An intelligent "chemical tongue" for high-order monitoring ATP-related physiological phosphates and ATP hydrolysis through diverse transduction principles.

For discriminating diverse analytes and monitoring a specific chemical reaction, the emerging multi-channel "chemical nose/tongue" is challenging multi-material "chemical nose/tongue". The former contributes greatly to integrating different transduction principles from a single sensing material, avoiding the need for complex design, high cost, and tedious operation involved with the latter. Therefore, this high-order sensing puts a particular emphasis on the effects of encapsulation. Herein, the plasmonic gold nanoparticles (Au NPs) are encapsulated as a core into the fluorescent guanine monophosphate-Tb3+ infinite coordination polymer nanoparticles (GMP-Tb ICPs) to obtain a core-shell nanocomposite named Au NPs@GMP-Tb ICPs. Hence, a dual-channel "chemical tongue" based on Au NPs@GMP-Tb ICPs is present to realize high-order sensing of adenosine triphosphate (ATP)-related physiological phosphates and the monitoring of ATP hydrolysis. Considering the affinity of Tb3+ towards P-O bonds, four inorganic phosphates and three nucleotide phosphates with different phosphate group numbers and steric hindrance effect directly regulate two stimulus responses (fluorescence intensity and UV-vis absorbance) of Au NPs@GMP-Tb ICPs. Robust statistical methods, such as linear discriminant analysis and hierarchical cluster analysis, are used to recognize each phosphate by the developed sensor array either in the aqueous solution or in complex media such as serum, together with efficiently monitored ATP hydrolysis at different intervals. These findings and blind test clarify that the designed "chemical tongue" guarantees interference resistance and strengthens analytical capacity, together with offering valuable insight into "lab-on-a-nanoparticle" development for monitoring specific chemical reactions.

Quadruple analyte responsive platform: Point-of-care testing and multi-coding logic computation based on metal ions recognition and selective response.

While it is recognized that instrumentation techniques can provide precise and sensitive solutions to heavy metal ion monitoring, it remains challenging to transform laboratory testing into a convenient, on-site, and quantitative sensing platform for point-of-care testing (POCT) in a resource-constrained setting. To address these limitations, an affordable and user-friendly colorimetric POCT sensing system is proposed here for selectively monitoring four metal ions (Fe3+, Co2+, Pb2+, and Cd2+) based on the sulfur quantum dots (S dots). Quadruple distinct visual signals (green, brown, precipitation, and bright yellow) are presented on the fabricated paper-based analytical devices (PADs) when mixing S dots and metal ions. The high-quality photographs of the PADs are captured by a scanner, while a smartphone App converts visual signals to HSV values. The quantitative analysis relies on the digital colorimetric reading, and the limits of detection are 0.59, 0.47, 0.82, and 0.53 µM for Fe3+, Co2+, Cd2+, and Pb2+, respectively. This metal ions-responsive platform is engineered as a smart strategy for multiple logic operations (YES, NOT, AND, INHIBIT, and NOR) by integrating multi-responsive blocks into the S dots with encoded patterns, which improves the computing capability. Accordingly, this strategy demonstrates its potential for on-site environmental testing and sophisticated molecular computation.

Smartphones and Test Paper-Assisted Ratiometric Fluorescent Sensors for Semi-Quantitative and Visual Assay of Tetracycline Based on the Target-Induced Synergistic Effect of Antenna Effect and Inner Filter Effect.

Development of selective and sensitive methods for on-site assay of tetracycline (TC) is of great significance for public health and food safety. Herein, a valid ratiometric fluorescence strategy using g-C3N4 nanosheets coupled with Eu3+ is designed for the assay of TC. In this strategy, both Eu3+ and g-C3N4 nanosheets serve as the recognition units of TC. The blue fluorescence of g-C3N4 nanosheets can be quenched by TC via the inner filter effect (IFE); meanwhile, the red fluorescence of Eu3+ can be enhanced by TC through the antenna effect (AE). The synergistic effect of AE and IFE caused by TC makes the developed ratiometric fluorescent sensor display a wide linear range for TC from 0.25 to 80 µM with a detection limit of 6.5 nM and a significant fluorescence color evolution from blue to red. Given its simplicity, free-label, excellent selectivity, high sensitivity, and recognizable color change, point-of-care testing systems, including smartphones and test paper-based assays, are developed for the visual sensing of TC. The integration of smartphones and test paper on a ratiometric fluorescent sensor greatly reduces the detection cost and time, providing a promising method for the qualitative discernment and semi-quantitative assay of TC on-site. Moreover, the potential application of the approach is also verified by detecting TC in milk.

