the dimerization process (NH2 coupling). The developed ECL active probe and the discovered facet-dependent formation kinetics of key intermediates provide a promising new tool and strategy for the understanding of electrochemical AOR mechanisms and the design of efficient electrocatalysts.
ABSTRACT
A commercial anti-cancer drug, axitinib, exhibits very stable dual emissions for discrimination of human serum albumin.
Subject(s)
Antineoplastic Agents , Axitinib , Axitinib/chemistry , Axitinib/pharmacology , Humans , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemistry , Serum Albumin, Human/chemistry , Fluorescent Dyes/chemistry , Molecular Structure , IsomerismABSTRACT
A commercially available naphthalene fluorophore serves as a ratiometric indicator for albumin, showcasing its applications in albumin-based supramolecular recognition.
Subject(s)
Fluorescent Dyes , Naphthalenes , Fluorescent Dyes/chemistry , Fluorescent Dyes/chemical synthesis , Naphthalenes/chemistry , Humans , Spectrometry, Fluorescence , Molecular Structure , Serum Albumin, Human/analysis , Serum Albumin, Human/chemistryABSTRACT
Metal-organic framework (MOF) glasses are an emerging class of glasses which complement traditional inorganic, organic and metallic counterparts due to their hybrid nature. Although a few zeolitic imidazolate frameworks have been made into glasses, how to melt and quench the largest subclass of MOFs, metal carboxylate frameworks, into glasses remains challenging. Here, we develop a strategy by grafting the zwitterions on the carboxylate ligands and incorporating organic acids in the framework channels to enable the glass formation. The charge delocalization of zwitterion-acid subsystem and the densely filled channels facilitate the coordination bonding mismatch and thus reduce the melting temperature. Following melt-quenching realizes the glass formation of a family of carboxylate MOFs (UiO-67, UiO-68 and DUT-5), which are usually believed to be un-meltable. Our work opens up an avenue for melt-quenching porous molecular solids into glasses.
ABSTRACT
Tracking pH fluctuations in food samples is important for ensuring food freshness. Fluorescent probes have been widely applied as promising tools for the on-site detection of pH changes; however, most of them can be applied only at either lower or higher pH ranges because their response structures commonly have a single acid dissociation constant (pKa). To address this problem, we designed a fluorescent sensor, called HMB, containing a methylpiperazine group with two pKa values, which exhibited a unique dual-color response to pH changes over a wide pH range. Furthermore, the HMB-based test strips are easily prepared and used as portable labels for the visual monitoring of food spoilage that results in microbial and anaerobic glycolytic pathways in real food (such as cheese and shrimp). To the best of our knowledge, this is the first fluorescent pH sensor with two pKa values, and we expect that this work will inspire more sensor designs for food quality control.
Subject(s)
Fluorescent Dyes , Seafood , Seafood/analysis , Fluorescent Dyes/chemistry , Food Quality , Food Packaging/methods , Hydrogen-Ion ConcentrationABSTRACT
With the phase-out of legacy per- and polyfluoroalkyl substances (PFASs), PFAS alternatives have been increasingly used in industrial production and daily life. However, available information on the occurrence of PFASs and PFAS alternatives in semi-enclosed bays remains limited. As a representative semi-enclosed bay in Guangdong Province, China, Shuidong Bay has experienced severe anthropogenic pollution (industrial, shipping, cultural, and domestic) in recent decades. Water pollution in Shuidong Bay has worsened, and PFASs have been identified as ubiquitous environmental pollutants in this bay. In this study, 23 PFASs, including 5 emerging PFASs, were analyzed in water, suspended particulate matter (SPM), and sediment samples collected from Shuidong Bay. We determined that perfluorobutanoic acid (PFBA) was the predominant PFAS compound in seawater, whereas 6:2 fluorotelomer sulfonic acid (FTS) and perfluorooctane sulfonamide acetate (FOSAA) were dominant in SPM and sediment, respectively. The sediment-water partitioning coefficients were greatly dependent on the perfluorinated carbon chain length. Chlorophyll a concentration had a significant effect on the dissolved concentrations of PFASs in seawater. The ecological risk assessment indicated that the PFASs detected in the seawater and sediment samples posed no considerable risks to aquatic organisms. This study provides a valuable reference for evaluating PFAS contamination in Shuidong Bay and conducting ecological risk assessments for aquatic organisms.
