Photoinduced Electron Transfer Mechanism Research Articles

Synthesis and structure of an aqueous stable Cu(II)-based coordination polymer with multifunctional fluorescence sensing property

Advanced methods for both biological and environmental hazardous pollutants are of sustained interest. Herein, a new coordination polymer, namely, [Cu2(OH)(1,2,4-bca)(bmoe)]·H2O (Cu-CP) has been hydrothermally constructed with a mix-ligand strategy, employing 1,2,4-benzenetricarboxylic acid (1,2,4-bca) and 1,1′-bis(1H-benzimidazolyl) oxydiethane (bmoe) as organic ligands. The intrinsic strong blue-light emission and the great stability in water solutions with the broad range of pH values (pH = 4 − 12) of Cu-CP provide a platform for practical fluorescence sensing application in water samples. Fluorescence measurements reveal that Cu-CP displays interesting multi-responsive dection activities toward toxic heavy-metal ions Cr2O72- / CrO42− / MnO4−, nitrofuran antibiotics nitrofurantoin (NFT) / nitrofurazone (NFZ) and acetylacetone (ACAC) in aqueous solutions achieving both high sensitivity and low detection limits (micromolar for Cr(VI) / Mn(VII) / ACAC and nanomolar for NFT / NFZ). Furthermore, the interference experiments have verified its excellent selectivity. A synergetic contribution of internal filtration effect (IFE) and Förster resonance energy transfer (FRET) between Cr2O72- / CrO42− / MnO4− and the framework of Cu-CP realize the fluorescence quenching behavior for Cr(VI) / Mn(VII) detection, while FRET, IFE and photoinduced electron transfer (PET) mechanisms are synergistically responsible in the case of NFT / NFZ, ACAC sensing supported by the molecular simulations and UV−vis spectral overlap experiments. This present work affords precious guidance for the effective and facile design and preparation of multifunctional luminescent coordination polymers with promising performance.

Design and controlled synthesis of molecularly imprinted fluorescence sensor supported by multifunctional magnetic covalent organic framework: Efficient detection of clofibric acid in the environment

While some studies have explored magnetic covalent organic frameworks (MCOFs) for fluorescence sensing, substantial research gaps remain, especially in integrating molecular imprinting technology (MIT). In this study, superparamagnetic Fe3O4 cores were modified, and a monomer-mediated in situ growth strategy was used to synthesize uniform, multifunctional MCOFs nanoparticles. Subsequently, molecularly imprinted polymers (MIPs) were synthesized via a sol-gel method and deposited on MCOFs, forming MCOFs-supported molecularly imprinted fluorescent sensors (MCOFs@MIPs) for trace analysis of clofibric acid (CLF). This was the first application of molecularly imprinted fluorescence sensing technology for detecting CLF. MCOFs@MIPs combined the superparamagnetism of Fe3O4, the stability and signal amplification of COFs, and the selectivity of MIPs for CLF. Studies demonstrated that MCOFs@MIPs had a maximum fluorescence response in isopropanol, with an optimal dosage of 0.39 mg/mL, an imprinting factor (IF) of 2.73, a detection limit of 94 nM, and a range of 0 ∼ 300 µM. Characterizations revealed that the fluorescence quenching of MCOFs@MIPs was based on a photoinduced electron transfer (PET) mechanism, with MCOFs@MIPs as donors and CLF as acceptors. MCOFs@MIPs were used to detect CLF in actual samples from food, water, agricultural products, cosmetics, and human metabolites. The detection results were consistent with those from high-performance liquid chromatography (HPLC). Additionally, the recoveries of MCOFs@MIPs for actual samples ranged from 94.4 % to 100.7 %, demonstrating exceptional reliability, reusability, and accuracy.

