Search Results (15)

Mercury and explosives are well-known hazards that affect the environment and threaten society. Mercury generally exists as inorganic mercuric (Hg²⁺) salts, and its detection via fluorometric response is highly notable. Likewise, mainstream explosives contains a nitro (−NO₂) moiety as a functional unit, and numerous reports have quantified them using fluorescence quenching. Among the available literature, there are still noticeable concerns about the environmental and biological applicability of luminescent pyrene derivaives-tunedfluorometric detection of Hg²⁺ and explosives. In the presence of Hg²⁺ ions, pyrene derivatives tend to form excimers, which can be tuned to the chelation-enhanced fluorescence (CHEF), photo-induced electron transfer (PET), or fluorescence resonance energy transfer (FRET), etc., to exhibit “Turn-On” or “Turn-Off” fluorescence responses. On the other hand, π-π stacking of emissive pyrene-derivatives may lead to J- or H-type aggregation via self-excimers (Py-Py*), which has been found to be quenched/enhanced by explosive hazards. In fact, −NO₂-containing explosives interact with pyrene derivatives, leading to exceptional fluorescence quenching or enhancement. This review details the use of pyrene derivatives toward the sensing of Hg²⁺ and explosives with demonstrated applications. Further, the design requirements, sensory mechanisms, advantages, limitations, and the future scope of using the reported pyrene derivatives in Hg²⁺ and explosives sensing are discussed. Full article

Using 5-methyl salicylaldehyde (2) as a reactant to react with different amines, 2-aminobenzimidazole (1a), 2-aminobenzothiazole (1b), and 2-aminopyridine (1c), respectively, three types of Schiff base fluorescent probes 3a–3c were designed and synthesized for selective detection of Al³⁺ in aqueous media. The structure of the compounds was acquired by ¹H NMR, ¹³C NMR, and X-ray single-crystal diffraction. Furthermore, their photochromic and fluorescent behaviors have been investigated systematically by fluorescence spectra. Compounds 3a–3c can exhibit high selectivity, sensitivity, and anti-interference properties towards Al³⁺ in aqueous media. Among them, the limit of detection (LOD) of probe 3b for Al³⁺ is 2.81 × 10⁻⁷ M. Notably, the response times of probes 3a–3c for Al³⁺ are 90 s, 80 s, and 80 s, respectively, which are much faster than most previously reported probes. The coordination stoichiometry between compounds 3a–3c and Al³⁺ has been verified to be 1:1 through the Job’s plot. After coordination with Al³⁺, the C=N isomerization of compounds 3a–3c is inhibited, leading to the closure of the excited state intramolecular proton transfer (ESIPT) effect. At the same time, the fluorescence intensity is significantly increased through chelation-enhanced fluorescence mechanism (CHEF), which is confirmed by density functional theory (DFT) calculations. In addition, probes 3a–3c can be potentially applied in the selective and high-precision detection of Al³⁺ in environmental systems. Full article

Quercetin forms complexes with various metals due to its structural attributes. It predominantly exhibits chelating activity at the 3-hydroxy/4-carbonyl group. Previously, coordination in synthetically obtained quercetin–zinc (II) complexes has been limited to this group. However, the expanded coordination observed in quercetin–iron complexes has opened avenues for diverse applications. Thus, synthesizing novel quercetin–zinc complexes with different coordination positions is a significant advance. In our study, we not only synthesized and comprehensively characterized a new quercetin–zinc (II) complex, Zn-Q, but also evaluated the structure and bioactivity of chelate complexes (Q+Zn) derived from co-treatment in cell culture mediums. The structure of the new compound Zn-Q was comprehensively characterized using 1D ¹H and 2D correlation spectroscopy (COSY), nuclear magnetic resonance (NMR), Fourier-transform infrared spectroscopy (FT-IR), ultraviolet–visible spectroscopy (UV-Vis), electrospray ionization mass spectrometer (ESI-MS), and X-ray diffraction analysis (XRD) analysis. Subcellular localization and absorption of these zinc (II) complexes were determined using the ZnAF-2 DA zinc ion fluorescence probe. Throughout the experiments, both Zn-Q and Q+Zn exhibited significant antioxidant, cell growth inhibitory, and anticancer effects in HepG2 and HCT116 cells, with Zn-Q showing the highest potential for inducing apoptosis via the caspase pathway. Tracking intracellular zinc complex absorption using zinc fluorescent probes revealed zinc (II) localization around the cell nucleus. Interestingly, there was a proportional increase in intracellular quercetin absorption in conjunction with zinc (II) uptake. Our research highlights the advantages of quercetin complexation with zinc (II): enhanced anticancer efficacy compared to the parent compound and improved bioavailability of both quercetin and zinc (II). Notably, our findings, which include enhanced intracellular uptake of both quercetin and zinc (II) upon complex formation and its implications in apoptosis, contribute significantly to the understanding of metal–polyphenol complexes. Moving forward, comprehensive functional assessments and insights into its mechanism of action, supported by animal studies, are anticipated. Full article

