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.

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.

Sensitive Determination of Metal Ions in Drinking Water by Capillary Electrophoresis Coupled with Contactless Conductivity Detection Using 18-Crown-6 Ether and Hexadecyltrimethylammonium Bromide as Complexing Reagents

A simple, economical, and sensitive capillary electrophoresis (CE) method integrated with capacitively coupled contactless conductivity detection was developed for the determination of metal ions such as K+, Na+, Mg2+, Sr2+, Ca2+ in drinking water. 18-Crown-6 ether and Hexadecyltrimethylammonium Bromide (CTAB) were employed as complexing reagents. The effects of electrolyte additives, citric acid buffer solution, and other separation conditions of CE were comprehensively investigated and carefully optimized. The best results were obtained in a running buffer solution composed of citric acid (12 mM), 18-crown-6 ether (0.2 mM), and CTAB (0.015 mM) at pH 3.5. Under these conditions, a complete separation of five metal ions was successfully achieved in less than 12 min. The limits of detection for the optimal procedure were determined to be in the range of 0.02 - 0.2 mg·L-1. The repeatability with respect to migration times and peak areas, expressed as relative standard deviations, was better than 2.3% and 5.1%, respectively. Evaluation of the efficiency of the methodology indicated that it was reliable for the determination of metal ions in six different brands of drinking water samples.

Mesoporous SiO_2 Nanoparticles:A Unique Platform Enabling Sensitive Detection of Rare Earth Ions with Smartphone Camera

Fast and sensitive detection of dilute rare earth species still represents a challenge for an on-site survey of new resources and evaluation of the economic value. In this work, a robust and low-cost protocol has been developed to analyze the concentration of rare earth ions using a smartphone camera. The success of this protocol relies on mesoporous silica nanoparticles(MSNs) with large-area negatively charged surfaces, on which the rare earth cations(e.g., Eu^(3+)) are efficiently adsorbed through electrostatic attraction to enable a ‘‘concentrating effect''. The initial adsorption rate is as fast as 4025 mg(g min)^(-1), and the adsorption capacity of Eu^(3+)ions in the MSNs is as high as 4730 mg g^(-1)(equivalent to ～41.2 M) at 70 °C. The concentrated Eu^(3+)ions in the MSNs can form a complex with a light sensitizer of 1,10-phenanthroline to significantly enhance the characteristic red emission of Eu^(3+)ions due to an ‘‘antenna effect'' that relies on the efficient energy transfer from the light sensitizer to the Eu^(3+)ions.The positive synergy of ‘‘concentrating effect'' and ‘‘antenna effect'' in the MSNs enables the analysis of rare earth ions in a wide dynamic range and with a detection limit down to ～80 nM even using a smartphone camera. Our results highlight the promise of the protocol in fieldwork for exploring valuable rare earth resources.

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.

Determination of toluene diisocyanate in synthetic-rubber track by ion chromatography with ultraviolet detection after alkaline suppressor

In the present work, a novel analytical method was proposed for the determination of toluene diisocyanate （TDI） in syntheticrubber track by ion chromatography （IC） coupled with an ultraviolet detector setting at 212 nm. TDI can be hydrolyzed to toluene diamine （TDA） which can be separated by cation-exchange IC easily. The optimum IC separation was performed on an IonPac CS12A column （150 mm ×4.0 mm） using 20 mmol L^-1 sodium sulfate, 10 mmol L^-1 sulfuric acid and 10% acetonitrile as eluent. It was found that a higher signal response of TDA could be obtained under alkaline condition. A suppressor was used to change the acidic eluent into alkaline one. 0.8 mol L^-1 potassium hydroxide was chosen as the optimum regeneration eluent. With the added suppressor and regenerant, signal response was magnified by about 16 times and lower limit of detection （LOD, 0.13 μg L^-1） was obtained. Within-day relative standard deviation （R.S.D.） was less than 3.6%. The recoveries of TDI spiked in synthetic-rubber track samoles were 96.4-110.6%.

