A highly selective colorimetric aqueous sensor for mercury

A new colorimetric mercury sensor is reported based on binding to terpyridine derivatives. It is able to selectively detect Hg II ions over a number of environmentally relevant ions including Ca II, Pb II, Zn II, Cd II, Ni II, Cu II, and others. The response time upon exposure to Hg II is instantaneous. By the "naked eye," the detection limit of Hg II is 2 ppm (25 microM) in solution. With a spectrometer, this detection limit is increased down to 2 ppb (25 nM), which is the current EPA standard for drinking water. The significant problem of mercury poisoning requires new methods of detection that are sensitive and selective. Here we report a new simple system that takes advantage of the unique optical properties generated by terpyiridine-Hg complexes.     

A ditopic colorimetric sensor for fluoride ion based on thiourea mercury complex

A novel ditopic chromogenic receptor, N-5-(8-hydroxy)quinoline-N'-4'-nitro-phenyl thiourea (1), was synthesized. The metal complex 1-Hg(2+) showed sensitive and highly selective responses to F(-) over other anions such as CH(3)CO(2)(-), H(2)PO(4)(-), HSO(4)(-) and Cl(-). 1-Hg(2+)-F(-) complex formed, which promoted the intramolecular charge transfer and led to a dramatic spectral change. The color of 1-Hg(2+) solution changed from colorless to red upon addition of F(-). Thus, a colorimetric assay of F(-) was developed in acetonitrile by naked-eye detection. F(-) behaved linearly in the 8.0 x 10(-6) to 2.0 x 10(-5) mol L(-1) concentration range with LOD as 1.4 x 10(-6) mol L(-1).     

Liquid chromatographic enantiomer separation of racemic amine using chiral crown ether stationary phase

Direct enantioseparation of racemic amine, amino-thiophene-2-yl-acetonitrile (TAN), on chiral crown ether stationary phase [Crownpak CR (+)] is described in this study. The elution behavior and the effect of acid additives on resolution of racemic amine, TAN, is intensely investigated. Moreover, the chiral recognition mechanism in this specific system is proposed based on computational methods with the density functional theory. Diastereomeric complexation of the ammonium ion of racemic amine inside the cavity of chiral crown ether appears essential for the chiral discrimination. The pH of the mobile phase containing acid additives also acts as an important factor for the chiral recognition.     

Novel bis (crown ether)-based potassium sensor for biological applications

Based on structure-selectivity studies on bis-benzo-crown ether derivatives, 2,2-bis[3,4-(15-crown-5)-2-nitrophenylcarbamoxymethyl]tetradecane (BME-44) was designed and synthesized. The performance characteristics of this new, highly lipophilic ionophore of the group of bis-nitrobenzo-15-crown-5 derivatives with urethane linkage when used in liquid membrane electrodes are evaluated with special regard to the requirements of biological and clinical applications. Potentiometric steady-state and flow-through dynamic data are presented to prove the sensor capabilities for clinical and physiological potassium determinations.Dedicated to Professor W. Simon on the occasion of his 60th birthday     

Solvent extraction of silver and thallium picrates with poly- and bis-(crown ether)s

Summary Solvent extraction of silver and thallium picrates by new poly- and bis(crown ether)s, which contain benzo-15-crown-5 or benzo-18-crown-6 moieties, was carried out in water-chloroform system. The poly- and bis(crown ether)s showed higher extractability for both metals than the corresponding monocyclic crown ethers.Especially poly- and bis(benzo-15-crown-5) were found to be quite effective extracting agents for Tl⁺.The extraction equilibrium constants and the complexation constants for the chloroform phase were also estimated.

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Lösungsmittelextraktion von Silber- und Thalliumpikraten mit Poly- und Bis-Kronenethern

Zusammenfassung Die Extraktion der Pikrate wurde in Wasser/Chloroform mit neuen Poly- und Bis-Kronenethern durchgeführt, die Benzo-15-Krone-5- oder Benzo-18-krone-6-Komponenten enthielten. Die Poly- und Bis-Kronenether wiesen für beide Metalle eine bessere Extrahierbarkeit auf als die entsprechenden monocyclischen Kronenether. Insbesondere Poly- und Bis(benzo-15-krone-5) erwiesen sich als wirkungsvolle Extraktionsmittel für Thallium(I). Die Extraktions-Gleichgewichtskonstanten und die Komplexbildungskonstanten für die Chloroformphase wurden bestimmt.

