Rhodamine hydrazone derivatives as Hg2+ selective fluorescent and colorimetric chemosensors and their applications to bioimaging and microfluidic system

In this paper, we report new rhodamine hydrazone derivatives bearing thiol and carboxylic acid groups as selective fluorescent and colorimetric chemosensors for Hg(2+). The ring-opening process of spirolactam enables the large fluorescent enhancement and colorimetric change upon the addition of Hg(2+). The sample containing Hg(2+) was mixed with one of the chemosensors in a microchannel where the sensor was examined using confocal laser scanning microscopy. A plot of the fluorescent intensities of both chemosensors versus the log concentration of Hg(2+) exhibited a linear response (r(2)=0.95) in the range of 1 nM-1 μM, and the detection limits were 1 nM and 4.2 nM, respectively. Both chemosensors also enable the visualization of Hg(2+) accumulated in the nematode Caenorhabditis elegans previously exposed to nanomolar concentrations of Hg(2+).     

Rhodamine-based chemosensing monolayers on glass as a facile fluorescent "turn-on" sensing film for selective detection of Pb2+

Rhodamine-based chemosensors 1 and 2 were synthesized and self-assembled onto glass surfaces for the selective fluorescent sensing of Pb(2+). The immobilized chemosensors showed fluorescent responses that were turned-on with Pb(2+) in CH(3)CN, selectively over various metal ions. The Pb(2+)-selective fluorescent switch of the immobilized chemosensors was also reversible, allowing for repeated use for Pb(2+) detection.     

Novel Fluorescent Chemosensors Based on Tryptophan Unit for Cu2+ and Fe3+ in Aqueous Solution

We reported four fluorescent chemosensors containing tryptophan units. The fluorescence spectrum titration experiments suggest that chemosensors 1, 2, 3 and 4 are highly selective for Cu²⁺ and Fe³⁺ over Li⁺, Na⁺, K⁺, Co²⁺, Zn²⁺, Ni²⁺, Hg²⁺ and Cr³⁺ via forming complexes with Cu²⁺ or Fe³⁺, which is confirmed by dramatical quench of fluoreseence in aqueous solution at pH 7.4, thus making all the chemosensors suitable for Cu²⁺ and Fe³⁺ fluorescent sensors.     

A color version of the Hinsberg test: 1 degrees -3 degrees amine indicator

The Hinsberg test to recognize the type of amine (1 degrees -3 degrees amines), which has been established for more than 100 years and well documented in textbooks, is not possible without conducting complicated organic reactions. We report for the first time unique chemosensors that are capable of showing selective color changes toward 1 degrees -3 degrees amines as a color version of the Hinsberg test. This simple and straightforward qualitative analysis, using the synthesized novel compounds herein, can be considered a new innovative tool for discriminating 1 degrees -3 degrees amines as an alternative to the historical Hinsberg test.     

Recent progress of calixarene-based fluorescent chemosensors towards mercury ions

In recent years, calixarene-based fluorescent chemosensors for mercury(II) are mushroom growth because of its intrinsic sensitivity. The design of the highly selective calixarene-based chemosensors towards mercury(II) is still a challenging task. In this paper, the progress of highly selective fluorescent sensor for mercury(II) based on calixarene derivatives is reviewed according to a mono-fluorophore chemosensor and a bi-fluorophore chemosensor. Some new developments such as calixarene-modified nanoparticles are also covered.     

基于咔唑衍生物的荧光化学传感器的合成及其对金属离子的选择性识别性能

以咔唑为原料合成了2个荧光化学传感器,所得化合物的组成和结构经元素分析以及质谱、红外光谱、核磁共振氢谱验证.通过在25℃下进行荧光光谱滴定,研究了传感器在体积比为1∶1的二甲基亚砜/水缓冲溶液[三羟甲基氨基甲烷盐酸盐(Tris-HCl),pH=7.4]中对Cu2+和Fe3+的选择性识别作用.结果表明,所合成的传感器与Cu2+和Fe3+形成1∶1的配合物并导致荧光猝灭,并对Cu2+离子和Fe3+离子具有较高的选择性识别和荧光传感性能.     

