Fluorescent Sensor Research Articles

A novel dual-function fluorescence sensor Eu/CDs@MOF-808 for the sensitive detection of adenosine triphosphate and uric acid

Designing and developing a reliable method for the detection of potential biomarker molecules are crucial for the early prevention and diagnosis of diseases. In this study, we present a novel functionalized metal–organic framework material (MOF-808) that is developed to construct ratiometric fluorescence sensing platforms (Eu/CDs@MOF-808) for the detection of adenosine triphosphate (ATP) and uric acid (UA). The fluorescent probe Eu/CDs@MOF-808 prepared through the in-situ encapsulation of fluorescent carbon dots (CDs) within the structure of MOF-808 exhibits excellent optical properties. Additionally, rare earth ions (Eu3+) are incorporated into the CDs@MOF-808 using a post-synthetic modification strategy. The presence of ATP significantly enhances the characteristic peak of carbon dots (CDs) at 440 nm, while the peak of Eu3+ at 614 nm remains relatively unchanged. Furthermore, the concentration of ATP exhibits a strong linear relationship with the ratiometric fluorescence intensity (F440/F614) in the concentration range of 0.5–450 μM, with a detection limit of 0.22 μM. Notably, the addition of uric acid (UA) to this fluorescence sensing platform leads to a marked reduction in the characteristic peak intensity of Eu3+, which results in a satisfactory linear relationship between the ratiometric fluorescence intensity and UA concentration in the concentration ranges of 0.04–300 μM and 300–650 μM, with a detection limit of 0.04 μM. Additionally, the fluorescent sensor has been successfully applied for the detection of ATP and UA in real serum and urine samples.

Emissive Hydrazone-Linked Covalent Organic Frameworks as Highly Sensitive and Selective Sensor for the Hydrazine Detection.

Covalent Organic Frameworks (COFs) exhibit a range of exceptional attributes, including notable porosity, outstanding stability, and a precisely tuned π-conjugated network, rendering them highly promising candidates for fluorescence sensors applications. In this study, the synthesis of two emissive hydrazone-linked COFs designed for hydrazine detection is presented. The partially conjugated structure of the hydrazone linkage effectively weakens the fluorescence quenching processes induced by aggregation. Additionally, the incorporation of flexible structural components further reduces conjugation, thereby enhancing luminescent efficiency. Remarkably, these COFs possess a significant abundance of heteroatoms, enabling distinctive interactions with hydrazine molecules, which in turn results in exceptional selectivity and sensitivity for hydrazine detection. The detection limit of these COFs reaches the nanomolar range, surpassing all previously reported COFs, thereby underscoring their superior performance in chemical sensing applications.

A handheld fluorescent platform integrated with a Sm(III)-CdTe quantum dot-based ratiometric nanoprobe for point-of-use determination of phosphate.

Phosphate (Pi) is crucial for various physiological processes and aquatic environments, which emphasizes the need for a simple, on-site sensor to promptly detect Pi for human health and environmental conservation. In this study, we propose a dual-emission ratiometric fluorescence sensor for highly sensitive and visual Pi detection. The sensor employs samarium ions (Sm3+) as a core component, with cadmium telluride quantum dots (CdTe QDs) and ofloxacin (OFL) serving as signal carriers. The CdTe-Sm(III)-OFL nanoprobe emits a purple fluorescence resulting from the red fluorescence of CdTe QDs and the blue-green fluorescence of OFL. The fluorescence of OFL is quenched by Sm3+ through fluorescence resonance energy transfer (FRET). Upon Pi interaction, the FRET process is disrupted due to the competitive Pi-Sm3+ binding, which leads to the fluorescence recovery of OFL while the red fluorescence of CdTe remains steady. This enables the construction of a ratiometric fluorescent sensor for Pi detection, manifesting as a color change from purple to blue. The sensor demonstrated a linear response for Pi detection within the range of 0.1-75 μM, with a low detection limit of 17.0 nM. By utilizing the distinct fluorescence responses of various physiological phosphates and employing chemometrics, this innovative dual-emission sensor accurately distinguishes among different physiological phosphates. Furthermore, a portable lab-on-paper device based on CdTe-Sm(III)-OFL, coupled with a smartphone-integrated mini-device, is developed for swift Pi detection using an ordinary smartphone. Analytical performance validated on environmental and biological samples demonstrates the sensor's excellent robustness and adaptability. This study introduces a pioneering approach to fabricate ratiometric fluorescence sensors and customize portable, cost-effective mini-devices for precise target detection, thus opening avenues for advanced sensing strategies in various applications.