     

Solvent extraction of alkaline earth metal picrates with poly- and bis(crown ether)s

Summary Solvent extraction of alkaline earth metal picrates with poly- and bis(crown ether)s containing benzo-15-crown-5- and benzo-18-crown-6 moieties was carried out in a water-chloroform system. The poly- and bis(crown ether)s showed larger extractability for the metal picrates than the corresponding monocyclic crown ethers. Especially, poly- and bis(benzo-15-crown-5), and bis(benzo-18-crown-6) were found to have relatively high extractability and selectivity for Ba²⁺ and Sr²⁺, respectively.

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Lösungsmittelextraktion von Erdalkalipikraten mit Hilfe von Poly- und Bis-Kronenethern

Zusammenfassung Poly- und Bis-Kronenether mit Benzo-15-krone-5- und Benzo-18-krone-6-Einheiten wurden zur Extraktion von Erdalkalipikraten im Wasser-Chloroform-System verwendet. Die genannten Ether zeigten eine bessere Extraktionsfähigkeit für die Pikrate als die entsprechenden monocyclischen Kronenether. Im Falle von Ba²⁺ und Sr²⁺ ergab sich eine besonders gute Extrahierbarkeit und Selektivität mit Poly- und Bis(benzo-15-krone-5)- und Bis(benzo-18-krone-6)-Ethern.

     

Synthesis,spectroscopic and spectrophotometric study of BODIPY appended crown ether sensor for ion detection

A novel fluoroionophore compound was synthesized from a boron dipyrromethene (BODIPY) fluorophore and 4′-formylbenzo-15-crown-5 ionophore groups. Photophysical properties of the BODIPY-crown compound were studied with UV–Vis and fluorescence spectroscopy. The effect of metalic cations (Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Ba²⁺, Al³⁺, Fe³⁺, Cu²⁺, Co²⁺, Zn²⁺, Ag⁺, Hg²⁺, Pb²⁺) on the absorption and fluorescence spectra of compound 2 was investigated. Blue shifts were detected in UV–Vis spectra upon addition of some metal ions (Al³⁺ > Fe³⁺ > Na⁺). At the same time, the emission intensity of this complex increased due to binding of Na⁺ ion to the benzo crown cavity. Additionally, a decrease in the intensity of the 630 nm emission peak and an increase in the intensity of the 570 nm emission peak was observed in the fluorescence emission spectra following addition of Al³⁺ and Fe³⁺ ions.     

邻菲咯啉冠醚衍生物为载体的伯胺药物电极及机理研究

合成了邻菲咯啉-18-冠-6等四种含邻菲咯啉结构的冠醚化合物, 并用作载体制备伯胺电极, 以苄胺为模型化合物, 研究了电极特性, 并制备了测试美西律药物的选择性电极。研究了实验条件对电极性能的影响。用正交多项式回归法优化电极的膜组成。苄胺电极的线性范围1.0×10^-5~0.1mol/L, 斜率55.6mV/pc, 检测下限2.0×10^-6mol/L。美西律电极的线性范围6.0×10^-6~0.1mol/L, 检测下限8.0×10^-7mol, 斜率58.0mV/pc。同时研究了冠醚推动伯胺穿透大块液膜的传输行为。     

Solvent extraction separation of rubidium with a crown ether for neutron activation analysis in rock samples

The extraction behavior of rubidium with a crown ether has been studied and methods for the separation and determination of rubidium have been developed. Rubidium was separated with tetraphenylborate from sample solution, and then quantitatively extracted into nitrobenzene by 18-crown-6 from 0.05 mol/l picric acid (pH 6) and back-extracted by 6 mol/l hydrochloric acid. Rubidium was determined by the neutron activation method in rock samples.     

