The Novel Fluorescent Probe Toward Yttrium(III) and its Bioimaging.

In this paper, the novel fluorescence probe XP based on Schiff-base was designed, synthesized and characterized, which could detect Y3+selectively and sensitively. The recognition mechanism of XP toward Y3+ was studied by Job's plot and HRMS. It was investigated that stoichiometric ratio of the probe XP conjugated with Y3+ was 1:2. And the detection limit was calculated as 0.30 µM. In addition, Y3+ was recognized by the test paper made from XP. And the probe XP could detect  Y3+ selectively in Caenorhabditis elegans and the main organs of mice. Thus, XP was considered to have some potential for application in bioimaging.

Portable smartphone-assisted ratiometric fluorescent test paper based on one-pot synthesized dual emissive carbon dots for visualization and quantification of mercury ions.

Dual-emissive fluorescent carbon dots (CDs) were prepared through the solvothermal method with citric acid and urea as raw materials and dimethylformamide as the solvent. Two emission peaks were observed at 465 nm and 630 nm. Hg2+ could selectively quench the fluorescence at 630 nm, but the fluorescence intensity at 465 nm was less affected. Accordingly, a ratiometric fluorescence sensor for Hg2+ detection was developed, with a linear detection range of 0.5-40 µM and a limit of detection (LOD) of 37 nM. The dual-emissive CDs were loaded on the surface of the filter paper to fabricate Hg2+ detection test paper. The color of the test paper could be changed from pink purple to blue by the addition of Hg2+, and thus the qualitative and quantitative detection of Hg2+ could be realized. The concentration distinguishable by the naked eye reached 50 µM, and the quantitative detection range was 5-10,000 µM. This method shows excellent selectivity for Hg2+ and can be used to detect Hg2+ in real water samples, providing a highly potential sensing platform for rapid on-site detection of mercury ions.

A Turn-On Quinazolinone-Based Fluorescence Probe for Selective Detection of Carbon Monoxide.

Carbon monoxide (CO) is a toxic, hazardous gas that has a colorless and odorless nature. On the other hand, CO possesses some physiological roles as a signaling molecule that regulates neurotransmitters in addition to its hazardous effects. Because of the dual nature of CO, there is a need to develop a sensitive, selective, and rapid method for its detection. Herein, we designed and synthesized a turn-on fluorescence probe, 2-(2'-nitrophenyl)-4(3H)-quinazolinone (NPQ), for the detection of CO. NPQ provided a turn-on fluorescence response to CO and the fluorescence intensity at 500 nm was increased with increasing the concentration of CO. This fluorescence enhancement could be attributed to the conversion of the nitro group of NPQ to an amino group by the reducing ability of CO. The fluorescence assay for CO using NPQ as a reagent was confirmed to have a good linear relationship in the range of 1.0 to 50 µM with an excellent correlation coefficient (r) of 0.997 and good sensitivity down to a limit of detection at 0.73 µM (20 ppb) defined as mean blank+3SD. Finally, we successfully applied NPQ to the preparation of a test paper that can detect CO generated from charcoal combustion.

Ratiometric fluorescence sensor for sensitive detection of inorganic phosphate in environmental samples.

Fast, simple, and low-cost on-site visualized detection of inorganic phosphate (Pi) is in great demand since phosphate is the major reason of eutrophication. In this work, a ratiometric fluorescent probe composed by green carbon dots (GCDs) and red carbon dots (RCDs) has been established for high-sensitivity and selective sensing of Pi. A trend of color change from red to green is observed for the detection of Pi under ultraviolet light and the detection limit is 0.09 µM in the range of 0 to 55 µM. Fluorescent test paper prepared from the probe solution was successfully applied to semi-quantitative visual detection of Pi in real-world water and soil samples, which shows great real-world application potentials.

Smartphone-assisted ratiometric fluorescence sensing platform for the detection of doxycycline based on BCNO QDs and calcium ion.

