A colorimetric and ratiometric fluorescent sensor for sequentially detecting Cu2+ and arginine based on a coumarin–rhodamine B derivative and its application for bioimaging

In this work, a colorimetric and ratiometric fluorescent sensor based on a coumarin–rhodamine B hybrid for the sequential recognition of Cu²⁺ and arginine (Arg) via the FRET mechanism was designed and synthesized. With the addition of Cu²⁺, the solution displayed a colorimetric change from pale yellow to pink which is discernible by the naked eye. Additionally, the fluorescence intensities of the sensor exhibited ratiometric changes for the detection of Cu²⁺ at 490 and 615 nm under a single excitation wavelength of 350 nm, which corresponded to the emissions of coumarin and rhodamine B moieties, respectively. The fluorescence color change could be visualized from blue to pink. The limits of detection were determined to be as low as 0.50 and 0.47 μM for UV-vis and fluorescence measurements, respectively. More importantly, the sensor not only can recognize Cu²⁺ and form a sensor-Cu²⁺ complex but can also sequentially detect Arg with the resulting complex. The detection limits for Arg were as low as 0.60 μM (UV-vis measurement) and 0.33 μM (fluorescence measurement), respectively. A fluorescence imaging experiment in living cells demonstrated that the fabricated sensor could be utilized in ratiometric fluorescence imaging towards intracellular Cu²⁺, which is promising for the detection of low-level Cu²⁺ and Arg with potentially practical significance.

A FRET-based colorimetric and ratiometric coumarin–rhodamine B fluorescent sensor was designed, and its sensing behaviors for sequentially detecting Cu²⁺ and arginine were studied systematically.     

An ‘‘off–on–off’’ sensor for sequential detection of Cu2+ and hydrogen sulfide based on a naphthalimide–rhodamine B derivative and its application in dual-channel cell imaging

A novel colorimetric and fluorometric sensor with unique dual-channel emission to sequentially detect Cu²⁺ and hydrogen sulfide (H₂S) was synthesized from naphthalimide–rhodamine B through the PET and FRET mechanism. The sensor showed a selective “off–on” fluorescence response with a 120-fold increase toward Cu²⁺, and its limits of detection were 0.26 μM and 0.17 μM for UV-vis and fluorescence measurements, respectively. In addition, 1–Cu²⁺ was an efficient “on–off” sensor to detect H₂S with detection limits of 0.40 μM (UV-vis measurement) and 0.23 μM (fluorescence measurement), respectively. Furthermore, the sensor can also be used for biological imaging of intracellular staining in living cells. Therefore, the sensor should be highly promising for the detection of low level Cu²⁺ and H₂S with great potential in many practical applications.

A novel colorimetric and fluorometric sensor with unique dual-channel emission to sequentially detect Cu²⁺ and hydrogen sulfide (H₂S) was synthesized from naphthalimide–rhodamine B through the PET and FRET mechanism.     

A novel coumarin-based colorimetric and fluorescent probe for detecting increasing concentrations of Hg2+in vitro and in vivo

Mercury has complex biological toxicity and can cause a variety of physiological diseases and even death, so it is of great importance to develop novel strategies for detecting trace mercury in environmental and biological samples. In this work, we designed a new coumarin-based colorimetric and fluorescent probe CNS, which could be obtained from inexpensive starting materials with high overall yield in three steps. Probe CNS could selectively respond to Hg²⁺ with obvious color and fluorescence changes, and the presence of other metal ions had no effect on the fluorescence changes. Probe CNS also exhibited high sensitivity against Hg²⁺, with a detection limit as low as 2.78 × 10⁻⁸ M. More importantly, the behavioral tracks of zebrafish had no obvious changes upon treatment with 10 μM probe CNS, thus indicating its low toxicity. The probe showed potential application value and was successfully used for detecting Hg²⁺ in a test strip, HeLa cells and living zebrafish larvae.

Mercury has complex biological toxicity and can cause a variety of physiological diseases and even death, so it is of great importance to develop novel strategies for detecting trace mercury in environmental and biological samples.     