A portable fluorescence sensing system for timely onsite perfluorooctane sulfonate detection based on an aggregate induced emission fluorescence sensor.

Perfluorooctane sulfonate (PFOS), a ubiquitous persistent organic pollutant, has aroused growing concern due to its adverse effects on human health. Timely onsite monitoring of PFOS in heavily contaminated areas is crucial for effective pollution management and prevention of its spread. However, relevant PFOS detection methods have rarely been reported. Herein, we developed a fluorescence sensing system capable of achieving timely onsite detection of PFOS under outdoor conditions. First, aggregate induced emission (AIE) fluorescence sensors, TPE-PAs, were synthesized. The optimized sensor could selectively interact with PFOS through electrostatic attraction and hydrogen bonding and exhibited prominent fluorescence enhancement after treating with PFOS. There was a good linear relationship between the fluorescence enhancement and PFOS concentration in the range of 0.05-30 ppm, and the limit of detection was measured to be 0.047 ppm. In addition, owing to the AIE fluorescence mechanism and high concentration of TPE-PAs in the sensing medium, the sensor demonstrated excellent anti-interference performance. Second, we developed a portable fluorometer, by modifying the power supply and sample cell of a tiny fluorometer, and further integrated this modified fluorometer, the prepared fluorescence sensor, standard PFOS solutions and other consumables into a portable test system. This test system showed good detection accuracy and reliability and successfully achieved timely onsite PFOS detection in real water samples.

A fluorescent sensor for rapid and quantitative aquatic bacteria detection based on bacterial reactive oxygen species using Ag@carbon dots composites.

A novel fluorescent sensor based on silver nanoparticle-carbon dot composites (Ag@CDs) has been developed for the rapid and quantitative detection of aquatic bacteria. The sensor operates on the principle of plasmon-enhanced resonance energy transfer, where the fluorescence of CDs is quenched by Ag nanoparticles and restored upon bacterial interaction due to the generation of reactive oxygen species. The Ag@CDs exhibit a linear response to bacterial concentration over the range 7 × 104 ~ 4 × 107 CFU·mL-1, with a low detection limit of 4 × 104 CFU·mL-1. The fluorescence recovery is rapid, reaching maximum intensity within 5 min. The method demonstrates high selectivity, with minimal interference from common ions and compounds found in municipal and industrial wastewater. The Ag@CDs-based 96-well plate assay for quantitative measurement of bacteria was developed. The assay's performance was further validated through the analysis of real water samples, showing a recovery of 94.0 ~ 102% for domestic wastewater and 97.6 ~ 106% for industrial wastewater. Also, Ag@CDs-based test strips assay for semi-quantitation were developed for rapid in-field aquatic bacteria detection. Ag@CDs can be conveniently integrated into 96-well plates and test strips, providing rapid on-site aquatic bacteria testing.

Pyrene‐Functionalized Silicon Hybrid Porous Polymer for an Efficient Adsorption of Dyes

AbstractPyrene‐functionalized silicon hybrid porous polymer (TAPPy‐HPP). The hybrid polymer was successfully prepared via a Schiff base reaction using tetra(4‐aminophenyl)pyrene (TAPPy) and tetra(4‐formylphenyl)silane (TFS) as the building blocks.. This hybrid polymer was characterized using IR, solid‐state 13C and 29Si NMR, and elemental analysis. Its morphology was analyzed by PXRD and SEM. Thermal analysis using Thermal analysis using TGA shows that the synthetic polymer has greater thermal stability than its monomers at a temperature of 5 % weight loss (Td5 %) of 392 °C. Although TAPPy‐HPP has a Brunauer‐Emmet‐Teller surface area of 45.4 m2 g−1, it adsorbed dyes with high efficiency, particularly the anionic dye Congo Red (CR), with an adsorption capacity of up to 358 m2 g−1. Moreover, TAPPy‐HPP showed excellent recycling and regenerative properties. This polymer is a promising candidate for a fluorescent chemical sensor for the absorption of dyes due to its exceptional physiochemical stability and intense luminescence.

