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.     

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

     

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).     

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.     

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。     

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。     

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。     

一种基于有机杂化溶胶-凝胶Hg2+敏感膜的研究

研究了基于有机杂化硅氧烷的Hg2 光化学传感膜,通过四甲氧基硅烷(TMOS)和二甲基二甲氧基硅烷(DMOS)进行缩聚,将5,10,15,20-四苯基卟啉磺酸钠与十六烷基三甲基溴化铵以离子对的形式包埋于溶胶-凝胶中,获得对Hg2 有灵敏荧光响应的溶胶-凝胶敏感膜.实验考察了传感膜的制备条件和响应性能.结果表明,在pH 8.0的Tris-HCl缓冲溶液中,Hg2 的浓度与传感膜的荧光猝灭比值在1.0×10-5～1.0×10-4mol·L-1范围内呈线性关系,传感膜具有响应时间短,指示剂不泄漏,测定重现性好,其他金属离子干扰小等优点.     

Hybrid Dispersion Dirac Semimetal and Hybrid Weyl Phases in Luttinger Semimetals: A Dynamical Approach

It is shown that hybrid Dirac and Weyl semimetals can be realized in a 3D Luttinger semimetal with quadratic band touching (QBT). This is illustrated using a periodic kicking scheme. In particular, the focus is on a momentum-dependent driving (nonuniform driving) and the realization of various hybrid Dirac and Weyl semimetals is demonstrated. A unique hybrid dispersion Dirac semimetal with two nodes is identified, where one of the nodes is linear while the other is dispersed quadratically. Next, it is shown that by tilting QBT via periodic driving and in the presence of an external magnetic field, one can realize various single/double hybrid Weyl semimetals depending on the strength of external field. Finally, it is noted that in principle, phases that are found in this work can also be realized by employing the appropriate electronic interactions.     

Electrospun nanofibers decorated with bio-sonochemically synthesized gold nanoparticles as an ultrasensitive probe in amalgam-based mercury (II) detection system

In this study, bio-ultrasound-assisted synthesized gold nanoparticles using Gracilaria canaliculata algae have been immobilized on a polymeric support and used as a glassy probe chemosensor for detection and rapid removal of Hg²⁺ ions. The function of the suggested chemosensor has been explained based on gold-amalgam formation and its catalytic role on the reaction of sodium borohydride and rhodamine B (RhB) with fluorescent and colorimetric sensing function. The catalyzed reduction of RhB by the gold amalgam led to a distinguished color change from red and yellow florescence to colorless by converting the amount of Hg²⁺ deposited on Au-NPs. The detection limit of the colorimetric and fluorescence assays for Hg²⁺ was 2.21 nM and 1.10 nM respectively. By exposing the mentioned colorless solution to air for at least 2 h, unexpectedly it was observed that the color and fluorescence of RhB were restored. Have the benefit of the above phenomenon a recyclable and portable glass-based sensor has been provided by immobilizing the Au-NPs and RB on the glass slide using electrospinning. Moreover, the introduced combinatorial membrane has facilitated the detection and removal of Hg²⁺ ions in various Hg (II)-contaminated real water samples with efficiency of up to 99%.     

Mercury removal from contaminated water by ultrasound-promoted reduction/vaporization in a microscale reactor

A new method is described for the removal of Hg(II) at trace level from waters using an ultrasound-promoted reduction/volatilization process. The method is accomplished in a sonoreactor (100 W power; 20 kHz frequency) by adding formic acid to induce the reduction of Hg(II) to Hg(0). In contrast to other treatments, it does not introduce further foreign substances for water decontamination. A reduction mechanism is proposed, which relies on the sonolytic decomposition of formic acid to yield reducing gases such as H(2) and CO, which in turn, causes the reduction of Hg(II). After the formation of Hg(0), its removal is facilitated by the degassing effect caused by ultrasound irradiation. Hg at 100 ng/mL concentration can be removed within 30 min with a yield of 90% from a 10 mL water volume. The presence of stabilizing anions or oxidants in waters may preclude the Hg removal. Effects of experimental variables such as treatment time, amplitude of the ultrasonic probe vibration, formic acid concentration and sample volume were investigated.     

鸡蛋蛋白孵化金纳米荧光团簇与其对污水中痕量Hg~(2+)的检测

金纳米荧光团簇作为一种新型纳米材料,毒性低,光稳定性好,斯托克位移较长。作为荧光探针,不容易由杂质造成干扰。因此,这类材料在环境监测领域引起了广泛的兴趣。然而,由于所选用的配体成本较高,反应条件复杂,目前绝大数合成金纳米荧光团簇的方法造价昂贵,不利于广泛应用。该工作建立了十分简便的方法,利用市售鸡蛋蛋清为天然蛋白质配体,价格低廉,无毒性,不需要任何复杂反应条件,在37℃的条件下孵化,水浴加热24h,得到亮度很高的红色荧光金纳米团簇,适合被普遍采纳。根据实验研究发现,所得到的金纳米团簇稳定性较好,其中激发光谱的最大峰位于470nm,而发射光谱的最大发射峰位于680nm,为典型的红色纳米荧光团簇,相应的荧光产率为8.76%。通过进一步研究发现,所得金纳米荧光团簇可设计为汞金属离子选择性探针。并根据荧光选择性淬灭现象,将其成功地应用于污水中Hg~(2+)的检测。检出限小于1ppb,满足安全饮用水的检出限要求。校准曲线的线性相关线数在99.8%以上。同时研究了实际样品中Hg~(2+)的加标回收测试。并与原子吸收法进行对比。在低浓度测试时,该方法有显著的优越性。在测定高浓度的Hg~(2+)时,两种方法的结果无明显差异,进一步说明了方法的准确性。该方法为天然水中Hg~(2+)的简便检测提供了有效而又经济实惠的手段。     