A naphthimide based fluorescent probe for the detection of thiophenols and its application in actual water and food

Thiophenol (PhSH) and its derivatives are widely employed as common industrial raw materials, while they also pose high toxicity for animals and aquatic organisms. Herein, a novel fluorescent probe P1 was constructed, based on photo-induced electron transfer (PET) mechanism, using naphthimide as the fluorophore and 7-nitrobenzoxadiazole as the recognizing group. Probe P1 exhibited an “Off-On” fluorescence recognition response to PhSH by nucleophilic substitution reaction. The probe displayed advantageous properties for the recognition of PhSH, including a chromogenic response, high selectivity, fast response (< 90 s), and a large Stokes shift (150 nm). In addition, probe P1 exhibited a good linear response to PhSH within the range of 0-9 μM, and the limit of detection (LOD) is 21 nM. Furthermore, probe P1 has been successfully applied for the efficient and rapid PhSH detection in environmental water and actual food samples.

A smartphone-integrated bimetallic ratiometric fluorescent probe for specific visual detection of tetracycline antibiotics in food samples and latent fingerprinting

Designing and preparing highly sensitive and accurate fluorescent chemosensors for monitoring tetracycline antibiotics remains a challenge. Herein, a fluorescent chemosensor based on lanthanide metal-organic frameworks (Ln-MOFs) is proposed to realize high-precision monitoring by adjusting the ratio of lanthanide ions. Ln-MOFs with good aqueous stability were prepared by a solvothermal method using Eu3+, Tb3+ and the ligand 4,4′,4″-s-triazine-2,4,6-triyltribenzoic acid (H3TATB) in DMF/NMP/H2O. The Ln-MOFs could recognize oxytetracycline (OTC) and doxycycline (DOX), and the detection limits of OTC and DOX were as low as 8.6 and 4.8 nM, respectively. In particular, Eu(1.4 μM)-Tb-MOF sensors were used for visual detection of OTC and DOX in combination with smartphones with detection lines as low as 9.8 nM and 14.2 nM, respectively. Meanwhile, Eu-MOF, Tb-MOF and Eu(1.4 μM)-Tb-MOF can be used for latent fingerprint (LFP) visualization, demonstrating their potential applications in the field of criminal case investigation. The developed probes were successfully applied to determining OTC and DOX in milk, beef and pork with recoveries ranging from 92.0 % to 109.63 % and relative standard deviations (RSDs) ranging from 1.83 % to 4.56 %. Eu(1.4 μM)-Tb-MOF is believed to utilize its lanthanide metal ion coordination and photoinduced electron transfer (PET) mechanism to achieve highly selective and accurate OTC and DOX detection, which is supported by experimental and density functional theory (DFT) calculations.

Lignin-Based Visible Light-Triggered Nitric Oxide Nanogenerator for Antibacterial Applications.

Nitric oxide (NO) has received growing attention as an effective antibacterial agent with broad-spectrum activity and a low risk of resistance. However, it remains challenging to develop effective, controllable, and biocompatible NO-releasing materials. Here, we report a novel NO nanogenerator (AL-BNN6-PEG) self-assembled by lignin, a UV-absorbing and hydrophobic NO donor (N,N'-disec-butyl-N,N'-dinitroso-1,4-phenylenediamine, BNN6), and PEG-DSPE2000. It was discovered that upon visible light irradiation (450-460 nm), BNN6 can be decomposed by lignin within micellar nanoparticles via a photoinduced electron transfer mechanism in the aqueous medium. Lignin not only served as a sustainable carrier, enhancing the water dispersity of BNN6, but also acted as a biocompatible photosensitizer, triggering BNN6 decomposition with the concomitant release of NO. As a result, the micellar nanoparticles displayed superior antibacterial effects against Gram-negative and Gram-positive bacteria upon visible light illumination. Moreover, MTT assay revealed the negligible cytotoxic effect of the micellar nanoparticles to the mouse fibroblast cells (L929). This research provides more insight into the BNN6 decomposition mechanism and demonstrates a straightforward, effective, and biocompatible strategy for controlled NO-mediated antibacterial applications.

Facile Molecular-Level Refinements for Carbon Quantum Dots via Hydrogen-Bonding-Assisted Selective Isolation.

