Chemometric Analysis of Excitation Emission Matrices of Fluorescent Nanocomposites

The performance of multivariate curve resolution (MCR-ALS) to decompose sets of excitation emission matrices of fluorescence (EEM) of nanocomposite materials used as analytical sensors was assessed. The two fluorescent nanocomposite materials were: NH₂-polyethylene glycol (PEG200) functionalized carbon dots, sensible to aqueous Hg(II) (CD); and, CdS quantum dots attached to the dendrimer DAB, sensible to the ionic strength of the aqueous medium (CdS-DAB). The structures of these sets of EEM, obtained as function of the Hg(II) concentration and ionic strength, are characterized by collinear properties (CD) and non-linear spectral variations (CdS-DAB). MCR-ALS was able to detect that the source of the collinearities is the presence of different size CD that show similar affinity towards Hg(II). Moreover, MCR-ALS was able to model the non-linear spectral variations of the CdS-DAB that are induced by varying ionic strength. The chemometric pre-processing of the fluorescent data sets using soft-modelling multivariate curve resolution like MCR-ALS is a critical step to transform these nanocomposites with interesting fluorescent proprieties into analytical useful nanosensors.     

A Highly Selective Turn-On Fluorescent Chemosensor for Zinc Ion in Aqueous Media

In the paper, a novel rhodamine6G based fluorescent chemosensor bearing 3-carbaldehyde chromone was designed and synthesized. According to the fluorescence behavior toward several metal ions, it showed highly selectivity and sensitivity to Zn(II) over other commonly coexistent metal ions (Cu(II), Cd(II), Hg(II), Mg(II), K(I), Pb(II), Fe(III) and Cr(III)) in aqueous environment (pH?=?7.4). Meanwhile the binding constant between Zn(II) and chemosensor achieved 6.21?×?10¹¹ M^?1 in aqueous media. Moreover, according to the Job plot, 1:1 stoichiometry between Zn(II) and sensor was deduced in aqueous media (pH?=?7.4). The good selectivity and sensitivity in aqueous media effectively enhanced the application value of the fluorescent chemosensor for Zn(II).     

Ce (III) - Porphyrin Sandwich Complex Ce<Subscript>2</Subscript>(TPP)<Subscript>3</Subscript>: A Rod-Like Nanoparticle as a Fluorescence Turn-Off Probe for Detection of Hg (II) and Cu (II)

In this study the researcher reports a novel, one step synthesized rod-like nanoparticles of cerium (III)—tetraphenylporphyrin sandwich complex as a spectrofluorometric sensor to measure trace amount of Hg (II) and Cu (II) metal ions. Moreover, the synthesized fluorescent probe was able to detect higher amounts (>10^?4 M) of Hg (II) in aqueous media by changing the color which can also be used as a selective mercury naked-eye sensor. The selectivity and sensitivity of the sensor based on its fluorescence quenching in the presence of Hg (II) and Cu (II) were studied according to the Stern-Volmer equation. The detection limit of the sensor was 16 nM for Hg (II) and about 2.34 μM for Cu (II) ions.

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Graphical Abstract Ce₂(TPP)₃ sandwich complex application as a fluorescent probe for measuring trace amounts of mercury and copper in real samples

     

基于碳量子点和罗丹明B的新型比率荧光试纸片检测水中Hg(Ⅱ)

水环境中Hg(Ⅱ)的污染对生态环境和人类健康危害极大，目前Hg(Ⅱ)的检测主要有原子光谱/质谱和电化学等方法，但存在检测仪器昂贵、操作繁琐及前处理复杂等缺点，难以在日常水环境中微量Hg(Ⅱ)现场检测的应用。因此，建立一种灵敏、准确、快捷和经济的水中Hg(Ⅱ)检测方法具有重要意义。试纸法是将普通的化学反应从玻璃仪器转移到试纸上进行的一种快速检测方法，利用试剂与目标物之间产生的化学反应，通过颜色的变化可对目标物进行定性或半定量检测，具有操作简便、快速等优点。碳量子点是一类粒径小于10 nm的碳基纳米材料，具有优异的荧光性能、较低的毒性和较高的化学稳定性。利用Hg(Ⅱ)对碳量子点的荧光具有灵敏和高效的猝灭作用，构建了一种双色比率荧光试纸片用于快速检测水中微量Hg(Ⅱ)的含量。其中，采用氮掺杂水溶性碳量子点（NCDs）作为荧光响应信号、罗丹明B（RhB）作为荧光内标信号，在单一波长（355 nm）激发下产生位于440和580 nm的双色荧光发射峰。当体系加入不同浓度Hg(Ⅱ)后，NCDs表面官能团与Hg(Ⅱ)之间的静电作用和金属配位协同作用使荧光发生猝灭，而RhB的荧光信号保持不变，利用440和580 nm双色荧光信号或其强度的比值（F₄₄₀/F₅₈₀），可实现对微量Hg(Ⅱ)的快速检测。实验对检测条件进行了优化，结果表明在HAc-NaAc缓冲液浓度为1 mmol·L-1、pH为7的条件下，F₄₄₀/F₅₈₀值与Hg(Ⅱ)浓度（0～3 μmol·L-1）呈现良好的线性关系，线性方程为F₄₄₀/F₅₈₀=-0.785 2ｃ_Hg(Ⅱ)+3.103 8，相关系数r＞0.99，以3倍标准偏差计算的检出限为2.7 nmol·L-1(n=9)。对湖水与自来水中Hg(Ⅱ)进行加标回收实验，其加标回收率在91.9%～117.9%之间，说明该方法灵敏、准确，能用于水中Hg(Ⅱ)的检测。同时，将NCDs和RhB浸渍于尼龙片上构建了双色比率荧光检测试纸片，在紫外灯（365nm）照射下可观测到试纸发射淡蓝紫色荧光。而随着Hg(Ⅱ)浓度的增加，荧光颜色从淡蓝紫色到橙色发生变化，每次检测时间只需3分钟，裸眼可检出Hg(Ⅱ)浓度低至10 nmol·L-1，实现了对水中微量Hg(Ⅱ)的灵敏、快速检测。此外，该方法对Hg(Ⅱ)的检测表现出良好的特异性。因此，基于碳量子点和罗丹明B构建的双色比率荧光试纸片具有携带方便、操作简单，以及灵敏和快速等优点，为水中微量Hg(Ⅱ)的快速检测提供了新的方法和思路。     

