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1.
The synthesis and electrochemical, optical, and cation-sensing properties of the ferrocene-triazole-pyridine triads 3 and 5 are presented. Azidoferrocene 1 and 1,1'-diazidoferrocene 4 underwent the "click" reaction with 2-ethynylpyridine to give the triads 3 and 5 in 81% and 68% yield, respectively. Electrochemical studies carried out in CH(3)CN in the presence of increasing amounts of Zn(2+), Ni(2+), Cd(2+), Hg(2+), and Pb(2+) metal cations, showed that the wave corresponding to the ferrocene/ferrocenium redox couple is anodically shifted by 70-130 mV for triad 3 and 167-214 mV for triad 5. The maximum shift of the ferrocene oxidation wave was found for 5 in the presence of Zn(2+). In addition, the low-energy band of the absorption spectra of 3 and 5 are red-shifted (Δλ = 5-10 nm) upon complexation with these metal cations. The crystal structures of compounds 3 and 5 and the complex [3(2)·Zn](2+) have been determined by single-crystal X-ray methods. (1)H NMR studies as well as density functional theory calculations have been carried out to get information about the binding sites that are involved in the complexation process.  相似文献   

2.
The synthesis and electrochemical, optical, and ion-sensing properties of ferrocene-imidazophenazine dyads are presented. Dyad 4 behaves as a highly selective chemosensor molecule for Pb(2+) cations in CH(3)-CN/H(2)O (9:1). The emission spectrum (λ(exc) = 317 nm) undergoes an important chelation-enhanced fluorescence effect (CHEF = 47) in the presence of Pb(2+) cations, a new low-energy band appeared at 502 nm, in its UV/vis spectrun, and the oxidation redox peak is anodically shifted (ΔE(1/2) = 230 mV). The presence of Hg(2+) cations also induced a perturbation of the redox potencial although in less extension than those found with Pb(2+) cations. Dyad 7, bearing two fused pyridine rings, has shown its ability for sensing Hg(2+) cations selectively through three channels: electrochemical, optical, and fluorescent; the oxidation redox peak is anodically shifted (ΔE(1/2) = 200 mV), a new low-energy band of the absorption spectrum appeared at 485 nm, and the emission spectrum (λ(exc) = 340 nm) is red-shifted by 32 nm accompanied by a remarkable chelation-enhanced fluorescent effect (CHEF = 165). Linear sweep voltammetry revealed that Cu(2+) cations induced oxidation of the ferrocene unit in both dyads. (1)H NMR studies have been carried out to obtain information about the molecular sites which are involved in the binding process.  相似文献   

3.
The compound bis[1,1'-N,N'-(2-picolyl)aminomethyl]ferrocene, L(1), was synthesized. The protonation constants of this ligand and the stability constants of its complexes with Ni(2+), Cu(2+), Zn(2+), Cd(2+) and Pb(2+) were determined in aqueous solution by potentiometric methods at 25 degrees C and at ionic strength 0.10 mol dm(-3) in KNO(3). The compound L(1) forms only 1:1 (M:L) complexes with Pb(2+) and Cd(2+) while with Ni(2+) and Cu(2+) species of 2 [ratio] 1 ratio were also found. The complexing behaviour of L(1) is regulated by the constraint imposed by the ferrocene in its backbone, leading to lower values of stability constants for complexes of the divalent first row transition metals when compared with related ligands. However, the differences in stability are smaller for the larger metal ions. The structure of the copper complex with L(1) was determined by single-crystal X-ray diffraction and shows that a species of 2:2 ratio is formed. The two copper centres display distorted octahedral geometries and are linked through the two L(1) bridges at a long distance of 8.781(10) Angstrom. The electrochemical behaviour of L(1) was studied in the presence of Ni(2+), Cu(2+), Zn(2+), Cd(2+) and Pb(2+), showing that upon complexation the ferrocene-ferrocenium half-wave potential shifts anodically in relation to that of the free ligand. The maximum electrochemical shift ([capital Delta]E(1/2)) of 268 mV was found in the presence of Pb(2+), followed by Cu(2+)(218 mV), Ni(2+)(152 mV), Zn(2+)(111 mV) and Cd(2+)(110 mV). Moreover, L(1) is able to electrochemically and selectively sense Cu(2+) in the presence of a large excess of the other transition metal cations studied.  相似文献   

4.
The synthesis, electrochemical, optical, and cation-sensing properties of ferrocene-pentakis(phenylthio)benzene dyads, linked through a putative cation-binding 2-azadiene bridge, are presented. Dyad 5 behaves as a highly selective dual-redox and chromogenic chemosensor molecule for Pb(2+) cations; the oxidation redox peak is anodically shifted (DeltaE(1/2) = 125 mV), and the low energy band of the absorption spectrum is red-shifted (Delta lambda = 119 nm) upon complexation with this metal cation. Linear sweep voltammetry and spectroelectrochemical studies revealed that Cu(2+) and Hg(2+) metal cations induced oxidation of the ferrocene unit. The isomeric dyad 7, in which the nitrogen atom and the ferrocene unit are in closer proximity, has shown its ability for sensing both Pb(2+) and Hg(2+) ions; the oxidation redox peak is anodically higher shifted (DeltaE(1/2) = 340 mV), and the low energy band of the absorption spectrum is lower red-shifted (Delta lambda = 61 nm) that those found for dyad 5. The changes in the absorption spectra are accompanied by dramatic color changes which allow the potential for "naked eye" detection. A further exciting property of dyad 7 is that it behaves as an electrochemically induced switchable chemosensor for Pb(2+) and Hg(2+) because of the low metal-ion affinity of the oxidized 7(*+) species for these metal cations. The experimental data and conclusions about the ion-sensing properties are supported by DFT calculations.  相似文献   