A highly selective colorimetric fluorescent probe for detection of Hg2+ and its application on test strips

An efficient fluorescent probe Pyr-Rhy based on pyrazole was developed, which can detect Hg²⁺ in water. Its fluorescence properties were studied by UV-vis and fluorescence spectroscopy, and the study results indicated that this probe can selectively detect Hg²⁺via complexation reaction, and then cause a remarkable color change from colorless to pink and a strong fluorescence enhancement can be observed. Furthermore, this probe showed high sensitivity with the detection limit down to 2.07 × 10⁻⁸ M, and its stoichiometric ratio toward Hg²⁺ ions was 1 : 1. The sensing mechanism was investigated by Job''s plot ¹H NMR titrations, and FT-IR spectra analysis, which demonstrated a chelation-enhanced fluorescence (CHEF) mechanism. More importantly, obvious color changes of sensor Pyr-Rhy can be observed when it was impregnated on filter paper testing strips and immersed in Hg²⁺ solution (water as solution), indicating its potential application for trace Hg²⁺ detection in environmental samples.

An efficient fluorescent probe Pyr-Rhy based on pyrazole was developed, which can detect Hg²⁺ in water.     

A solvent-dependent chemosensor for fluorimetric detection of Hg2+ and colorimetric detection of Cu2+ based on a new diarylethene with a rhodamine B unit

A novel solvent-dependent chemosensor 1o based on a diarylethene containing a rhodamine B unit has been designed. It could be used as a dual-functional chemosensor for selective detection of Hg²⁺ and Cu²⁺ by monitoring the changes in the fluorescence and UV-vis spectral in different solvents. A striking fluorescence enhancement at 617 nm was observed in DMSO upon the addition of Hg²⁺. However, 1o showed a remarkable absorption band appeared with maximum absorption at 555 nm after the addition of Cu²⁺ in THF. The results of ESI-MS spectra and Job''s plot confirmed a 1 : 1 binding stoichiometry between 1o and the two ions. The limits of detection of Hg²⁺ and Cu²⁺ were determined to be 0.14 μM and 0.51 μM, respectively. A 1 : 2 demultiplexer circuit was constructed by using UV light as data input, Cu²⁺ as the address input, and the absorbance at 555 nm and the absorbance ratio of (A₆₀₃/A₂₇₄) as the dual data outputs.

A novel solvent-dependent chemosensor based on a diarylethene derivative for fluorescent “turn-on” recognition of Hg²⁺ and colorimetric detection of Cu²⁺ was synthesized, its multi-controllable photoswitchable behaviors with light and chemical stimuli were investigated.     

A ratiometric fluorescence probe for the selective detection of H2S in serum using a pyrene-DPA–Cd2+ complex

A ratiometric and selective hydrogen sulfide (H₂S) detection probe was proposed based on the pyrene-DPA–Cd²⁺ complex through the metal ion displacement approach (MDA) mechanism. While most MDA-based fluorescence probes with paramagnetic Cu²⁺ have focused on the development of a simple turn-on sensor using the broad spectral range of fluorescence enhancement, this ratiometric probe exhibited unchanged monomer emission as a built-in internal reference with an increase in excimer emission with added H₂S. The demonstrated probe showed a rapid response (within 1 min) and a high sensitivity, with 70 nM as the limit of detection. The selectivity for H₂S over cysteine, homocysteine and glutathione was confirmed, and reliable fluorescence enhancement, which could be monitored by the naked eye, was observed upon irradiation with handheld UV light. In addition, this detection system was successfully applied to detect H₂S in human serum without interference from biological molecules.

The pyrene-DPA–Cd²⁺ complex is demonstrated as a ratiometric fluorescence probe for selective hydrogen sulfide detection in serum based on a metal displacement approach.     

Correction: A highly selective ratiometric fluorescent probe for the cascade detection of Zn2+ and H2PO4− and its application in living cell imaging

Correction for ‘A highly selective ratiometric fluorescent probe for the cascade detection of Zn²⁺ and H₂PO₄⁻ and its application in living cell imaging’ by Kui Du et al., RSC Adv., 2017, 7, 40615–40620.