Redox induced dual-signal optical sensor of carbon dots/MnO2 nanosheets based on fluorescence and second-order scattering for the detection of ascorbic acid.

In order to detect ascorbic acid (AA) sensitively, a dual-signal optical sensor of a nanosystem with carbon dots (CDs)/MnO2 nanosheets based on fluorescence and second-order scattering (SOS) has been constructed. Here, MnO2 nanosheets, both as a fluorescence quencher and signal transducer of SOS, quench the blue fluorescence of CDs by an inner filter effect. Under the excitation of 300 nm, the nanosystem shows a fluorescence emission peak at 405 nm and a SOS peak at 610 nm, respectively. With the increase of AA , the lamellar structure of MnO2 nanosheets is etched into a smaller nanostructure, causing a decrease of the fluorescence recovery of CDs (405 nm) and decrease of the SOS signal of the MnO2 nanosheets (610 nm). According to the simultaneous changes of fluorescence and SOS signals, a dual-signal optical sensor toward AA is successfully constructed. Satisfactorily, the optical sensor for AA detection shows a detection limit of 88 and 105 nM for fluorescence and SOS, respectively. The practical application of the designed sensor is verified through the detection of AA content in vitamin C tablets, and satisfactory results are obtained Graphical Abstract A dual-signal sensor of fluorescence (FL) and second-order scattering (SOS) based on the carbon dot (CD) and MnO2 nanosheet system for ascorbic acid (AA) detection is constructed, in which CDs are used for the FL mode and MnO2 nanosheets are used for the SOS mode.

Multifunctional Binding Strategy on Nonconjugated Polymer Nanoparticles for Ratiometric Detection and Effective Removal of Mercury Ions.

Developing a multifunctional platform for the selective detection and effective removal of toxic ions is a major challenge when addressing heavy metal contamination in environmental science. Herein, novel nonconjugated polymer nanoparticles (PNPs) called mercaptosuccinic acid-thiosemicarbazide PNPs (MT-PNPs) with appealing fluorescence and stability are synthesized via facile one-step hydrothermal treatment for attractive sensing and simultaneous removal of mercury(II). Interestingly, aggregation-induced fluorescence switch-off and scattering enhancement are found upon the addition of Hg2+, rendering MT-PNPs as a ratiometric sensor for selective and accurate Hg2+ monitoring. A wide linear range (0.1-1471 µM) and a low detection limit (95 nM) are obtained. This dual-signal opposite responses triggered by Hg2+ originate from the formation of MT-PNP-Hg2+ congeries via the multisite binding between S,N,O-containing groups of MT-PNPs and mercury. Meanwhile, target-induced aggregation renders an effective Hg2+ separation from contaminative aqueous media by MT-PNPs, which exhibits a satisfactory absorption efficiency of 90.42% within 50 min. Upon the simple Na2S treatment, the MT-PNPs can be regenerated and reused. This work thus delivers an applicable method for the ratiometric detection and effective removal of mercury with the novel nonconjugated PNPs, offering potential in tackling the problem of heavy metal ion pollution for environmental monitoring and remediation.

Smartphone assisted colorimetric and fluorescent triple-channel signal sensor for ascorbic acid assay based on oxidase-like CoOOH nanoflakes.