Novel colorimetric sensor for mercury (Ⅱ) based on layer-by-layer assembly of unmodified silver triangular nanoplates

A simple layer-by-layer deposition technique was used to fabricate the multilayer thin films of unmodified silver triangular nanoplates(AgTNPs).The multilayer of AgTNPs thin films were fabricated by alternate deposition of each anionic sodium citrate stabilized AgTNPs and cationic poly(diallyldimethylammonium chloride).All prepared AgTNPs multilayer thin films were exhibited a strong plasmon band at the wavelength of 667 nm,which confirmed the formation of AgTNPs onto the substrate.The characteristics of the multilayer thin films were investigated using contact angle measurement,UV-visible spectroscopy,X-ray diffraction analysis(XRD),atomic force microscope(AFM)and field emission scanning electron microscope(FESEM).As these films are to be used as a mercury(II)colorimetric sensor,the changes in optical properties of the films were evaluated for various mercury(Ⅱ)concentrations.AgTNPs assembled into thin films showed a strong color shift from blue to mauve and colorless when exposed to mercury(Ⅱ).The constructed multilayer thin films exhibited excellent color changes of mercury(II) with a linear range between 0.5 and 20 ppm.The limit of detection(LOD) and limit of quantitation(LOQ) were 0.45 ± 0.002 and 1.52 ± 0.002 ppm,respectively.The recovery values of AgTNPs multilayer thin films are satisfactory in the range of 100.1%-106.4%when applied to determining mercury(Ⅱ) in water samples.     

A novel fluorescence sensor for K+ based on bis-Bodipy: The ACQ effect controlled by cation complexation of pseudo crown ether ring

Three novel bis-Bodipy 3a–3c bridged with crown ether chain were prepared in yields of 70–78%. Their complexation absorption and fluorescent spectra for fourteen metal ions suggested that compound 3b exhibited the selective response for K⁺ with obvious ACQ effect. The association constant of compound 3b with K⁺ was 4.3 × 10⁵ M^?1 and 1:1 complex mode was deduced. The complexation mechanism of ACQ effect controlled by cation complexation of pseudo crown ether ring was confirmed by the fluorescent titrations, complexation FT-IR spectra, complexation ¹H NMR spectra, complexation ESI-MS spectra and contrast experiment of similar mono-Bodipy derivative. The K⁺ was binded in the cavity of a pseudo crown ether ring, leading to the closed distance for two Bodipy units and then enhancing the ACQ effect obviously. Both the structure of the crown ether chain and two Bodipy units were decisive factors for the selective fluorescence sensor for K⁺.     

Label-free colorimetric sensor for mercury(II) and DNA on the basis of mercury(II) switched-on the oxidase-mimicking activity of silver nanoclusters

In this paper, a novel colorimetric biosensor for Hg²⁺ and DNA molecules is presented based on Hg²⁺ stimulated oxidase-like activity of bovine serum albumin protected silver clusters (BSA-Ag NCs). Under mild conditions, Hg²⁺ activated BSA-Ag NCs to show high catalytic activity toward the oxidation of 3,3′,5, 5′-tetramethylbenzidine (TMB) using ambient dissolved oxygen as an oxidant. The oxidase-like activity of BSA-Ag NCs was “switched-on” selectively in the presence of Hg²⁺, which permitted a novel and facile colorimetric sensor for Hg²⁺. As low as 25 nmol L⁻¹ Hg²⁺ could be detected with a linear range from 80 nmol L⁻¹ to 50 mmol L⁻¹. In addition, the sensing strategy was also employed to detect DNA molecules. Hg²⁺ is known to bind very strongly and specifically with two DNA thymine bases (T) to form thymine–Hg²⁺–thymine (T–Hg²⁺–T) base pairs. The hairpin-structure was disrupted and Hg²⁺ ions were released after hybridization with the DNA target. By coupling the Hg²⁺ switched-on the oxidase-mimicking activity of BSA-Ag NCs, we developed a novel label-free strategy for facile and fast colorimetric detection of DNA molecules. More important, target DNA can be detected as low as 10 nmol L⁻¹ with a linear range from 30 to 225 nmol L⁻¹. Compared with other methods, this method presents several advantages such as the independence of hydrogen peroxide, high sensitivity and good selectivity, avoiding any modification or immobilization of DNA, which holds a great potential of metal NCs for clinical application in biosensing and biotechnology.     

