Zinc selective chemosensor based on pyridyl-amide fluorescence

Chemosensors are developed to image zinc ions. Fluorescence enhancement due to Zn²⁺ binding is an excellent way to detect its presence. A chemosensor for Zn²⁺ based on dipicolylamine (DPA) groups connected by a pyridyl amide backbone has been synthesized. Addition of 2-chloroacetyl chloride to 2,6-diaminopyridine affords 2,6-bis(chloroethylamido)pyridine, which is converted to the sensor BADPA-P by 2,2′-dipicolylamine displacement of chlorine. This compound along with two others, the mono-DPA, ADPA-P and the benzyl in place of pyridyl, BADPA-B, present three potential Zn²⁺ sensors. It was found that BADPA-P in the presence of Zn²⁺ shows a large increase in fluorescence, whether in polar organic or aqueous environments. Its fluorescence in the presence of Cd²⁺, unlike with Zn²⁺, is not enhanced when excited at longer wavelengths. Proton NMR measurements, indicate two Zn²⁺ ions bind to BADPA-P. Also, Zn²⁺ enhances fluorescence even when other metal ions are present.     

A new selective fluorescence chemosensor for Cu(II) in water

A new chemosensor for the Cu(II) ion has been realized by connecting via an amido bond an anthracenyl residue to the all cis 2,4,6-triamino-1,3,5-trihydroxycyclohexane ligand (TACI). This sensor is able to detect micromolar concentrations of Cu(II) ions in water at pH 7 without interference with many other divalent transition metal ions.     

A highly selective fluorescence chemosensor for Pb(II) in neutral buffer aqueous solution

A 3,4-dimethylthieno[2,3-b]thiophene-based fluorogenic probe bearing benzo[d]-thiazole-2-thio unit (sodium 3,4-bis ((benzo[d]thiazol-2-ylthio)methyl) thieno [2, 3-b]thio-phene-2, 5-dicarboxylate) was developed as a novel fluorescent chemosensor with high selectivity towards Pb(II) over other cations tested. The new probe exhibited good water solubility and only sensed Pb(II) among metal ions examined in neutral 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid buffer solution. The selectivity and sensitivity of fluorogenic probe to Pb(II) were discussed on the basis of experimental results.     

A highly selective chemosensor for nickel(II) based on fluorescence quenching of a bispyrazole derivative

Research on Chemical Intermediates - A novel bispyrazole, 2,6-bis(5-phenyl-1H-pyrazol-3-yl)-pyridine, was designed and synthesized. The bispyrazole showed extreme selectivity for Ni2+ over other...     

A new tripodal rhodamine B derivative as a highly selective and sensitive fluorescence chemosensor for copper(II)

A new tripodal rhodamine B derivative 2 was designed and synthesized by tripodal trialdehyde and rhodamine B hydrazide for the first time. This derivative could be used as a fluorescent chemosensor for the selective and sensitive determination of copper(II) in Tris-HCl buffer and ethanol aqueous mixed media. Under the optimum conditions described herein, fluorescence enhancement at 557/577 nm was linearly related to the concentration of copper(II) in the range of 0.10 to 10.00×10⁻⁵ mol·L⁻¹, with a correlation coefficient of R ²=0.9964 (n=15) and a detection limit of 1.129×10⁻⁷ mol·L⁻¹ (the relative standard deviation for five repeated measurements at 4.00×10⁻⁵ mol·L⁻¹ Cu(II) was 2.2%). The absorbance measurements at 557 nm were linearly related to the concentration of Cu(II) in the range of 0.50 to 25.00×10⁻⁵ mol·L⁻¹, with a correlation coefficient of R ²=0.9948 (n=13) and a detection limit of 3.338×10⁻⁷mol·L⁻¹. Supported by the Foundation of the Governor of Guizhou Province, China (Grant No. 200617) and the Talented Person Foundation of Guizhou University (Grant No. 2007039)     

A novel selective fluorescent chemosensor for Cu（Ⅱ）

A novel fluorescence enhancement Cu~(2 ) chemosensor derived from coumarin was prepared.Emission study found that it exhibits evident Cu~(2 )-amplified fluorescence prior to Co~(2 ),Pb~(2 ),Mg~(2 ),Mn~(2 ),Ni~(2 ),Zn~(2 ),Fe~(3 ),Ag~ and Cd~(2 ),and the largest emission enhancement factor is about 9 at a ratio of 2:1 (chemosensor 1/Cu~(2 )).     