Ascorbic acid (AA) is an important diet-derived antioxidant to human body. Thus, efficient and accurate detection of AA is of considerable significance in food analysis. Herein, smartphone assisted colorimetric and fluorescent triple-channel signal sensor has been developed for AA monitoring based on oxidase-like CoOOH nanoflakes. CoOOH nanoflakes can efficiently catalyze the oxidation of p-phenylenediamine (p-PD) into reddish brown p-PDox. The carbon dots (C-dots) are further introduced, of which the fluorescence can be quenched by p-PDox. However, in the presence of AA, the CoOOH nanoflakes is reduced and thus collapsed. As a result, the oxidation of p-PD is restrained, and thus the fluorescence of C-dots keeps strong. Based on AA induced light color, low absorbance, and strong fluorescence, triple-channel signal sensor has been proposed for AA determination. The AA assay shows a dynamic response range from 0.5 to 10 µM with a detection limit of 0.09 µM. The method assay allows detection of AA in real samples such as fruit juices. Combination with portable smartphone, the developed sensor is potential for AA determination in resource-poor settings.

Conversion of Fluorescence Signals into Optical Fingerprints Realizing High-Throughput Discrimination of Anionic Sulfonate Surfactants with Similar Structure Based on a Statistical Strategy and Luminescent Metal-Organic Frameworks.

To date, the effective discrimination of anionic sulfonate surfactants with tiny differences in structure, considered as environmentally noxious xenobiotics, is still a challenge for traditional analytical techniques. Fortunately, a sensor array becomes the best choice for recognizing targets with similar structures or physical/chemical properties by virtue of principal component analysis (PCA, a statistical technique). Herein, because of the beneficial construction of the statistical strategy and use of two types of luminescent metal-organic frameworks (LMOFs, NH2-UiO-66 and NH2-MIL-88) as sensing elements, high-throughput discrimination and detection of five anionic sulfonate surfactants and their mixtures are nicely realized for the first time. Significantly, the stacking interaction of aromatic rings and dynamic quenching play essential roles in the generation of diverse fluorescence responses and unique fingerprint maps for individual anionic sulfonate surfactants. Moreover, the mixtures of anionic sulfonate surfactants are also satisfactorily distinguished in environmental water samples, demonstrating the practicability of the sensor array. On the basis of the PCA method, this strategy converts general fluorescence signals into unique optical fingerprints of individual analytes, providing a new opportunity for the application of LMOFs in the field of analytes recognition.

Dual-emission ratiometric nanoprobe for visual detection of Cu(II) and intracellular fluorescence imaging.

Copper is an essential mineral nutrient for the human body. However, excessive levels of copper accumulated in the body can cause some diseases. Therefore, it is great significant to establish a sensitive bioprobe to recognize copper ions (Cu2+) in vivo. In our work, nitrogen-doped carbon dots (N-CDs) and gold nanoclusters (Au NCs) are selected as luminescent nanomaterials and the Au NCs/N- CDs nanohybrids is successfully synthesized by coupling method. The Au NCs/N-CDs exhibited characteristic dual-emission peaks at 450 and 620 nm when excited by a single-wavelength of 380 nm. When different amounts of Cu2+ are introduced, the fluorescence intensity of the Au NCs is gradually weakened and fluorescence intensity of the N-CDs is almost unchanged, which can facilitate the visual detection of Cu2+. The Au NCs/N-CDs nanohybrid possesses good selectivity to Cu2+ with a limit of detection (LOD) is 3.5 µM and linear detection range of 10-150 µM. Visualization detection of Cu2+ is implemented by using nanoprobe in water samples. Furthermore, the ratiometric nanoprobe is utilized to the toxicity test of liver cancer cells, indicating excellent biocompatibility and low toxicity. This nanoprobe has been used to the intracellular fluorescence imaging. Moreover, this method is expected to be used to monitor the changes of Cu2+ concentration in hepatocytes.

Metal-Organic Framework as a Chemosensor Based on Luminescence Properties for Monitoring Cetyltrimethylammonium Bromide and Its Application in Smartphones.

Rapid and sensitive detection of surfactants has attracted more and more attention since surfactants not only cause water pollution but also affect the health of human beings. Luminescent metal-organic frameworks combining unique optical property and inherent permanent porosity for guest-host encapsulation are widely used in fluorescence detection. Here we report a ratiometric fluorescent probe (denoted as UiO-66-NH2@PB) based on a Zr-based metal-organic framework (UiO-66-NH2) and a fluorescent dye, phloxine B (PB), for visual and fluorescent determination of cationic surfactants (cetyltrimethylammonium bromide; CTAB). The intensity ratio of dual-emission sensor exhibits a linear response to the CTAB concentrations of 0.1-17 µM and obtains a low detection limit (0.074 µM). Moreover, this method has been successfully utilized to monitor CTAB in the environmental water samples with satisfied recoveries. Importantly, this work provides a new insight into developing smartphone-based sensor to realize a rapid, on-site visual and quantification-based detection of CTAB.

