Review of Cellulose Nanocrystal-based Fluorophore Materials and Their Application in Metal Ion Detection

Cellulose nanocrystals （CNCs）, a unique and promising natural material extracted from native cellulose, have attracted considerable attention owing to their physical properties and special surface chemistry. This review focuses on chemical conjugation strategies that can be used for preparation of ？uorescent-molecule labeled CNCs and the development of biomaterials. Furthermore, their application in the detection of metal ions and future development prospects are discussed. We hope to provide a clear view of the strategies for surface fluorescent modifcation of CNCs and their application in detection of metal ions.

Nanopore-Based Metal Ion Detection and Metal Ion-Mediated Nanopore Sensing

With the continuous development of nanotechnology,single-molecule nanopore detection has become a popular research topic.In this review,we summarize the application of biological nanopores for metal ions detection as well as overview the function of metal ions in the ion-mediated nanopore detection of different analytes in recent decades.According to the previous reports,biological nanopores utilize two strategies to detect metal ions.First,the specific binding sites are engineered in the nanopore to slow down the translocation rate of metal ions,resulting in the diverse specific current blockage signals.Secondly,the external molecule probes are added in the detection system to interact with metal ions,leading to the characteristic changes in the signals.At the same time,the external addition of metal ions into the nanopore detection systems enhances the sensitivity and selectivity through the changes of pore charges,the coordination with analytes or indirect detection.This review provides a summary on the role of metal ions in the application of nanopore detection technology.

Carbon Dots-Doped Electrospun Fibers for Simultaneous Metal Ion Detection and Adsorption of Dyes

The required treatment and monitoring of contaminants in wastewater reinforces the development of low-cost adsorbents/chemosensors,introducing advantages relative to the detection/removal of toxic metals and dyes.Herein,it is reported a two-step process of fabrication of fluorescent carbon dots via the hydrothermal treatment of amino acids for the following encapsulation in electrospun fibers.The prominent anionic behavior of electrospun fibers of Eudragit L100 was explored for adsorption of cationic dyes(methylene blue and crystal violet)-with the prevailing electrostatic interaction of parts being favored by the formation of monolayers on the surface of adsorbents.On the other hand,the controlled release of carbon dots(CDs)from fibers to the reactor can be explored for a second application:the nitrogen ligands from released glycine-based carbon dots can be explored to indicate the presence of metal ions in aqueous solution.Our experiment resulted in a quenching in the fluorescence of the CDs in order of 90%in the emission of particles in the response of the presence of Fe^(3+) ions,characterizing a promising perspective for this experimental system.

Thiourea functionalized CdSe/CdS quantum dots as a fluorescent sensor for mercury ion detection

CdSe/CdS quantum dots （QDs） functionalized by thiourea （TU） were synthesized and used as a fluorescent sensor for mercury ion detection. The TU-functionalized QDs were prepared by bonding TU via electrostatic interaction to the core/shell CdSe/CdS QDs after capping with thioglycolic acid （TGA）. It was observed that the fluorescence of the functionalized QDs was quenched upon the addition of Hg^2＋. The quantitative detection of Hg^2＋ with this fluorescent sensor could be conducted based on the linear relationship between the extent of quenching and the concentration of Hg^2＋ added in the range of 1-300 μg.L^-1, A detection limit of 0.56 μg.L^-1 was achieved. The sensor showed superior selectivity for Hg^2＋ and was successfully applied to the determination of mercury in environmental samples with satisfactory results

Hydroxylated graphene quantum dots as fluorescent probes for sensitive detection of metal ions

Highly sensitive methods are important for monitoring the concentration of metal ions in industrial wastewater.Here,we developed a new probe for the determination of metal ions by fluorescence quenching.The probe consists of hydroxylated graphene quantum dots(H-GQDs),prepared from GQDs by electrochemical method followed by surface hydroxylation.It is a non-reactive indicator with high sensitivity and detection limits of 0.01μM for Cu2+,0.005μM for Al3+,0.04μM for Fe3+,and 0.02μM for Cr3+.In addition,the low biotoxicity and excellent solubility of H-GQDs make them promising for application in wastewater metal ion detection.