Affiliation c was incomplete in the original publication; the corrected version is shown below.The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.     

An aggregation-induced emission-based fluorescence turn-on probe for Hg2+ and its application to detect Hg2+ in food samples

In this work, we presented a new tetraphenylethene-derived fluorescent probe TPE-M for Hg²⁺ detection in an aqueous solution. Probe TPE-M is molecularly dissolved in CH₃OH/PBS (20 mM, pH = 7.4) (3 : 7, v/v) mixed solution and is almost non-emissive. Reaction of TPE-M with Hg²⁺ leads to release of an AIE-active precursor 4, and results in a significant fluorescence enhancement. The Hg²⁺ recognition process has some distinct advantages including rapid response, high selectivity and sensitivity, strong anti-interference ability, and a low detection limit (4.16 × 10⁻⁶ M). Moreover, the probe is applicable to detect Hg²⁺ in real food samples such as shrimp, crab and teas, suggesting the practical applicability of TPE-M.

A new AIE-based fluorescent probe TPE-M for Hg²⁺ detection in an aqueous solution has been developed.     

A dual colorimetric probe for rapid environmental monitoring of Hg2+ and As3+ using gold nanoparticles functionalized with d-penicillamine

A highly sensitive and selective colorimetric assay for the dual detection of Hg²⁺ and As³⁺ using gold nanoparticles (AuNPs) conjugated with d-penicillamine (DPL) was developed. When Hg²⁺ and As³⁺ ions coordinate with AuNP-bound DPLs, the interparticle distance decreases, inducing aggregation; this results in a significant color change from wine red to dark midnight blue. The Hg4f and As3d signals in the X-ray photoelectron spectra of Hg²⁺ (As³⁺)-DPL-AuNPs presented binding energies indicative of Hg²⁺–N(O) and As³⁺–N(O) bonds, and the molecular fragment observed in time-of-flight secondary ion mass spectra confirmed that Hg²⁺ and As³⁺ coordinated with two oxygen and two nitrogen atoms in DPL. The detection of Hg²⁺ and As³⁺ can be accomplished by observing the color change with the naked eye or by photometric methods, and this was optimized to provide optimal probe sensitivity. The assay method can be applied for environmental monitoring by first selectively quantifying Hg²⁺ in water samples at pH 6, then estimating the As³⁺ concentration at pH 4.5. The efficiency of the DPL-AuNP probe was evaluated for the sequential quantification of Hg²⁺ and As³⁺ in tap, pond, waste, and river water samples, and absorbance ratios (A₇₃₀/A₅₂₅) were correlated with Hg²⁺ and As³⁺ concentrations in the linear range of 0–1.4 μM. The limits of detection in water samples were found to be 0.5 and 0.7 nM for Hg²⁺ and As³⁺, respectively. This novel probe can be utilized for the dual determination of Hg²⁺ and As³⁺, even in the presence of interfering substances in environmental samples.

A highly sensitive and selective colorimetric assay for the dual detection of Hg²⁺ and As³⁺ using gold nanoparticles (AuNPs) conjugated with d-penicillamine (DPL) was developed.     

A colorimetric and fluorescent chemosensor for Hg2+ based on a photochromic diarylethene with a quinoline unit

A new colorimetric and fluorescent ‘on–off’ chemosensor, 1O, based on a photochromic diarylethene with a quinoline unit was designed and synthesized. The chemosensor 1O demonstrated selective and sensitive detection of Hg²⁺ ions in the presence of other competitive metal ions in acetonitrile. The stoichiometric ratio of the sensor 1O for Hg²⁺ was determined to be 1 : 1, and the limit of detection of the probe 1O was calculated to be 56.3 nM for Hg²⁺. In addition, a molecular logic circuit with four inputs and one output was successfully constructed with UV/vis light and metal-responsive behavior. ESI-MS spectroscopy, Job''s plot analysis, and ¹H NMR titration experiments confirm the binding behavior between 1O and Hg²⁺.

A new colorimetric and fluorescent ‘on–off’ chemosensor, 1O, based on a photochromic diarylethene with a quinoline unit was designed and synthesized.     