A novel colorimetric and ratiometric fluorescence sensor has been established based on boron carbon oxynitride quantum dots (BCNO QDs) and Ca2+ for the detection of doxycycline (DOX). BCNO QDs were synthesized by microwave-assisted method with boric acid and ethylenediamine. The fluorescence of BCNO QDs at 425 nm was quenched due to the electrostatic interaction and inner filter effect with doxycycline. Meanwhile, doxycycline was combined with Ca2+ to form a fluorescence complex, which generated a new fluorescence peak at 520 nm. The fluorescence intensity ratio (F520/F425) has a good linear relationship with doxycycline concentration, and the detection limit is 25 nM. Moreover, the fluorescence of the reaction solution showed a concentration-dependent visual color change from blue to green. In order to facilitate further application, a portable fluorescent test paper which is easy to store was prepared. The RGB values of the reaction solution and corresponding test paper were identified by smartphone, and the visual detection of doxycycline was performed by digital image colorimetric analysis. The application of smartphone and fluorescent test paper can effectively shorten the detection time and simplified the operation, providing an effective scheme for quantitative detection of doxycycline in actual samples. Overall, this work provides a method for the detection of doxycycline and shows that the BCNO QDs have great potential application in food safety.

Tris(bipyridine)ruthenium(II)-functionalized metal-organic frameworks for the ratiometric fluorescence determination of aluminum ions.

A novel ratiometric fluorescence probe was designed for the determination of Al3+ by self-assembling of NH2-MIL-101(Fe) and [Ru(bpy)3]2+. Under the excitation wavelength of 360 nm, the NH2-MIL-101(Fe)@[Ru(bpy)3]2+ presented a dual-emitting luminescent property at 440 and 605 nm, respectively. In the presence of Al3+, the blue fluorescence of NH2-MIL-101(Fe)@[Ru(bpy)3]2+ at 440 nm was enhanced remarkably, while the red emission at 605 nm was almost not influenced. Therefore, taking the fluorescence at 440 nm as the report signal and 605 nm as the reference signal, quantitative determination was achieved for Al3+ concentration in the ranges 0.2-25 µM and 25-250 µM. The limit of detection (LOD) and limit of quantification (LOQ) were calculated to be 73 nM and 244 nM, respectively. The sensing mechanisms were studied by theoretical calculation and optical spectra. The analysis of real food samples confirmed the suitability of the proposed method. More importantly, portable fluorescent test papers were successfully manufactured to provide a strategy for visual, rapid, and on-site detection of Al3+.

A Fluorescent Probe for the Fast Detection of Hypochlorite and its Applications in Water, Test Strip and Living Cells.

Hypochlorite (ClO-) mediated by oxidative stress play an important role in the body's defense system due to their physiological and pathological significance. In this work, a new and simple probe was designed and synthesized to detect hypochlorite. This probe could rapidly respond to hypochlorite in a short time (20 s) in aqueous media, and showed excellent selectivity and sensitivity, and a wide pH range of 3 ̶ 12, as well as the low detection limit of 1.44 nM. In addition, it was successfully applied to the detection of ClO- in water sample, test paper experiment, and cell imaging.

Fluorescent and visual assay of H2O2 and glucose based on a highly sensitive copper nanoclusters-Ce(III) fluoroprobe.

Herein, we synthesized and characterized glutathione-capped copper nanoclusters (CuNCs) using a convenient one-pot chemical reduction approach based on glutathione as capping and reducing agents. The Ce(III) induced aggregation-induced emission of CuNCs to form a CuNCs-Ce3+ fluoroprobe due to electrostatic and coordination interactions between Ce3+ and CuNCs. In contrast to CuNCs, the fluorescent intensities (FLs) of CuNCs-Ce3+ were enhanced by ~ 40-fold concomitant with 20-nm blue-shift of the maximum emission, and a 3.45-fold lengthening of the average fluorescent lifetime. The FLs of CuNCs-Ce3+ were selectively quenched at 650 nm by hydrogen peroxide (H2O2) via the redox reaction. Based on this phenomenon, the sensitive assay of H2O2 was realized, and the linear range spanned over the range of 14-140 µM. Notably, the visualization of the fluorescence quenched effect of H2O2 could be easily attained. Additionally, glucose could be specifically oxidized by glucose oxidase to produce H2O2, and thus the detection of glucose was achieved according to changes in the concentrations of H2O2. Under optimized conditions, the fluorescent assay of glucose based on the CuNCs-Ce3+ system offered the linear range of 8-48 µM with detection limit of 2.4 µM. Meanwhile, high selectivity of the as-constructed fluorescent assay allows the sensitive detection of H2O2 and glucose in real-world care products and human serum samples, showing a great application potential in their conventional monitoring.

Ratiometric fluorescence determination of chlortetracycline based on the aggregation of copper nanoclusters triggered by aluminum ion.

