Review on the application of upconversion nanomaterials in heavy metal detection

As a widespread element,heavy metals have a significant impact on human health and threaten human health.It is of great significance to develop analytical technologies that can detect heavy metal ions quickly and accurately.In comparison to conventional fluorescent materials such as organic dyes,quantum dot(QD)labels,and carbon quantum dots(CD),fluorescence detection technology utilizing lanthanide(Ln)ion-doped upconversion nanoparticles(UCNPs)stands out due to its distinctive attributes.These include a notably reduced autofluorescence background,enhanced tissue penetration capabilities,biocompatibility with cellular tissues,and minimal photodamage inflicted on biological samples.The utilization of this technology has garnered considerable attention across multiple fields.In the domain of heavy metal detection,traditional laboratory methods necessitate costly instrumentation and a fully equipped laboratory,involving intricate sample processing procedures and protracted detection periods,as well as a demand for skilled personnel.In contrast,the implementation of this material offers rapid and cost-effective detection,significantly mitigating the technical barriers for operators.Consequently,this represents an exceptional avenue to curtail expenses and broaden the scope of detection within the analytical process.This paper reviews the research progress of UCNPs in the detection of heavy metal ions,encompassing a brief elucidation of the luminescence principle of upconversion nanomaterials and commonly used detection principles.Additionally,it provides a detailed overview of the research status of several common non-metal ions and essential heavy metals.Furthermore,it summarizes the current focal points in UCNP detection and discusses the challenges and prospects associated with it.

A new Eu-MOF for ratiometrically fluorescent detection toward quinolone antibiotics and selective detection toward tetracycline antibiotics

Development of new self-calibrating fluorescent sensing methods has been a popular research field with the aim of protecting the human health and environment sustainability. In this work, a novel Eu-based metal organic framework(MOF) Eu(2,6-NDC)(COO)(BUC-88) was developed by employing 2,6-NDC(2,6-naphthalenedicarboxylic acid) as bridging ligands. BUC-88 performed different sensing process toward quinolone antibiotics and tetracyclines antibiotics in terms of fluorescence intensity and color. BUC-88exhibited excellent selectivity and sensitivity detection property toward enrofloxacin(ENR), norfloxacin(NOR) and ciprofloxacin(CIP) over other Pharmaceutical and Personal Care Products(PPCPs), accomplishing the detection limit of 0.12 μmol/L, 0.52 μmol/L, 0.75 μmol/L, respectively. Notably, BUC-88 acted as an excellent fluorescence sensor for tetracyclines antibiotics with fast response time(less than 1 s), high selectivity and sensitivity(LODs = 0.08 μmol/L). The fluorescent detection method was successfully used for visual and ultrasensitive detection of ENR, NOR, CIP and tetracycline hydrochloride(TC) in lake water with satisfied recovery from 99.75% to 102.30%. Finally, the photoinduced electron transfer and the competitive absorption of ultraviolet light are the main mechanisms for sensitive detection toward quinolone antibiotics and tetracyclines antibiotics.

Fluorescent Detection of Cu(Ⅱ) by Chitosan-based AIE Bioconjugate

Detection of Cu（Ⅱ） is very important in disease diagnose, biological system detection and environmental monitoring. Previously, we found that the product TPE-CS prepared by attaching the chromophores of tetraphenylethylene（TPE） to the chitosan（CS） chains showed excellent fluorescent properties. In this study, we tried to use TPE-CS for detecting Cu（Ⅱ） because of the stable complexation of CS with heavy metals and the luminosity mechanism of the Restriction of Intramolecular Rotations（RIR） for aggregation-induced emission（AIE）-active materials. The fluorescence intensity changed when TPE-CS was contacted with different metal ions, to be specific, no change for Na;, slightly increase for Hg;, Pb;, Zn;, Cd;, Fe;, Fe;due to the RIR caused by the complexation between CS and metal ions. However, for Cu;, an obvious fluorescence decrease was observed because of the Photoinduced-Electron-Transfer（PET）. Moreover, we found that the quenched FL intensity of TPE-CS was proportional to the concentration of Cu（Ⅱ） in the range of 5 μmol/L to 100 μmol/L, which provided a new way to quantitatively detect Cu（Ⅱ） . Besides, TPE-CS has excellent water-solubility as well as absorbability（the percentage of removal, R = 84%）, which is an excellent detection probe and remover for Cu（Ⅱ） .