Al(iii)-responsive “off–on” chemosensor based on rhodamine derivative and its application in cell imaging

In this work, a new rhodamine chemosensor (P) with excellent photochromic properties upon vis irradiation was designed and synthesized. The fabricated chemosensor P could detect Al³⁺via the opening of the spirolactam ring of the rhodamine unit with high selectivity and sensitivity. The spirolactam ring opening was confirmed by NMR and infrared spectroscopy. Upon binding with Al³⁺, the generated 1 : 1 P-Al³⁺ complex, confirmed by Job''s plot titrations and mass spectrometry analysis, could exhibit a remarkable fluorescence enhancement with a limit of detection (LOD) of 0.16 μM. Furthermore, the sensing of P to Al³⁺in vivo was also studied quantitatively and qualitatively in detail, and the results showed that the coordination between P with Al³⁺ was reversible in living cells.

In this work, a new rhodamine chemosensor (P) with excellent photochromic properties upon vis irradiation was designed and synthesized.     

Synthesis,structure–fluorescence relationships and density functional theory studies of novel naphthalimide–piperazine–pyridine-based polystyrene sensors for Hg(ii) detection

Two novel naphthalimide–piperazine–pyridine-based polystyrene solid-phase fluorescent sensors PS-NA and PS-ND with different lengths of the linker were synthesized and shown to be able to detect Hg(ii) ions. Their structures were characterized by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) analysis. Fluorescence properties, including response time, pH effects, fluorescence titration, metal ion selectivity and regeneration, were investigated and compared. Sensor PS-NA displayed a higher fluorescence response to Hg(ii) than PS-ND, with a lower detection limit of 1.01 μM. The detection mechanism involving the Hg(ii) chelation-induced photo-induced electron transfer (PET) was proposed with the aid of density functional theory (DFT) calculations. Sensors PS-NA and PS-ND with seven other similar sensors from our previous studies were collected together for thorough structure–fluorescence relationship (SFR) studies. Sensor PS-NA being recyclable and environmentally friendly was successfully employed in the fluorescence detection of Hg(ii) in real water samples, indicating its good potential in practical application.

Naphthalimide-appended polystyrene fluorescent sensors.     

A pH tuning single fluorescent probe based on naphthalene for dual-analytes (Mg2+ and Al3+) and its application in cell imaging

In this study, a naphthalene Schiff-base P which serves as a dual-analyte probe for the quantitative detection of Al³⁺ and Mg²⁺ has been designed. The proposed probe showed an ‘‘off–on’’ fluorescent response toward Al³⁺ in ethanol–water solution (1 : 9, v/v, pH 6.3, 20 mM HEPES) over other metal ions and anions, while the detection by the probe could be switched to Mg²⁺ by regulating the pH from 6.3 to 9.4. The sensing mechanisms of P to Al³⁺/Mg²⁺ are attributed to inhibition of the photo-induced electron transfer (PET) process by the formation of 1 : 1 ligand–metal complexes. More importantly, the probe was applied successfully in living cells for the fluorescent cell-imaging of Al³⁺ and Mg²⁺.

In this study, a naphthalene Schiff-base P which serves as a dual-analyte probe for the quantitative detection of Al³⁺ and Mg²⁺ has been designed.     

A ratiometric fluorescent sensor for detection of metformin based on terbium–1,10-phenanthroline–nitrogen-doped-graphene quantum dots