Separation and Detection of Lanthanide Ions with Nitrilotri (methylenephosphonic) Acid as Complexing Agent and Eluent by IPC

A mixture containing eleven lanthanide ions was separated and detected on an anion exchange co lumn by ion chromatography with indirect photometry detection (IPC).An aqueous solution of 1.5×10 -2 mol/L nitrilotri(methylenephosphonic) acid and 2.5×10 -3 mol/L tiron was used as the eluent in which the former served as complexing agent and eluent,the latter played as color reagent and eluent.The effects of acidity,concentration and composition of eluent on the retention behavior of the analytes and detection sensitivity are discussed.

A Simple and Rapid Method for the Detection of Non-Ionic Surfactants

A spectrophotometric approach for the detection of non-ionic surfactant (Triton X-100) has been proposed in this paper. This method does not involve extraction of the ion-associate with harmful solvents, but employs adhesion of the ion-association of potassium/non-ionic surfactants complex and tetraphenylporphyrin tetrasulfonic acid obtained by vigorous shaking. The adhered ion-associate was dissolved with water and its absorbance was measured. The sensitivity for Triton X-100 was determined to be 0.146 (expressed as absorbance of 1 mg/L solution). The adhesion tendency of ion-associate was found to be dependent on the water contact angle, which in turn was influenced by a high adhesion of the ion-associate and by low blank values. In this respect, a tetrafluo-roethylene vessel was found to be the most suitable for the detection of non-ionic surfactants. This spectrophotometrical method is simply and rapidly performed by a procedure based on mechanical shaking and can be employed to detect non-ionic surfactants containing more than 7 polyethylene oxide units.

Electrocatalytic Oxidation and Ion Chromatography Detection of S_2O^(2-)_3, SO^(2-)_3, I^- and SCN^- at Glassy Carbon Electrode with Functionalized Multi-Wall Carbon Nanotubes Film

In this research, a glassy carbon electrode modified with the functionalized multi-wall carbon nanotubes(MWNT-COOHs) film was used as an amperometric sensor for the determination of S_2O^(2-)_3, SO^(2-)_3, I^- and SCN^-. The electrochemical behavior of those oxidizable inorganic anions at this modified electrode was studied by means of cyclic voltammetry(CV). The experimental results indicate that the modified electrode exhibits a high electrocatalytic activity towards the oxidation of those anions with a relatively high sensitivity, a good stability and a long-life. Separated by ion chromatography(IC) with 1.25 mmol/L H_2SO_4 as an eluent, those oxidizable anions can be determined by the MWNT-COOHs modified electrode successfully. Under the optimal chromatographic conditions, the detection limits are 1.5×10^(-7) mol/L for S_2O^(2-)_3, 2.5×10^(-7) mol/L for SO^(2-)_3, 1.2×10^(-7) mol/L for I^- and 2.0×10^(-7) mol/L for SCN^-, respectively. The method was applied successfully to the determination of those anions in environmental water

Ion Radiation Detection Using Implanted Ultrahigh Molecular Weight Polyethylene Structures (UHMWPE)

The effect of ion implantation, including Ar+ ion with influences (1 × 1013 - 1015 ions/cm2), on the electrical and optical properties of ultrahigh molecular weight polyethylene (UHMWPE) were investigated with particular emphasis placed on the sensor performance to be used in the field of radiation detection. The obtained results focusing on the effect of the different influences showed a significant change in the electrical conductivity, capacitance and loss tangent. The absorption spectra for UHMWPE samples were recorded and the values of the allowed direct and indirect optical energy gap (Eopt)d, (Eopt)in of UHMWPE and energies of the localized states for the virgin and implanted samples were calculated. We found that the optical energy gap values decreased as the radiation dose increased. The results can be explained on the basis of the ion beam radiation-induced damage in the linear chains of UHMWPE, with cross-linking generated after implantation. The observed changes in both the optical and the electrical properties suggest that the UHMWPE film may be considered as an effective material to achieve ion-radiation detection at room temperature.