A novel method for synthesizing and refining high-purity carbon quantum dots (CQDs) using citric acid and diethylenetriamine as precursors is presented, achieved through molecular-level control by exploiting the differences in hydrogen-bonding strength. This process involves precipitation using melamine, extraction into ethanol, and encapsulation with (3-aminopropyl)triethoxysilane (APTES). The resulting APTES-encapsulated CQDs exhibited an enhanced color purity, higher photoluminescence quantum yield, and improved fluorescence stability over a broad pH range. Utilizing these well-defined high-purity CQDs with uniform surface states, it has been revealed that ferric ions are photochemically sensed through the inner filter effect (IFE) mechanism, while mercury ions are detected through the photoinduced electron transfer (PET) mechanism. The versatility of CQDs, coupled with our advanced refinement technology, is expected to contribute significantly to the development of advanced research applications, particularly in displays and sensors.

Redox-active sp2-c connected metal covalent organic frameworks for selective detection and reductive separation of uranium

It is economically desirable to develop a material that can simultaneously detect and recover uranium. Herein, a CC-bridged two-dimensional metal-covalent organic framework (Cu-BTAN-AO MCOF) was constructed by condensation of metal single crystals with a rigid structure (Cu3(PyCA)3) and cyano monomers (BTAN) via Knoevenagel reaction for simultaneous detection and adsorption of uranium. The amidoxime group within the pore and the presence of unsaturated Cu(I) in the framework facilitate the adsorption of uranyl ions onto the amidoxime group, leading to fluorescence quenching via the photoinduced electron transfer (PET) mechanism, achieving a detection limit of as low as 167 nM uranyl ions. Furthermore, Cu-BTAN-AO demonstrates exceptional efficiency in capturing uranium from wastewater characterized by rapid kinetics and superior selectivity. It is noteworthy that Cu-BTAN-AO is the first example of simultaneous detection, adsorption and chemical reduction of uranium using metal centers and functional groups in MCOF, indicating that Cu-BTAN-AO has great potential for the detection and recovery of uranium-containing wastewater. This design strategy may also be applicable to advancing sensing and energy materials for other important metal ions.

New porous organic framework Py-PDA CHOF as fluorescent chemosensor for detecting 2,4,6-trinitrophenol in environmental samples

Covalent bonds and hydrogen bonds linked porous organic frameworks (CHOFs) as a new type of porous organic framework connected by both covalent bonds and hydrogen bonds has been reported recently. Py-PDA CHOF was synthesized using 4,4′,4′’,4′’’-(pyrene-1,3,6,8-tetrayl)tetraaniline (Py) and 2,6-pyridinedicarboxaldehyde (PDA) as building blocks. It has porous crystalline framework and exceptional thermal stability. The suspension of Py-PDA CHOF in ethanol exhibits a highly selective and sensitive “on-off” fluorescence response towards 2,4,6-trinitrophenol (TNP), with exceptionally low detection limit. The powder X-ray diffraction (PXRD) confirmed the collapse of the Py-PDA CHOF after interaction with TNP and acid, and this result further indicated the presence of hydrogen bonds within the framework. The absorption competition quenching (ACQ) and photoinduced electron transfer (PET) mechanism are responsible for fluorescence quenching of Py-PDA CHOF by TNP. As a fluorescent chemosensor capable of detecting explosives, Py-PDA CHOF holds potential application for the identification and detection of TNP in water and soil samples.

Computational insights into the underlying mechanism of zinc ion-specificity of the fluorescent probe, BDA-1

Ion specificity is crucial for developing fluorescence probes. Using a recently reported optical sensor (BDA-1) of Zn2+ as a representative, we carried out extensive quantum chemical calculations on its photophysical properties using density function theory. According to the calculated optimized geometries, excitation energies and transition oscillator strengths, the weak fluorescence of BDA-1 observed in experiments is attributed to the suppression of fluorescence emission by efficient internal conversion, rather than the previously proposed photoinduced electron transfer (PET) mechanism. With the addition of Zn2+ or Cd2+ ions, the tetradentate chelates [M:BDA-1-H+]+ (M=Zn, Cd) are produced. According to frontier molecular orbital and interfragment charge transfer analyses of these complexes, PET is preferentially confirmed to occur upon photo-excitation. Notably, as one coordination bond in the excited [Cd:BDA-1-H+]+ complex is significantly weakened in comparison to that of [Zn:BDA-1-H+]+, their molecular orbital compositions in the S1 state are completely different. As a result, absorption and radiation transitions of [Zn:BDA-1-H+]+ both have considerable oscillator strength, while fluorescence radiation from the excited [Cd:BDA-1-H+]+ is doubly suppressed. This difference causes that the fluorescence intensity of BDA-1 is sensitive to the addition of metal ions, and exhibits the zinc ion-specificity.

