Luminescence Detection Research Articles

Ultra-low limit of luminescent detection of gossypol by terbium(III)-based metal-organic framework

The widespread use of gossypol-containing animal feed and cottonseed oil poses a great threat to water quality and livestock and human health, and there is an urgent need for a sensor for the rapid detection of trace amounts of gossypol in aqueous solutions and cottonseed oil. As a result, an unprecedented three-dimensional metal-organic framework sensor based on terbium(III) and a flexible ligand 4-(3,5-dicarboxyphenoxy)isophthalic acid (H4L) was developed. Tb-MOF, {[Tb(H2O)(HL)]·0.5MeCN·0.25 H2O}n, is highly stable in water and polar organic solvents and exhibits terbium-centered luminescence with 44% quantum yield. Suspensions of MOF in water and ethanol demonstrate a luminescence quenching response to cotton phytotoxicant gossypol with an unprecedented low detection limit of 0.76 nM and 1.89 nM, correspondingly, without interference from the components of cottonseed oil and blood plasma, making it suitable for the detection and determination of gossypol in real-life water and oil samples. Significantly, Tb-MOF is the first highly efficient sensor that uses water as a solvent to detect trace amounts of gossypol, and it can visualize and quantify gossypol in edible-grade cottonseed oil as well, which proves its great potential for practical application. In addition, Tb-MOF exhibited a detection limit for Fe3+ (0.23 μM) among the lowest reported for lanthanide-based MOFs in aqueous solutions so far.

Combining Upconversion Luminescence, Photothermy, and Electrochemistry for Highly Accurate Triple-Signal Detection of Hydrogen Sulfide by Optically Trapping Single Microbeads.

The detection of hydrogen sulfide (H2S), the third gas signaling molecule, is a promising strategy for identifying the occurrence of certain diseases. However, the conventional single- or dual-signal detection can introduce false-positive or false-negative results, which ultimately decreases the diagnostic accuracy. To address this limitation, we developed a luminescent, photothermal, and electrochemical triple-signal detection platform by optically trapping the synthetic highly doped upconversion coupled SiO2 microbeads coated with metal-organic frameworks H-UCNP-SiO2@HKUST-1 (H-USH) to detect the concentration of H2S. The H-USH was first synthesized and proved to have stable structure and excellent luminescent, photothermal, and electrochemical properties. Under 980 nm optical trapping and 808 nm irradiation, H-USH showed great detection linearity, a low limit of detection, and high specificity for H2S quantification via triple-signal detection. Moreover, H-USH was captured by optical tweezers to realize quantitative detection of H2S content in serum of acute pancreatitis and spontaneously hypertensive rats. Finally, by analyzing the receiver operating characteristic (ROC) curve, we concluded that triple-signal detection of H2S was more accurate than single- or dual-signal detection, which overcame the problem of false-negative/positive results in the detection of H2S in actual serum samples.

Erianin suppresses constitutive activation of MAPK signaling pathway by inhibition of CRAF and MEK1/2

Constitutive activation of RAS-RAF-MEK-ERK signaling pathway (MAPK pathway) frequently occurs in many cancers harboring RAS or RAF oncogenic mutations. Because of the paradoxical activation induced by a single use of BRAF or MEK inhibitors, dual-target RAF and MEK treatment is thought to be a promising strategy. In this work, we evaluated erianin is a novel inhibitor of CRAF and MEK1/2 kinases, thus suppressing constitutive activation of the MAPK signaling pathway induced by BRAF V600E or RAS mutations. KinaseProfiler enzyme profiling, surface plasmon resonance (SPR), isothermal titration calorimetry (ITC), cellular thermal shift assay, computational docking, and molecular dynamics simulations were utilized to screen and identify erianin binding to CRAF and MEK1/2. Kinase assay, luminescent ADP detection assay, and enzyme kinetics assay were investigated to identify the efficiency of erianin in CRAF and MEK1/2 kinase activity. Notably, erianin suppressed BRAF V600E or RAS mutant melanoma and colorectal cancer cell by inhibiting MEK1/2 and CRAF but not BRAF kinase activity. Moreover, erianin attenuated melanoma and colorectal cancer in vivo. Overall, we provide a promising leading compound for BRAF V600E or RAS mutant melanoma and colorectal cancer through dual targeting of CRAF and MEK1/2.