Simple synthesis of silver nanocluster composites AgNCs@PE-g-PAA by irradiation method and fluorescence detection of Cr^(3+)

Silver nanoclusters(AgNCs)are a new type of nanomaterials with similar properties to molecules and unique applications.The applications of AgNCs can be significantly expanded by combining them with different matrix materials to obtain AgNC composites.Using irradiation techniques,we developed a simple two-step method for preparing silver nanocluster composites.First,polyacrylic acid(PAA)chains were grafted onto the surface of a PE film as templates(PE-g-PAA).Subsequently,silver ions were reduced in situ on the surface of the template material to obtain the AgNC composites(AgNCs@PE-g-PAA).The degree of AgNC loading on the composite film was easily controlled by adjusting the reaction conditions.The loaded AgNCs were anchored to the carboxyl groups of the PAA and wrapped in the graft chain.The particle size of the AgNCs was only 4.38±0.85 nm,with a very uniform particle size distribution.The AgNCs@PE-g-PAA exhibited fluorescence characteristics derived from the AgNCs.The fluorescence of the AgNCs@PE-g-PAA was easily quenched by Cr^(3+)ions.The composite can be used as a fluorescence test paper to realize visual detection of Cr^(3+).

Preparation of Nitrogen-doped Carbon Dots from Coke Powder as a Fluorescent Chemosensor for Selective and Sensitive Detection of Cr (Ⅵ)

The nitrogen-doped carbon dots(N-CDs)were prepared by using coke powder as carbon source and one-step hydrothermal method.The N-CDs were studied as a fluorescent chemosensor for determining Cr(Ⅵ)in water.The selective,sensitive,reproducibility and stability of as-prepared N-CDs were investigated.The morphology,composition and properties of N-CDs were characterized by a series of methods.The fluorescence quenching of N-CDs by Cr(Ⅵ)was explored.The experimental results reveal that the obtained N-CDs have great hydrophilicity and strong luminescence properties,which demonstrates the successful doping of nitrogen into the CDs.The surface-active groups and emission wavelength range of CDs increase due to the electronegativity and electron donor effect of doping N atom.Furthermore,the N-CDs exhibit good photochemical properties for the detection of Cr(Ⅵ),including a wide linear range from 0.3 to 200μM(R^(2)=0.9935)and a low detection limit of 0.10μM at the signal-to-noise ratio of 3(S/N=3).Moreover,the N-CDs as a sensor was used successfully for Cr(Ⅵ)detection in real water samples with recovery rates of 99.9%-110.6%.This sensor also shows highly reproducibility and stability.The N-CDs fluorescent chemical sensor may be a potential candidate for applying in the field of other fluorescent chemical sensing,catalysis,photoelectric devices and other fields.

Synthesis of Carbon dots from Biomass Chenpi for the Detection of Hg^(2+)

Biomass-derived carbon dots(C-dots)are considered a very important carbon material in metal ion detection of their small environmental impact,simple preparation process,and relatively low cost.A green approach for synthesizing biomass-derived C-dots from Chenpi using a hydrothermal method without further processing is proposed in the present study.The as-synthesized C-dots show excellent fluorescence properties,superior resistance to UV irradiation photobleaching,and high photostability in salt-containing solutions.The C-dots were used in the form of label-free fluorescent probes for sensitively detecting Hg^(2+)selectively.The outcome relationship behaved linearly and was established based on a given range between 10–300 nM concentration,with a detection limit of 7.0 nM.This green strategy obtains a high C-dot quantum yield of 10.8%and satisfactory results in detecting Hg^(2+)in actual water samples.