基于功能核酸的水中汞离子荧光检测方法

二价汞离子作为一种重要的环境污染物，一直以来受到国内外广泛关注。基于T-T错配的Hg2+检测极大依赖于汞选择性寡聚核苷酸（MSO）的设计，利用SYBR Green I对目前所报道的汞离子探针进行了优化，研究了若干种MSO探针与Hg2+的结合响应，在对探针二级结构进行分析和讨论的基础上，提出最优的富T探针序列，并由此建立了一种基于SYBR Green I的水中汞离子快速、便捷的荧光检测方法。最终测得3种实际水样的加标回收率在82.8％~101.8％之间，相对标准偏差小于15%，表明该方法受环境基质的影响较小，可应用于实际水样中的汞离子检测。     

Raman Spectra and Solvent-Solute Interaction of Mercury(II)-Thiocyanate Complexes in Some Aprotic Donor Solvents

Raman spectra of the species Hg(SCN)₂, [Hg(SCN)₃], and [Hg(SCN)₄]^2- in solution of ten aprotic donor solvents have been investigated in the region of the Hg-S vibration. Observed frequency values of measured band of Hg(SCN)₂ and [Hg(SCN)₃] in different solutions correlate well with donor strength of the solvents. There is a linearity between Hg-S frequency decreasing and increasing of the interaction of the solvent molecules with the mercury (II) ion in the thiocyanate complexes. No significant frequency changes have be found for [Hg(SCN)₄]^2-. Evidence based on the frequency shifts and depolarization ratios in various solvents supports the view that the Hg(SCN)₂ in solution undergos departure from linearity as a result of increasing solvent coordination to the mercury (II) ion. Almost constant frequencies of Hg-S vibration of [Hg(SCN)₄]^2- in all investigated solvents suggest a regular tetrahedral structure of the ion in solution having much larger radius than corresponding HgX₄ (X=Cl,Br,I) ions.     

Two Highly Sensitive and Selective Colorimetric “Off-On” Rhodamine-Based Fluorescent Chemosensor for Hg(II) in Aqueous Media

Two novel rhodamine derivatives were designed and synthesized. They were successfully characterized by HR-MS, ¹H NMR and ¹³C NMR. They were found to exhibit a reversible colorimetric response and exhibit high selectivity and sensitivity for Hg(II) ion over other commonly coexistent metal ions. Their selectivity is excellent, and the detection of Hg(II) at ppb level is possible. The colorimetric and fluorescent response to Hg(II) can be conveniently detected even by the naked eye, which provides a facile method for visual detection of Hg(II).     

基于FRET机理的荧光探针的合成及其对汞离子的识别

基于FRET机理设计合成了一个包含罗丹明6G及香豆素的汞离子荧光探针Rh-6G-coumarin(RC),研究了它的光谱性能及对汞离子的识别作用。在V(C₂H₅OH)∶V(H₂O)=9∶1溶液中加入汞离子后,575 nm处荧光强度迅速增大,荧光由蓝色变为明亮的红色,同时溶液的颜色由黄色变为红色。溶液中其他金属离子,如Na⁺、K⁺、Mg²⁺、Fe²⁺、Co²⁺、Pb²⁺、Zn²⁺、Cd²⁺和Cr³⁺对汞离子的荧光识别没有太大影响。该探针可在较宽的pH ( 4~10)范围内识别汞离子。光谱滴定实验表明,汞离子与RC以2∶1的计量比形成了配合物。     