Development of selective high affinity antagonists, agonists, and radioligands for the P2Y1 receptor

The P2Y(1) receptor is a member of the P2Y family of nucleotide-activated G protein-coupled receptors, and it is an important therapeutic target based on its broad tissue distribution and essential role in platelet aggregation. We have designed a set of highly selective and diverse pharmacological tools for studying the P2Y(1) receptor using a rational approach to ligand design. Based on the discovery that bisphosphate analogues of the P2Y(1) receptor agonist, ADP, are partial agonists/competitive antagonists of this receptor, an iterative approach was used to develop competitive antagonists with enhanced affinity and selectivity. Halogen substitutions of the 2-position of the adenine ring provided increased affinity while an N(6) methyl substitution eliminated partial agonist activity. Furthermore, various replacements of the ribose ring with symmetrically branched, phosphorylated acyclic structures revealed that the ribose is not necessary for recognition at the P2Y(1) receptor. Finally, replacement of the ribose ring with a five member methanocarba ring constrained in the Northern conformation conferred dramatic increases in affinity to both P2Y(1) receptor antagonists as well as agonists. These combined structural modifications have resulted in a series of selective high affinity antagonists of the P2Y(1) receptor, two broadly applicable radioligands, and a high affinity agonist capable of selectively activating the P2Y(1) receptor in human platelets. Complementary receptor modeling and computational ligand docking have provided a putative structural framework for the drug-receptor interactions. A similar rational approach is being applied to develop selective ligands for other subtypes of P2Y receptors.     

Highly effective fluorescent and colorimetric sensors for pyrophosphate over H2PO4- in 100% aqueous solution

[Structure: see text]. This study demonstrated that Zinpyr-1*Zn2+ acts as a fluorescent and colorimetric sensor for pyrophosphate at pH 7.4. In addition, Zinpyr-1*Cu2+ and DIARB-1*Cu2+ complexes were found to act as selective fluorescent sensors for pyrophosphate. Furthermore, the chemosensors Zinpyr-1*Zn2+ and Zinpyr-1*Cu2+ show highly selective and ratiometric fluorescence changes for pyrophosphate compared with H2PO4-.     

Fluorescein-based fluorescent and colorimetric chemosensors for copper in aqueous media

Two new fluorescein-based chemosensors for Cu²⁺ were designed with highly selective “off-on” behavior, one of them working in both absorption and emission, the other only in absorption. Binding to Cu²⁺ binding is reversible, as indicated by the bleaching of the color when the metal is extracted. The compounds form the basis for rapid, selective and sensitive Cu²⁺ chemosensors in aqueous media.     

A highly selective and sensitive fluorescence sensing system for distinction between diphosphate and nucleoside triphosphates

Among the numerous chemosensors available for diphosphate (P(2)O(7)(4-), PPi) and nucleoside triphosphates (NTPs), only a few can distinguish between PPi and NTPs. Hence, very few bioanalytical applications based on such selective chemosensors have been realized. We have developed a new fluorescence sensing system for distinction between PPi and NTPs based on the combination of two sensors, a binuclear Zn(II) complex (1·2Zn) and boronic acid (BA), in which one chemosensor (1·2Zn) shows signal changes depending on the PPi (or NTP) concentration, and the other (BA) blocks the signal change caused by NTPs; this system enables the distinction of PPi from NTPs and is sensitive to nanomolar concentrations of PPi. The new sensing system has been successfully used for the direct quantification of RNA polymerase activity.     

Sugar-anionic clay composite materials: intercalation of pentoses in layered double hydroxide