A new rhodamine-based chemosensor exhibiting selective Fe(III)-amplified fluorescence

[structure: see text] A new fluorescent probe 3 was synthesized, and it exhibited high selectivity for Fe(III) over other commonly coexistent metal ions in both ethanol and water. Upon the addition of Fe(III), the spirocyclic ring of 3 was opened and a significant enhancement of visible color and fluorescence in the range of 500-600 nm was observed.     

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).     

A highly selective turn-on fluorescent chemosensor for copper(II) ion

A new pyrene derivative (1) containing a diaminomaleonitrile moiety exhibits high selectivity for Cu²⁺ detection. Significant fluorescence enhancement was observed with chemosensor 1 in the presence of Cu²⁺. However, the metal ions Ag⁺, Ca²⁺, Cd²⁺, Co²⁺, Fe²⁺, Fe³⁺, Hg²⁺, Mg²⁺, Mn²⁺, Ni²⁺, Pb²⁺, and Zn²⁺ produced only minor changes in fluorescence values for the system. The apparent association constant (K_a) of Cu²⁺ binding in chemosensor 1 was found to be 5.55×10³ M⁻¹. The maximum fluorescence enhancement caused by Cu²⁺ binding in chemosensor 1 was observed over the pH range 5-7.5.     

A highly selective ‘off-on’ fluorescence chemosensor for Cr(III)

An ‘off-on’ fluorescence chemosensor for the selective signalling of Cr(III) has been designed exploiting the guest-induced inhibition of the photoinduced electron transfer signalling mechanism. The system shows an approximately 17-fold Cr(III)-selective chelation-enhanced fluorescence response in tetrahydrofuran and the system is highly selective against the background of environmentally and biologically relevant metal ions.     

A rhodamine-cyclen conjugate as a highly sensitive and selective fluorescent chemosensor for Hg(II)

A rhodamine-cyclen conjugate (1) behaves as a highly sensitive and selective fluorescent chemosensor for Hg(2+). The high emission selectivity is due to the formation of 1-Hg(2+) 1:2 complex leading to spirocycle opening of 1.     

Design of a semirigid molecule as a selective fluorescent chemosensor for recognition of Cd(II)

A new 8-hydroxyquinoline-based chemosensor possessing a semirigid structure was designed, and its fluorescent sensing behavior toward metalions was investigated. A prominent fluorescence enhancement only for Cd(2+) was found in aqueous methanol solution. The results clearly suggest that the specific semirigid structure could selectively accommodate Cd(2+) according to ionic radius, which would effectively suppress the intramolecular radiationless transitions from the n pi* state to enhance the fluorescence response.     

Synthesis of triazolyl anthracene as a selective fluorescent chemosensor for the Cu(II) ion

The Cu(I)-catalyzed azide-alkyne cycloaddition reaction (CuAAC) has been used to synthesize an anthracene-based fluorescent compound that undergoes strong fluorescence quenching in the presence of Cu(II). Fluorescence studies indicate that the compound forms a 1:1 complex and can be used to quantitatively determine micromolar concentrations of Cu(II) in aqueous solution.     

Highly selective colorimetric naked-eye Cu(II) detection using an azobenzene chemosensor

Colorimetric azobenzene based chemosensors 1 and 2 were designed for detection of transition-metal ions such as Cu(II) under physiological pH conditions. The internal charge transfer (ICT) sensors are highly colored, absorbing in the green. For 1, the Cu(II) recognition gives rise to red-to-yellow color changes that are visible to the naked-eye and reversible upon addition of EDTA, whereas for 2, which lacks the aromatic o-methoxy chelating group, no such changes were observed.     

A novel highly selective fluorescent chemosensor for Hg（Ⅱ） in fully aqueous media

A novel fluorescent Hg~(2 ) chemosensor based on dithia-dioxa-monoaza crown ether was synthesized in four steps from inexpensive starting materials.This new sensor exhibited very strong fluorescence response to Hg~(2 ) (F_(Hg~(2 ))/F_(free)>130) and it was highly selective to Hg~(2 ) over the other metal ions by more than 45-fold.     