Elaborate Design of Two Novel Fluorescent Zinc-based Metal-Organic Frameworks for Highly Efficient Tetracycline Antibiotics Detection

The abuse of tetracycline antibiotics has caused great harm to human health and ecosystems.Developing inexpensive,convenient and sensitive methods for the detection of tetracycline antibiotics is highly desirable.Herein,based on the H_(4)ddp ligand[H_(4)ddp=3-(3,5-dicarboxyphenyl)pyridine-2,6-dicarboxylic acid],two novel zinc-based metal-organic frameworks(MOFs){[Zn_(3)(ddp)_(2)(H_(2)O)_(4)]·3H_(2)O}n(Zn1-ddp)and{[Zn_(3)(ddp)_(2)(H_(2)O)_(4)]·3H_(2)O}n(Zn2-ddp)were successfully designed by delicate structural regulation.Both Zn1-ddp and Zn2-ddp exhibited excellent water and chemical stability and showed excellent fluorescence quenching performance for tetracycline antibiotics.Notably,the more advanced framework structure and better fluorescent performance make Zn1-ddp more sensitive than Zn2-ddp in fluorescent detection with a detection limit of 0.29µmol/L for tetracycline(TC),0.09µmol/L for doxycycline(DOX),0.10µmol/L for minocycline(MIN)and metacycline(MEL),0.19µmol/L for chlortetracycline(CTC),and 0.67µmol/L for oxytetracycline(OTC)among tetracycline antibiotics.The fluorescence quenching mechanism of Zn1-ddp and Zn2-ddp for tetracycline antibiotics detection was deeply investigated.The reasons for the superior detection performance of Zn1-ddp over Zn2-ddp were also analyzed in depth through Fourier transform infrared spectrophotometry(FTIR),X-ray photoelectron spectroscopy(XPS)analysis and framework structure analysis.The developed method opens up a new perspective for antibiotics detection based on zinc-based MOFs.

Applying an AIE type fluorescent probe in the detection of tetracycline antibiotics

The typical representative TPB(tetraphenyl-1,3-butadiene)molecule with AIE effect was used as a fluorescent probe,and the specific recognition of tetracycline antibiotics was achieved through the comparison of the experimental results of the quenching of TPB by nine antibiotics of different types,which indicated that tetracycline antibiotics were found to quench TPB to the greatest extent,while the quenching of other antibiotics(e.q.chloramphenicol,aminoglycoside,sulfonamides,and quinolone)was not obvious.Then the quantitative relationship between the concentration of antibiotic solution and the effect of fluorescence quench was investigated by taking oxytetracycline among tetracycline antibiotics as an example,and the detection limit was calculated.Finally,it was found that the UV absorption spectra of tetracycline hydrochloride and the fluorescence excitation spectra of TPB had high overlap,while the overlap between the UV absorption spectra of other antibiotics,such as sulfadimethoxine,and the fluorescence laser spectrum of TPB was low,which fulfilled the fluorescence internal filtering effect.The fluorescence probe has stable properties,low cost and strong anti-interference ability,which makes the method more valuable in the practical detection of tetracycline.This study indicates great potent in the detection of antibiotics.

Determination of Diphenytriazol (DL111-IT) in Rabbit Plasma by High-Performance Liquid Chromatography with Fluorescence Detection

Aim To develop an HPLC method with fluorescence detection for the assay ofDL111-IT in rabbit plasma. Methods DL111-IT and internal standard glybenzcyclamide in rabbit plasmawere extracted with chloroform. The determination was performed on a Diamonsil ODS-C_(18) column(150 mm x 4.6 mm, 5 μm) with a mobile phase of acetonitrile and 0.025 mol·L^(-1) diammoniumhydrogen phosphate buffer (pH 5.0, adjusted by phosphoric acid) (60:40, V/V) at a flow-rate of 1.0mL·min^(-1) . Fluorescence detector was operated at excitation wavelength of 250 nm and emissionwavelength of 332 nm. Results The calibration curve in plasma was linear from 1.00 - 20.00ng·mL^(-1) ( r = 0.999 6, n = 5). The method afforded average extracting recoveries of 85.3% ±1.3%, 84.9% ± 2.7% and 85.8% ± 1.8%, and the average method recoveries were 99.5% ±0.4%, 102.1%± 1.8% and 101.3% ± 2.4% for the high (20.00 ng·mL^(-1)) , middle (10.00 ng·mL^(-1)) and low (1.00 ng·mL^(-1)) check samples, respectively. The intra-day (n = 5) and inter-day (n = 5) precisions(RSD) were less than 3.0% and 7.0%, respectively. The limit of detection and quantitation for themethod were 0.3 ng·mL^(-1) (S/N = 3) and 1 ng·mL^(-1) (S/N = 10, RSD<7.0%) plasma sample,respectively. Conclusion The developed method was accurate, sensitive, simple and could be used forpharmacokinetic study of DL111- IT.