A smartphone-coalesced nanoprobe for high selective ammonia sensing based on the pH-responsive biomass carbon nanodots and headspace single drop microextraction.

Ammonia concentration together with pH values are important and closely linked indexes for aqueous systems. Rapid on-site determination of ammonia or pH is of great significance to environmental monitoring. In this work, a pH-switchable nanoprobe based on biomass carbon dots (CDs) is developed using a smartphone as a simple and handy instrument. The CDs demonstrate sensitive pH response in wide linear ranges of 6.1-13.6, and 2.0-13.6 with colorimetric and fluorescent channels, respectively. It is the pH-induced aggregation that governs the color and fluorescence switch. With the pH evolution caused by the dissolution of ammonia, the smartphone-integrated nanoprobe is applied to ammonia detection with a broad range of 0.5-300 mM. Moreover, the headspace single drop microextraction strategy can concentrate ammonia from matrix, offering a remarkably high selectivity for ammonia determination. Finally, the practical applications of this method for ammonia analysis obtained satisfactory results.

A facile and label-free ratiometric optical sensor for selective detection of norepinephrine by combining second-order scattering and fluorescence signals.

In this work, a facile and label-free ratiometric sensor is constructed for selective determination of norepinephrine (NE) by coupling second-order scattering (SOS) and fluorescence, two different and independent optical signals. Herein, polyethyleneimine (PEI) dilute solution medium shows an intensive SOS signal without any fluorescence response. Interestingly, NE can be selectively induced by PEI to emit bright fluorescence, and meanwhile causes an observable decrease in the SOS signal due to the interactions between NE and PEI. The simultaneous variation of the two independent signals can be used for ratiometric sensing of NE. Under the optimal conditions, the resultant ratiometric sensor displays high sensitivity and selectivity toward NE by simultaneously monitoring fluorescence and SOS signals with the same excitation wavelength. The proposed sensor exhibits a good linear relationship versus NE concentration in the range of 10.0 nM-45.0 µM with a detection limit of 2.0 nM (S/N = 3) and has been successfully applied to the determination of NE in real samples without the use of any extra reagent. The combination of fluorescence and SOS signals provides a new scheme for ratiometric sensor design, greatly simplifying experimental procedure and effectively enhancing detection accuracy. Moreover, the proposed analytical strategy further broadens the application of dilute solutions of polymers in research into optical sensor and green analytical chemistry. Graphical abstract.

Label-free fluorescent discrimination and detection of epinephrine and dopamine based on bioinspired in situ copolymers and excitation wavelength switch.

A simple and label-free fluorescence turn-on method is proposed for the discrimination and detection of epinephrine (Ep) and dopamine (DA) via polyethyleneimine (PEI)-initiated in situ copolymerization and excitation wavelength switch. The PEI solution in the presence of Ep, DA and the mixture of Ep and DA are denoted as PEp-PEI, PDA-PEI and MEp+DA, respectively. In this study, PEI aqueous solution medium initiates the auto-oxidization of Ep and DA and the bioinspired copolymerization. These resultant copolymers emit yellow-green fluorescence color with a fluorescence emission maximum at 515 nm. Interestingly, these fluorescent copolymers exhibit distinct different excitation spectra, although Ep and DA are structurally very similar. PDA-PEI exhibits only one excitation peak at 385 nm, and PEp-PEI shows dual-excitation mode with two significant excitation peaks at 328 nm and 405 nm, respectively. MEp+DA also shows dual-excitation mode with two excitation peaks at 330 nm and 395 nm, respectively. Thus, individual Ep, DA, and their mixture can be discriminated based on the different excitation spectral shapes and peak locations of PEp-PEI, PDA-PEI and MEp+DA. Furthermore, the quantitative analysis of Ep and DA in mixture can also be achieved by switching excitation wavelength between 330 and 395 nm and monitoring the fluorescence emission intensity of MEp+DA at 515 nm. The fluorescence intensity of MEp+DA only related to the concentration of Ep when excited at 330 nm. Moreover, the concentration of DA can also be calculated by subtracting the fluorescence intensity of PEp-PEI from the total fluorescence intensity when excited at 395 nm. The resultant method has been used to simultaneously detect Ep and DA in human urine samples. The proposed fluorescence system is facile, eco-friendly, low-cost, and time-saving, and also provides a new and simple path for discriminating analogues.