Highly Selective and Sensitive Chemosensor for Hg2+ Based on the Naphthalimide Fluorophore

A new OFF-ON fluorescent chemosensor (H1) composed of a naphthalimide fluorophore and a 6-[(quinolin-8-yloxy)methyl]pyridin-2-ylmethanamine receptor has been synthesized and characterized by infra-red, (1)H NMR, (13)C NMR and mass spectrometry. The developed chemosensor H1 exhibited good turn-on and reversible responses toward Hg(2+), with excellent selectivity and sensitivity, in a neutral buffered aqueous solution. Other common metal ions did not interfere with the fluorescence-enhancement response to Hg(2+). Furthermore, the chemosensor H1, at a concentration of 10?μM, showed a rapid and linear response toward Hg(2+) in the concentration range 0-10?μM. On addition of 10?μM Hg(2+), the fluorescence intensity of H1 was enhanced about 4-fold. The detection limit was calculated to be 63?nM. The association constant was 1.11?×?10(5)?M(-1). The fluorescence quantum yield and lifetime of H1/Hg(2+) were 0.42 and 3.83?ns, respectively.     

A new rhodamine B-based “off–on” fluorescent chemosensor for Cu2+ in aqueous media

A new fluorescent probe 1 (P1) for Cu²⁺ based on rhodamine B was designed and synthesized. P1 exhibits high sensitivity and selectivity for sensing Cu²⁺ and color changes from colorless to pink in aqueous media. Selective fluorescent enhancement of P1 was attributed to ring-opening from the spirolactam (nonfluorescent) to ring-opened amide (fluorescent). A chemosensor based on rhodamine B has a good potential application to the determination of Cu²⁺ in environmental and biological systems.     

Hg-coordination studies of oligopeptides containing cysteine,histidine and tyrosine by 199mHg-TDPAC

In order to study the interaction of histidine- and tyrosine-containing peptide chains with Hg(II), the nuclear quadrupole interaction (NQI) of ^199mHg in the Hg complexes of the oligopeptides Alanyl–Alanyl–Histidyl–Alanyl–Alanine-amid (AAHAA–NH₂) and Alanyl–Alanyl–Tyrosyl–Alanyl–Alanine-amid (AAYAA–NH₂) was determined by time differential perturbed angular correlation and is compared with previous data on Alanyl–Alanyl–Cysteyl–Alanyl–Alanyl (AACAA–OH). The ^199mHg–NQIs depend on the oligopeptide to Hg(II) stoichiometry and indicate that two-fold and four-fold coordinations occur for the bound Hg(II). This revised version was published online in August 2006 with corrections to the Cover Date.     

A Long Wavelength Excitable Fluorophore; Chloro Phenyl Imino Propenyl Aniline (CPIPA) for Selective Sensing of Hg (II)

In this study, a very sensitive and highly selective irreversible optical chemical sensor (optode) for mercury ions was described. The sensing scheme was based on the interaction of Hg (II) with a newly synthesized fluoroionophore; chloro phenyl imino propenyl aniline (CPIPA) in plasticized PVC membrane. The sensor membranes were tested for the determination of mercury ion in aqueous solutions by batch and flow-through methods. The optodes allow determination of Hg (II) in the working range of 1.0 × 10⁻⁹–1.0 × 10⁻⁵ M with a detection limit of 4.3 ppb. The sensor exhibited excellent selectivity for Hg (II) with respect to several common alkali, alkaline earth and transition metal ions. The association constant of the 1:1 complex formation for Hg (II) was found to be K_a = 1.86 × 10⁵ M⁻¹. The CPIPA exhibited high fluorescence quantum yield, long excitation and emission wavelength and high Stokes’ shift values in the solid matrix which makes it compatible with solid state optics.     

Impact of Mercury(II) on proteinase K catalytic center: investigations via classical and Born-Oppenheimer molecular dynamics

Mercury(II) has a strong affinity for the thiol groups in proteins often resulting in the disruption of their biological functions. In this study we present classical and first-principles, DFT-based molecular dynamics (MD) simulations of a complex of Hg(II) and proteinase K, a well-known serine protease with a very broad and diverse enzymatic activity. It contains a catalytic triad formed by Asp39, His69, and Ser224, which is responsible for its biological activity. It was found previously by X-ray diffraction experiments that the presence of Hg(II) inhibits the enzymatic action of proteinase K by affecting the stereochemistry of the triad. Our simulations predict that (i) the overall structure as well as the protein backbone dynamics are only slightly affected by the mercury cation, (ii) depending on the occupied mercury site, the hydrogen bonds of the catalytic triad are either severely disrupted (both bonds for mercury at site 1, and the His69–Ser224 contact for mercury at site 2) or slightly strengthened (the Asp39–His69 bond when mercury is at site 2), (iii) the network of hydrogen bonds of the catalytic triad is not static but undergoes constant fluctuations, which are significantly modified by the presence of the Hg(II) cation, influencing in turn the triad’s ability to carry out the enzymatic function—these facts explain the experimental findings on the inhibition of proteinase K by Hg(II).