Subject(s)
Alkanesulfonic Acids , Fluorocarbons , Water Pollutants, Chemical , Bays , Chlorophyll A , Water Pollutants, Chemical/analysis , Environmental Monitoring , Water , Fluorocarbons/analysis , China , Particulate Matter/analysis , Alkanesulfonic Acids/analysisABSTRACT
Albuminuria is a crucial urine biomarker of human unhealthy events such as kidney diseases, cardiovascular diseases, and diabetes. However, the accurate diagnosis of albuminuria poses a significant challenge owing to the severe interference from urine fluorescence and urine drugs. Here, we report a novel flavone-based fluorescent probe, DMC, by incorporating the FA1-targeting methylquinazoline group into a flavone skeleton with the extend π-conjugation. DMC exhibited a rapid response time, high sensitivity, and selectivity towards human serum albumin (HSA) in urine. Moreover, the red-shifted fluorescence and the FA1-targeted HSA-binding of DMC efficiently mitigated the interference from both urine fluorescence and urine drug metabolites. Furthermore, the establishment of a portable testing system highlighted the potential for point-of-care testing, offering a user-friendly and accurate approach to diagnose A2-level and A3-level albuminuria. We expect that the success of this DMC-based diagnostic platform in real urine samples can signify a significant advancement in early clinical diagnosis of albuminuria and its associated diseases.
Subject(s)
Flavones , Fluorescent Dyes , Humans , Albuminuria/diagnosis , Serum Albumin, Human/analysis , Point-of-Care TestingABSTRACT
Rational design of crystalline porous materials with coupled proton-electron transfer has not yet been reported to date. Herein, we report a donor-acceptor (D-A) π-π stacking hydrogen-bonded organic framework (HOF; HOF-FJU-36) with zwitterionic 1,1'-bis(3-carboxybenzyl)-4,4'-bipyridinium (H2 L2+ ) as acceptor and 2,7-naphthalene disulfonate (NDS2- ) as donor to form a two-dimensional (2D) layer. Three water molecules were situated in the channels to connect with acidic species through hydrogen bonding interactions to give a 3D framework. The continuous π-π interactions along the a axis and the smooth H-bonding chain along the b axis provide the electron and proton transfer pathways, respectively. After 405â nm light irradiation, the photogenerated radicals could simultaneously endow HOF-FJU-36 with photoswitchable electron and proton conductivity due to coupled electron-proton transfer. By single-crystal X-ray diffraction (SCXRD) analyses, X-ray photoelectron spectroscopy (XPS), transient absorption spectra and density functional theory (DFT) calculations, the mechanism of the switchable conductivity upon irradiation has been demonstrated.
ABSTRACT
The electronic conductivity (EC) of metal-organic frameworks (MOFs) is sensitive to strongly oxidizing guest molecules. Water is a relatively mild species, however, the effect of H2 O on the EC of MOFs is rarely reported. We explored the effect of H2 O on the EC in the MOFs (NH2 )2 -MIL-125 and its derivatives with experimental and theoretical investigations. Unexpectedly, a large EC increase of 107 on H2 SO4 @(NH2 )2 -MIL-125 by H2 O was observed. Brønsted acid-base pairs formed with the -NH2 groups, and H2 SO4 played an important role in promoting the charge transfer from H2 O to the MOF. Based on H2 SO4 @(NH2 )2 -MIL-125, a high-performance chemiresistive humidity sensor was developed with the highest sensitivity, broadest detection range, and lowest limit of detection amongst all reported sensing materials to date. This work not only demonstrated that H2 O can remarkably influence the EC of MOFs, but it also revealed that post-modification of the structure of MOFs could enhance the influence of the guest molecule on their EC to design high-performance sensing materials.
ABSTRACT
Highly dispersed metal sites on the surface of silica, achieved from immobilization of metal precursor within hydroxyl groups, has gained increasing attention in the field of heterogeneous catalyst. However, the special role of adsorbed water derived by hydroxyl groups on the silica is generally ignored. Herein, a new understanding of adsorbed water on the formation of highly dispersed tetrahedral Co(II) (Td-cobalt(II)) sites is illustrated. It is indicated that sufficient adsorbed water induces the transformation of precursor of Co(NO3)2 into intermediate of [Co(H2O)6]2+. Subsequently, [Co(H2O)6]2+ makes the highly dispersed Td-cobalt(II) sites to be available during direct H2-reduction process. A systematic characterization and DFT calculation prove the existence of the adsorbed water and the importance of the intermediate of [Co(H2O)6]2+, respectively. The as-synthesized catalyst is attempted to the propane dehydrogenation, which shows better reactivity when compared with other reported Co based catalysts.