Determination of fluorinated quinolone antibacterials by ion chromatography with fluorescence detection

For preparing fluorinated quinolone antibiotic medicine locally used in stomatology, simultaneous determination of norfloxacin, ciprofloxacin, and enoxacin was carried out by multiphase ion chromatography with fluorescence detection. Quinolone antibiotics were separated by Dionex OmniPac PAX-500 column with an eluent of 15 mmol/L H2SO4 and 35% methanol （v/v） at a flow-rate of 1.0 ml/min and detected with fluorescence with excitation and emission wave lengths of 347 ran and 420 ran respectively. The detection limits （S/N=3） of norfloxacin, ciprofloxacin and enoxacin were 50, 105 and 80 ng/ml respectively. The relative standard deviations of retention time, peak area and peak height were less than 1.1% and good linear relationship resulted. The developed method was applied to pharmaceutical formulations and biological fluids.

The Development of A Fluorescence Polarization Immunoassay for Aflatoxin Detection

A fluorescence polarization immunoassay （FPIA） was developed for the analysis ofaflatoxins （AFs） using an anti-aflatoxin B1 （AFB1） monoclonal antibody and a novel fluorescein-labeled AFB1 tracer. The FPIA showed an IC50 value of 23.33 ng/mL with a limit of detection of 13.12 ng/mL for AFB1. The cross-reactivities of AFB1, AFB2, AFG1, AFG2, AFM1, and AFM2 with the antibody were 100%, 65.7%, 143%, 23.5%, 111.4%, and 2%, respectively. The group-specificity of anti-AFB1mAb indicated that the FPIA could potentially be used in a screening method for the detection of total AFs, albeit not AFG2 and AFM2. The total time required for analyzing 96 samples in one microplate was less than 5 rain. This study demonstrates the potential usefulness of the FPIA as a rapid and simple technique for monitoring AFs.

New HPLC Method with Experimental Design and Fluorescence Detection for Analytical Study of Antihypertensive Mixture,Amlodipine and Valsartan

New HPLC method was developed for determination of amlodipine and valsartan in their binary mixture as a part of routine control of combined formulations. The method was validated to meet official requirements including selectivity, stability, linearity, precision and accuracy. Chromatography was carried out using a LiChrospher RP-18 column, a mixture containing acetonitrile, phosphate buffer of pH 3.5 and methanol (45:45:10, v/v/v) and new fluorescence detection at 255 nm for excitation and 448 nm for emission. The effect of methanol content, pH of the buffer, flow rate, detection wavelengths and column temperature was estimated in robustness study, according to a plan defined by the Plackett-Burman design. For identification of significant effects, both graphical and statistical methods were used. Ro-bustness for dissolution test was checked estimating the effects of paddle speed, temperature and pH of dissolution medium. The method was proved to complying with all official guidelines. Therefore, it is suitable for determination of amlodipine and valsartan in their binary mixtures for different analytical and pharmaceutical purposes.

Determination of Amino Acids in an Individual Erythrocyteby Capillary Electrophoresis with Intracellular FITC-derivatization and Laser-induced Fluorescence Detection

A novel approach for analysis of amino acids in individual erythrocytes was established. In this method, the derivatization reagent was introduced into the living cells by electroporation. After derivatization, the amino acids in a single cell were determined by capillary electrophoresis with laser-induced fluorescence detection.

Research of Confocal Laser Induced Fluorescence Detection System for Micro-fluidic Chip

The characteristics such as signal noise ratio（SNR） and sensitivity of the fluorescence detection system for micro-fluidic chip influence the performance of the whole system extremely. The confocal laser induced fluorescence detection system is presented. Based on the debugging of optical and circuit modules, the results of detecting the samples are given and analyzed theoretically, and the improved project is put forward.