The intercalation of non-ionized guest pentoses (ribose and 2-deoxyribose) into the Mg-Al and Zn-Al layered double hydroxides (LDHs) was carried out at 298 K by the calcination-rehydration reaction using the Mg-Al and Zn-Al oxide precursors calcined at 773 K. The resulting solid products reconstructed the LDH structure with incorporating pentoses, and the maximum amount of ribose intercalated by the Mg-Al oxide precursor was approximately 20 times that by the Zn-Al oxide precursor. The ribose/Mg-Al LDH was observed to have the expanded LDH structure with a broad (003) spacing of 0.85 nm. As the thickness of the LDH hydroxide basal layer is 0.48 nm, the interlayer distance of the ribose/Mg-Al LDH is 0.37 nm. This value corresponds to molecular size of ribose in thickness (0.36 nm), supporting that ribose is horizontally oriented in the interlayer space of LDH. The maximum amount of ribose intercalated by the Mg-Al oxide precursor was approximately 5 times that of 2-deoxyribose. Ribose is substituted only by the hydroxyl group at C-2 position for 2-deoxyribose. Therefore, the number of hydroxyl group of sugar is essentially important for the intercalation of sugar molecule into the LDH, suggesting that the intercalation behavior of sugar for the LDH was greatly influenced by hydrogen bond between hydroxyl group of the intercalated pentose and the LDH hydroxide basal layers.     

Ferrocene-thiophene dyads with azadiene spacers: electrochemical, electronic and cation sensing properties

The synthesis, electrochemical, electronic and cation sensing properties of ferrocene-thiophene ligands, linked by 2-aza-1,3-butadiene bridges, whose characteristics have been systematically varied by introducing the ferrocene moiety at the 1- or 4-position of the aza bridge, are presented. Spectroelectrochemical studies revealed the presence of low-energy bands in the partially oxidized forms, which indicate the existence of intramolecular electron-transfer between the iron center and the organic bridges. Some of the reported ligands have also shown to be efficient chemosensors for metal ions. Compounds 5a and 5b function as highly selective chemosensors for Mg2+ ions, while not showing any response to Ca2+ or alkali metal ions, whereas ligand 3b shows a selective sensing response to the soft Cd2+ metal ions over Hg2+ cations.     

Rhodamine-based chemosensing monolayers on glass as a facile fluorescent “turn-on” sensing film for selective detection of Pb

Rhodamine-based chemosensors 1 and 2 were synthesized and self-assembled onto glass surfaces for the selective fluorescent sensing of Pb²⁺. The immobilized chemosensors showed fluorescent responses that were turned-on with Pb²⁺ in CH₃CN, selectively over various metal ions. The Pb²⁺-selective fluorescent switch of the immobilized chemosensors was also reversible, allowing for repeated use for Pb²⁺ detection.     

Molecular recognition and fluorescence sensing of monophosphorylated peptides in aqueous solution by bis(zinc(II)-dipicolylamine)-based artificial receptors

The phosphorylation of proteins represents a ubiquitous mechanism for the cellular signal control of many different processes, and thus selective recognition and sensing of phosphorylated peptides and proteins in aqueous solution should be regarded as important targets in the research field of molecular recognition. We now describe the design of fluorescent chemosensors bearing two zinc ions coordinated to distinct dipicolylamine (Dpa) sites. Fluorescence titration experiments show the selective and strong binding toward phosphate derivatives in aqueous solution. On the basis of (1)H NMR and (31)P NMR studies, and the single-crystal X-ray structural analysis, it is clear that two Zn(Dpa) units of the binuclear receptors cooperatively act to bind a phosphate site of these derivatives. Good agreement of the binding affinity estimated by isothermal titration calorimetry with fluorescence titration measurements revealed that these two receptors can fluorometrically sense several phosphorylated peptides that have consensus sequences modified with natural kinases. These chemosensors display the following significant features: (i) clear distinction between phosphorylated and nonphosphorylated peptides, (ii) sequence-dependent recognition, and (iii) strong binding to a negatively charged phosphorylated peptide, all of which can be mainly ascribed to coordination chemistry and electrostatic interactions between the receptors and the corresponding peptides. Detailed titration experiments clarified that the phosphate anion-assisted coordination of the second Zn(II) to the binuclear receptors is crucial for the fluorescence intensification upon binding to the phosphorylated derivatives. In addition, it is demonstrated that the binuclear receptors can be useful for the convenient fluorescent detection of a natural phosphatase (PTP1B) catalyzed dephosphorylation.     

Fluorescent anion chemosensors using 2-aminobenzimidazole receptors

Simple and easy-to-make fluorescent anion chemosensors using 2-aminobenzimidazole moieties as binding subunits showed selective anion-induced fluorescent changes. The receptors effectively recognized fluoride, chloride, bromide, acetate, dihydrogen phosphate ions with a 1:1 stoichiometry.     