ABSTRACT
Under high temperature anhydrous conditions, it is still a formidable challenge to improve the performance of proton-conducting materials based on H3 PO4 and elucidate its proton conduction mechanism. Herein, a highly stable covalent triazine frameworks (CTFs) based on H3 PO4 is reported. The more pyridinic nitrogen CTFs contain, the higher proton conductivity is. Compared with H3 PO4 @CTF-L with less pyridinic nitrogen, H3 PO4 @CTF-H has a higher proton conductivity of 1.6×10-1 â S cm-1 at 150 °C under anhydrous conditions, which does not decay after about 18â months exposure in air. The high proton conductivity is associated with the formation and breaking of the activated Ntriazine â¯H+ â¯H2 PO4 - pairs by pyridinic nitrogen of CTFs. The outstanding long-term stability is mainly attributed to the ultra-strong triazine skeleton structure of CTFs.
ABSTRACT
To create an artificial structure to remarkably surpass the sensitivity, selectivity and speed of the olfaction system of animals is still a daunting challenge. Herein, we propose a core-sheath pillar (CSP) architecture with a perfect synergistic interface that effectively integrates the advantages of metal-organic frameworks and metal oxides to tackle the above-mentioned challenge. The sheath material, NH2-MIL-125, can concentrate target analyte, nitro-explosives, by 1012 times from its vapour. The perfect band-matched synergistic interface enables the TiO2 core to effectively harvest and utilize visible light. At room temperature and under visible light, CSP (TiO2, NH2-MIL-125) shows an unexpected self-promoting analyte-sensing behaviour. Its experimentally reached limit of detection (â¼0.8 ppq, hexogeon) is 103 times lower than the lowest one achieved by a sniffer dog or all sensing techniques without analyte pre-concentration. Moreover, the sensor exhibits excellent selectivity against commonly existing interferences, with a short response time of 0.14 min.
ABSTRACT
Background: Beryllium and its compounds are carcinogenicity, but the mechanisms through which this occurs have yet to be clarified. Accumulating evidence exists that long noncoding RNAs (lncRNAs) play an important role in occurrence and development of cancer. Aims and Methods: To explore the carcinogenic mechanism of beryllium, human bronchial epithelial cells (16HBE) were treated with 50 µM beryllium sulfate (BeSO4) for 45 passages (~23 weeks). The expression levels of lncRNA SNHG7, SNHG11, SNHG15, MIR22HG, GMPS, and SIK1 were detected at passage 0 (P0), 15 (P15), 25 (P25), 35 (P35), and 45 (P45). Results: The results indicated that enhanced cell proliferation, extensive clones in soft agar, protein expressions of up-regulated matrix metalloproteinase 9 (MMP9), matrix metalloproteinase 2 (MMP2), proliferating cell nuclear antigen (PCNA), cyclin D1, and down-regulated p53 were all observed at the 45th passage in 16HBE cells. Thus, BeSO4-transformed 16HBE cells (T-16HBE) were established. Meanwhile, the study found that the expression of lncRNA SNHG11 was elevated during malignant transformation. Knockdown of SNHG11 in T-16HBE cells blocked cell proliferation, invasion, and migration, and decreased the protein levels of MMP9, MMP2, PCNA, cyclin D1, but increased p53. Conclusions: The studies revealed that SNHG11 acts as an oncogene in the malignant transformation of 16HBE cells induced by BeSO4, which signifies progress in the study of the carcinogenic mechanism of beryllium.
ABSTRACT
The layer-by-layer liquid-phase epitaxy (LBL-LPE) method is widely used in preparing metal-organic framework (MOF) thin films with the merits of controlling thickness and out-of-plane orientation for superior performances in applications. The LBL-LPE growth mechanism related to the grain boundary, structure defect, and orientation is critical but very challenging to study. In this work, a novel "in-plane self-limiting and self-repairing" thin-film growth mechanism is demonstrated by the combination study of the grain boundary, structure defect, and orientation of Cu3 (HHTP)2 -xC thin film via microscopic analysis techniques and electrical measurements. This mechanism results a desired high-quality MOF thin film with preferred in-plane orientations at its bottom for the first time and is very helpful for optimizing the LBL-LPE method, understanding the growth cycle-dependent properties of MOF thin film, and inspiring the investigations of the biomimetic self-repairing materials.