Metformin (MTF), an effective biguanide and oral antihyperglycemic agent, is utilized to control blood glucose levels in patients with type II diabetes mellitus, and the determination of its concentration in biological fluids is one of the main issues in pharmacology and medicine. In this work, highly luminescent nitrogen-doped graphene quantum dots (N-GQDs) were modified using terbium (Tb³⁺)–1,10-phenanthroline (Phen) nanoparticles (NPs) to develop a dual-emission ratiometric fluorescent sensor for the determination of MTF in biological samples. The synthesized N-GQDs/Tb–Phen NPs were characterized using different techniques to confirm their physicochemical properties. The N-GQDs/Tb–Phen NPs showed two characteristic emission peaks at 450 nm and 630 nm by exciting at 340 nm that belong to N-GQDs and Tb–Phen NPs, respectively. The results indicated that the emission intensity of both N-GQDs and Tb–Phen NPs enhanced upon interaction with MTF in a concentration-dependent manner. Also, a good linear correlation between the enhanced fluorescence intensity of the system and MTF concentration was observed in the range of 1.0 nM–7.0 μM and the limit of detection (LOD) value obtained was 0.76 nM. In addition, the prepared probe was successfully used for the estimation of MTF concentration in spiked human serum samples. In conclusion, the reported dual-emission ratiometric fluorescent sensor can be used as a sensitive and simple fluorimetric method for the detection of MTF in real samples.

Shcematic representation of the MTF detection by an enhancing mechanism.     

A ratiometric fluorescent probe for the detection of β-galactosidase and its application

Herein, a coumarin fluorescent probe (Probe 1) was developed for the ratiometric detection of β-galactosidase (β-gal) activity. The detection range was 0–0.1 U mL⁻¹ and 0.2–0.8 U mL⁻¹, and the limit of detection (LOD) was 0.0054 U mL⁻¹. Moreover, the luminous intensity of Probe 1 increased gradually with increase in β-gal activity. It could be observed under 254 nm UV irradiation by the naked eye. Furthermore, this method only required a small amount of sample (20 μL) and a short analytical time (30 min) for the detection of β-gal activity with a low LOD. Probe 1 was successfully used to detect β-gal activity in real fruit samples, and can be applied to the quantitative and qualitative detection of β-gal activity.

A ratiometric fluorescent probe was successfully used as a tool to determine β-galactosidase activity in fruits.     

A real-time ratiometric fluorescent probe for imaging of SO2 derivatives in mitochondria of living cells

A real-time ratiometric fluorescent probe (IN-CZ) for highly selective detection of sulfite was designed and synthesized, which is based on modulating the intramolecular charge transfer (ICT) of the hemicyanine dye platform. The mechanism of using the probe is mainly through the Michael addition that occurs between IN-CZ and sulfite with a detection limit of 2.99 × 10⁻⁵ M. IN-CZ displays a fast response (within 1 minute) and is highly selective for SO₃²⁻/HSO₃⁻ over ROS, biologically relevant ions, biological mercaptans and other reactive species. More importantly, IN-CZ was suitable for ratiometric fluorescence imaging in living cells, by real-time monitoring of SO₃²⁻/HSO₃⁻ changes in mitochondria targeted in living cells.

A real-time ratiometric fluorescent probe (IN-CZ) for highly selective detection of sulfite was designed and synthesized, which is based on modulating the intramolecular charge transfer of the hemicyanine dye platform.     

On-site,rapid and visual method for nanomolar Hg2+ detection based on the thymine–Hg2+–thymine triggered “double” aggregation of Au nanoparticles enhancing the Tyndall effect

This work describes a new nanosensor for the simple, rapid, portable, colorimetric analysis of mercury(ii) (Hg²⁺) ions by combining the sensitive Tyndall effect (TE) of colloidal Au nanoparticles (AuNPs) with specific thymine–Hg²⁺–thymine (T–Hg²⁺–T) coordination chemistry for the first time. For the TE-inspired assay (TEA), in the presence of Hg²⁺ in a sample, the analyte can selectively mediate the hybridization of three types of flexible single-stranded DNAs (ssDNAs) to form stable rigid double-stranded DNAs (dsDNAs) via the T–Hg²⁺–T ligand interaction. Subsequent self-assembly of the dsDNAs with terminal thiol groups on the AuNPs'' surfaces led to their “double” aggregation in addition to the lack of sufficient ssDNAs as the stabilizing molecules in a high-salt solution, resulting in a remarkably enhanced TE signal that positively relied on the Hg²⁺ level. The results demonstrated that such a TEA method enabled rapid naked-eye qualitative analysis of 625 nM Hg²⁺ within 10 min with an inexpensive laser pointer pen as an inexpensive handheld light source to generate the TE response. Making use of a smartphone for portable TE readout could further quantitatively detect the Hg²⁺ ions in a linear concentration range from 156 to 2500 nM with a limit of detection as low as 25 nM. Moreover, the developed equipment-free nanosensor was also used to analyze the Hg²⁺ ions in real samples including tap water, drinking water, and pond water, the obtained recoveries were within the range of 93.68 to 108.71%. To the best of our knowledge, this is the first report of using the AuNPs and functional nucleic acids to design a TE-based biosensor for the analysis of highly toxic heavy metal ions.