Highly sensitive and stable SERS probes of alternately deposited Ag and Au layers on 3D SiO2 nanogrids for detection of trace mercury ions

The hazard of Hg ion pollution triggers the motivation to explore a fast, sensitive, and reliable detection method. Here, we design and fabricate novel 36-nm-thick Ag-Au composite layers alternately deposited on three-dimensional （3D） periodic SiO2 nanogrids as surface-enhanced Raman scattering （SERS） probes. The SERS effects of the probes depend mainly on the positions and intensities of their localized surface plasmon resonance （LSPR） peaks, which is confirmed by the absorption spectra from finite-difference time-domain （FDTD） calculations. By optimizing the structure and material to maximize the intrinsic electric field enhancement based on the design method of 3D periodic SERS probes proposed, high performance of the Ag-Au/SiO2 nanogrid probes is achieved with the stability further enhanced by annealing. The optimized probes show the outstanding stability with only 4.0% SERS intensity change during 10-day storage, the excellent detection uniformity of 5.78% （RSD）, the detection limit of 5.0 × 10-12 M （1 ppt）, and superior selectivity for Hg ions. The present study renders it possible to realize the rapid and reliable detection of trace heavy metal ions by developing high- performance 3D periodic structure SERS probes by designing novel 3D structure and optimizing plasmonic material.

SERS-based mercury ion detections:principles,strategies and recent advances

Mercury ion(Hg^(2+)),known as one of the highly toxic and soluble heavy metal ions,is causing serious environmental pollution and irreversible damage to the health.It is urgent to develop some rapid and ultrasensitive methods for detecting trace mercury ions in the environment especially drink water.Surface-enhanced Raman scattering(SERS)is considered as a novel and powerful optical analysis technique since it has the significant advantages of ultra-sensitivity and high specificity.In recent years,the SERS technique and its application in the detection of Hg^(2+)have become more prevalent and compelling.This review provides an overall survey of the development of SERS-based Hg^(2+)detections and presents a summary relating to the basic principles,detection strategies,recent advances and current challenges of SERS for Hg^(2+)detections.

Sign Response Mechanism of TCA Self-assembled Fluorescence Probe for Cu^2＋ Detection： FRET Evidence by DFT

A new type of self-assembled molecule ON-OFF fluorescence probe for toxic transition metal ions, made up of thiacalix[4]arene, micelle and fluorescence group, has been studied by DFT/TDDFT method combined with experiment spectra. Since the mechanism of the optical quenching signal response of such self-assembled micelle probe has always been a controversial issue of uncertainty, the spatial construction and geometric structures of the functional units of probe in the Cu2＋ ion detecting process were calculated and the mechanism was investigated by the molecular transition orbital pairs method to explore the origination of ON-OFF fluorescence sign response. The results presented that the signal response mechanism of the micelle probe is ascribed to F？rster resonance energy transfer（FRET） which provides new sights different from most of the conclusions by the related research work reported.

Functional decoration on a regenerable bifunctional porous covalent organic framework probe for rapid detection and adsorption of copper ions

Developing fluorescence porous probe for detecting and eliminating Cu^(2+) contamination in water or biosystem is an essential research project that has attracted considerable attention.However,improving the fluorescence detecting efficiency while enhancing the adsorption capacity of the porous probe is of great challenge.Herein,a bifunctional two-dimensional imine-based porous covalent organic framework(TTP-COF)probe was designed and synthesized from 1,3,5-tris(4-aminophenyl)benzene(TAPB)and 2,4,6-Triformylphloroglucinol(TP)ligand.TTP-COF displayed rapid detection of Cu^(2+)(limit of detection(LOD)=10 nmol·L^(−1) while achieving a high adsorption capacity of 214 mg·g^(−1)(pH=6)at room temperature with high reusability(>5 cycles).The key roles and contributions of highπ-conjugate and delocalized electrons in TABP and functional–OH groups in TP were proved.More importantly,the fluorescence quenching mechanism of TTP-COF was studied by density functional theory theoretical calculations,revealing the crucial role of intramolecular hydrogen bonds among C=N and–OH groups and the blocking of the excited state intramolecular proton transfer process in detecting process of Cu^(2+).