Au nanoparticles decorated graphitic carbon nitride nanosheets as a sensitive and selective fluorescence probe for Fe3+ and dichromate ions in aqueous medium

Graphitic carbon nitride mutated with metal nanoparticles has captivated great interest as an effective fluorescent sensor for the detection of harmful ions present in water. In the present work, bulk-gCN was synthesized using melamine as precursor, and further Au-gCN nanocomposite were fabricated via in-situ direct reduction deposition method. The structural, morphological, compositional, stability and optical properties of bulk gCN and Au-gCN nanocomposite were examined using various scattering and spectroscopic techniques such as HRTEM, XPS, XRD and SEM. The synthesized bulk gCN straggles during selectivity studies with different cations and anions because of its uneven surface morphology, however in Au-gCN gold nanoparticles are uniformly distributed on the gCN sheets which results in its enhanced selectivity over bulk gCN. This leads to the fabrication of an optical sensor for Fe3+ and Cr2O72− ions with limit of detection of 4.62 and 2.77 μM, respectively. The sensing of Fe3+ ions corresponds to the photoinduced electron transfer (PET) mechanism, while the detection of chromate species is associated with an inner filter effect (IFE). The practical applicability of the sensor was also evaluated for different environmental water samples. The high stability, sensitivity, and specificity of Au-gCN nanocomposite make it a potential fluorescent probe for Fe3+ and Cr2O72− ions in water samples.

Ion coordination and chelation in Eu-MOFs matrices: Ultrafast fluorescence visual quantification monitoring of antibiotic residues

Rapid monitoring of trace antibiotics in the field in real time is essential for environment forewarning and human health. High sensitivity and real-time on-site quantitative monitoring of antibiotic residues can be accomplished by integrating portable sensors alongside fluorescent optics to construct an intelligent sensing platform that smoothly eliminates the instability of conventional detection methods. In this study, a ratiometric fluorescence sensor for the ultrasensitive detection of pefloxacin was built employing the photoinduced electron transfer (PET) mechanism from red Eu-MOFs to Mn2+-PEF complex. A visual color change results from the photoinduced electron transfer process from manganese ions to pefloxacin weakening the ligand metal charge transfer (LMCT) process in Eu-MOFs. This enables the ultrafast visible detection of pefloxacin and produces a transient shift in visual color with a detection limit as low as 15.4 nM. For the detection of pefloxacin in water, tomato, and raw pork samples, various sensing devices based on the developed fluorescent probes exhibit good practicability and accuracy. With the development of the ratiometric fluorescence sensing probe, it is now possible to quickly and quantitatively identify pefloxacin residues in the environment, offering a new method for ensuring the safety of food and people's health.

Dual fluorescence response of calix[4]arene-1,8-naphthalimide derivatives towards Hg(II) /Cr(VI) and their antimicrobial studies of transparent biofilms with hyaluronic acid

In this study, 4-sulfo-1,8-naphthalimide calixarene of derivatives were prepared (3 and 4) then transparent biofilms of the Ag salts of these compounds were formed in the presence of hyaluronic acid (HA), and antimicrobial properties were investigated. In chemosensor studies, the sensing ability behavior of 3 and 4 towards some cations and anions was investigated by fluorescence spectroscopy. It was observed that the prepared chemosensors show selectivity towards Hg(II) and Cr(VI). Ligand-ion interaction occurs according to the photo-induced electron transfer (PET) mechanism. The stoichiometric ratio was calculated by using Stern-Volmer plot method and binding constant Ksv values were found as 5.2 × 107 M−1 and 5.5 × 107 M−1 for 3-Hg(II) and 4-Hg(II) complexes, respectively and 4.0 × 107 M−1 and 4.3 × 107 M−1 for 3-Cr(VI) and 4-Cr(VI) complexes. The detection limits of the complexes of 3-Hg(II) and 4-Hg(II) are 6.35 × 10−12and 6.81 × 10−12, while those of 3-Cr(VI) and 4-Cr(VI) are 1.41 × 10- 11and 8.37 × 10−12, respectively. As a result of the antimicrobial test performed with these compounds, it was observed that the most effective material was HA-3Ag, which showed a significant antibacterial effect against Sarcina lutea (S. lutea) at a minimum inhibitory concentration (MIC) value of 0.097 mg/mL.