ABSTRACT
CONTEXT: Ellagic acid (EA) is a phenolic constituent in certain fruits and has largely been recognized for its role as an antioxidant compound. OBJECTIVE: To evaluate the effect of EA on beryllium sulphate-induced splenic toxicity in rats. MATERIALS AND METHODS: Male Sprague-Dawley rats were divided into four groups. The first group was used as control. Group 2 was exposed to BeSO4 (12 mg/kg, b.w.). Groups 3 and 4 were treated with EA (100 and 300 mg/kg, b.w.) daily for 6 weeks after exposing to BeSO4 (12 mg/kg, b.w.). Various biochemical and molecular biomarkers were assessed in blood and spleen. RESULTS: BeSO4-intoxicated rats showed significant higher WBC (6.74 ± 0.20 × 109/L vs. 11.02 ± 1.31 × 109/L, p < 0.05), Neu (1.14 ± 0.11 × 109/L vs. 2.45 ± 0.42 × 109/L, p < 0.05), Lym (3.80 ± 0.83 × 109/L vs. 9.64 ± 1.99 × 109/L, p < 0.05), and PLT (868.4 ± 43.2 × 109/L vs. 1408 ± 77.57 × 109/L, p < 0.05) than normal control animals. Moreover, an increase in MDA with depletion of GSH and SOD activity (all p < 0.05) occurred in the spleen of rats treated with BeSO4. Furthermore, BeSO4-treated rats displayed significantly higher levels of apoptotic markers (Bax, Caspase-3, PARP) (all p < 0.05). EA administration resulted in a significant reversal of hematological and apoptotic markers in beryllium sulphate-intoxicated rats. DISCUSSION AND CONCLUSIONS: Our results suggest EA treatment exerts a significant protective effect on BeSO4-induced splenic toxicity in rats.
Subject(s)
Ellagic Acid , Spleen , Animals , Beryllium , Ellagic Acid/pharmacology , Male , Oxidative Stress , Rats , Rats, Sprague-DawleyABSTRACT
The N6-methyladenosine (m6A) refers to the methylation of the N6 position of adenosine of RNA adenine. The modification of m6A is one of the most abundant epigenetic modifications in eukaryotic mRNA and non-coding RNA and is controlled by methyltransferases and demethylases. The biological mechanism and significance of m6A have been discovered with the development of m6A sequencing. Various m6A complex components regulate the function of m6A on mRNA. Methyltransferase-like 3 (METTL3) is one of the earliest identified m6A methyltransferases which regulate the functions of m6A. A large number of studies have shown that METTL3 establishes a cross-talk with tumor cells and development of various human diseases. In this review, we will briefly elaborate on the role of METTL3 in biological function, epithelial-mesenchymal transition (EMT), inflammatory response and sensitivity to the resistance of chemo radiotherapies. The underlying molecular mechanism demonstrated by METTL3 may provide a possible target for treating and diagnosing human diseases.
Subject(s)
Biological Phenomena , Methyltransferases , Adenosine/metabolism , Humans , Methylation , Methyltransferases/genetics , Methyltransferases/metabolism , RNA, Messenger/metabolismABSTRACT
Beryllium and its compounds can cause pulmonary interstitial fibrosis through mechanisms that are not yet clear. Long non-coding RNA (lncRNA) is implicated in various diseases. The molecular toxicity of beryllium sulfate (BeSO4) was investigated through the RNA-seq analysis of the lncRNA and mRNA whole-transcriptome of BeSO4-treated 16HBE cells. A total of 1014 lncRNAs (535 upregulated and 479 downregulated) and 4035 mRNAs (2224 upregulated and 1811 downregulated) were found to be significantly dysregulated (|logFC| ≥> 2.0, p < 0.05) in the BeSO4-treated groups when compared with the control group. Five differentially expressed lncRNAs and mRNAs were verified by qRT-PCR. KEGG analysis showed that lncRNA regulates the ECM receiver interaction and PI3K/AKT signaling pathways, etc. In addition, H19:17, lnc-C5orf13-1:1, lnc-CRYAA-17:1, lnc-VSTM5-1:11, and lnc-THSD7A-7:1 may regulate BeSO4-induced 16HBE cytotoxicity through ceRNA mechanism. The results of this study will provide some theoretical support for the study of the toxic mechanism of beryllium and its compounds.