Detecting phosphate using lysine-sensitized terbium coordination polymer nanoparticles as ratiometric luminescence probes.

Probes for detecting phosphate ions (Pi) are required for environmental monitoring and to protect human health. Here, novel ratiometric luminescent lanthanide coordination polymer nanoparticles (CPNs) were successfully prepared and used to selectively and sensitively detect Pi. The nanoparticles were prepared from adenosine monophosphate (AMP) and Tb3+, and lysine (Lys) was used as a sensitizer (through the antenna effect) to switch on Tb3+ luminescence at 488 and 544nm while Lys luminescence at 375nm was quenched because of energy transfer from Lys to Tb3+. The complex involved is here labeled AMP-Tb/Lys. Pi destroyed the AMP-Tb/Lys CPNs and therefore decreased the AMP-Tb/Lys luminescence intensity at 544nm and increased the luminescence intensity at 375nm at an excitation wavelength of 290nm, meaning ratiometric luminescence detection was possible. The ratio between the luminescence intensities at 544 and 375nm (I544/I375) was strongly associated with the Pi concentration between 0.1 and 6.0μM, and the detection limit was 0.08μM. The dual-emission reverse-change ratio luminescence sensing method can exclude environmental effects, so the proposed assay was found to be very selective. The method was successfully used to detect Pi in real water samples, and acceptable recoveries were found, suggesting that the method could be used in practice to detect Pi in water samples.

Molecularly Imprinted Polymer-Based Luminescent Chemosensors

Molecularly imprinted polymer (MIP)-based luminescent chemosensors combine the advantages of the highly specific molecular recognition of the imprinting sites and the high sensitivity with the luminescence detection. These advantages have drawn great attention during the past two decades. Luminescent molecularly imprinted polymers (luminescent MIPs) towards different targeted analytes are constructed with different strategies, such as the incorporation of luminescent functional monomers, physical entrapment, covalent attachment of luminescent signaling elements on the MIPs, and surface-imprinting polymerization on the luminescent nanomaterials. In this review, we will discuss the design strategies and sensing approaches of luminescent MIP-based chemosensors, as well as their selected applications in biosensing, bioimaging, food safety, and clinical diagnosis. The limitations and prospects for the future development of MIP-based luminescent chemosensors will also be discussed.

A simple synthesis method of microsphere immunochromatographic test strip for time-resolved luminescence detection of folic acid

Folic acid (FA) is an ingredient that must be added to infant milk powder to avoid potential defects. Rapid, sensitive and reliable detection methods are needed to determined FA addition levels. Thus, this study established a microsphere immunochromatographic test strip for time-resolved luminescence detection (TRLM-ICTS) based on carboxyl-functionalized time-resolved luminescent microspheres (Eu-TRLMs) prepared by a one-step method as fluorescent markers for the immediate quantitative detection of FA in milk powder. Eu-TRLMs prepared by the one-step method showed good dispersion, high stability and strong fluorescence intensity, which is improving the sensitivity of TRLM-ICTS. In the performance evaluation of TRLM-ICTS, the detection limit was 0.487 ng mL−1, the recovery rate was 97.3–105 %, and the actual sample detection results were in line with those of UPLC-MS/MS. TRLM-ICTS has the advantages of rapid, high sensitivity and strong specificity and could as a practical quantitative detection method for the detection of FA in milk powder.