Maize (Zea mays L.) is one of the most widely grown cereals in the world. Its cultivation is affected by abiotic stress caused by climate change, in particular, drought. Zinc (Zn) supplied by foliar nutrition can increase plant resistance to water stress by enhancing physiological and enzymatic antioxidant defence mechanisms. One of the possibilities to reduce the effect of drought on plant production is also the utilization of trehalose. In order to confirm the effect of the foliar application of selected forms of Zn (0.1% w/v solution)—zinc oxide micro- (ZnO) and nanoparticles (ZnO^NP), zinc sulphate (ZnSO₄) and zinc chelate (ZnEDTA)—a pot experiment in controlled conditions was conducted in combination with trehalose (1% w/v solution) on selected growth parameters of maize exposed to the drought stress. A significant effect of coapplication of Zn and trehalose on chlorophyll content, chlorophyll fluorescence parameters, root electrical capacity, weight of maize aboveground biomass (AGB) and Zn content in AGB was found. At the same time, the hypothesis of a positive effect of carbohydrates on increasing the uptake of foliar-applied Zn was confirmed, especially for the ZnEDTA and ZnSO₄. This paper presents the first empirical evidence of the trehalose addition to sprays for zinc foliar fertilization of maize proving to be an effective way of increasing the resistance of maize grown under drought stress conditions. Full article

Ag nanomaterials are promising candidates for the discovery of next-generation antibiotics with a high antibacterial effect against multi-drug resistant strains. This paper reports a simple synthesis of novel water-soluble glutathione-capped silver nanoclusters (GSH-Ag NCs) with an enhanced antibacterial activity. According to thin layer chromatography (TLC), the synthesized GSH-Ag NCs are an individual fraction of the same composition without any impurities. According to matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) and energy dispersive X-ray (EDX) analyses, the silver core of the GSH-Ag NCs contains approximately 35 silver atoms, and the molecular weight of these nanoclusters is about 11 kDa. The fabricated silver nanoclusters have a reddish fluorescence (λex/λem = 509/645 nm), with a large Stokes shift (>130 nm), and ultra-small size (less than 2 nm) according to transmission electron microscopy (TEM) data and dynamic light scattering (DLS) analysis. The antibacterial activity and minimal inhibitory concentrations of the silver nanoclusters towards Escherichia coli, Staphylococcus aureus, Bacillus cereus and Enterobacter cloacae were evaluated using the agar well-diffusion method and resazurin metabolism assay. The antibacterial activity of chelated silver in the nanoclusters was found to be significantly higher compared to the activity of free silver ions. To explain the possible mechanisms underlying the antibacterial actions of the GSH-Ag nanoclusters, molecular docking was performed, and prospective bacterial targets were identified using AutoDock. Full article

A significant emission enhancement (>100-fold) of glutathione-capped bimetallic gold and copper nanoclusters (AuCuNC@GSH) was achieved by assembling with Al³⁺ ions and by assembly-induced emission enhancement (AIEE). Further chelation of myricetin to Al³⁺ resulted in emission quenching of AuCuNC-Al³⁺, which was applied to specifically detect myricetin. Two linear responses were shown in the range of 0–1.5 μM and 1.5–50 μM, separately, leading to a low limit of detection at 8.7 nM. The method was successfully and accurately applied to myricetin determination in grape juice, which showed good application for real samples. Finally, the in-depth mechanism revealed that both the chelation of myricetin and Al³⁺ and the inner filter effect (IFE) between myricetin-Al³⁺ and AuCuNC-Al³⁺ greatly contributed to the quenching response of myricetin. Therefore, the present study provides an easy way to improve the fluorescence property of metal nanoclusters. Additionally, it supplies a cost-effective and easily performed approach to detect myricetin with high selectivity and sensitivity. Full article