FRET-Based Dual-Color Carbon Dot Ratiometric Fluorescent Sensor Enables the Smartphone-Integrated Device for Noninvasive and Portable Diagnosis of Chronic Kidney Disease.

Cystatin C (Cys C), a crucial renal disease marker for chronic kidney disease (CKD), plays a vital role in early diagnosis and treatment guidance. However, most current methods for detecting Cys C rely on a single signal and find it difficult to perform noninvasive and portable diagnosis. Here, we developed a ratiometric fluorescent carbon dot (CD) detection system for point-of-care testing (POCT) of Cys C through fluorescence resonance energy transfer (FRET). The detection is based on the hydrolysis effect of papain on a bovine serum albumin (BSA) scaffold and the specific inhibitory effect of Cys C on papain, endowing high-resolution color variance. Moreover, a low-cost, portable, yet reliable smartphone-assisted miniaturized device for real-time quantitative POCT of Cys C has been developed with a limit of detection (LOD) as low as 0.4 μg/mL. This sensing platform can effectively differentiate patients from healthy volunteers, which facilitates self-screening for healthy individuals and home monitoring for CKD patients.

A Schiff-Base Molecular Probe for Selective Fluorescence Sensing of Maleic Acid with Recognition of Maleic Acid in Food Additives and Cell Imaging.

The 2,4-dinitrophenylhydrazine based Schiff base (L) acts as an effective fluorescence sensor for the selective detection of maleic acid. The detection limit of L towards maleic acid is observed to be 1.29 × 10-7 M. A 1:1 binding stoichiometry between L and maleic acid was obtained using Bensi-Hilderbrand method. The binding constant (Ka) was measured to be 5.17 × 106 M-1. The sensing behavior of L was confirmed through analysis using FT-IR, DLS and SEM analysis, alongside DFT calculations. Theoretical assessments clearly suggest that the L's mono-protonation and complexation in the solvent medium are the primary mechanisms in the sensing process. Additionally, L is used to imaging the maleic acid in living cells, demonstrating its potential biological uses. In addition, recognition of maleic acid in food additives was reported.

Acid Sensors Based on Luminochromism of Solid‐State Excimer Emission of Pyrene‐Modified Polyhedral Oligomeric Silsesquioxane

To obtain solid‐state fluorescence sensors, it is essential to simultaneously obtain solid‐state emission and stimuli‐responsiveness. In this research, the modified polyhedral oligomeric silsesquioxane (POSS) tethered with pyrenes was synthesized and we confirmed that both demands for developing solid‐state fluorescence sensors can be satisfied. The POSS derivative exhibited strong emission even in the solid state. In particular, we found that exposure of the POSS films to trifluoroacetic acid vapor resulted in a significant red‐shift of the peak wavelength of the emission band. Excitation spectroscopy and comparison with model compounds suggest that this significant red‐shift should be attributable to the formation of static excimer, meaning a preformed dimer in the ground state induced by protonation of the secondary amino groups. These results indicate that POSS is a promising scaffold for a solid‐state fluorescence sensor.

A Novel Fluorescent Sensor for Detecting Ag+ and Hg2+ ions: A Combination of Theoretical and Experimental Studies.

A new fluorescent sensor based on diethylaminosalicylaldehyde-thiosemicarbazide (DST) was studied using a combination of density functional theory calculations and experimental investigations. DST was able to detect the metal ions Ag+ and Hg2+ in the presence of various competing metal ions and anions, with detection limits of 0.45 and 0.34 µM, respectively. The DST sensor could operate in a fully aqueous environment and within a wide pH range from 5 to 9. Density functional theory studies supported the experimental findings in determining the stable structures of the DST sensor and the complexes between DST and the Ag+ and Hg2+ ions, as well as elucidating the fluorescence ON-OFF mechanism in the DST sensor and the complexes.