Fluorescence sensing probe based on functionalized mesoporous MOFs for non-invasive and detection of dopamine in human fluids

Abnormal amount of dopamine (DA) in human body is closely relate to various diseases, such as Parkinson's disease, pheochromocytoma. Real-time monitoring DA is crucial for disease warning, diagnosis and treatment. Currently, most methods rely on invasive blood testing for detecting DA, which is only completed with the aid of the medical staffs in hospitals. Herein, a non-invasive fluorescence visual strategy is developed for the real-time monitoring DA, based on luminescent nanoparticles and modified mesoporous zeolite imidazole framework (ZIF-8-NH2) dodecahedrons. During the reaction process, DA is enriched through the spatial configuration of ZIF-8-NH2 and hydrogen bonding effect. The luminescence of Cr3+-doped zinc gallate (ZnGa2O4:Cr3+, ZGC) is inhibited by the photo-induced electron transfer (PET) mechanism to realize sensitively detecting DA. The intelligent sensing platform based on the designed fluorescence probe and color recognition system is structured for real-time detection of DA in urine. Furthermore, a skin-fitting hydrogel patch is prepared by combining a fluorescent probe with chitosan, which enables sensitive and accurate detection of DA in sweat without the complex sample pretreatment. The non-invasive fluorescence detection method provides an effective strategy for quantitatively monitoring DA in human fluids.

Luminol-Eu3+-Gd3+-functionalized mesoporous silica for ultrasensitive detection of tetracycline antibiotics and smartphone-assisted sensing analysis

An organic-inorganic hybrid nanoprobe, namely LML-D-SBA@Eu3+-Gd3+, was constructed, with SBA-15 acting as the carrier material, and luminol and Eu3+ acting as fluorescence channels to achieve ratiometric signals that eliminate external interference (accurate detection). Gd3+ was used as a sensitizer to amplify the red emission of Eu3+ (ultrasensitive detection). In TCs detection, the luminol emission at 428 nm was quenched due to the photoinduced electron transfer mechanism, and the Eu3+ emission at 617 nm was sensitized due to the synergistic energy transfer from TCs and Gd3+ to Eu3+. The fluorescence intensity at 617 and 428 nm showed ratiometric changes as indicated by notable color changes from blue to red. The detection limits for TC and OTC were 0.21 and 0.08 ng/mL, respectively. To realize a facile, rapid, and cost-effective detection, we constructed a portable intelligent sensing platform based on smartphones, and it demonstrated great potential for on-site detection of TCs.

Selective dual sensing strategy for free and vitamin D3 micelles in food samples based on S,N-GQDs photoinduced electron transfer.