The aggregation-induced emission (AIE) characteristic of copper nanoclusters (CuNC) was for the first time used to construct a ratiometric fluorescence probe (CuNC-Al3+) for detection of chlortetracycline (CTC). Aluminum ion (Al3+) can aggregate free CuNC and make it emit a bright and stable red fluorescence. A slight excess of Al3+ in CuNC-Al3+ solution can form a CTC-Al3+ complex to limit the conformational rotation of CTC molecule and enhance CTC fluorescence. So, the red fluorescence of CuNC-Al3+ probe and the enhanced CTC fluorescence are used as a reference signal and a response signal to detect CTC, respectively. The method developed shows a good linear relationship between the CTC concentration and the fluorescence intensity ratio (I495/I575) in the range 0.1-3.0 µM, and the detection limit is 25.3 nM (S/N = 3). In addition, the fluorescent color of CuNC-Al3+ probe changes from red to yellow-green as the concentration of CTC increases. Based on this observation, a fluorescent test paper has also been fabricated. Schematic illustration of Al3+ inducing CuNC to produce AIE performance and detecting CTC.

Nitrogen, boron-doped Ti3C2 MXene quantum dot-based ratiometric fluorescence sensing platform for point-of-care testing of tetracycline using an enhanced antenna effect by Eu3.

The Ti3C2 MXene quantum dots (Ti3C2 MQDs) derived from Ti3C2 MXene have received much attention because of their remarkable advantages in biosensing. Nevertheless, the functionalization of Ti3C2 MQDs to improve their properties is just in its infant stage. Herein, we firstly synthesized nitrogen and boron co-doped Ti3C2 MQDs (N, B-Ti3C2 MQDs) with good water solubility, strong stability, and high optical characteristics. The N, B-Ti3C2 MQDs exhibit excitation wavelength-dependent blue photoluminescence with optimal excitation/emission peaks at 335/439 nm. Nowadays, the development of fast and real-time detection of tetracycline (TC) in animal derived food is very essential. In this work, a novel point-of-care testing (POCT) platform was established based on ratiometric fluorescence method using N, B-Ti3C2 MQDs coupled with Eu3+. Upon addition of TC in the Eu3+/N, B-MQDs system, blue fluorescence emission of N, B-Ti3C2 MQDs was quenched and red fluorescence emission of Eu3+ was enhanced gradually, which was ascribed to the synergistic inner filter effect and antenna effect. Moreover, we prepared test papers with N, B-Ti3C2 MQDs and Eu3+ for TC detection based on the change of fluorescence color, which could be recognized by color recognizer app installed in the smartphone. Therefore, great promise for POCT of TC is given with the merits of simplicity and visible detection possibility. The proposed method demonstrated a low detection limit of 20 nM. Application of the platform for TC quantification in milk samples opened a novel means for the potential use of N, B-Ti3C2 MQDs in food safety.

A Flexible Chemosensor Based on Colorimetric and Fluorescent Dual Modes for Rapid and Sensitive Detection of Hypochlorite Anion.

A flexible chemosensor has been developed based on colorimetric and fluorescent dual modes using tetraphenylethylene-centered tetraaniline (TPE4A) for rapid and sensitive detection of hypochlorite anion. The fluorescent probe TPE4A exhibits a unique aggregation-induced emission (AIE) character which is proved by a blue shift of the fluorescent peak from 544 to 474 nm with the water equivalents increasing. With the addition of hypochlorite in solution, the absorbance of the probe changes and the responding fluorescence color can be observed to change from light green to purple. The detection limit of hypochlorite is 1.80 × 10-4 M in solution, and the visual detection limit is 1.27 µg/cm2 with the naked eye for the flexible paper-based chemosensor. The proposed flexible chemosensors show a good selectivity and sensitivity which has great potential for effective detection of hypochlorite anions without any spectroscopic instrumentation.

Evaluation of Fluorescent Cu2+ Probes: Instant Sensing, Cell Permeable Recognition and Quantitative Detection.

By incorporating a rhodamine spirolactam structure as the recognition site for Cu2+, two novel probes were synthesized through a connection of rhodamine 6G acylhydrazine and 5-formyl-6-hydroxyl-4-methylcoumarin/2,4-dihydroxybenzaldehyde. In the recognition process of probes towards Cu2+, the spirolactam ring exhibited opening and closing, accompanying an instant and specific change in fluorescence and in color, which could also achieve a naked-eye and semiquantitative recognition of aqueous Cu2+ besides the fluorescent Cu2+ detection method. Fluorescent analyses and ECV304 cell imaging further revealed the probes' good optical stability, instant response, low toxicity, and membrane permeability, which offers future possibilities for the probes' instant detection and the real-time tracking of Cu2+ in biological systems.