Genetically encoded green fluorescent sensor for probing sulfate transport activity of solute carrier family 26 member a2 (Slc26a2) protein

Genetically encoded fluorescent biosensors became indispensable tools for biological research, enabling real-time observation of physiological processes in live cells. Recent protein engineering efforts have resulted in the generation of a large variety of fluorescent biosensors for a wide range of biologically relevant processes, from small ions to enzymatic activity and signaling pathways. However, biosensors for imaging sulfate ions, the fourth most abundant physiological anion, in mammalian cells are still lacking. Here, we report the development and characterization of a green fluorescent biosensor for sulfate named Thyone. Thyone, derived through structure-guided design from bright green fluorescent protein mNeonGreen, exhibited a large negative fluorescence response upon subsecond association with sulfate anion with an affinity of 11 mM in mammalian cells. By integrating mutagenesis analyses with molecular dynamics simulations, we elucidated the molecular mechanism of sulfate binding and revealed key amino acid residues responsible for sulfate sensitivity. High anion selectivity and sensitivity of Thyone allowed for imaging of sulfate anion transients mediated by sulfate transporter heterologously expressed in cultured mammalian cells. We believe that Thyone will find a broad application for assaying the sulfate transport in mammalian cells via anion transporters and exchangers.

Nitrogen and Sulfur Co-doped Carbon Dots for Ratiometric Fluorometric Determination of Mercury Ions.

Nitrogen and sulfur co-doped carbon dots (N, S-CDs) were prepared for dual-channel ratiometric fluorescence determination of mercury ions (Hg2+). The dual-emission N, S-CDs were synthesized using a simple one-pot hydrothermal treatment. When excited with visible light, N,S-CDs exhibited two emission peaks at 390 and 500nm. Notably, the presence of Hg2+ caused a considerable decrease in the fluorescence of N, S-CDs at 500nm, mainly due to the static quenching effect. In comparison, the fluorescence at 390nm was almost unchanged. With a limit of detection (LOD) of 0.21 µM for Hg2+, the N, S-CDs were successfully applied to the unlabeled ratiometric fluorescence determination of Hg2+ in actual water samples with good recoveries (94.5-107.8%). In conclusion, this developed ratiometric fluorescent sensor provides a reliable, environmentally friendly, rapid, and efficient platform for detecting Hg2+ in environmental applications.

Time-Lapse Live-Cell Imaging Using Fluorescent Protein Sensors in Outflow Pathway Cells Under Fluid Flow Conditions.

The role of shear stress in regulating aqueous humor (AH) outflow and intraocular pressure (IOP) in the trabecular meshwork (TM) and Schlemm's canal (SC) of the eye is an emerging field. Shear stress has been shown to activate mechanosensitive ion channels in TM cells and induce nitric oxide production in SC cells, which can affect outflow resistance and lower IOP. Live-cell imaging using fluorescent protein sensors has provided real-time data to investigate the physiological relationship between fluid flow and shear stress in the outflow pathway cells. The successful application of time-lapse live-cell imaging in primary cultured cells has led to the identification of key cellular and molecular mechanisms involved in regulating AH outflow and IOP, including the role of autophagy and primary cilia as mechanosensors. This chapter presents a detailed protocol for conducting time-lapse live-cell imaging under fluid flow conditions in the outflow pathway cells.

Defect-Enabled Superior Negative Thermal Quenching in Palmierite Ba9La(VO4)7:Eu3+ for WLED In Situ Temperature Measuring.

Negative thermal quenching (NTQ) of the phosphors is critically important for both scientific research and practical applications, but the design of efficient NTQ phosphors is still a challenging task. Herein, we report a new strategy for developing NTQ materials by cation-vacancy engineering. Specifically, a new color-tunable Ba9La1-x(VO4):xEu3+ (BLVO:xEu3+) phosphor with abundant intrinsic cation vacancy was developed, exhibiting superior NTQ behavior under 365 nm excitation. The NTQ performance can be modulated via adjusting Eu3+ doping levels, and the emission intensity of Eu3+ ions in the BLVO:0.20Eu3+ phosphor increased by 275% at 473 K compared to room temperature. Furthermore, the reported material emitting bright white light under 365 nm excitation was well-suited for use in white light-emitting diode (WLED) phosphor and fluorescent temperature sensors, exhibiting outstanding color-rendering index (90.1) in lighting and high sensitivity (Sa = 11.83% K-1, Sr = 2.33% K-1) in temperature detecting. Lastly, the operating temperature of WLED at different currents can be monitored and displayed in real time through emission spectroscopy. All of the results demonstrated that the designed NTQ BLVO:xEu3+ can be used as a single-phase white phosphor and optical thermometry. This work provides a fresh perspective for designing high-efficient NTQ phosphors and expands the application of phosphors in WLED in situ temperature detection.