Split luciferase-based assay to detect botulinum neurotoxins using hiPSC-derived motor neurons

Botulinum neurotoxins (BoNTs) have been widely used clinically as a muscle relaxant. These toxins target motor neurons and cleave proteins essential for neurotransmitter release like Synaptosomal-associated protein of 25 kDa (SNAP-25). In vitro assays for BoNT testing using rodent cells or immortalized cell lines showed limitations in accuracy and physiological relevance. Here, we report a cell-based assay for detecting SNAP-25-cleaving BoNTs by combining human induced Pluripotent Stem Cells (hiPSC)-derived motor neurons and a luminescent detection system based on split NanoLuc luciferase. This assay is convenient, rapid, free-of-specialized antibodies, with a detection sensitivity of femtomolar concentrations of toxin, and can be used to study the different steps of BoNT intoxication.

Tunable Luminescence of Silver Nanoclusters Confined in SOD/FAU Zeolites and Selective Sensing for Organic Amine

A series of Ag-zeolite luminescent composites are prepared based on SOD and FAUY zeolites, and the effect of zeolite host particle size on their dynamic luminescent emission properties was discussed for the first time. The relationship between zeolite particle size and the nucleation of silver nanoclusters (AgNCs) is revealed. With the increase of zeolite particle size from nanometers to microns, the luminescent color of both Ag-SOD and Ag-Y composites shows significant blue shift. The observed tunable luminescence can be accounted for the slower nucleation rate of AgNCs in micron-scale zeolites with longer channels, resulting in smaller nuclearity of AgNCs within large-size zeolites, through the characterization of extended X-ray absorption fine structure, implying the important roles played by the zeolite themselves in determining the luminescence properties. Moreover, the composites prepared by us feature simple signal transduction, fast response (30 s), and excellent selectivity and sensitivity for discriminative luminescence detection of triethylamine and ethylamine, and they have good reversible luminescence response after sensing HAc gas, which might imply the potential applications in the volatile organic amine detection and information encryption field.

Study of the inhibition effects on glutathione peroxidase immobilized on MNPs using a stopped-flow microfluidic system

A stopped-flow microfluidic system to monitor glutathione peroxidase (GPx) activity and evaluate potential inhibitors of the enzyme has been developed based on the integration of the microfluidic chip in the reaction/detection zone. This integration supposes the physical alignment at the optimal location of the microfluidic channel, both the magnetically retained enzyme microreactor (MREµR) and the remote luminescence detection using a focused bifurcated fiber optic bundle (BFOB) connected to a conventional spectrofluorometer detector. The method is based on the coupling of two competitive oxidative chemical reactions, in which glutathione (GSH) and homovanillic acid (HVA) competed for their interaction with hydrogen peroxide in the presence of the magnetically retained GPx-MNPs. The biocatalytic reaction was followed by monitoring the fluorescence of the biphenyl-HVA dimer formed. The dynamic range of the calibration graph was 0.45–10 µmol L−1, expressed as GSH concentration with a detection limit of 0.1 µmol L−1 (r2 = 0.9954, n = 10, r = 3). The precision expressed as the relative standard deviation (RSD%) was between 0.5 and 3.9%. The stopped-flow microfluidic system showed a sampling frequency of 25 h−1. The method was applied to the study of GPx inhibition provided by three inhibitory compounds, two metallic ions Hg(II) and Cu(II) and t-butyl hydroperoxide, and their presence in liquid samples, as water, milk, and edible oil. Recovery values between 88.7 and 99.4% were achieved in all instances.Graphical

Real‐Time In Situ Volatile Organic Compound Sensing by a Dual‐Emissive Polynuclear Ln‐MOF with Pronounced LnIII Luminescence Response

AbstractLanthanide metal–organic frameworks (Ln‐MOFs) are promising for luminescence detection of volatile organic compound (VOC) vapors, but usually suffer from the silent or quenched Ln3+ emission. Herein, we report a new dual‐emissive Eu‐MOF composed of the coordinatively unsaturated Eu9 clusters that afford abundant open metal sites to form a confined “binding pocket” to facilitate the preconcentration and recognition of VOCs. Single‐crystal structural analyses reveal that specific analytes can replace the OH oscillators in the first coordination sphere of Eu3+ and form a unique hydrogen‐bonding second‐sphere adduct tying adjacent Eu9 clusters together to minimize their nonradiative vibrational decay. With the promoted Eu3+ luminescence, the MOF realizes real‐time in situ visual sensing of THF vapor (<1 s) and shows a quantitative ratiometric response to the vapor pressure with a limit of detection down to 17.33 Pa. Also, it represents a top‐performing ratiometric luminescent thermometer.