A reliable nanotechnological sensing strategy, based on anS,N-co-doped graphene quantum dot (GQD) platform, has been developed to distinctly detect two key variants of vitamin D3, specifically the free (VD3) and the nanoencapsulated form (VD3Ms). For this purpose, food-grade vitamin D3 micelles were self-assembled using a low-energy procedure (droplet size: 49.6 nm, polydispersity index: 0.34, ζ-potential: -33 mV, encapsulation efficiency: 90 %) with an innovative surfactant mixture (Tween 60 and quillaja saponin). Herein, four fluorescent nanoprobes were also synthesized and thoroughly characterized: S,N-co-doped GQDs, α-cyclodextrin-GQDs, β-cyclodextrin-GQDs, and γ-cyclodextrin-GQDs. The goal was to achieve a selective dual sensing strategy for free VD3 and VD3Ms by exploiting their distinctive quenching behaviors. Thus, the four nanosensors allowed the individual sensing of both targetsto be performed (except α-CD-GQD for VD3Ms), but S,N-GQDs were finally selected due to selectivity and sensitivity (quantum yield, QY= 0.76) criteria. This choice led to a photoinduced electron transfer (PET) mechanism associated with static quenching, where differentiation was evidenced through a displayed 13-nm hypsochromic (blue) shift when interacting with VD3Ms. The reliability of this dual approach was demonstrated through an extensive evaluation of analytical performance characteristics. The feasibility and accuracy were proven in commercial food preparations and nutritional supplements containing declared nanoencapsulated and raw VD3, whose results were validated by a paired Student's t-test comparison with a UV-Vis method. To the best of our knowledge, this represents the first non-destructive analytical approach addressing the groundbreaking foodomic trend to distinctly detect different bioactive forms of vitamin D3, while also preserving their native nanostructures as achemical challenge, thus providing reliable information about their final stability and bioavailability.

Ultrasound-assisted synthesis of a Eu3+-functionalized ZnII coordination polymer as a fluorescent dual detection probe for highly sensitive recognition of HgII and L-Cys

A new ZnII coordination polymer (CP) based on 2,3-pyrazine dicarboxylic acid (H2pzdc) and 4,4′-bipyridine (bpy) (ZCP) was synthesized using a facile slow evaporation method. Single-crystal X-ray diffraction revealed that ZCP is a two-dimensional porous CP, [Zn2(pzdc)2(bpy)(H2O)2] n , with van der Waals forces as the dominant interaction within its layers forming a 63 network. Employing energetic ultrasound irradiation, nanoscale ZCP (nZCP) was successfully synthesized and Eu3+ ions were incorporated within its host lattice (Eu@nZCP). The resulting platform exhibits superior fluorescence characteristics and demonstrates notable optical durability. Therefore, it was used as a dual detection fluorescent sensing platform for the detection of mercury and L-cysteine (L-Cys) in aqueous media through a turn-off/on strategy. In the turn-off process, the fluorescence emission of Eu@nZCP progressively quenches by the addition of HgII via a photo-induced electron transfer (PET) mechanism. The fluorescence of Eu@nZCP is quenched to establish a low fluorescence background through the incorporation of HgII. This devised turn-on fluorescent system is suitable for the recognition of L-Cys (based on the strong affinity of L-Cys to the HgII ion) through a quencher detachment mechanism. This method attained a relatively wide linear range, spanning from 0.001 to 25 µM, with the low detection limit of 5 nM for the sensing of HgII. Also, the corresponding limit of detection (LOD) for L-Cys is 8 nM in a relatively wide linear range, spanning from 0.001 to 40 µM.

Design and Construction of the Uranyl Coordination Polymer with Multifunction Stimulus Response: Fluorescent Sensors for Halide Ions and Photochromism.

It can provide ideas for the use of uranium elements in the treatment of spent fuel from nuclear wastewater to explore the application potential of uranium element. Thus, it is necessary to research the structure and properties of a novel uranyl coordination polymer (CP) for uranium recovery and reuse. Herein, we designed and prepared a new uranyl CP U-CMNDI based on UO22+ and H2CMNDI (H2CMNDI = N, N'-bis(carboxymethyl)-1,4,5,8-naphthalenediimide). Structural analysis shows that two uranyl ions are connected by two parallel deprotonated CMNDI ligands to form a discrete uranyl dimer structure. U-CMNDI can act as a potential stimulus-responsive halide ion sensor by a fluorescence "turn on" response in water. The limit of detection for fluoride (F-), bromide (Br-), iodide (I-), and chloride (Cl-) is 5.00, 5.32, 5.49, and 5.73 μM, respectively. The fluorescence "turn on" behavior is based on the photoinduced electron transfer (PET) mechanism between halide ions and electron-deficient NDI cores. In addition, U-CMNDI demonstrates a color response to ultraviolet light, exhibiting reversible photochromic behavior with a notable color change. The color change mechanism can contribute to the PET process and the radical process.