Fluorescence detection of Europiumdoped very small superparamagnetic iron oxide nanoparticles in murine hippocampal slice cultures

In the late 1980s,superparamagnetic iron oxide nanoparticles（SPIO）moved into focus as contrast agents in magnetic resonance imaging（MRI）,due to their strong relaxivity and resulting higher resolution of images.At the time,no one anticipated their high potential in basic research or for medical diagnostic andtreatment. Since then, SPIO have been evaluated notonly as spe- cific markers for MRI, but also for cell labeling and tracking （Li et al., 2013）.

Fuzzy Pattern Recognition System for Detection of Alga Distribution

To realize the on-line measurement and make analysis on the density of algae and their cluster distribution, the fluorescent detection and fuzzy pattern recognition techniques are used. The principle of fluorescent fiber-optic detection is given as well as the method of fuzzy feature extraction using a class of neural network.

Fluorescence Turn-On/Off Responses of In(Ⅲ)-MOF to Short-Chain Perfluorocarboxylic Acids

Short-chain perfluorocarboxylic acids(PFCAs) are a class of persistent organic pollutants that are widely used as substitutes for long-chain PFCAs. However, they also pose a non-negligible risk to ecosystems. In this study, we demonstrated that a fluorescent metal–organic framework(MOF)(named V-101) constructed from In^(3+)and an aromatic-rich tetratopic carboxylate ligand 5-[2,6-bis(4-carboxyphenyl) pyridin-4-yl] isophthalic acid(H4BCPIA) exhibited highly efficient turn-off and turn-on fluorescence responses toward five short-chain PFCAs in water and methanol, respectively. The limits of detection of V-101 toward five short-chain PFCAs are down to μg/L level, and it showed good anti-interference abilities toward short-chain PFCAs in the presence of common metal ions. The major mechanisms associated with fluorescence responses were molecular collisions and interactions between V-101 and short-chain PFCAs. This work demonstrates that the structure variety of MOFs imparts them with the potential of MOFs in the detection of short-chain PFCAs for pollution control.

A Fluorescent In (Ⅲ) Metal-Organic Framework for Explosives Detection

Anovel metal-organic framework{[In_(3)(TATAT)_(2)]·3CH_(3)NH_(3)·7NMF·8H_(2)O}[JLU-MOF101,H_(6)TATAT=5,5′,5″-(1,3,5-triazine-2,4,6-triyl)tris-(azanediyl)triisophthalate,NMF=N-methyl-formamide]with cor topology has been synthesized under solvothermal conditions.The framework of JLU-MOF101 is constructed by{In(COO)_(4)}-nodes and a hexacarboxylic organic ligand.JLU-MOF101 exhibits excellent fluorescence properties in N,N-dimethylformamide(DMF)solution,and its emission spectrum can be greatly overlapped with the ultraviolet absorption spectra of trinitrophenol(TNP)and 2,4-dinitrophenol(2,4-DNP).As a result,JLU-MOF101 exhibits excellent performance of fluorescence quenching for TNP and 2,4-DNP.In addition,we demonstrate the selective detection capability of JLU-MOF101 through a large number of anti-interference tests.

Droplet microfluidic chip for precise monitoring of dynamic solution changes

In this work,an automated microfluidic chip that uses negative pressure to sample and analyze solutions with high temporal resolution was developed.The chip has a T-shaped channel for mixing the sample with a fluorescent indicator,a flow-focusing channel for generating droplets in oil,and a long storage channel for incubating and detecting the droplets.By monitoring the fluorescence intensity of the droplets,the device could detect changes in solution accurately over time.The chip can generate droplets at frequencies of up to 42 Hz with a mixing ratio of 1:1 and a temporal resolution of 3–6 s.It had excellent linearity in detecting fluorescein solution in the concentration range 1–5μM.This droplet microfluidic chip provides several advantages over traditional methods,including high temporal resolution,stable droplet generation,and faster flow rates.This approach could be applied to monitoring calcium ions with a dynamic range from 102 to 107 nM and a detection limit of 10 nM.