Real-Time In Situ Volatile Organic Compound Sensing by a Dual-Emissive Polynuclear Ln-MOF with Pronounced LnIII Luminescence Response.

Lanthanide metal-organic frameworks (Ln-MOFs) are promising for luminescence detection of volatile organic compound (VOC) vapors, but usually suffer from the silent or quenched Ln3+ emission. Herein, we report a new dual-emissive Eu-MOF composed of the coordinatively unsaturated Eu9 clusters that afford abundant open metal sites to form a confined "binding pocket" to facilitate the preconcentration and recognition of VOCs. Single-crystal structural analyses reveal that specific analytes can replace the OH oscillators in the first coordination sphere of Eu3+ and form a unique hydrogen-bonding second-sphere adduct tying adjacent Eu9 clusters together to minimize their nonradiative vibrational decay. With the promoted Eu3+ luminescence, the MOF realizes real-time in situ visual sensing of THF vapor (<1 s) and shows a quantitative ratiometric response to the vapor pressure with a limit of detection down to 17.33 Pa. Also, it represents a top-performing ratiometric luminescent thermometer.

An upconverted nanoparticle-porphyrin metal-organic framework platform for near-infrared detection of nitenpyram.

A ratiometric nitenpyram (NIT) upconversion luminescence sensor UCNPs-PMOF was fabricated from a metal-porphyrin organic framework (PMOF) and pretreated UCNPs. The reaction between NIT and the PMOF releases the H2TCPP (5,10,15,20-tetracarboxyl phenyl) porphyrin ligand, which enhances the absorption of the system at 650 nm, and reduces the upconversion emission intensity of the sensor at 654 nm through a luminescence resonance energy transfer (LRET) mechanism, thus achieving the quantitative detection of NIT. The detection limit was 0.21 μM. Meanwhile, the emission peak of UCNPs-PMOF at 801 nm does not change with the concentration of NIT, and the emission intensity ratio (I654 nm/I801 nm) is used to achieve the ratiometric luminescence detection of NIT, and the detection limit is 0.22 μM. UCNPs-PMOF has good selectivity and anti-interference to NIT. In addition, it has a good recovery rate in actual sample detection, which indicates that it has high practicability and reliability in NIT detection.

Luminescence detection of CH2Cl2 by varying Cu⋯Cu interactions in a flexible porous coordination polymer

A flexible Cu(i) coordination polymer is reported as the luminescence sensor for the detection of CH2Cl2. The adsorption of guest molecules lengthens the Cu⋯Cu distance, resulting in luminescent blue shifts and higher emission energy.

Rapid and quantitative detection of the inflammatory marker neopterin based on a visible luminescent Zn(II)-Eu(III) nanocluster.

A high-nuclearity Zn(II)-Eu(III) nanocluster was synthesized for the rapid and quantitative luminescence detection of neopterin as an inflammatory marker.

Interaction of N-nitrosamines with binuclear copper complexes for luminescent detection.