Oxidation etching induced dual-signal response of carbon dots/silver nanoparticles system for ratiometric optical sensing of H2O2 and H2O2-related bioanalysis.

Ratiometric sensing suffers from less interference and can obtain more accurate results than single-signal assay. Here, a new ratiometric optical sensing strategy for H2O2 detection is developed by etching silver nanoparticles (AgNPs) to deactivate fluorescence resonance energy transfer (FRET) and reduce Rayleigh scattering based on a hyphenated technique of fluorescence and second-order Rayleigh scattering (SRS). The ratiometric detection of H2O2 is achieved through exploiting a hybrid system fabricated by fluorescent carbon dots and silver nanoparticles (CDs/AgNPs). In the CDs/AgNPs system, the fluorescence of CDs is quenched because of FRET, and the scattering is strong due to the intrinsic high light-scattering power of AgNPs. With the introduction of H2O2, the AgNPs are etched and the CDs are released from the AgNP surface, resulting in the fluorescence enhancement and scattering decline. As a result, ratiometric sensing of H2O2 can be achieved based on the CDs/AgNPs system by simultaneous collection of fluorescence and SRS signals. The sensing system is further used for H2O2-generation bioanalysis, and as a proof-of-concept, ratiometric assay of glucose and evaluation of glucose oxidase activity are performed successfully. This work provides a new perspective for sensing applications of plasmonic nanoparticles.

Proton-controlled synthesis of red-emitting carbon dots and application for hematin detection in human erythrocytes.

The Red-emitting nitrogen-doped carbon dots (N-CDs) are synthesized using o-phenylenediamine by a one-step method, and can serve as a fluorescent probe for "turn off" detection of hematin in human red cells. The red-emitting N-CDs can be obtained only in acidic conditions and the emission of the red-emitting N-CDs is pH-dependent, indicating proton-controlled synthesis and emission. The red-emitting N-CDs are 2.7 nm in mean size and have a uniform dispersion and exhibit a high quantum yield (12.8%) and great optical properties. The developed sensing system for hematin displays a linear response from 0.4 to 32 µM with a detection limit of 0.18 µM. Importantly, this fluorescent probe demonstrates a good potential practicability for the quantitative detection of hematin in complex matrixes. Graphical abstract ᅟ.

Green Synthesis of Blue Fluorescent P-doped Carbon Dots for the Selective Determination of Picric Acid in an Aqueous Medium.

A fluorescence method for the determination of picric acid (PA) using phosphorus-doped carbon dots (P-CDs), synthesized from ß-cyclodextrin and sodium pyrophosphate, is described. The P-CDs are very uniform and monodisperse with a diameter of about 2.8 nm. Under an excitation of 350 nm, the P-CDs emit bright blue fluorescence with an emission peak at 440 nm. The as-synthesized P-CDs serve as a sensitive, selective, and label-free fluorescent probe for the detection of PA. Based on an inner filter effect between PA and P-CDs, a linear response is obtained for PA from 0.1 to 10 µM with a detection limit of 82 nM. Finally, this sensing system has been demonstrated to have practicability for PA detection in the environmental water samples.

Adenosine-derived doped carbon dots: From an insight into effect of N/P co-doping on emission to highly sensitive picric acid sensing.

