Turn-on fluorescence sensing of nucleoside polyphosphates using a xanthene-based Zn(II) complex chemosensor

Fluorescence sensing with small molecular chemosensors is a versatile technique for elucidation of function of various biological substances. We now report a new fluorescent chemosensor for nucleoside polyphosphates such as ATP using metal-anion coordination chemistry. The chemosensor 1-2Zn(II) is comprised of the two sites of 2,2'-dipicolylamine (Dpa)-Zn(II) as the binding motifs and xanthene as a fluorescent sensing unit for nucleoside polyphosphates. The chemosensor 1-2Zn(II) selectively senses nucleoside polyphosphates with a large fluorescence enhancement (F/F(o) > 15) and strong binding affinity (K(app) approximately = 1 x 10(6) M(-1)), whereas no detectable fluorescence change was induced by monophosphate species and various other anions. The 'turn-on,' fluorescence of 1-2Zn(II) is based on a new mechanism, which involves the binding-induced recovery of the conjugated form of the xanthene ring from its nonfluorescent deconjugated state which was formed by an unprecedented nucleophilic attack of zinc-bound water. The selective and highly sensitive ability of 1-2Zn(II) to detect nucleoside polyphosphates enables its bioanalytical applications in fluorescence visualization of ATP particulate stores in living cells, demonstrating the potential utility of 1-2Zn(II).     

Highly sensitive detection of mercury (II) in aqueous media by tetraphenylporphyrin with a metal ion receptor

We provide a highly sensitive and selective assay to detect Hg²⁺ in aqueous solutions using a novel β-functionalised porphyrin-based chemosensor 5 at room temperature. The binding properties of the chemosensor 5 for cations were examined by UV–vis spectroscopy and ¹H NMR. The results indicate that a 1:1 stoichiometric complex is formed between chemosensor 5 and mercury (II) ion. The recognition mechanism between chemosensor 5 and metal ion was discussed based on their absorbance changes and the chemical shift changes when they interact with each other. Control experiments revealed that chemosensor 5 has a selective response to mercury (II) ion compared with other metal ions.     

In vivo monitoring of mercury ions using a rhodamine-based molecular probe

Exposure to mercury causes severe damage to various tissues and organs in humans. Concern over mercury toxicity has encouraged the development of efficient, sensitive, and selective methods for the in vivo detection of mercury. Although a variety of chemosensors have been exploited for this purpose, no in vivo monitoring systems have been described to date. In this report, we describe an irreversible rhodamine chemosensor-based, real-time monitoring system to detect mercury ions in living cells and, in particular, vertebrate organisms. The chemosensor responds rapidly, irreversibly, and stoichiometrically to mercury ions in aqueous media at room temperature. The results of experiments with mammalian cells and zebrafish show that the mercury chemosensor is cell and organism permeable and that it responds selectively to mercury ions over other metal ions. In addition, real-time monitoring of mercury-ion uptake by cells and zebrafish using this chemosensor shows that saturation of mercury-ion uptake occurs within 20-30 min in cells and organisms. Finally, accumulation of mercury ions in zebrafish tissue and organs is readily detected by using this rhodamine-based chemosensor.     

<Emphasis Type="Italic">N,N′</Emphasis>-Bis(9-anthrylmethyl)diamines as fluorescent chemosensors for transition metal cations

N,N′-Bis(9-anthryl)-substituted diamines, imidazolidines, and hexahydropyrimidines were synthesized, and their luminescence properties and complexing ability were studied. N,N′-Bis(9-anthrylmethyl)ethane-1,2-diamine and N,N′-bis(9-anthrylmethyl)butane-1,4-diamine were found to be effective and selective PET chemosensors for Zn²⁺ and H⁺, respectively. 2-[1,3-Bis(9-anthrylmethyl)hexahydropyrimidin-2-yl]-6-methoxyphenol can be used as fluorescent chemosensor for mercury(II) cations.     

A squaraine-based near IR fluorescent chemosensor for Calcium

A red to NIR emitting, highly Ca²⁺-specific fluorescent chemosensor has been synthesized. In pH 7.2 aqueous buffers, the chemosensor signals Ca²⁺ by a decrease in emission intensity, whereas large excess of Mg²⁺ ions have no effect on either the absorption or the emission spectrum. The chemosensor is likely to be the prototype of a new generation of laser-diode excitable fluorescent chemosensors for Calcium.     