A Novel Donor-Acceptor Fluorescent Sensor for Zn2+ with High Selectivity and its Application in Test Paper.

A novel donor-acceptor fluorescent sensor was designed and synthesized. The sensor exhibited high selectivity and sensitivity to Zn2+ in acetonitrile solution. When 3.0 equiv. of Zn2+ was added gradually, the emission intensity at 500 nm increased 54-fold, accompanied by the fluorescent color of the solution changed from dark to green. Job's plot and ESI-MS were carried out to verify a 1:1 stoichiometric complex was formed between the sensor and Zn2+. The limit of detection (LOD) to Zn2+ was measured to be 2.81 × 10-9 mol L-1. Moreover, the sensor not only could be used to detect Zn2+ in practical water samples with high accuracy, but also could be made into test paper for the qualitative detection for Zn2+.

A Highly Selective Fluorescence "Turn on" and Absorbance-Ratiometric Detection of Al3+ in Totally H2O and its Application in Test Paper.

A novel naphthalene based fluorescence probe NBDH was designed and synthesized. Probe NBDH exhibited highly selective and sensitive responses towards Al3+ in HEPES-NaOH buffer solution (pH = 7.4). In addition, the detection of NBDH to Al3+ could be achieved through dual channels embodied in significant fluorescent turn-on signal and ratiometric absorbance response. The stoichiometry ratio of NBDH-Al3+ was 1:1 by fluorescence job' plot and binging mechanism was further varified by the FT-IR, NMR titration and HRMS. Furthermore, NBDH was achieved in real sample detection, and a series of color test paper were developed for visual detecting Al3+ ions.

Development of a paper-based method to detect Hg2+ in waste water using iturin from Bacillus subtilis.

Colorimetric, fluorescence, and paper-based method were developed to measure the Hg2+ level in water using iturin A, a lipopeptide produced by Bacillus subtilis. Firstly, iturin was used to synthesize highly stable and uniformly sized silver nanoparticles (AgNPs). Secondly, the iturin-AgNPs were found to be highly selective and sensitive to Hg2+. The absorbance of the reaction system showed a good linear correlation with the Hg2+ concentration from 0.5 to 5 mg/L at 450 nm in the UV-Vis spectroscopy detection with the limit of detection (LOD) of 0.5 mg/L. When the reaction system was detected by fluorescence measurement, a good linear relationship was found between the fluorescence intensity and Hg2+ concentration from 0.05 to 0.5 mg/ at 415 nm with the LOD of 0.05 mg/L. Lastly, a paper-based detection method was developed. The developed method was successfully used to detect Hg2+ in contaminated polluted waters and showed acceptable results in terms of sensitivity, selectivity and stability. The paper-based method could distinguish Hg2+ at levels higher than 0.05 mg/L, thereby meeting the guidelines of the effluent quality standard for industries (0.05 mg/L). In summary, this method can be used daily by various industries to monitor the Hg2+ level in effluent water.

White-light emissive upconversion nanoparticles for visual and colorimetric determination of the pesticide thiram.

The authors describe the use of white-light emitting upconversion nanoparticles (WL-UCNPs) for visual detection of the pesticide thiram. The method is demonstrated to undergo a better discernable color change upon target binding. The WL-UCNPs are modified with the lead(II)-dithizone complex which acts as the energy acceptor and recognition unit. This leads to quenching of the blue (475 nm) and green (545 nm) emissions of the WL-UCNPs, while the red emission (650 nm) remains unaffected. Upon addition of thiram, the quenched emissions are recovered, with a linear signal increase in the range from 2 nM to 20 nM of thiram and a limit of detection of 0.26 nM. The nanoprobe was further integrated into a test paper for visual detection. The concentration-dependent color change that varies from red to cyan and bluish violet and then to white can be visually distinguished. Graphical abstract Schematic presentation of a white-light emissive upconversion nanoparticle based test paper for color-discernable detection of the pesticide thiram. The test stripe exhibits a concentration-dependent color variation spanning from red, cyan, to bluish violet, and at last to white.

Europium(III) modified silicone nanoparticles for ultrasensitive visual determination of tetracyclines by employing a fluorescence color switch.