Cu(I) from tetrakis(acetonitrile)copper(I) hexafluorophosphate ([Cu(MeCN)4]PF6) was complexed with five structurally related phosphines containing N-heterocycles. The interactions between the resulting complexes and some N-nitrosamines were studied using X-ray crystallography as well as emission spectroscopy. Upon complexation, three phosphine ligands bridge two Cu(I) centers to give paddlewheel type structures that displayed a range of emission wavelengths spanning the visible region. N-Nitrosodimethylamine (NDMA) was shown to coordinate to one of the two copper centers in some of the paddlewheel complexes in the solid state and this interaction also quenches their emissions in solution. The influence of the weakly coordinating anion on crystal and spectroscopic properties of one of the paddlewheel complexes was also examined using tetrakis(acetonitrile)copper(I) perchlorate ([Cu(MeCN)4]ClO4) as an alternative Cu(I) source. Similarly, copper(II) perchlorate hexahydrate (Cu(ClO4)2·6H2O) was used for complexation to observe the impact of metal oxidation state on the two aforementioned properties. Lastly, the spectroscopic properties of the complex between Ph2P(1-Isoquinoline) and Cu(I) was shown to exhibit solvent dependence when the counterion is ClO4-. These Cu(I) complexes are bench stable solids and may be useful materials for developing a fluorescence based detection method for N-nitrosamines.

Highly Selective MOF-Based Turn-Off Luminescence Detection of Hg2+ Ions in an Aqueous Medium and Its Dual Functional Catalytic Activity toward Aldol Condensation and β-Enamination Reactions.

A new organic ligand, 5-(carboxyformamido)isophthalic acid (5-CFIA), was prepared and employed for the synthesis of two compounds [M3(C10H4O7N1)2(8H2O)]·H2O (M = Cd, Mn). The compounds have three-dimensionally extended structures. Both the compounds were found to be luminescent at room temperature. The luminescence nature was exploited for the detection of Hg2+ ions in an aqueous medium with good selectivity. The interactions between Hg2+ ions and the compounds quench the luminescence intensity and act as a turn-off sensor. Both the compounds exhibited low limits for the detection of Hg2+ ions and in the range mandated by the WHO. The interactions between Hg2+ ions and the compound involve the -NH group, which was probed using Raman and IR spectroscopic techniques. These studies provide important pointers toward the mechanism of this turn-off luminescence behavior. The compounds were explored for base-catalyzed aldol condensation and Lewis acid-promoted β-enaminoester formation reactions. The aldol condensation reaction uses the -NH functionality as a base. The studies indicate that the electron-withdrawing group produces products with higher yields. The β-enaminoester reaction uses the Lewis acid centers, and the studies reveal that the electron-withdrawing groups produce lesser yields of the products. The catalytic nature of the reaction and recyclability of the catalysts were also established. The catalytic reactions employ ethanol (aldol condensation) and no solvent (β-enaminoester), which suggests that the reactions are green and environmentally friendly. The Mn compound was observed to be anti-ferromagnetic.

Scanning x-ray excited optical luminescence of heterogeneity in halide perovskite alloys

Understanding the optoelectronic properties of optically active materials at the nanoscale often proves challenging due to the diffraction-limited resolution of visible light probes and the dose sensitivity of many optically active materials to high-energy electron probes. In this study, we demonstrate correlative synchrotron-based scanning x-ray excited optical luminescence (XEOL) and x-ray fluorescence (XRF) to simultaneously probe local composition and optoelectronic properties of halide perovskite thin films of interest for photovoltaic and optoelectronic devices. We find that perovskite XEOL stability, emission redshifting, and peak broadening under hard x-ray irradiation correlates with trends seen in photoluminescence measurements under continuous visible light laser irradiation. The XEOL stability is sufficient under the intense x-ray probe irradiation to permit proof-of-concept correlative mapping. Typical synchrotron XRF and nano-diffraction measurements use acquisition times 10–100x shorter than the 5-second acquisition employed for XEOL scans in this study, suggesting that improving luminescence detection should allow correlative XEOL measurements to be performed successfully with minimal material degradation. Analysis of the XEOL emission from the quartz substrate beneath the perovskite reveals its promise for use as a real-time in-situ x-ray dosimeter, which could provide quantitative metrics for future optimization of XEOL data collection for perovskites and other beam-sensitive materials. Overall, the data suggest that XEOL represents a promising route towards improved resolution in the characterization of nanoscale heterogeneities and defects in optically active materials that may be implemented into x-ray nanoprobes to complement existing x-ray modalities.