Sensitive and Selective Fluorescent Chemosensors Combining Multiple PET Processes for Ag+ Sensing

In this work, a novel fluorescent chemosensor combining multiple photoinduced electron transfer(PET) processes for the detection of Ag⁺ ion was synthesized. The PET processes were derived from the lone electron pair of the selenium donors and the tertiary nitrogen atom of the coumarin fluorophore, which have not yet been used in the fluorescent chemosensor designed for Ag⁺ ion. Interestingly, the chemosensors showed fluorescent responses to Ag⁺ ion with a fluorescence enhancement factor of 3-5-fold by blocking the intramolecular PET quenching pathways. Furthermore, the probe exhibited high selectivity and sensitivity for Ag⁺ ion over other relevant species with detection limit down to 10 nmol/L level. The chemosensors also showed excellent performances in analyzing natural water samples. The chemosensors developed herein represent a new strategy for the PET fluorescent chemosensor design for the detection of Ag⁺ ion.     

Fluorescent chemosensors for mercury(II) cations

The condensation of 4,5-dimethoxy-2-(morpholin-4-yl)aniline with anthracene-9-carbaldehyde gave N-(anthracen-9-ylmethyl)-4,5-dimethoxy-2-(morpholin-4-yl)aniline, a selective and efficient fluorescent chemosensor for mercury(II) cations.     

Through bond energy transfer (TBET)-based fluorescent chemosensors

Excitation energy transfer is one of the crucial issues in photophysical and photochemical process of any muti-chromophoric molecular systems, such as energy harvester and fluorescent chemosensor. Through bond energy transfer (TBET)-based fluorescent chemosensors are composed of three main parts: energy donor, energy acceptor, and rigid linker. Comparing with the often used Förster resonance energy transfer (FRET) mechanism, TBET does not require spectral overlap, thus it may enable more possible combination of energy donors and acceptors to be employed and afford higher sensitivity toward targets through ratiometric fluorescence. In this review, we highlight the recent progress in the design and biological applications of the organic TBET-based fluorescent chemosensors during 2014–2019, which will provide profound guidance for designing powerful chemosensors as well as exploring further biological applications.     

Tuning the selectivity of two chemosensors to Fe(III) and Cr(III)

Two rhodamine-based chemosensors (1 and 2) were designed, and their sensing behavior toward metal ions was investigated by fluorescence spectroscopies. 1 and 2 achieved tuning the selectivity to Fe(III) and Cr(III) in 100% aqueous solution, whereas other ions including Cd(II), Co(II), Cu(II), Ni(II), Zn(II), Mg(II), Ba(II), Pb(II), Na(I), and K(I) induced basically no spectral change, which constituted a Fe(III)-selective and a Cr(III)-selective fluorescent chemosensor, respectively.     

Fluorescent and colorimetric sensors for detection of lead, cadmium, and mercury ions

Exposure to even very low levels of lead, cadmium, and mercury ions is known to cause neurological, reproductive, cardiovascular, and developmental disorders, which are more serious problems for children particularly. Accordingly, great efforts have been devoted to the development of fluorescent and colorimetric sensors, which can selectively detect lead, cadmium, and mercury ions. In this critical review, the fluorescent and colorimetric sensors are classified according to their receptors into several categories, including small molecule based sensors, calixarene based chemosensors, BODIPY based chemosensors, polymer based chemosensors, DNA functionalized sensing systems, protein based sensing systems and nanoparticle based sensing systems (197 references).     

A fluorescent "turn-on" probe for the dual-channel detection of Hg(II) and Mg(II) and its application of imaging in living cells

A novel rhodamine-based fluorescent chemosensor (RND) was synthesized that contains two independent fluorophores and acts as a very sensitive, selective and reversible off-on probe for Hg(II). Importantly, this newly developed sensing system exhibited different fluorescent responses toward Hg(II) and Mg(II) at 589 nm and 523 nm, respectively. RND also displayed detectable color change upon treatment with Hg(II). Results from confocal laser scanning microscopy experiments demonstrated that this chemosensor is cell permeable and can be used as a fluorescent probe for monitoring Hg(II) or Mg(II) in living cells. This probe can also indirectly detect glutathione (GSH) and cysteine (Cys) with good linear relationships.     

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.     

Highly sensitive and selective fluorescent chemosensor for Ag+ based on a coumarin-Se2N chelating conjugate

A highly sensitive and selective fluorescent chemosensor SC1 for Ag(+) based on a coumarin-Se(2)N chelating conjugate has been synthesized and characterized. Due to inhibiting a photoinduced electron transfer (PET) quenching pathway, a fluorescent enhancement factor of 4-fold is observed under the binding of the Ag(+) cation to the chemosensor SC1 with a detection limit down to the 10(-8) M range.     