Supramolecular Sensor for Astringent Procyanidin C1: Fluorescent Artificial Tongue for Wine Components

An artificial tongue that detects astringent components for a comprehensive evaluation of taste has not been established to date. Herein, we first propose fluorescent polythiophene (PT) derivatives ( S1 – S3 ) modified with 3-pyridinium boronic acid as supramolecular chemosensors for wine components including astringent procyanidin C1. After numerous attempts for the synthetic conditions, more than 95 mol % of the PT unit was modified with the pyridinium boronic acid moiety. To evaluate the PT derivatives as chemosensors of the artificial tongue, qualitative and quantitative analyses were performed with four types of wine components (i.e., sweet, sour, bitter, and astringent tastes) in combination with pattern recognition models. Notably, procyanidin C1 in the actual wine sample was successfully detected in a quantitative manner. In other words, we have established an authentic artificial tongue using PT based supramolecular chemosensors.     

Cyclen-functionalized perylenebisimides as sensitive and selective fluorescent sensors for Pb2+ in aqueous solution

Cyclen-functionalized perylenediimides PBI-1 and PBI-2 were first synthesized as highly sensitive and selective fluorescent chemosensors for Pb(2+) in aqueous solution. PBI-2 shows a better selectivity for Pb(2+) in the presence of other metal ions and, importantly, it can successfully enter the cell and be applied in imaging of living cells.     

Covalent Labeling of Nucleosides with VIII‐ and VI‐Valent Osmium Complexes

Osmium tetroxide complexes with nitrogen ligands [Os(VIII)L] have been widely applied as probes of the DNA structure and as electroactive labels of DNA. Here we describe the electrochemical behavior of Os(VIII)2,2‐bipyridine (Os, bipy)‐base‐labeled nucleosides. We show that electroactive label can be introduced also in the nucleoside ribose residues using six‐valent osmium complex. Cyclic voltammograms of sugar‐Os(VI)‐modified ribosides are similar but not identical to those of the base‐modified ribosides. Our results showing the electroactivity of sugar modified ribosides pave the way to facile end‐labeling of RNA.     

Silica-based optical chemosensors for detection and removal of metal ions

Because some metal ions are highly toxic even at trace level, a constant demand of developing methods for monitoring and removing these metal ions is extremely urgent. Silica-based optical chemosensors are supposed as good alternatives to classical instrumental methods for detecting and adsorbing metal ions, due to their effect and lower price. Silica nanoparticles, silica gel and mesoporous silica are used as supporting platforms to fabricate optical chemosensors. They have certain properties containing high porosity and expectant adsorption capacity. Chromogenic-type and fluorogenic-type optical probes, such as azobenzene, naphthalimide and rhodamine, are grafted to the surface of silica-based materials by sol–gel reaction, the limit of detection, response time and selective properties of optical sensors are improved sequentially. In this paper, the articles of silica-based optical chemosensors are retrospected since 2008, describing silica-based optical sensors used for sensing metal ions. The sensing mechanism, optical phenomenon, detection limit, adsorption capacity and application are also reviewed.     

Design of Dual‐Emission Chemosensors for Ratiometric Detection of ATP Derivatives

Nucleoside pyrophosphate (nucleoside PP) derivatives are widespread in living cells and play pivotal roles in various biological events. We report novel fluorescence chemosensors for nucleoside PPs that make use of coordination chemistry. The chemosensors, which contain two Zn^II–dipicolylamine units, bind strongly to nucleoside PPs (K_app>10⁶ M ^?1) in aqueous solution and sense them by a dual‐emission change. Detailed fluorescence and UV/Vis spectral studies revealed that the emission changes of the chemosensors upon binding to nucleoside PPs can be ascribed to the loss of coordination between Zn^II and the acridine fluorophore. This is a unique sensing system based on the anion‐induced rearrangement of the coordination. Furthermore, we demonstrated the utility of these chemosensors in real‐time monitoring of two important biological processes involving nucleoside PP conversion: the apyrase‐catalyzed hydrolysis of nucleoside PPs and the glycosyl transfer catalyzed by β‐1,4‐galactosyltransferase.