The various synthetic routes of carbon dots (C-dots) feature a considerable step toward their potential use in chemical sensors and biotechnology. Herein, by coupling phosphorus and nitrogen element introduction, the adenosine-derived N/P co-doped C-dots with fluorescence enhancement were achieved. By separately employing adenosine, adenosine monophosphate, adenosine diphosphate, and adenosine-5'-triphosphate as precursors, the effect of N/P co-doping on the fluorescence emission is discussed in detail. The formed C-dots with adenosine monophosphate exhibited strong blue fluorescence with a high quantum yield of 33.81%. Then the C-dots were employed as a fluorescent probe and utilized to develop a fast, sensitive, and selective picric acid sensor. The fluorescence of C-dots can be quenched by picric acid immediately, giving rise to a picric acid determination down to 30 nM. The possible mechanism of fluorescence quenching was discussed, which was proved to be inner filter effect and static quenching. Moreover, this method has the potential to detect picric acid in environmental water samples.

A resonance Rayleigh scattering sensor for detection of Pb2+ ions via cleavage-induced G-wire formation.

A resonance Rayleigh scattering (RRS) aptasensor was fabricated for detection of Pb2+via hairpin-like label-free substrate and G-wire for signal amplification. A hairpin-like DNA substrate contains a sequence in the loop labeled with ribonucleobase A and c-myc sequence in the stem. When hybridized with 8-17 DNAzyme in the presence of Pb2+, the sequence in the loop was activated and cleaved. Hundreds of c-myc sequences departing from the 8-17 DNAzyme yield nanowires superstructure called G-wire in the presence of Mg2+. The polymer G-wire was demonstrated by the RRS spectrum, polyacrylamide gel electrophoresis, and AFM. The RRS intensity was enhanced by the product G-wires, and the RRS signal at 370nm was linear with the logarithm of Pb2+ concentration in the range of 2.0nM to 5.0µM. This method was selective for Pb2+ even coexisting with other metal ions at high concentrations and was successfully applied to the determination of Pb2+ in real samples. The aptasensor holds a great promise for universal RRS sensing platform for sensitive detection of various metal ions just by changing the sequence of the probe in the loop and DNAzyme.

A colorimetric and fluorometric dual-signal sensor for arginine detection by inhibiting the growth of gold nanoparticles/carbon quantum dots composite.

A bidimensional optical sensing platform which combines the advantages of fluorescence and colorimetry has been designed for arginine (Arg) detection. The system was established by monitoring the influence of Arg on the growth of gold nanoparticles/carbon quantum dots (Au/CQDs) composite, and the CQDs synthesized by ethylene glycol were used as the reducing and stabilizing agent in this paper. Considering that Arg is the only amino acid with guanidine group and has the highest isoelectric point (pI) value at 10.76, Arg would carry positive charges at pH 7.4. Consequently, the positively charged guanidine group of Arg could attract AuCl4- and CQDs through electrostatic interaction, which inhibited the growth of Au/CQDs composite. Thereby, the color of the system almost did not change and the fluorescence quenching of CQDs was prevented in the presence of Arg. Based on the color change a low detection limit for Arg was 37nM, and a detection limit of 450nM was obtained by fluorescence spectroscopy. Moreover, this dual-signal sensor also revealed excellent selectivity toward Arg over other amino acids. Besides, Arg can be detected in urine samples with satisfactory results, which demonstrate the potential applications for real analysis.

Carbon quantum dots prepared with polyethyleneimine as both reducing agent and stabilizer for synthesis of Ag/CQDs composite for Hg2+ ions detection.

A stable silver nanoparticles/carbon quantum dots (Ag/CQDs) composite was prepared by using CQDs as reducing and stabilizing agent. The CQDs synthesized with polyethyleneimine (PEI) showed an extraordinary reducibility. When Hg2+ was presented in the Ag/CQDs composite solution, a color change from yellow to colorless was observed, accompanied by a shift of surface plasmon resonance (SPR) band and decrease in absorbance of the Ag/CQDs composite. On the basis of the further studies on TEM, XPS and XRD analysis, the possible mechanism is attributed to the formation of a silver-mercury amalgam. Hence, a two dimensional sensing platform for Hg2+ detection was constructed upon the Ag/CQDs composite. Based on the change of absorbance, a good linear relationship was obtained from 0.5 to 50µM for Hg2+. And the limit of detection for Hg2+ was as low as 85nM, representing high sensitivity to Hg2+. More importantly, the proposed method also exhibits a good selectivity toward Hg2+ over other metal ions. Besides, this strategy demonstrates practicability for the detection of Hg2+ in real water samples with satisfactory results.