Fluorescence Color Change Research Articles

Photochromic Perovskite Nanocrystals for Ultraviolet Dosimetry.

Excessive ultraviolet (UV) radiation has serious damage to human's health, therefore the development of visible, portable, and wearable sensor for monitoring UV radiation, especially the cumulative UV dosage, is highly desired but full of challenges. Herein, a wearable and flexible UV dosimeter based on photochromic perovskite nanocrystals (PNCs) is designed. The obtained CsPbCl3 PNCs dispersed in dibromomethane (PNCs-DBM) undergo continuous, vivid, and multiple (from very weak purple to blue, cyan, and finally strong green) color change in response to UV radiation. It is demonstrated that the UV-induced degradation of DBM and subsequent anion-exchange reaction between CsPbCl3 and Br-, play a crucial role in the color change of PNCs-DBM. The properties of continuous fluorescence color change and enhanced fluorescence intensity enable the construction of sensitive and visible UV dosimeter. Furthermore, by integrated photochromic PNCs with flexible bracelet or PDMS substrate, a wearable UV sensor or a multi-indicator array for the detection of solar UV dosage is developed. This work may advance the fundamental understanding about photochromic perovskite, and show promising application of perovskite nanomaterials in easily fabricated, low-cost, visualized, and wearable solar UV dosimeter.

A non-FRET DNA reporter that changes fluorescence colour upon nuclease digestion.

Fluorescence resonance energy transfer (FRET) reporters are commonly used in the final stages of nucleic acid amplification tests to indicate the presence of nucleic acid targets, where fluorescence is restored by nucleases that cleave the FRET reporters. However, the need for dual labelling and purification during manufacturing contributes to the high cost of FRET reporters. Here we demonstrate a low-cost silver nanocluster reporter that does not rely on FRET as the on/off switching mechanism, but rather on a cluster transformation process that leads to fluorescence color change upon nuclease digestion. Notably, a 90 nm red shift in emission is observed upon reporter cleavage, a result unattainable by a simple donor-quencher FRET reporter. Electrospray ionization-mass spectrometry results suggest that the stoichiometric change of the silver nanoclusters from Ag13 (in the intact DNA host) to Ag10 (in the fragments) is probably responsible for the emission colour change observed after reporter digestion. Our results demonstrate that DNA-templated silver nanocluster probes can be versatile reporters for detecting nuclease activities and provide insights into the interactions between nucleases and metallo-DNA nanomaterials.

Dihydroacridine-functionalized pillar[5]arene with optical response towards alanine derivative

Aiming at the construction of novel macrocycle-based fluorescence probes, herein we have designed and synthesized a new functionalized pillar[5]arene (P[5]A-Ac) with the pillar[5]arene as the macrocyclic host and the dihydroacridine moiety as the fluorescence indicator. The stable host–guest complexing between P[5]A-Ac and alanine derivative (Ala-OEt) was confirmed by Job’s plot, Uv–vis and 1H NMR titration experiments. More importantly, remarkable fluorescence color change from blue towards light yellow was observed upon adding Ala-OEt to the solution of P[5]A-Ac, implying the dihydroacridine-functionalized pillar[5]arene could serve as a new fluorescence probe for the detection of alanine derivative.

Enhanced Molecularly Imprinted Fluorescent Test Strip for Rapid and Visual Detection of Norfloxacin via a Smartphone.