Isolating the genes responsible for cadmium (Cd) accumulation and tolerance in oilseed rape and uncovering their functional mechanism is of great significance for guiding genetic improvement to cope with heavy metal pollution. In this study, we screened the cDNA library of Brassica napus cv. Westar using a yeast genetic complementation system and isolated BnMT2-22a, BnMT2-22b and BnMT3b, which can mediate Cd tolerance in yeast. They all have two cysteine-rich domains in their sequence. Ectopic expression of these MTs demonstrated that all of them enhanced Cd and Cu tolerance in yeast, but had no effect on Mn and Zn tolerance. The fusion of the red fluorescent protein mRFP did not affect their function in mediating Cd tolerance, and using these functional fusion proteins we observed that they were all localized in cytosol. Meanwhile, their expression in yeast did not affect the accumulation of Cd in the yeast transformants. Gene expression analyses found that BnMT2-22a, BnMT2-22b and BnMT3b were all induced by Cd in roots, and BnMT3b was also significantly induced in shoots. These results indicate that the genes BnMT2-22a, BnMT2-22b and BnMT3b isolated with cDNA library screening can mediate Cd tolerance, and they may detoxify Cd via cytosolic chelation. Full article

Bifunctional luminescence metal-organic frameworks with unique nanostructures have drawn ongoing attention for simultaneous determination and elimination of metal ions in the aqueous environment, but still remain a great challenge. In this work, three-dimensional hierarchical titanium metal-organic framework (Ti-MOF) microflowers were developed by a secondary hydrothermal method for not only highly sensitive and selective detection of Al(III), but also simultaneously efficient decontamination. The resulting Ti-MOF microflowers with a diameter of 5–6 μm consisted of nanorods with a diameter of ∼200 nm and a length of 1–2 μm, which provide abundant, surface active sites for determination and elimination of Al(III) ions. Because of their substantial specific surface area and superior fluorescence characteristics, Ti-MOF microflowers are used as fluorescence probes for quantitative determination of Al(III) in the aqueous environment. Importantly, the specific FL enhancement by Al(III) via a chelation-enhanced fluorescence mechanism can be utilized for selective and quantitative determination of Al(III). The Al(III) detection has a linear range of 0.4–15 µM and a detection limit as low as 75 nM. By introducing ascorbic acid, interference of Fe(III) can be avoided to achieve selective detection of Al(III) under various co-existing cations. It is noteworthy that the Ti-MOF microflowers exhibit excellent adsorption capacity for Al(III) with a high adsorption capacity of 25.85 mg g⁻¹. The rapid adsorption rate is consistent with a pseudo-second order kinetic model. Ti-MOF is a promising contender as an adsorbent and a fluorescent chemical sensor for simultaneous determination and elimination of Al(III) due to its exceptional water stability, high porosity, and intense luminescence. Full article

Peat-derived organic matter, as powerful chelators, is of great significance for the transport of Fe to the ocean and the enhancement of dissolved Fe. However, the iron binding capacity of molecular weight (MW)-fractionated dissolved organic matter is variable, due to its structure and composition heterogeneity. In this work, we used the standard Pahokee Peat fulvic acid (PPFA) as an example, and investigated the spectroscopy properties and Fe(III) binding ability of PPFA and different molecular weight fractions by UV–Vis absorbance and fluorescence spectroscopy and the Donnan Membrane Technique (DMT). The results showed binding sites for Fe(III) at the 263 nm and >320 nm regions in differential absorbance spectra. Upon increasing the iron concentration to 18.00 μmol·L⁻¹, the critical binding capacity was exceeded, which resulted in a decrease in absorbance. Fe(III) was found to prefer to bind to humic-like components, and ultraviolet humic-like fluorophores displayed stronger binding strength. High molecular weight PPFA fractions (>10 kDa) possessed more aromatic and hydrophobic components, displayed a higher degree of humification, and exhibited higher metal binding potential. Furthermore, the speciation analysis and stability constant (^cK) were calculated using Donnan membrane equilibrium. The correlation between ^cK values and PPFA spectral properties demonstrated that aromaticity, hydrophobicity, molecular weight and humification degree were crucial indices of PPFA–Fe(III) affinity. Significantly, the humification degree, represented by HIX, showed the strongest correlation (r = 0.929, p = 0.003), which could be used to estimate the binding strength. This study provides further understanding of the complexation mechanism of iron and DOM in the peat environment and identifies the considerable effect of molecular weight. Full article