A highly selective and sensitive fluorescent PET (photoinduced electron transfer) chemosensor for Zn(II)

The naphthalimide derivative 1 was designed as a fluorescence PET sensor for Zn(II); 1 showed excellent selectivity for Zn(II) at pH 7.4, even in the presence of other competitive cations, the emission, being pH independent above pH 3.5, was switched on upon Zn(II) recognition.     

A coumarin based highly selective fluorescent chemosensor for sequential recognition of Cu2+ and PPi

In this study, we have successfully synthesized a new coumarin based fluorescent chemosensor 1, in which tren and quinolone are introduced as receptors for sequential recognition of Cu²⁺ and PPi. The structure of chemosensor 1 was characterized by ¹H NMR, ¹³C NMR and ESI-HR-MS. Sensor 1 showed an obvious “on-off” fluorescence quenching response toward Cu²⁺, and the quenching efficiency reached a maximum of 99.6% with the addition of 20 equiv. of Cu²⁺. The 1-Cu²⁺ complex showed an “off-on” fluorescence enhancement response toward PPi over many competitive anions, especially HPO₄^2? and H₂PO₄^?. The detection limit of sensor 1 was 1.9?×?10^?6?M to Cu²⁺ and 5.96?×?10^?8?M to PPi. In addition, sensor 1 showed a 1:1 binding stoichiometry to Cu²⁺ and sensor 1-Cu²⁺ showed a 2: 1 binding stoichiometry to PPi in CH₃CN/HEPES buffer medium (9:1 v/v, pH?=?7.4). The stable pH range of sensor 1 to Cu²⁺ and 1-Cu²⁺ to PPi was from 4 to 8.     

Coumarin-based tripodal chemosensor for selective detection of Cu(II) ion and resultant complex as anion probe through a Cu(II) displacement approach

In this paper, a novel tripodal fluorescent receptor based on naturally occurring coumarin was synthesized and its ionic recognition properties were fully investigated by spectroscopic techniques. As revealed by the results, tripodal 1 exhibits excellent selectivity toward copper(II) by forming a 1:1 complex with triazole N as the main binding sites. And the resulted 1·Cu²⁺ complex shows recognition ability toward H₂PO₄^? by metal displacement approach. The recognition mechanism was further investigated by computer calculation.     

Anthracene-tethered aminomethyl oxadiazole chemosensor: a probe offering selective chromo- and fluorogenic signalings for targeting Cu(II)

A new optical chemosensor featuring anthracene as a fluorophore and an aminomethyl oxadiazole moiety as a bidentate chelate has been synthesized. From photophysical studies, we find the probe to offer remarkably selective chromo- and fluorogenic signaling responses towards biologically and environmentally significant Cu²⁺. In the presence of Cu²⁺, fluorescence is quenched to the extent of 95%, while the absorbance due to the anthracene chromophore is nearly completely bleached out. On the other hand, Li⁺, Na⁺, K⁺, Ba²⁺, Ca²⁺, Zn²⁺, Mg²⁺, Cd²⁺, Co²⁺, Ni²⁺, Ag⁺, Pb²⁺ and Hg²⁺ even at 10 times higher concentration than Cu²⁺ do not cause detectable photophysical perturbations. The stability constants, logK for Cu²⁺ were calculated to be 4.36 and 4.76 on the basis of spectrophotometric and fluorimetric titrations, respectively. However, logKs for other metal ions are too low (<0.1) to pose any interferences in the optical detection of Cu²⁺. Though, not fully defined, the uncommon phenomenon of the absorbance bleaching by Cu²⁺ is tentatively explained by invoking the involvement of non-covalent anthracene-Cu²⁺ complex.     

Fluorescent chemosensor based on Schiff base for selective detection of zinc(II) in aqueous solution

A chemosensor 1, based on the Schiff base, is easily prepared by reacting tryptophan and 2-hydroxy-1-naphthaldehyde in methanol. The optical properties of 1 are investigated in buffered aqueous solution, which displays specific recognition to Zn²⁺, and especially avoids the interference of Cd²⁺ when 1 is tested against a range of physiological and environmentally relevant metal ions. Such a novel fluorescent probe can also be used to detect Zn²⁺ in live cells.