Paper-based test strips with on-site visual detection have become a hot spot in the field of target detection. Yet, low specific surface area and uneven deposition limit the further application of test strips. Herein, a novel "turn-on" ratio of molecularly imprinted membranes (Eu@CDs-MIMs) was successfully prepared based on a Eu complex-doped polyvinylidene fluoride membrane for the selective, rapid and on-site visual detection of norfloxacin (NOR). The formation of surface-imprinted polymer-containing carbon dots (CDs) improves the roughness and hydrophilicity of Eu@CDs-MIMs. Fluorescence lifetimes and UV absorption spectra verified that the fluorescence enhancement of CDs is based on the synergistic effect of charge transfer and hydrogen bonding between CDs and NOR. The fluorescent test strip showed a linear fluorescent response within the concentration range of 5-50 nM with a limit of detection of 1.35 nM and a short response time of 1 min. In comparison with filter paper-based test strips, Eu@CDs-MIMs exhibit a brighter and more uniform fluorescent color change from red to blue that is visible to the naked eye. Additionally, the applied ratio fluorescent test strip was combined with a smartphone to translate RGB values into concentrations for the visual and quantitative detection of NOR and verified the detection results using high-performance liquid chromatography. The portable fluorescent test strip provides a reliable approach for the rapid, visual, and on-site detection of NOR and quinolones.

Designing Yolk-Shell Nanostructures for Reversible Water-Vapor-Responsive Dual-Mode Switching of Fluorescence and Structural Color.

Metal halide perovskites offer ample opportunities to develop advanced optoelectronic devices. This work showcases that the integration of metal halide perovskites into metal oxide nanoshells with controllable interior cavities can enable water-vapor-responsive dual-mode switching of fluorescence and structural color. Through a ship-in-a-bottle method to introduce a controlled amount of CsPbBr3 into MnO2 nanoshells, we have designed CsPbBr3@MnO2 yolk-shell nanostructures, which can uptake a defined amount of water to exhibit rapid (less than 1 s) and reversible (≥100 cycles) responses in both fluorescence on-off and color change when exposed to dynamic water vapor. These responses originate from the water-triggered phase transformation of CsPbBr3 to CsPb2Br5 and the structural color change of the MnO2 shell. The altered electronic and bonding structure at the oxide-halide interface, rapid water accumulation in the yolk-shell cavity, and protective effect of the oxide shell facilitate the reversible transformations. The response characteristics of the yolk-shell nanostructures have been further demonstrated in fabricating patterned films capable of multiple fluorescence/structural color responses, highlighting their potential for applications in advanced anticounterfeiting and encryption.

A Ratiometric Biosensor Containing Manganese Dioxide Nanosheets and Nitrogen-Doped Quantum Dots for 2,4-Dichlorophenoxyacetic Acid Monitoring.

Nanomaterials are desirable for sensing applications. Therefore, MnO2 nanosheets and nitrogen-doped carbon dots (NCDs) were used to construct a ratiometric biosensor for quantification of 2,4-dichlorophenoxyacetic acid. The MnO2 nanosheets drove the oxidation of colorless o-phenylenediamine to OPDox, which exhibits fluorescence emission peaks at 556 nm. The fluorescence of OPDox was efficiently quenched and the NCDs were recovered as the ascorbic acid produced by the hydrolyzed alkaline phosphatase (ALP) substrate increased. Owing to the selective inhibition of ALP activity by 2,4-D and the inner filter effect, the fluorescence intensity of the NCDs at 430 nm was suppressed, whereas that at 556 nm was maintained. The fluorescence intensity ratio was used for quantitative detection. The linear equation was F = 0.138 + 3.863·C 2,4-D (correlation coefficient R2 = 0.9904), whereas the limits of detection (LOD) and quantification (LOQ) were 0.013 and 0.040 μg/mL. The method was successfully employed for the determination of 2,4-D in different vegetables with recoveries of 79%~105%. The fluorescent color change in the 2,4-D sensing system can also be captured by a smartphone to achieve colorimetric detection by homemade portable test kit.