A colormetric and fluorescent chemosensor for adenosine-5′-triphosphate based on rhodamine derivative

A rhodamine spirolactam derivative (1) was developed as a colormetric and fluorescent chemosensor for adenosine-5′-triphosphate (ATP) via hydrogen bonds interaction. As far as we know, this is the first case to explore ATP-induced ring-opening of spirolactam in rhodamine derivatives. It exhibited a highly sensitive “turn-on” fluorescent response toward ATP with a 47-fold fluorescence intensity enhancement under 20 equiv. of ATP added. The chemosensor can be applied to the quantification of ATP with a linear range covering from 1.0 × 10⁻⁷ to 2.0 × 10⁻⁴ M and a detection limit of 2.5 × 10⁻⁸ M. The experiment results show that the response behavior of 1 toward ATP is pH independent in medium condition (pH 6.0–8.0). Most importantly, the novel chemosensor has well solved the problem of serious interferences from other nucleoside polyphosphates such as ADP and AMP generally met by previously reported typical fluorescent chemosensors for ATP. Moreover, the response of the chemosensor toward ATP is fast (response time less than 3 min). In addition, the chemosensor can be used for the fluorescence assay for protein kinase activity with satisfactory results. The chemosensor for ATP based on hydrogen bonds interaction provided a novel strategy for the design of colormetric and ratiometric fluorescent probes for other target anions with high sensitivity and selectivity.     

Pyrene-linked triazole-modified homooxacalix[3]arene: a unique C3 symmetry ratiometric fluorescent chemosensor for Pb2+

A new type of fluorescent chemosensor based on homooxacalix[3]arene was synthesized. The fluorescent sensor was highly selective for Pb(2+) in comparison with other metal ions tested by enhancement of the monomer emission of pyrene. The C(3) symmetric structure of homooxacalix[3]arene has potential application in the development of a new ratiometric fluorescent chemosensor for heavy metal ions.     

8-Hydroxyquinoline derivative as a fluorescent chemosensor for zinc ion.

8-Hydroxyquinoline derivative 1 as a fluorescent chemosensor for Zn2+ was synthesized. Because Cd2+ is often found with Zn2+ in the environment and can form fluorescent complexes with chelating fluorophores, a potentially important property of chemosensors for Zn2+ is their selectivity for Zn2+ over Cd2+. The Zn2+ or Cd2+ complexes of 1 gave an emission band from the 1:1 complex, but the fluorescence intensity for Cd2+ was a half of that for Zn2+. Ligand 1 is suited for use as a fluorescent chemosensor for Zn2+.     

识别过渡金属离子的1,8-萘二甲酰亚胺多胺衍生物荧光传感器的研究

A series of fluorescent chemosensors 1-3 were synthesized to detect transition metal ions. At the room temperature, fluorescence intensities of these chemosensors in acetonitrile without transition metal ions were found to be very weak, due to the process of the e±cient intramolecular photoinduced electron transfer (PET). However, after addition of the transition metal ions, the chemosensor 1-3 exhibits obvious fluorescence enhancement. Moreover, the intensity of the fluorescence emission of chemosensors increases significantly in the presence of Zn2+ and Cd2+. The fluorescent chemosensors with different polyamine as receptors show diverse a±nity abilities to the transition metal ions and signal the receptor-metal ion interaction by the intensity change of fluorescence emission.     

Stereochemical and regiochemical trends in the selective detection of saccharides

Several discreet sugar-boronate complexes exist in solution. This is due to the complex equilibria between isomeric species of even the simplest monosaccharides. In the current investigation, we determine the regio- and stereochemical features of the various equilibrating sugar isomers that induce signal transduction in boronic acid chemosensors such as 1 as well as 2 and 3. We present a unique example of a chemosensor (1) that is selective for ribose, adenosine, nucleotides, nucleosides, and congeners. As a result of this study, we are able to predict and achieve selective fluorescence and colorimetric responses to specific disaccharides as a consequence of their terminal sugar residue linkage patterns and configurations. We also find that the combined use of chemosensors exhibiting complementary reactivities may be used cooperatively to obtain enhanced selectivity for ribose and rare saccharides.     

Development of a reversible fluorescent gold sensor with high selectivity

We have designed and synthesized the highly selective and reversible fluorescent chemosensor 1 for Au(3+) by modifications on the fluorescent copper chemodosimeter 2, and we have further demonstrated that chemosensor 1 could be employed to image Au(3+) in living cells.     

Facile synthesis of rhodamine-based highly sensitive and fast responsive colorimetric and off-on fluorescent reversible chemosensors for Hg2+: preparation of a fluorescent thin film sensor

Fluorescence-active chemosensors (L1-L4), comprising a rhodamine scaffold and a pseudo azacrown cation-binding subunit, have been proposed and characterized as a fluorescent chemosensor for Hg(2+). An on-off type fluorescent enhancement was observed by the formation of the ring-opened amide form of the rhodamine moiety, which was induced by the interactions between Hg(2+) and the chemosensor. Upon the addition of Hg(2+), an overall emission change of 350-fold was observed, and the selectivity was calculated to be 300 times higher than Cu(2+) for receptors L2-L4. A polymeric thin film can be obtained by doping poly(methyl methacrylate) or PMMA with chemosensor L2. Such a thin film sensor can be used to detect Hg(2+) with high sensitivity and can be recovered using diluted NaOH.