Design, synthesis, and spectrofluorimetric analysis of a novel fluorene-based chemosensor for the selective detection of picric acid

Fluorene-based probes are efficient candidates for sensing nitroaromatics and toxins. A novel fluorophore based on fluorene and terephthalaldehyde 1,4-YBF (1,4-ylidene-bis-fluorene) has been designed and synthesized for the efficient sensing of 2,4,6-trinitrophenol (picric acid) in solution. X-ray crystallographic studies, NMR, and mass analyses revealed the molecular stacking and exact structure of 1,4-YBF, which was further structurally optimised using the DFT technique. The optical properties of the newly synthesized compound were studied using UV–Vis and spectrofluorimetric analyses. The fluorophore was subjected to detailed sensing studies of various nitroaromatics, among which it was identified that picric acid (PA) exhibited the maximum quenching efficiency. The excellent sensing ability of the fluorophore was probably attributed to the photoinduced electron transfer (PET) mechanism. Further, pH studies and interference studies, along with its high selectivity towards PA and an LOD of 0.314 µM, revealed 1,4-YBF to be efficient in the detection of picric acid at a micromolar level.

A captivating approach to elevate the detection of Al3+ ions incorporates the utilization of a tripodal receptor intricately embellishing the surface of zinc oxide

The FDA (Food and Drug Administration, (USA)) lists ZnO as a material that is widely acknowledged to be safe. ZnO NPs with a range of tiny particle sizes were made using the precipitation process. ZnO nanoparticles' surface is embellished with a tripodal sensor containing naphthol units. The assembly with the same receptor decorated on ZnO NPs is contrasted with the cation detection capabilities of the purified tripodal receptor. The UV–visible spectrophotometric analysis was conducted to study the state transitions of the receptor and the decorated ZnO receptor. A positive selectivity to Al3+ cations is determined by the fluorescence study under ideal circumstances. The particle size and surface morphologies are determined by DLS and SEM analysis for the same receptor − TP1 and embellished with a tripodal receptor TP2. Using a fluorescence switch-on Photoinduced Electron Transfer (PET) mechanism, the receptor coated on ZnO detects the presence of Al3+ ions with specificity. The binding constant value was determined using the B-H plot equation. Binding stoichiometry for [TP1-Al3+, TP2-Al3+] showed a 1:1 ratio. The fluorescence switches ON-OFF process of the ZnO surface adorned − TP2 with Tripodal receptor- TP1 was used to create molecular logic gates, which can function as a module for sensors and molecular switches. The addition of Na2EDTA in the solution of the [TP1; TP2 − Al3+] complex resulted in a noticeable reduction in the emission of fluorescence. This finding offers compelling support for the reversibility of the chemosensor. To enable the practical application of this sensor, we have developed a cassette containing receptors TP1 and TP2. Successfully, it can detect Al3+ metal ions. We performed a comprehensive assessment of the dependability and appropriateness of our approach in measuring the concentration of Al3+ ions in wastewater produced by important industrial procedures.

Density Functional Theory Calculations on Fluorescence-Enhanced Mechanisms of the Optical Sensor for Zinc Ions, ADPA.

N-(9-anthracenylmethyl)-N-(2-pyridinylmethyl)-2-pyridinemethanamine (ADPA) as a specific ion sensor for Zn2+ has been widely applied. Although the photo-induced electron transfer (PET) mechanism was proposed previously, its fluorescence-enhanced effect still remains somewhat ambiguous, according to unknown influences of non-radiative energy decay pathways, such as intersystem crossing and internal conversion. Herein, a thorough study using density functional theory has been performed for low-lying electronic states of the ADPA monomer and hydrated ADPA-Zn2+ complex. Based on interfragment charge transfer analyses, we quantitatively calculated the amount of transferred electrons in the monomer and complex, providing solid evidences for the PET mechanism and in line with the conclusion of frontier molecular orbital analyses. Moreover, the ISC process of S1→T2 was confirmed to play a considerable role in the excitation energy relaxation process of the ADPA monomer, but this influence was significantly suppressed in the hydrated ADPA-Zn2+ complex. These results provide additional clues for the design of new metal ion-specific fluorescence probes.