Tetraphenylethylene fused pyrrolo[3,2-b]pyrrole derivatives with reversible mechanofluorochromic and aggregation-induced emission enhancement characteristics

Modification on typical of molecular unit with aggregation-induced emission (AIE)/aggregation-induced emission enhancement (AIEE) can play a important role in obtaining solid-state fluorescence materials and mechanofluorochromic (MFC) materials. We utilize the multicomponent reaction of TPE-containing aldehyde, arylamine and butane-2,3-dione in the presence of iron(III) perchlorate to design and synthesize two novel MFC materials by combination of the tetraphenylethylene (TPE) and pyrrolo [3,2-b]pyrrole core units. Investigation of CHW-1 and CHW-2 aggregation-induced emission behaviors indicated that these materials all exhibited AIEE properties. Subsequent mechanochromic luminescence tests exhibited reversible mechanochromism natures that involve fluorescent color change from green to yellow (Grinding-induced spectral shift (△λ): 35 nm and 38 nm, respectively). Then the datas (including SEM, PXRD and DSC) revealed that this mechanofluorochromism was ascribed to the transformation of crystal state to the amorphous form. Moreover, CHW-1 and CHW-2 could be applied for optical recording devices and security printing.

Dipyridine‐Thiophene‐Based Fluorescent Probe: Synthesis, Crystal Structure, and Selective Recognition of Cu2+ Ions

AbstractAn efficient fluorescent sensory platform was designed and synthesized for recognition of copper ion (Cu2+) in presence over other competing ions. The probe DTBPA 1 was displayed fluorescence color change upon addition of Cu2+ ion which was also characterized by spectroscopic techniques especially the fluorescence and colorimetric methods. The probe showed turn‐off fluorescence response to the Cu2+ ion. The limit of detection for the probe was found to be 0.789 μM while binding stoichiometry for the probe to metal ion was found to be 2 : 1 tested by Jobs analysis. The binding constant for the probe was found to be 1.13×106 M−1. Further the probe was utilized for detection of trace amount of Cu2+ ion in real water sample with recoveries 98.24 %~104 %. The molecule was further utilized in test strip application. The calculated fluorescence quantum yield was found to be 3.2. The theoretically Density Functional Theory (DFT) calculations were performed for the probe using Gaussian 16 ab initio/DFT quantum chemical simulation and the DFT calculations were supporting the experimental findings.

Synthesis and application of hypochlorite ratiometric fluorescence probe based on cellulose

Cellulose is the most abundant natural polymer with good biocompatibility and easy modification characteristics. In this paper, a novel cellulose fluorescence probe CNS for detecting ClO− was prepared by modifying microcrystalline cellulose (MCC). The fluorescence detection results indicate that CNS exhibits a highly specific “ratiometric” and “colorimetric” fluorescence response to ClO−. In the presence of ClO−, the fluorescence color changes from green to cyan. In addition, the color of the solution changes from yellow to colorless, which can be observed with the “naked eye”. Considering the good selectivity and anti-interference ability of CNS, the probe can be used for the detection of ClO− in real water samples. Importantly, CNS composite films and test papers were prepared and showed practicability in the detection of ClO−, highlighting its broad application potentials.

Luminescent Porous Organic Crystals for Adsorptive Separation of Toluene and Methylcyclohexane.

A butterfly-shaped phenothiazine derivative, PTTCN, was synthesized to obtain pure organic porous crystals for the highly efficient absorptive separation of toluene (Tol) and methylcyclohexane (Mcy). Due to the presence of three polar cyano groups and nonplanar conformation, these molecules self-assembled into a hydrogen-bonded organic framework (X-HOF-5) with distinct cavities capable of accommodating Tol molecules through multiple hydrogen-bonding interactions. Upon solvent removal via heating, the activated X-HOF-5 retained its cavity structure albeit with altered stacking arrangements, accompanied by a remarkable fluorescent color change from cyan to green. X-HOF-5a can undergo a phase transformation into X-HOF-5 upon reabsorption of Tol, while exhibiting no accommodation of Mcy due to the weak intermolecular interaction between PTTCN and Mcy. This suggests that the activated HOF material prefers Tol over Mcy. Moreover, X-HOF-5a may selectively accommodate Tol in a Tol/Mcy equimolar mixture, and the purity of Tol can reach 97% after release from the framework. Additionally, it is noteworthy that the HOF material exhibits recyclability without any discernible loss in performance.