Fluorescence Behavior and Emission Mechanisms of Poly(ethylene succinamide)and Its Applications in Fe^(3+)Detection and Data Encryption

Conventional fluorescent polymers are featured by large conjugation structures.In contrast,a new class of fluorescent polymers without any conjugations is gaining great interest in immerging applications.Polyamide is a typical member of the conjugation-free fluorescent polymers.However,studies on their electrophotonic property are hardly available,although widely used in many fields.Herein,poly(ethylene succinamide),PA24,is synthesized;its chemical structure confirmed through multiple techniques(NMR,FTIR,XRD,etc.).PA24 is highly emissive as solid and in its solution at room temperature,and the emission is excitation and concentration dependant,with an unusual blue shift under excitation from 270 nm to 320 nm,a hardly observed phenomenon for all fluorescent polymers.Quite similar emission behavior is also observed under cryogenic condition at 77 K.Its emission behavior is thoroughly studied;the ephemeral emission blue-shift is interpreted through Förster resonance energy transfer.Based on its structures,the emission mechanism is ascribed to cluster-triggered emission,elucidated from multianalyses(NMR,FTIR,UV absorbance and DLS).In presence of a dozen of competitive metal ions,PA24 emission at 450 nm is selectively quenched by Fe^(3+).PA24 is used as probe for Fe^(3+)and H_(2)O_(2) detections and in data encryption.Therefore,this work provides a novel face of polyamide with great potential applications as sensors in different fields.

Recent advances in photoelectrochemical sensors for detection of ions in water

Over the last 50 years,the explosive adoption of modern agricultural practices has led to an enormous increase in the emission of non-biodegradable and highly biotoxic ions into the hydrosphere.Excess intake of such ions,even essential trace elements such as Cu^(2+)and F^(-),can have serious consequences on human health.Therefore,to ensure safe drinking water and regulate wastewater discharge,photoelectrochemical(PEC)online sensors were developed,with advantages such as low energy consumption,inherent miniaturization,simple instrumentation,and fast response.However,there is no publicly available systematic review of the recent advances in PEC ion sensors available in the literature since January 2017.Thus,this review covers the various strategies that have been used to enhance the sensitivity,selectivity,and limit of detection for PEC ion sensors.The photoelectrochemically active materials,conductive substrates,electronic transfer,and performance of various PEC sensors are discussed in detail and divided into sections based on the measurement principle and detected ion species.We conclude this review by highlighting the challenges and potential future avenues of research associated with the development of novel high-performance PEC sensors.

Expediting carbon dots synthesis by the active adaptive method with machine learning and applications in dental diagnosis and treatment

Synthesis of functional nanostructures with the least number of tests is paramount towards the propelling materials development. However, the synthesis method containing multivariable leads to high uncertainty, exhaustive attempts, and exorbitant manpower costs. Machine learning (ML) burgeons and provokes an interest in rationally designing and synthesizing materials. Here, we collect the dataset of nano-functional materials carbon dots (CDs) on synthetic parameters and optical properties. ML is applied to assist the synthesis process to enhance photoluminescence quantum yield (QY) by building the methodology named active adaptive method (AAM), including the model selection, max points screen, and experimental verification. An interactive iteration strategy is the first time considered in AAM with the constant acquisition of the furnished data by itself to perfect the model. CDs exhibit a strong red emission with QY up to 23.3% and enhancement of around 200% compared with the pristine value obtained through the AAM guidance. Furthermore, the guided CDs are applied as metal ions probes for Co^(2+) and Fe^(3+), with a concentration range of 0–120 and 0–150 µM, and their detection limits are 1.17 and 0.06 µM. Moreover, we also apply CDs for dental diagnosis and treatment using excellent optical ability. It can effectively detect early caries and treat mineralization combined with gel. The study shows that the error of experiment verification gradually decreases and QY improves double with the effective feedback loops by AAM, suggesting the great potential of utilizing ML to guide the synthesis of novel materials. Finally, the code is open-source and provided to be referenced for further investigation on the novel inorganic material prediction.