Ultrasensitive and selective spectrofluorimetric determination of Hg(II) using a dimercaptothiadiazole fluorophore

The present work describes the ultrasensitive and selective spectrofluorimetric determination of Hg(II) using 2,5-dimercaptothiadiazole (DMT) as a fluorophore. DMT shows an emission maximum at 435 nm while exciting at 330 nm. The colorless solution of DMT changes into a highly emittive yellow color immediately after the addition of 0.5 μM Hg(II) and nearly 245-fold increase in emission intensity at 435 nm was observed. These changes were ascribed to the complex formation between Hg(II) and DMT. Based on the fluorescence enhancement, the concentration of Hg(II) was determined. The binding constant value (K_A=1.8620×10⁴ mol⁻¹ L) suggests that there is a strong binding force between Hg(II) and DMT. The fluorescence quantum yield of DMT-Hg(II) complex was found to be 4-fold higher than that of DMT, indicating that the DMT-Hg(II) complex was highly emittive than the DMT. Interestingly, the emission intensity was increased even in the presence of 0.1 pM Hg(II). The fluorophore showed an extreme selectivity towards 100 nM Hg(II) in the presence of 50,000-fold higher concentrations of Na⁺, K⁺, Ca²⁺, Mg²⁺, Fe²⁺, Fe³⁺, Cd²⁺, Cr³⁺, Mn²⁺, Zn²⁺, Co²⁺, Ni²⁺, Cl⁻, SO₄²⁻, NO₃⁻ ions and 1000-, 500- and 200-fold higher concentrations of Cu²⁺, Pb²⁺ and Ag⁺ ions, respectively, as interferences. The lowest detection of 18 pg L⁻¹ Hg(II) (LOD=3S/m) was achieved for the first time using DMT by fluorimetry. The proposed method was successfully utilized for the determination of Hg(II) in tap water, river water and industrial waste water samples.     

新型汞离子CQDs-CuNCs比率荧光探针的构建及在螃蟹中的应用

汞是一种典型的低剂量高毒性物质，广泛存在于环境和水体中，可通过食物链传递并累积，从而对人体造成危害。因此，准确快速的监测食品中汞离子（Hg2+）含量对于保障食品安全具有重要意义。目前，常用的Hg2+检测方法包括液相色谱-原子荧光光谱法（LC-AFS）、电感耦合等离子质谱法（ICP-MS）、电化学法和荧光分析法。比率型荧光探针具有双发射荧光特性，其中内置校准功能可降低因探针浓度和各种环境因素产生的检测误差，可以有效的克服单发射荧光探针的不足。本研究提出了基于碳量子点（CQDs）和铜纳米簇（CuNCs）的新型比率型荧光探针用于螃蟹中Hg2+的快速检测。主要研究内容和结果如下：（1）CQDs-CuNCs复合体系的制备。以蔗糖为碳源，聚乙二醇为钝化剂，通过微波介导法合成CQDs；以抗坏血酸为还原剂和稳定剂通过水热法合成CuNCs，后通过自组装制成CQDs-CuNCs复合体系。（2）CQDs-CuNCs复合体系的表征。利用高倍透射电子显微镜（HRTEM）、紫外-可见吸收光谱（UV-Vis）、荧光光谱（FL）和傅里叶变换红外光谱（FTIR）对CQDs-CuNCs复合体系表征，结果显示，该研究成功合成了具有双发射特性的CQDs-CuNCs比率型荧光探针。（3）CQDs-CuNCs复合体系的稳定性测试。将CQDs-CuNCs比率型探针与传统的单通道CuNCs探针的稳定性进行对比。结果表明，当探针浓度漂移和测量温度波动时，CQDs-CuNCs比率型探针比单发射的CuNCs抗干扰能力更强，稳定性更高。（4）CQDs-CuNCs复合体系对Hg2+的检测。当Hg2+存在时，复合体系中的CuNCs发生团聚，而CQDs基本不受影响，导致443 nm处的CuNCs荧光猝灭而545 nm处的CQDs荧光强度几乎不变。依据荧光强度的比值（I_{443 nm}/I_{545 nm}）与Hg2+浓度的关系实现定量检测。在对标准Hg2+检测时，CQDs-CuNCs复合体系的I_{443 nm}/I_{545 nm}和单发射CuNCs的猝灭率与Hg2+浓度（0.1～12 μmol·L-1）均呈现良好的线性关系，相关系数分别达到0.994 7和0.991 6，检测限（3σ/S）分别为2.83和3.62 nmol·L-1。在螃蟹样品检测中，CQDs-CuNCs比率型探针和单发射的CuNCs得到回收率分别为102.5%~105.4%和104.2%~112.5%，说明CQDs-CuNCs复合体系比单发射CuNCs对Hg2+具有更高的灵敏性和稳定性。以上结果表明，本研究所构建的CQDs-CuNCs比率型荧光探针能够用于食品中Hg2+的快速、准确检测。