Fluorescence color change of supramolecular polymer networks controlled by crown ether-cation recognition.

We report a fluorescent supramolecular polymer networks (SPNs) system based on crown ether-cation recognition. The polymer side chains bear ammonium cations, which can be recognized by host molecules with a B15C5 unit and a quinoline group at each end. The quinoline group makes the host molecule exhibit blue fluorescence. After the formation of SPNs, the recognition of the crown ether-cation transforms the blue fluorescence into yellow fluorescence. The accompanying fluorescence color change during the formation of SPNs makes it with potential applications in the fields of display, printing, information storage, and bioimaging.

Dual-mode detection of 2,6-pyridinedicarboxylic acid based on the enhanced peroxidase-like activity and fluorescence property of novel Eu-MOFs.

2,6-Pyridinedicarboxylic acid (DPA) is a significant biomarker of anthrax, which is a deadly infectious disease for human beings. However, the development of a convenient anthrax detection method is still a challenge. Herein, we report a novel europium metal-organic framework (Eu-MOF) with an enhanced peroxidase-like activity and fluorescence property for DPA detection. The Eu-MOF was one-step synthesized using Eu3+ ions and 2-methylimidazole. In the presence of DPA, the intrinsic fluorescence of Eu3+ ions is sensitized, the fluorescence intensity linearly increases with an increase in DPA concentration, and the fluorescence color changes from blue to purple. Simultaneously, the peroxide-like activity of the Eu-MOF is enhanced by DPA, which can promote the oxidation of TMB to oxTMB. The absorbance values increase linearly with DPA concentrations, and the colorimetric images change from colorless to blue. The dual-mode detection of DPA has good sensitivity with a colorimetric detection limit of 0.67 μM and a fluorescent detection limit of 16.67 nM. Moreover, a simple detection method for DPA was developed using a smartphone with the RGB analysis system. A portable kit with standard color cards was developed using paper test strips. The proposed methods have good practicability for DPA detection in real samples. In conclusion, the developed Eu-MOF biosensor offers a valuable and general platform for anthrax diagnosis.

Electrothermally powered synergistic fluorescence-colour/3D-shape changeable polymer gel systems for rewritable and programmable information display.

Intelligent luminescent materials for rewritable and programmable information display have long been expected to be used to address potential environmental concerns stemming from the extensive use of disposable displays. However, most reported luminescence-colour changeable examples are chemically responsive and not well programmed to sequentially deliver different information within a single system. Additionally, they may suffer from residual chemical accumulation caused by the repeated addition of chemical inks and usually have poor rewritability. Herein, we draw inspiration from the bioelectricity-triggered information display mechanism of chameleon skin to report a robust electrothermally powered polymer gel actuator consisting of one soft conductive graphene/PDMS film and one humidity-responsive fluorescence-colour changeable CD-functionalized polymer (PAHCDs) gel layer. Owing to the good electrocaloric effect of the bottom graphene film and excellent hygroscopicity of the top PAHCDs gel layer, the as-designed actuator could be facilely controlled to exhibit reversible and synergistic 3D-shape/fluorescence-colour changeable behaviours in response to alternating electricity and humidity stimuli. On this basis, robust rewritable information display systems are fabricated, which enable not only on-demand delivery of written information, but also facile rewriting of lots of different information by the synergization of electroheat/humidity-triggered local 3D-deformation and fluorescence-colour changes. This work opens new avenues of research into rewritable information display and potentially inspires the future development of intelligent luminescent materials.

An AIE probe for simultaneous monitoring of endogenous and exogenous hypochlorite and Zn2+ at dual channels in living cells.

Zn2+ and ClO- may be associated with a variety of pathologies, and their simultaneous measurement is crucial for disease diagnosis and environmental protection. In this work, we synthesized an independent AIE probe, HNTE, through a one step reaction. The probe HNTE displayed a distinctive fluorescence color change from deep yellow to blue for ClO- and to green for Zn2+. More importantly, the probe HNTE could simultaneously detect endogenous and exogenous ClO- and Zn2+ in living cells colorimetrically via the blue and green channels.