Fabrication of a novel mixed-valent copper-based coordination polymer as a fluorescent sensor for selective and efficient detection of multiple analytes

A novel three-dimensional fluorescent mixed-valent copper-based coordination polymer (CP), namely {[CuICuII4(triazol)6(bpta)2]Cl}n (Cu-CP), was synthesized hydrothermally in the presence of Cu(II) ion, 2,4,6-tri(1H-1,2,4-triazol-1-yl)-1,3,5-triazine (TTT), and 2,2′,4,4′-biphenyltetracarboxylic acid (H4bpta). The structure of the Cu-CP was studied using single-crystal X-ray diffraction (SCXRD) and powder X-ray diffraction (PXRD). Interestingly, the crystallographic data revealed that a part of Cu(II) ions were reduced in situ to Cu(I) ions as well as the nitrogen-containing ligand TTT was converted to triazol, which possessed excellent fluorescence characteristics as a transition metal ion with a d10 electronic configuration, prompting further investigation into the fluorescence sensing properties of Cu-CP. The results confirmed that Cu-CP exhibited excellent fluorescence performance which an outstanding candidate as a fluorescence sensor for Fe3+, Cr2O72−, CrO42−, MnO4− and nitrobenzene (NB), with a low limit of detection. For ethylene glycol (EG) detection, Cu-CP showed high-efficiency fluorescence enhancement across a range of temperatures. The underlying mechanism of fluorescence enhancement was investigated through comprehensive experimental studies.

Polymer organic framework-based ratiometric fluorescent probe for non-enzymatic glucose detection

Fluorescent pyrene-based polymer organic frameworks (POFs) PY-POFs were designed and synthesized by a facile solvothermal route for glucose detection, employing melamine, aromatic dialdehydes, 1-pyrenecarboxaldehyde, and phenylboronic acid as building blocks. The structure and photophysical properties of as-prepared POFs were systematically characterized via Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, N2 adsorption isotherms and fluorescence spectroscopy. The PY-POFs possessed intrinsic microporosity derived from extensively interlinked aminal structures, boasting specific surface areas reaching 192 m²/g, pore volumes extending to 0.8079 cm³/g, pore diameters of up to 17 nm, and an average particle dimension of ∼ 31 nm. In addition, the PY-POFs exhibited a dual-wavelength emission of pyrene excimer (λem = 472 nm) and monomer (λem = 382, 400, and 422 nm). When exposed to glucose, the former emission decreased while the latter increased, corresponding to the conformational transition of pyrene molecule from excimer to monomer. The non-enzymatic ratiometric fluorescent sensor displayed remarkable sensitivity towards glucose within 10−200 μM range, with a limit of detection (LOD) of 5.6 µM. Moreover, the glucose detection ability of PY-POFs was also in vivo demonstrated within zebrafish. Application of this sensor to real samples such as human saliva and DMEM biological matrix presented satisfactory results and good reproducibility. These results indicate that the fluorescent glucose sensor PY-POFs have broader prospects for utilization within biological studies.

Ultrabright silicon nanoparticles combined with o-phenylenediamine for ratiometric fluorescence and smartphone imaging dual-mode detection of nitrite

Nitrite (NO2−) is widely present in the natural environment and human daily life. Excessive NO2− can cause harm to the environment and human health. Herein, silicon nanoparticles (SiNPs) with a fluorescence quantum yield of up to 70 % were synthesised using a one-pot hydrothermal method and combined with the common and inexpensive o-phenylenediamine (OPD) to achieve the detection of NO2−. Upon the addition of NO2−, the blue fluorescence of the SiNPs was quenched due to static quenching and Förster resonance energy transfer (FRET), while the yellow fluorescence of benzotriazole, the reaction product of OPD and NO2−, was enhanced, resulting in the fluorescence color change from blue to yellow. Based on these phenomena, a ratiometric fluorescence sensor integrated with smartphone imaging technology was developed. This sensor is notable for its portability, cost-effectiveness, and satisfactory detection limits (0.016 μM for ratiometric fluorescence and 1.64 μM for smartphone imaging). Importantly, it demonstrates high reliability and practicability in detecting NO2− in real water and food samples. This broadens the application of SiNPs in the sensing field and introduces new possibilities for NO2− detection in complex sample matrices.