Modulation of red-light emission from carbon quantum dots in acid-based environment and the detection of chromium(Ⅲ)ions

ⅢIn this study,the carbon quantum dots,which can emit sharp red light(R-CQDs)under optical excitation,were synthesized via simple heat treatment of wine lees.The features of the photoluminescence(PL)emission from R-CQDs in solutions with different p H values and with metal ions were examined.The intensity of the PL emission from R-CQDs depends sensitively on the p H values of the solutions with the R-CQDs.Interestingly,the p H-response of the PL intensity is reversible and can be enhanced linearly in the p H value range from 4 to 12,indicating that the R-CQDs can be applied for the p H sensor.Furthermore,the quench of the PL emission from R-CQDs can be observed when adding chromium(Ⅲ)ions into the solution with R-CQDs.This effect can be utilized for selective and quick detection of chromium(Ⅲ)ions in solutions simply via the standard PL measurement.The interesting and important findings from this work can be applied to explore more practical applications of the CQDs prepared cheaply and easily.

Electrochemiluminescence of 1,8-Naphthalimide-Modified Carbon Nitride for Cu^(2+) Detection

It is essential to screen novel luminophores and co-reactants for the development of electrochemiluminescence(ECL)systems.In this work,a series of 1,8-naphthalimide-modified graphitic carbon nitride(CN/1,8-NDI_(x))ECL luminophores were successfully developed for the quantitative determination of Cu^(2+)with K_(2)S_(2)O_(8)as a co-reactant.When CN/1,8-NDI_(x)was immobilized on the surface of the glassy carbon electrode(GCE),a strong ECL signal could be produced(at a potential of-1.3 V vs.Ag/AgCl),which was threefold stronger than that of unmodified g-C_(3)N_(4).The intensity of ECL could be linearly quenched by Cu^(2+)over a concentration range from 5×10^(-9)to 1×10^(-4)mol/L,and with a low limit of detection(LOD)of0.86 nmol/L.Our results may provide a new perspective on the novel ECL platforms development.

Preparation of highly luminescent nitrogen and sulfur co-doped carbon nanoparticles for iron(Ⅲ)ions detection and cell imaging

Highly photoluminescent nitrogen and sulfur co-doped carbon nanoparticles（CNPs） ca. 56 nm have been prepared through a green one-step hydrothermal synthesis route by using millet powder as carbon sources, in which the nitrogen and sulfur co-doping improves the photoluminescent efficiency of the CNPs. The as-prepared CNPs display excellent fluorescent properties and low biotoxicity with a relatively high quantum yield of 30.4%, which have been applied for bioimaging and highly sensitive and selective detection of iron（III） ions.

Highly selective and sensitive colorimetric chemosensor based on tricarboyanine for detection of Ag^(+) in industrial wastewater

An efficient fluorescent probe 1 based on tricarbocyanine derivative was designed and synthesized,which can detect Ag^(+) in real industrial wastewater.UV-V is absorption and fluorescent emission spectra of probe 1 were carried out and indicated this probe can bind Ag^(+) via complexation reaction,then leading to a remarkable color change from blue to light red.Furthermore,probe 1 showed high sensitive performance and excellent selectivity toward Ag^(+) over other common metal ions in neutral pH.The sensing mechanism was proposed and further confirmed by ^(1)H NMR,which demonstrate analyte-induced destruction of the π-electron system could be shorten by the disruption of the pull-push π-conjugation system in probe 1.Moreover,a test strip was prepared by filter paper immersing in probe 1 solution,which further provide its potential application for trace Ag^(+) detection in real industrial wastewater.