A new equipment-free colorimetric nanosensor was initially developed for quantitative point-of-need detection of nanomolar Hg²⁺ ions based on the enhancement in Tyndall effect of Au nanoparticles via their target-triggered “double” aggregation.     

A ratiometric fluorescence assay for acetylcholinesterase activity and inhibitor screening based on supramolecular assembly induced monomer–excimer emission transition of a perylene probe

A ratiometric fluorescence assay for acetylcholinesterase activity is established, which is based on controlled perylene probe assembly and monomer–excimer transition. In a buffer solution, a perylene probe with two negatively charged groups (PDI-DHA) mainly exists in monomeric form. In the presence of cationic lauroylcholine and lauric acid, PDI-DHA can form supramolecular assemblies and the perylene excimer emission can be observed. AChE can catalyze the hydrolysis of lauroylcholine to anionic lauric acid and choline. The hydrolysis process can trigger the breakdown of the supramolecular assemblies. The perylene excimer recovers to the monomeric form because of the de-aggregation of the probe. The excimer–monomer transition can be detected, and a ratiometric fluorescence assay for AChE activity and inhibitor screening is therefore established.

The PDI-DHA can aggregate to form supramolecular assemblies when mixed with lauroylcholine and lauric acid, and is employed as a ratiometric fluorescence probe for the detection of AChE activity.     

Two novel colorimetric fluorescent probes: Hg2+ and Al3+ in the visual colorimetric recognition environment

Two new dual channel Schiff base fluorescent probes, Tri-R6G and Tri-Flu, were synthesized, and can detect Hg²⁺ and Al³⁺, respectively. The two probes were characterized by FTIR, ¹H NMR, ¹³C NMR and HRMS, and their optical properties were detected by UV and FL. Test results showed the probes'' detection of Hg²⁺ and Al³⁺ compared to other metal ions (Ag⁺, Co²⁺, Cd²⁺, Mg²⁺, Cu²⁺, Ni²⁺, Ba²⁺, Pb²⁺, Cr³⁺, Al³⁺, Zn²⁺, Hg²⁺, K⁺, Ga²⁺ and Fe³⁺), respectively. Besides, the detection limits were determined to be 1.61 × 10⁻⁸ M and 1.15 × 10⁻⁸ M through the standard curve plot, respectively. The photoelectron transfer (PET) mechanism was guessed by the Job''s plot and the infrared titration. Corresponding orbital electron distribution and molecular geometry configurations of the compounds were predicted by density functional theory (DFT). In addition, the prepared test paper changed from white to pink when the target ion was detected. The color changed from colorless to pink in a solution having a concentration of 10⁻⁵ M.

Two new dual channel Schiff base fluorescent probes, Tri-R6G and Tri-Flu, were synthesized, and can detect Hg²⁺ and Al³⁺, respectively.     

A ratiometric fluorescent probe for detection of exogenous mitochondrial SO2 based on a FRET mechanism

A novel imidazo[1,5-a]pyridine-hemicyanine based ratiometric fluorescent probe for detection of mitochondrial SO₂ was designed and synthesized. The probe is based on a fluorescence resonance energy transfer (FRET) mechanism. It exhibits high selectivity and sensitivity towards SO₃²⁻ with a fast response time (3 min) and detection limit of 0.13 μM. Further, it showed low cytotoxicity and was successfully applied to image exogenous mitochondrial SO₂ in cells.

A novel imidazo[1,5-a]pyridine-hemicyanine based ratiometric fluorescent probe for detection of mitochondrial SO₂ was designed and synthesized.