A distinctive and proficient fluorescent switch for ratiometric recognition of the menacing cyanide ion: biological studies on MDA-MB-231 cells.

A new fluorescent ratiometric switch (BOHB) was developed for swift and selective detection of cyanide ions in aqueous media without any interference from other competitive anions. Upon gradual addition of cyanide ions into the probe solution, a prominent fluorescence color change from yellow to cyan was observed under a UV chamber. The fluorescence changes thus observed were ratiometric, and the detection limit of this new probe was found to be (22.1 ± 0.89) μM, suggesting that the efficiency of BOHB for the detection of cyanide ions is brilliant even at a minute level. The blue shift in fluorescence intensity upon the addition of cyanide ions was attributed to the deprotonation mechanism of acidic protons present in BOHB. This phenomenon was further explored using 1H-NMR study, which supported the mechanism. Further, stability study was performed over a period of 5 days to prominently establish the stability of BOHB. The probe is also highly capable of recognizing CN- within a very short time-span (almost 15 seconds), thereby making it a brilliant fluorescent switch for the swift recognition of CN-. Furthermore, BOHB was employed for real water sample analysis to display its practical application. Besides, the easy-to-prepare dipstick experiment provides a simple, reusable and recyclable protocol for the suitable qualitative identification of CN-. Lastly, triple negative breast adenocarcinoma (MDA-MB-231) cells were made susceptible to CN- sensing in a biological system, thereby making BOHB a biomarker tool.

Detection of intracellular microRNA-21 for cancer diagnosis by a nanosystem containing a ZnO@polydopamine and DNAzyme probe.

MicroRNAs (miRNAs) are a series of single-stranded non-coding ribonucleic acid (RNA) molecules which associated closely with various human diseases. Efficient strategies for detecting miRNAs are of great significance to cancer diagnosis and prognosis. Here we provide a novel nanosystem that can be applied for the detection of miRNAs. The nanosystem consists of a single-stranded deoxyribonucleic acid (DNA) probe and a probe carrier. The DNA probe was designed based on a deoxyribozyme (DNAzyme) with several necessary functional sequences and two fluorescent dyes labeled at proper sites. The ZnO@polydopamine (ZnO@PDA) nanomaterial serves not only as a probe carrier, but also as a supplier of Zn2+ that can activate the DNAzyme. The DNA probe will undergo a conformation alteration induced by miRNA-21, which then trigger the DNAzyme catalyzed self-cleavage reaction with the assist of Zn2+ provided by ZnO decomposition under weak acid environment. A change of fluorescent color will occur due to the interruption of fluorescence resonance energy transfer between the two fluorescent dyes, and the dissociated miRNA-21 can repeatedly induce the above responses to amplify the fluorescence signal. The feasibility of the whole procedure was demonstrated by various experiments. This nanosystem showed a good selectivity towards miRNA-21, and under the optimal incubation time of 2 hours, a good linear relationship was obtained in a concentration range of 0.01-2.0 nM with a detection limit of 3.8 pM. In in vivo detection, an obvious fluorescence color change from red to green can be observed in the presence of miRNA-21. The results proved that this miRNA detection strategy has a broad application prospect in tumor diagnosis and miRNA related biological studies.