Silicon nanoparticles (SiNPs) modified with Eu(III) were synthesized and are shown to be a viable ratiometric fluorescent probe for tetracycline antibiotics. SiNPs/Eu under 405 nm excitation display two emissions, viz. a strong cyan colored fluorescence peaking at 497 nm and a weak pink fluorescence peaking at 622 nm. On addition of tetracyclines (chlortetracycline, tetracycline, doxycycline), the fluorescence at 497 nm is reduced, while the one at 622 nm is increased. Thus, the visible color of fluorescence changes from cyan to pink. This was exploited to design ratiometric fluorometric method for detecting tetracyclines. The method has a limit of detection that is lower by a factor of about 1000 when compared to the use of SiNPs only. A test paper was prepared with the SiNPs/Eu and then applied for the visual semi-quantitative detection of tetracyclines. With the addition of tetracyclines, the test paper exhibited a dosage-sensitive color conversion from cyan to pink with a visually discernible scale as low as 0.4 µM. Graphical abstract Tetracyclines decrease the fluorescence at 497 nm of europium (III) modified silicon nanoparticles (SiNPs/Eu) due to the inner filter effect and increase the one at 622 nm due to an antenna effect. Thus the fluorescence color of SiNPs/Eu changes from cyan to pink. Based on this color switch, a ultrasensitive and visual determination strategy for tetracyclines is proposed.

Ratiometric fluorometric determination of the anthrax biomarker 2,6-dipicolinic acid by using europium(III)-doped carbon dots in a test stripe.

Europium(III)-doped carbon dots (Eu-CDs) were prepared from citric acid and europium nitrate via a one-pot pyrolytic method. The Eu-CDs emit intense blue fluorescence (with excitation/emission peaks at 365/465 nm), are water soluble and biocompatible. On addition of 2,6-dipicolinic acid (DPA; an anthrax biomarker), ligand-to-ion energy transfer occurs from DPA to Eu(III) which has a red emission peaking at 615 nm. This results in an increase of the intensity of the red fluorescence. DPA can be detected by the ratio of fluorescence intensities at 616 and 475 nm. The method has an analytical range that extends from 5 to 700 nmol·L-1, with a 5 nmol·L-1 detection limit. The Eu-CDs also were incorporated into a test paper for visual detection of DPA with a portable UV lamp and a smartphone. In this case, the detection limit is 1 µmol·L-1. The Eu-CDs internalize well into HeLa cells, and this paves the way to bioimaging. Graphical abstract Schematic of a method for visual detection of 2,6-dipicolinic acid (DPA, an anthrax biomarker) by using a test stripe impregnated with europium(III)-doped carbon dots (Eu-CDs).

Test Paper for Colorimetric Inspection of Fatty Acids and Edible Oils.

Fatty acids (FAs) are of interest to the areas of food science and medicine because they are important dietary sources of fuel for animals and play important roles in many biological processes. The health effects of FAs are different due to the diversity of olefinic bonds in the alkyl chains including number, position and configuration. However, the discrimination of FAs is difficult from a chemical sensing perspective due to the lack of diversity in terms of functional groups. Until now, only a few chemosensors have been developed for selective sensing of FAs based on their overall shape, however they are still limited in discrimination of FAs with subtle structural differences, moreover, they cannot be used for rapid and in situ inspections. Herein, for the first time, we designed a test paper for in situ colorimetric inspection for FAs based on the combination of the highly selective binding of Ag⁺ to olefinic bonds and Ag⁺ mediated color variation of 3,3',5,5',-tetramethylbenzidine. As a result, the sensor exhibited high sensitivity and good selectivity for five FAs with subtle structural differences. Furthermore, our method described herein was successfully applied to monitor the structural variations of FAs and quality changes in mixture edible hot pot oils with heat treatment in time course. Hence, the test paper presented herein holds great potential in the inspection of fats and edible oils in food industries.

[Determination of cadmium in human urine by colloidal gold immunochromatographic assay].

Objective: To establish the method of colloidal gold immunochrom atographic assay for detecting cadmium ions rapidly. Methods: The anti-cadmium ion monoclonal antibody-gold conjugate was labeled on the binding pad, cadmium ion hapten and goat anti-mouse IgG were coated on nitrocellulose membrane as the detection line (T line) and quality control line (C line) respectively. The sample pad, colloidal gold bonding pad, nitrocellulose membrane and absorption pad were orderly assembled on the PVC board to cut into a test paper strip. The qualitative results of the assay were visualized in color. Results: When detecting the human urine cadmium ions, the results were tested qualitativly within 15 minutes. The detection limit was 30 µg/L. No cross-reactivity with other heavy metal ions. The test paper strip could be stored at 4 ℃ for 3 months. Conclusion: The method has the advantages of low cost, strong specificity, good stability and reliable results, and is suitable for rapid screening of cadmium poisoning of enterprise and occupational health.