Electrochemical Sensing of Heavy Metal Ions based on Monodisperse Single-crystal Fe_3O_4 Microspheres

Single-crystal Fe_3 O_4 with monodisperse microspheres structure has been used for individual electrochemical detection of heavy metal ions. Morphology and structure of the as-prepared Fe_3 O_4 microspheres were characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM) and X-ray diffraction(XRD). Meanwhile the electrochemical properties of the Fe_3 O_4 microspheres modified glass carbon electrodes(GCE) were characterized by cyclic voltammetry(CV) and electrochemical impedance spectroscopy(EIS), and the enhanced electrochemical response in stripping voltammetry for individual detection of Pb(Ⅱ), Hg(Ⅱ), Cu(Ⅱ), and Cd(Ⅱ) was evaluated using square wave anodic stripping voltammetry(SWASV). With high specific surface area and excellent catalytic activity toward heavy metal ions, the as-prepared monodisperse and single-crystal Fe_3 O_4 microspheres show a preferable sensing sensitivity(22.2 μA/μM) and limit of detection(0.0699 μM) toward Pb(Ⅱ). Furthermore, the electrochemical sensor of Fe_3 O_4 microspheres exhibits excellent stability and it also offers potential practical applicability for the determination of heavy metal ions in real water samples. This study provides a potential simple and low cost iron oxide for the construction of sensitive electrochemical sensors applied to monitor and control the pollution of toxic metal ions.

Fluorescence color tuning of dual-emission carbon quantum dots pro-duced from biomass and their use in Fe3+and Cu2+detection

Using simple and eco-friendly ethanol solvothermal treatment,dual-emission biomass carbon quantum dots(D-BCQDs)were synthesized from biomass viburnum awabuki leaves.Under excitation with 413 nm wavelength light two emission peaks appeared at 490 and 675 nm and the dots could be tuned to emit crimson,red,purplish red,purple and blue-gray fluorescence by changing the solvothermal temperature from 140℃ to 160,180,200 and 240℃,respectively.XPS and FTIR characterization in-dicated that the fluorescence color was mainly determined by surface oxidation defects,elemental nitrogen and sp^(2)-C/sp^(3)-C hybrid-ized structural domains.The D-BCQDs could not only detect Fe^(3+)or Cu^(2+),but also quantify the concentration ratio of Fe^(3+)to Cu^(2+)in a solution containing both,demonstrating their potential applications in the simultaneous detection of Fe^(3+)and Cu^(2+)ions.

纳米材料在食品重金属离子快速检测中的应用研究进展

纳米材料因具有比表面积大、良好稳定性、特殊的结构、易于修饰、良好的生物相容性等优点,已被广泛应用于食品中重金属离子检测领域。文章重点综述了碳纳米管、石墨烯、碳量子点、金属有机骨架、纳米酶等纳米材料在食品中重金属离子检测方面的研究与应用现状,并展望了纳米材料在食品中重金属离子检测领域面临的挑战和应用前景。

Magnetic-optical dual functional Janus particles for the detection of metal ions assisted by machine learning

Functional polymer microspheres have broad application prospects in various fields,such as metal ion detection,adsorption,separation,and controlled drug release.However,integrating different functions in a single microsphere system is a significant challenge in this field.In this work,we prepared multicompartmental emulsion droplets utilizing microfluidic technology.Fe3O4 magnetic nanoparticles were added to one of the compartments of the emulsion droplets as functional particles,and Janus microspheres were obtained after curing.Fluorescent probes enter the two compartments of the Janus microspheres by diffusion.The fluorescence changes of the microspheres were observed in situ and captured through a fluorescence microscope.The images are processed by image recognition software and a Python program.The“fingerprint”of the detected metal ions is obtained by dimensionality reduction of the data through Principal Component Analysis.We employ different algorithms to build Machine Learning models for predicting the metal ion species and concentration.The variation of fluorescence intensity of the three fluorescent probes and the corresponding R,G,and B channel values and time are used as descriptors.The results show that the Random Forest,K-neighborhood(KNN),and Neural Network models demonstrated a better predicted effect with a variance(R2)greater than 0.9 and a smaller root mean square error;among them,the KNN model predicted the most accurate results.