A practical hydrazine-carbothioamide-based fluorescent chemosensor TCC (N-(4-chlorophenyl)-2-(thiophene-2-carbonyl)hydrazine-1-carbothioamide) was applied for Zn²⁺ detection. TCC exhibited selective fluorescence emission for Zn²⁺ and did not show any interference with other metal ions. In particular, TCC was utilized for the detection of Zn²⁺ in paper strips, zebrafish and real water samples. TCC could detect Zn²⁺ down to 0.39 μM in the solution phase and 51.13 μM in zebrafish. The association ratio between TCC and Zn²⁺ was determined to be 2:1 by ESI-mass and Job plot. The sensing mechanism of TCC for Zn²⁺ was illustrated to be a chelation-enhanced fluorescence process through spectroscopic experiments and theoretical calculations. Full article

A tight junction (TJ) makes a physical barrier in the epidermal cells of skin. Ultraviolet (UV) light may disrupt the TJ barrier, but the mechanism has not been well clarified. Weak UVB (5 mJ/cm²) caused mislocalization of claudin-1 (CLDN1), a component of the TJ strand, and disruption of TJ barrier in human keratinocyte-derived HaCaT cells. The UVB-induced mislocalization of CLDN1 was inhibited by monodansylcadaverine (MDC), a clathrin-dependent endocytosis inhibitor, suggesting that UVB enhances the internalization of CLDN1. Transepidermal electrical resistance and paracellular flux of lucifer yellow, a fluorescent hydrophilic marker, were rescued by MDC. UVB changed neither the total nor phosphorylation levels of CLDN1, but it increased both mono-ubiquitination and tyrosine nitration levels of CLDN1. Fluorescence measurements revealed that UVB increased intracellular free Ca²⁺, nitric oxide (NO), and peroxynitrite contents, which were inhibited by Opsin2 (OPN2) siRNA, suggesting that OPN2 functions as a UVB sensor. The effects of UVB were inhibited by an antagonist of transient receptor potential type vanilloid 1 (TRPV1) and Ca²⁺ chelator. Both NO donor and peroxynitrite donor induced the mislocalization of CLDN1 and disruption of TJ barrier, which were rescued by a NO synthase (NOS) inhibitor and a peroxynitrite scavenger. Weak UVB irradiation induced the disruption of TJ barrier mediated by mislocalization of CLDN1 in HaCaT cells. The OPN2/TRPV1/NOS signaling pathway may be a novel target for preventing destruction of the TJ barrier by UVB irradiation. Full article

A new fluorescent chemosensor for copper (II) and subsequent anion sensing was designed and fully characterized. The sensor consisted of a 1,8-naphthalimide core, bearing two terminal dipicolylamine (DPA) receptor units for binding metal cations, and an ethoxyethanol moiety for enhanced water solubility. The DPA units are connected to position 4 of the fluorophore via a triazine-ethylenediamine spacer. Fluorescence titration studies of the chemosensor revealed a high selectivity for Cu²⁺ over other divalent ions, the emissions were strongly quenched upon binding, and a stability constant of 5.52 log units was obtained. Given the distance from DPA chelating units and the fluorophore, quenching from the Cu²⁺ complexation suggests an electron transfer or an electronic energy transfer mechanism. Furthermore, the Cu²⁺-sensor complex proved to be capable of sensing anionic phosphate derivatives through the displacement of the Cu²⁺ cation, which translated into a full recovery of the luminescence from the naphthalimide. Super-resolution fluorescence microscopy studies performed in HeLa cells showed there was a high intracellular uptake of the chemosensor. Incubation in Cu²⁺ spiked media revealed a strong fluorescent signal from mitochondria and cell membranes, which is consistent with a high concentration of ATP at these intracellular sites. Full article