Synthesis of polyfluoroalkylated glycerol and crown ether

Perfluoroalkylated glycerol (5, 9) and crown ethers (22, 23, 24) were synthesized starting from glycerol. 5 was synthesized by allylation of glycerol 1,2-acetonide followed by perflu-oroalkylation initiated with sodium dithionite, reduction of iodide and hydrolysis in good overall yield and was shown to poccess good surface activities. Glycerol bis-ether (9) was synthesized in a similar way. Allyloxymethyl crown ethers (15, 16, 18) were prepared as key intermediates through multi-step reactions, which were then perfluoroalkylated to give the title crown ethers 22, 23 ,24.     

A new colorimetric and fluorimetric sensor for metal cations based on poly(propilene amine) dendrimer modified with 1,8-naphthalimide

A new fluorescent first generation poly(propylene amine) dendrimer (PPI), peripherally modified with 4(butylamino-substituted-1,8-naphthalimide), has been synthesized and characterized. Its photophysical characteristics in organic solvents of different polarities were studied, and the influence of sodium hydroxide on its spectral characteristics in N,N-dimethylformamide is discussed. The complexes formed between the dendrimer and metal cations in solution have been studied with regard to the potential applications of the new dendrimer as a colorimetric and fluorescent sensor for metal ions. The fluorescence intensity of the dendrimer in the presence of metal cations (Zn²⁺, Co²⁺, Pb²⁺, Mn²⁺, Cu²⁺ and Fe³⁺) increases substantially revealing its sensor potential.     

Structure and stability of supramolecular crown ether complexes

Despite the fact that the complexation of ammonium cations with ionophores like crown ethers plays an important role in biological and industrial processes, there is still a lack of theoretical methods to reproduce or even predict the host–guest complex structures or their thermodynamic stabilities in an accurate manner. Hence, the development of ionophores has often relied on a trial‐and‐error approach and the synthetic efforts associated with this have been enormous, so far. Therefore, theoretical methods for the reliable prediction of binding affinities of crown ether derivatives with ammonium ions would be an indispensable tool for the rational design of new receptors with tailored properties. Here, we suggest a computationally efficient but still accurate theoretical approach. It is tested for a model system consisting of 18‐crown‐6 ether and an ammonium cation, but is invented for application to much larger complexes. The accuracy of various approximate quantum‐chemical methods, based on density functional theory (DFT) and many‐body perturbation theory, is evaluated against the gold standard CCSD(T) in the basis set limit as internal reference. An important aspect is the consideration of dispersion interactions in DFT methods, for which the dispersion‐correction by Grimme was employed. For all selected methods, the basis‐set dependence of calculated interaction energies was investigated. © 2015 Wiley Periodicals, Inc.     

Synthesis and application of crown ether tagged triarylphosphines

Crown ether tagged triarylphosphines 1 and 2 were synthesised and applied in Mitsunobu and Heck reactions, their reactivity being evaluated against triphenylphosphine- and polymer-bound triphenylphosphine. Purification of the reactions was effected by post-reaction sequestration onto an ammonium functionalised solid-phase.     

Influence of the angle between two crown ether moieties on supramolecular copolymerization of bis(crown ether)s and bisparaquat homoditopic monomers

Bis(crown ether) homoditopic monomers containing two bis(p-phenylene)-34-crown-10 moieties with different angles(180° for monomer 3,120°for monomer 4,and 60°for monomer 5) and a complementary bisparaquat homoditopic monomer(7) were designed and synthesized.The three bis(crown ether) monomers could organize into linear supramolecular polymers in concentrated solutions in CHCl3/CH3CN with the bisparaquat monomer 7,as demonstrated by 1 H NMR and viscosity studies. The pseudorotaxanes or supramolecular polymers...     

不同溶剂对硝酸钕盐冠醚配合物振子强度的影响

本文通过Judd-Ofelt理论测定并计算了硝酸钕冠醚配合物吸收光谱的振子强度, 讨论了不同溶剂对配合物振子强度及其对称性的影响。     

Photoinduced template synthesis of cyclobutane-containing crown ether

The photoinitiated [2+2]-cycloaddition of 1,5-bis[2-(3-phenyl-3-oxoprop-1-en-1-yl)phenoxy]-3-oxapentane in solution was studied. In the presence of potassium cations, the reaction is intramolecular and gives crown ether containing the γ-truxin-type cyclobutane fragment (anti, head-to-head) as the major product. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 204–206, January, 2008.