Glucose emission spectra through mid-infrared passive spectroscopic imaging of the wrist for non-invasive glucose sensing

Non-invasive blood glucose sensing can be achieved using mid-infrared spectroscopy, although no practical device based on this method has yet been developed. Here, we propose mid-infrared passive spectroscopic imaging for glucose measurements from a distance. Spectroscopic imaging of thermal radiation from the human body enabled, for the first time in the world, the detection of glucose-induced luminescence from a distance. In addition, glucose emission spectra of the wrist acquired at regular intervals up to 60 min showed that there was a strong correlation between the glucose emission intensity and blood glucose level measured using an invasive sensor. Thus, the new technology proposed here is expected to be applied to real-time monitoring of diabetic patients to detect hypoglycemic attacks during sleep and to detect hyperglycemia in a population. Moreover, this technology could lead to innovations that would make it possible to remotely measure a variety of substances.

A Golgi Apparatus‐Targetable Probe Based on Lanthanide Complexes for Ratiometric Time‐Gated Luminescence Detection of Hydrogen Sulfide

AbstractDevelopment of bioanalytical methods for selective and accurate detection of H2S in living samples is essential for understanding the pathological and physiological functions of this gasotransmitter in biological systems. Here we report a Golgi apparatus‐targetable lanthanide complex‐based luminescent probe, Golgi‐ABTTA‐Eu3+/Tb3+, that can be used for accurately determining H2S in aqueous solution and living cells via the ratiometric time‐gated luminescence (RM‐TGL) technique. This probe is composed of 2,2′:6′,2′′‐terpyridine‐Eu3+/Tb3+ mixed complexes as the luminophore, 4‐azidobenzyl‐ether as the responsive moiety, and sulfanilamide as the Golgi apparatus‐targeting moiety. Upon reaction with H2S, accompanied by the cleavage of 4‐azidobenzyl group from the probe molecule, the long‐lived emission of Tb3+ complex at 540 nm is significantly enhanced, while that of Eu3+ complex at 610 nm is obviously reduced. It was noted that the I540/I610 ratio increased by 8.8 times after the probe was exposed to H2S, which enabled H2S to be detected with RM‐TGL method. After being incubated with living cells, the probe molecules were selectively accumulated in the Golgi apparatus, which allowed H2S in the Golgi apparatus to be successfully imaged in RM‐TGL mode.

Solid–liquid convertible hydrogel mediated by dual-functional cellulose nanofiber/Eu–dipicolinic acid/carbon dot complexes for high-precision sequential luminescence detection of cupric ion and oxytetracycline

A portable, sensitive, rapid, specific, and environment-friendly polyvinyl alcohol–borax (PB) hydrogel fluorescence probe was synthesized for the sequential sensing of Cu2+ and oxytetracycline (OTC) in wastewater. The aminated 2,2,6,6-tetramethylpiperidinooxy-oxidized cellulose nanofibers/europium complexes/carbon dot (ATOCN/Eu(DPA)3/CD) complex was added to the PB matrix. With the assistance of ATOCNs, the in-situ polymerized ATOCN/Eu(DPA)3/CD complexes were well-dispersed in the hydrogel and enhanced the mechanical properties of the hydrogel. The prepared hydrogel could be converted from solid to liquid by adjusting the water content to reduce the deviations caused by the solid probe detection. The probe not only induced evident fluorescence quenching and instantaneous response to Cu2+ at 430 nm and OTC at 617 nm but also exhibited a high selectivity to Cu2+ and OTC. The detection limits for Cu2+ and OTC were 0.031 and 0.019 mg L−1, respectively. Fluorescence recover was achieved by adding S2− for CuS precipitate formation and for the thermal decomposition of OTC. After repeatedly recovering the fluorescence for 10 times, the fluorescence intensity at 430 nm was restored to 79% of the original intensity and that at 617 nm was stored to 95%. The results show that hydrogels have remarkable potential applicability in detecting Cu2+ and OTC in wastewater.