A Novel Rhodamine‐Tetraphenylporphyrin Fluorescence Probe for Imaging Mercury In Vitro and In Vivo

ABSTRACTA highly selective fluorescent sensor Por‐RBO for determination of Hg2+ was designed and synthesized with Rhodamine B and Tetraphenylporphyrin. The sensor can determine the Hg2+ of a solution within the pH 5.0–8.0, free from interference of other metal ions. When detected in buffer solution, the fluorescence was the strongest when five times the concentration of Hg2+ ion was added. Calculated by fluorescence titration method, the detection limit of sensor Por‐RBO for Hg2+ ion was as low as 0.12 μmol/L. The geometries of Por‐RBO and Por‐RBO‐Hg2+ were optimized at the B3LYP/6‐31G** level by density functional theory. The charge distribution, orbital interactions, and bonding characteristics were analyzed and compared in detail to discuss the recognition mechanism and structure–fluorescence property relationships. The results of cell fluorescence imaging and CCK‐8 experiments indicate that the sensor Por‐RBO exhibits lower cytotoxicity. Por‐RBO can be used for fluorescence distribution imaging of Hg2+ in living cells.

Metal organic frameworks (MOFs)-based fluorescent CA125 analysis: A comparative study of the quenching effects of MIL-101, Cu-MOF, ZIF-8, UiO-66

Metal-organic frameworks (MOFs) are a class of materials with highly ordered pore structures. Due to their unique physical and chemical properties, they show great potential in the field of biosensors. Some MOFs can adsorb fluorescently labeled nucleic acid aptamers through various interaction mechanisms (such as electrostatic interactions, π-π stacking, hydrogen bonding, etc.). These interactions not only ensure the stable binding of the aptamers but also allow for their controlled release under specific conditions (such as changes in pH, temperature, or the presence of specific molecules). This mechanism provides multiple possibilities for the design of biosensors. Herein, we have systematically compared the quenching effects of widely used MOFs that can bind to aptamers, i.e., Fe-MOF (MIL-101), Cu-MOF, Zn-MOF (ZIF-8) and Zr-MOF (UiO-66). The study on the kinetics, quenching efficiency, and influencing factors such as ionic strength pH and temperature is performed. Interestingly, Cu-MOF exhibits superior quenching abilities to the other three materials in both the quenching efficiency and kinetics. Thus, a Cu-MOF based fluorescent sensor is reported to detect the ovarian cancer marker carbohydrate antigen 125 (CA125), which provides convenient detection performance (assay time about 10 min), and a detection range from 0.1 to 400 ng/mL. Moreover, it is designed in a simple mix-and-detect format and can be directly applied to clinical sample detection. This work may offer guidance for the choice of MOFs and elaborate design of biosensors.

Determination of sudan III using nitrogen and sulfur co-doped carbon quantum dots with fluorescence enhancement effect

Sudan III, a synthetic azo dye, is commonly used for coloring oils, waxes, and various plastics. However, its unauthorized presence in food and food products poses serious health hazards, including potential carcinogenic effects. In this study, we investigated the application of nitrogen and sulfur co-doped carbon quantum dots (N,S-CQDs) as a fluorescence sensor to detect trace amounts of sudan III. When exposed to trace amounts of sudan III, the fluorescence signal of N,S-CQDs was significantly enhanced. Under optimal conditions (pH 5.0 and an incubation time of 4 minutes), the fluorescence enhancement of N,S-CQDs showed a linear relationship with sudan III concentration in the range of 7.5 x 10-10 to 1.0 x 10-8 M, with a limit of detection of 2.0 x 10-10 M (equivalent to 0.07 ppb). The method demonstrated high accuracy (recovery from 91.5% to 103.5%), good reproducibility (RSD < 3.86%), and excellent selectivity for sudan III over other azo dyes. We successfully applied this developed method to analyze sudan III in chili sauce and chili powder samples, cross-checking differences between results less than 10% with LC-MS/MS analysis.