A pillar[5]arene-based side-chain pseudorotaxanes and polypseudorotaxanes as novel fluorescent sensors for the selective detection of halogen ions

A pseudorotaxane and its polypseudorotaxanes formed between pillar[5]arene moieties and noctylpyrazinium cations as novel fluorescent sensors for the selective detection of halogen ions were reported.A collapse of these pillar[5]arene-based pseudorotaxanes and polypseudorotaxanes occurred upon the addition of Cl,Br,and I（tetrabutylammonium salts）,respectively,leading to their fluorescence recovery.The fluorescence enhancement of the pseudorotaxane and the polypseudorotaxanes increases in the order of I

Dual-property blue and red emission carbon dots for Fe(Ⅲ)ions detection and cellular imaging

The excitation wavelength-dependent and-independent emissions are two crucial fluorescent properties of carbon dots(CDs).However,CDs reported till date exhibit only one of these properties,which limits their practical applications.Herein,dual-property carbon dots(DCDs)with both the excitation wavelength-dependent and-independent emissions were synthesized via a facile onestep solvothermal method using 4-(2-pyridylazo)-resorcinol as the carbon precursor.The multi-functional applications of the resulting DCDs were also evaluated.The asprepared DCDs exhibited not only excellent monodispersity,high photostability,and storage stability,but also low toxicity,good biocompatibility,and cellular bioimaging capability.In addition,the DCDs exhibited excitation-dependent emission photoluminescence under low excitation wavelengths.The DCDs exhibited good Fe3+detection by quenching the blue emission fluorescence and showed a relatively low Fe3+detection limit of 0.067 lmol·L-1 based on three times signal-to-noise criteria(R2=0.99).Furthermore,the DCDs showed excitation-independent emission at low excitation wavelengths and exhibited red emission at about 598 nm to avoid damage to the body.These results demonstrate the excellent bioimaging properties of the DCDs.Owing to their dual PL properties,the as-prepared DCDs exhibited multi-functional applications:Fe3+detection and A549 cell bioimaging.These results will be helpful in developing novel CDs for applications in various fields.

Microwave-assisted synthesis of colorimetric and fluorometric dual-functional hybrid carbon nanodots for Fe^(3+) detection and bioimaging

Carbon nanodots(CDs) based fluorescent nanoprobes have recently drawn much attention in chemo-/bio-sensing and bioimaging.However,it is still challenging to integrate the colorimetric and fluorometric dual readouts into a single CD.Herein,novel hybrid CDs(HCDs) are prepared by a simple microwave-assisted reaction of citric acid(CA),branched polyethyleneimine(BPEI) and potassium thiocyanate(KSCN).As-prepared HCDs show extraordinary properties,including excitation-dependent emission,satisfactory fluorescence quantum yield(46.8%),excellent biocompatibility and optical stability.Significantly,the fluorescence intensity at 450 nm exhibits linear correlation over the Fe^(3+)concentration from 1 mmol/L to 150 mmol/L with a detection limit(LOD) of 52 nmol/L.Meanwhile,the solution color changes from colorless to orange,and the absorbance at 460 nm increased linearly with Fe^(3+)concentration ranging from 0.02 mmol/L to 5 mmol/L(LOD:3.4 mmol/L).All the evidence illustrates that the HCDs can be conditioned for specific Fe^(3+)sensing with colorimetric and fluorometric dual readouts,which has also been verified with paper-based microchips.The possible mechanism is attributed to the specific interactions between surface functional groups on the HCDs and Fe^(3+).Additionally,the HCDs are successfully applied in sensing Fe^(3+)in wastewater and living cells,demonstrating its potential applications in future environment monitoring and disease diagnosis.

Separation and determination of pyrrolidinium ionic liquid cations by ion chromatography with direct conductivity detection

A method for rapid and simultaneous determination of multiple pyrrolidinium ionic liquid cations by ion chromatography with direct conductivity detection was developed.Chromatographic separations were performed on a cation exchange column using ethylenediamine-acetonitrile as the mobile phase.The effects of chromatographic column and the mobile phase,as well as the column temperature on the retention of the cations were investigated.The retention rules of the cations under different chromatographic conditions were formulated.The retention of the cations followed the carbon number rule.The method has been successfully applied to the determination of three ionic liquids synthesized by a chemical laboratory.