Broad application prospects near-infrared carbonized polymer dots combined with machine learning for the detection of Cu2+ in seawater and aquatic products

A highly selective and sensitive fluorescence sensor, using the decision tree (DT) machine learning, was successfully fabricated for the quantitative detection of Cu2+, which is based on near-infrared carbonized polymer dots (r-CPDs). Using o-phenylenediamine and 1,3,5-benzene tricarboxylic acid as raw materials first to synthesize the r-CPDs (quantum yield of 32.9%), which pyrrole NH ring can specifically form metal chelates with Cu2+ hiding the electron leap result in the fluorescence burst, by a one-step hydrothermal synthesis method. Furthermore, the fluorescence sensor based on the r-CPDs was fabricated for ultra-sensitively detect Cu2+ in the range of 0.5–80.0 nM (R2 =0.9986) in aqueous environments and aquatic products with relative standard deviation (RSD) below 4.4% and a limit of detection (LOD) of 0.24 nM. Combined with the machine learning algorithm model, the r-CPDs fluorescence color changes accompanied by different Cu2+ concentrations were classified. A self-developed smartphone application equipped with 3D printing technology to prepare portable cartridges successfully applied to rapid real-time detection of trace Cu2+ in various practical samples. The experimental results show that the method has not only convenient for calculating but also accurate. Generally, this study displayed a perfect fusion of r-CPDs fluorescence sensors with machine learning which applied to the determination of Cu2+ in environmental and aquatic products.

Gelation behavior and solvent-, thermo, acid-fluorochromic behavior of acylhydrazone derivative

Recently, there has been significant interest in multi-functional organic materials due to their unique properties and potential applications. One such material is PAD, an acyl-hydrazone derivative substituted with –OH and a triphenylamine group. PAD is capable of forming stable organogels in various solvents such as benzene, chlorobenzene, dichloromethane, and 1,2-dichloroethane. The organogels formed in benzene, dichloromethane, and 1,2-dichloroethane exhibit gelation-induced emission enhancement (GIEE) behavior, while not very obvious for chlorobenzene organogel. Additionally, PAD displays fluorescence switching behavior in response to changes in solvent and temperature. PAD-A emits blue fluorescence around 460 nm, while PAD-T emits green fluorescence at 485 nm. Interestingly, when PAD-T is annealed at 170 °C for 15 min, the fluorescence color changes from green to blue, and the emission wavelength shifts from 485 nm to 444 nm. Furthermore, regardless of whether it is in a solid, organogel, or solution form, PAD exhibits fluorescence quenching properties when exposed to acid (TFA) due to the protonation effect.

Peptide‐Based Organic‐Inorganic Hybrid Self‐Assemblies for Ultrasensitive and Visual Detection of Heparin

AbstractAccurate point‐of‐care testing (POC) of low molecular weight heparin (LMWH) can efficiently promote its rational use in the prevention and treatment of thromboembolic diseases but still remain a key challenge. Herein, a peptide‐derived supramolecular self‐assembly system is reported for ultrasensitive and visual detection of LMWH. Two different peptides are designed and modified by gold nanocluster (AuNC) and tetraphenylethene (TPE), respectively, to co‐assemble into nanoparticles, enabling the loading and co‐recognition of LMWH. Owing to two‐wavelength emission from the co‐assemblies at 624 and 460 nm that is highly sensitive to LMWH, such assemblies realize ratio‐type detection of LMWH. The sensitivity of the AuNC‐peptide to LMWH significantly increases when co‐assembling with TPE‐peptide, while that of TPE‐peptide maintains in a high level, enabling a balanced and ultrahigh sensitivity of both two fluorophores. Such self‐assemblies reach an extreme limit of detection of 0.0004 IU mL−1 and realize dramatic fluorescence color change when loading trace concentration of LMWH, which can be simply distinguished by naked‐eye. Thus, by preparing Pep2@AuNC/TPE‐Pep1 test strips the POC testing of LMWH in real thrombus patient samples has achieved. It provides a promising tool for on‐site and real‐time monitoring of anticoagulation therapy to guide LMWH titration into the therapeutic window.

Molecular Accessibility and Diffusion of Resorufin in Zeolite Crystals.

Invited for the cover of this issue is the group of Professor Bert Weckhuysen at Utrecht University. The image depicts the change in fluorescence color of a resorufin dye molecule when it is protonated and confined inside the micropores of zeolite-β. Read the full text of the article at 10.1002/chem.202302553.