The current research mainly focuses on transforming low-quality waste into value-added nanomaterials and investigating various ways of utilising them. The hydrothermal preparation of highly fluorescent N-doped carbon dots (N–CDs) was obtained from the carboxymethylcellulose (CMC) of oil palm empty fruit bunches and linear-structured polyethyleneimines (LPEI). Transmission electron microscopy (TEM) analysis showed that the obtained N–CDs had an average size of 3.4 nm. The N–CDs were monodispersed in aqueous solution and were strongly fluorescent under the irradiation of ultra-violet light. A detailed description of the morphology and shape was established using Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). It was shown that LPEI were successfully tuned the fluorescence (PL) properties of CDs in both the intrinsic and surface electronic structures, and enhanced the quantum yield (QY) up to 44%. The obtained N–CDs exhibited remarkable PL stability, long lifetime and pH-dependence behaviour, with the excitation/emission maxima of 350/465.5 nm. Impressively, PL enhancement and blue-shifted emission could be seen with the dilution of the original N–CDs solution. The obtained N–CDs were further applied as fluorescent probe for the identification of Cu²⁺ in aqueous media. The mechanism could be attributed to the particularly high thermodynamic affinity of Cu²⁺ for the N-chelate groups over the surface of N–CDs and the fast metal-to-ligand binding kinetics. The linear relationship between the relative quenching rate and the concentration of Cu²⁺ were applied between 1–30 µM, with a detection limit of 0.93 µM. The fluorescent probe was successfully applied for the detection of Cu²⁺ in real water. Moreover, a solid-state film of N–CDs was prepared in the presence of poly (vinyl alcohol) (PVA) polymer and found to be stable even after 72-h of continuous irradiation to UV-lamp. In contrast to the aqueous N–CDs, the composite film showed only an excitation independent property, with enhanced PL QY of around 47%. Due to the strong and stable emission nature of N–CDs in both aqueous and solid conditions, the obtained N–CDs are ideal for reducing the overall preparation costs and applying them for various biological and environmental applications in the future. Full article

Aminolevulinic acid (ALA) is the first metabolite in the heme biosynthesis pathway in humans. In addition to the end product heme, this pathway also produces other porphyrin metabolites. Protoporphyrin (PpIX) is one heme precursor porphyrin with good fluorescence and photosensitizing activity. Because tumors and other proliferating cells tend to exhibit a higher level of PpIX than normal cells after ALA incubation, ALA has been used as a prodrug to enable PpIX fluorescence detection and photodynamic therapy (PDT) of lesion tissues. Extensive studies have been carried out in the past twenty years to explore why some tumors exhibit elevated ALA-mediated PpIX and how to enhance PpIX levels to achieve better tumor detection and treatment. Here we would like to summarize previous research in order to stimulate future studies on these important topics. In this review, we focus on summarizing tumor-associated alterations in heme biosynthesis enzymes, mitochondrial functions and porphyrin transporters that contribute to ALA-PpIX increase in tumors. Mechanism-based therapeutic strategies for enhancing ALA-based modalities including iron chelators, differentiation agents and PpIX transporter inhibitors are also discussed. Full article

This study synthesized a europium (Eu³⁺) complex Eu(DBM)₃Cl-MIP (DBM = dibenzoyl methane; Cl-MIP = 2-(2-chlorophenyl)-1-methyl-1H-imidazo[4,5-f][1,10]phenanthroline) dispersed in a benzyl methacrylate (BMA) monomer and treated with ultraviolet (UV) light for polymerization. Spectral results showed that the europium complex containing an antenna, Cl-MIP, which had higher triplet energy into the Eu³⁺ energy level, was an energetically enhanced europium emission. Typical stacking behaviors of π–π interactions between the ligands and the Eu³⁺-ion were analyzed using single crystal X-ray diffraction. Regarding the luminescence performance of this europium composite, the ligand/defect emission was suppressed by dispersion in a poly-BMA (PBMA) matrix. The underlying mechanism of the effective enhancement of the pure Eu³⁺ emission was attributed to the combined effects of structural modifications, defect emissions, and carrier charge transfer. Fluorescence spectra were compared to the composite of optimized Eu³⁺ emission where they were subsequently chelated to four metal ions via carboxylate groups on the BMA unit. The optical enhanced europium composite clearly demonstrated highly efficient optical responses and is, therefore a promising application as an optical detection material. Full article