Protein-mimicking nanoparticle(Protmin)-based nanosensor for intracellular analysis of metal ions

In this study, we designed and applied proteinmimicking nanoparticles(Protmin) as an intracellular nanosensor for in vivo detection of lead ions(Pb^(2+)).Monodispersed gold nanoparticles(Au NPs) of 13 nm in diameter were modified using poly-adenine-tailed Pb^(2+)-specific 8–17 DNAzyme to form a spherical and functional Protmin. Substrate strands modified with a fluorophore at the 50 end and a quencher at the 30 end were bound to DNAzyme. Pb^(2+) facilitated cleavage of DNAzyme to release the fluorophore-modified short strands to generate fluorescence. We observed rapid kinetics of the Protmin nanosensor, for which the typical assay time was 10 min.Further, we demonstrated the Protmin nanosensor could readily enter living cells and respond to Pb^(2+) in the intracellular environment. The broad of range of Protmindesigns will be useful for advancing biological and medical applications.

Investigation of photoelectron action in cubic AgCl emulsion doped with formate ions

In recent years, the formate ion （HCO2^-） as a kind of hole-to-electron converter has attracted much attention of photographic researchers. The formate ions can trap photo-generated holes, eliminate or reduce the electron loss caused by electron-hole recombination in latent image formation process. Through the hole-to-electron conversion, it can also release an extra electron or electron carrier, improving photosensitivity. In this paper the microwave absorption and dielectric spectrum detection technique is used to detect the time evolution behaviour of free photoelectrons generated by 35ps laser pulses in cubic AgCl emulsions doped with formate ions. The influence of different doping conditions of formate ions on the photoelectron decay kinetics of AgC1 is analysed. It is found that when the HCO2^- content is 10^-3mol/mol Ag and the doping position is 90% the electron decay time and lifetime reach their maxima due to the efficient trap of holes by formate ions.

铕修饰硅纳米颗粒可视化检测铜离子

为了实现对水中铜离子(Cu^(2+))的检测,设计开发了比率荧光探针铕修饰硅纳米颗粒(Eu-DPA@SiNPs)。在探针中,SiNPs作为参比信号,Eu^(3+)为响应信号,而2,6-吡啶二羧酸(DPA)作为“天线”敏化Eu^(3+)。采用透射电子显微镜(TEM)、傅里叶变换红外光谱(FTIR)、X射线衍射图谱(XRD)、紫外可见吸收光谱(UV-Vis)对探针进行形貌和结构的表征,用荧光光谱测试其检测性能。结果表明:当DPA与Eu^(3+)的摩尔比为0.5∶1时,探针具有最大淬灭效率;探针为均匀分散的球形颗粒,平均直径为26.15 nm;探针中加入Cu^(2+)后,10 s即反应完全,在0.2~13.0μmol/L范围呈现良好的线性关系,检出限(LOD)为0.41μmol/L,远低于美国环境保护署所规定的饮用水中Cu^(2+)含量最大允许限值,并成功将探针应用到实际水样中检测Cu^(2+);进一步制备了荧光检测试纸,实现了对Cu^(2+)的便携、可视化和半定量检测。

离子色谱电化学检测器测定化妆品中玻色因含量

建立了测定化妆品中玻色因含量的离子色谱分析方法。试样用去离子水分散,超声提取,经Dionex CarboPac MA1 IC(4 mm×250 mm)色谱柱分离后,用电化学检测器,积分安培检测,并采用液相色谱-质谱联用仪定性确证。结果显示,玻色因的线性范围为1~200μg/mL,方法检出限为0.01%(S/N=3),定量限为0.03%(S/N=10),相关系数R^(2)>0.999。在3个浓度加标水平下,方法平均回收率为90.5%~98.5%,相对标准偏差为0.7%~3.7%。该分析方法简便、准确、快速,适用于化妆品样本中玻色因含量的测定。

软包装锂离子电池表面凹坑缺陷检测方法

软包装锂离子电池表面凹坑缺陷对比度低、缺陷区域过小且存在反光,传统方法很难进行准确检测。提出一种基于图像增强和改进DeepLabV3网络的软包装锂离子电池表面凹坑缺陷检测方法。通过分析表面凹坑缺陷图像特征,采用图像增强算法对图像进行预处理,以增强凹坑缺陷对比度。对DeepLabV3网络进行改进,使用ResNet101作为特征提取网络,同时引入位置注意力模块,使得模型更加关注于凹坑缺陷相关特征,提升网络的检测精度。改进后的网络在自制数据集上的平均交并比达到85.98%,缺陷检测准确率达到98.33%。