5.
A chiral polymer incorporating an (R,R)-salen moiety was synthesized by the polymerization of (R,R)-1,2-diaminocyclohexane with 2,5-dibutoxy-1,4-di(salicyclaldehyde)-1,4-diethynyl-benzene by a nucleophilic addition-elimination reaction. The fluorescence responses of the (R,R)-salen-based polymer toward various metal ions were investigated by fluorescence spectra. Compared with other cations, such as Na(+), K(+), Mg(2+), Ca(2+), Mn(2+), Fe(2+), Fe(3+), Co(2+), Ni(2+), Cu(2+), Ag(+), Cd(2+), Hg(2+), and Pb(2+), Zn(2+) can lead to a pronounced fluorescence enhancement as high as 7.8-fold together with an obvious blue-shift change of the chiral polymer. More importantly, the fluorescent color of the polymer changed to bright blue instead of weak yellow after addition of Zn(2+), which can be easily detected by the naked eye. The results indicate that this kind of chiral polymer, incorporating an (R,R)-salen moiety as a receptor in the main chain backbone, can exhibit high sensitivity and selectivity for Zn(2+) recognition.  相似文献   

6.
Ohki A  Kim JS  Suzuki Y  Hayashita T  Maeda S 《Talanta》1997,44(6):1131-1135
Lipophilic acyclic dibenzopolyether diamides, 12 kinds, have been designed to prepare solvent polymeric membrane ion-selective electrodes (ISEs) for Pb(2+). The ionophores include 1,5-bis[2-(N,N-dialkylcarbamoylmethoxy)phenoxy]-3-oxapentanes1-4, 1,5-bis[2-(N,N-dialkylcarbamoylpentadecyloxy)phenoxy]-3-oxapentanes 5-8, and 1,2-bis[2-(2'-N,N-dialkylcarbamoylpentadecyloxy)phenoxy]ethanes 9-12. Linear response concentration range of the ISE based on 9 is 3 x 10(-2) - 1 x 10(-6) M of Pb(2+) (average slope = 28.5 mV decade(-1)). Potentiometric selectivities of the ISEs based on 1-12 for Pb(2+) over other heavy metal cations, alkali metal cations, and alkaline earth metal cations have been assessed. These ISEs exhibit remarkably high selectivities for Pb(2+) relative to heavy metal cations, such as Cu(2+), Fe(2+), and Ni(2+), the selectivity coefficients (K(Pot)(Pb,Cu)) being 5 x 10(-5) - 6 x 10(-5) for 1-4 and ca. 6 x 10(-4) for 9. For the Pb(2+) selectivities over alkali metal cations, such as Na(+) and K(+), 9 which has an ethylene glycol spacer and a N,N-diethyl group is superior to other dibenzopolyether diamide ionophores 1-8 and 10-12.  相似文献   

7.
The response of a monoaza-15-crown-5 with an optically active aminobenzoxazinone moiety to divalent cations was investigated. The crown ether was found to undergo a strong emission shift to the blue when complexed with specific divalent metals that have ionic diameters between 1.9-2.4 A. Consequently the photoactive macrocycle is responsive to Mg(2+), Ca(2+), Ba(2+), Sr(2+), Cd(2+), and particularly responsive to Hg(2+)and Pb(2+). Macrocycle emission spectra are shown to be a function of cation concentration. Alkaline metal cations and smaller transition metals ions such as Ni(2+), Co(2+)and Zn(2+)do not cause significant changes in the macrocycle emission spectra. Emission, absorption, and complex stability constants are determined. Mechanisms of cation selectivity and spectral emission shifts are discussed. Challenges involving immobilization of the macrocycle while preserving its spectral response to cations are explored.  相似文献   

8.
Warmke H  Wiczk W  Ossowski T 《Talanta》2000,52(3):449-456
The influence of metal cations Li(+), Na(+), K(+), Cs(+), Mg(2+), Ca(2+), Sr(2+), Ba(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Pb(2+) and Al(3+) on the spectroscopic properties of the dansyl (1-dimethylaminonaphthalene-5-sulfonyl) group covalently linked to monoaza crown ethers 1-aza-15-crown-5 (1,4,7,10,-tetraoxa-13-azacyclopentadecane) (A15C5) and 1-aza-crown-6 (1,4,7,10,13-pentaoxa-16-azacyclooctadecane) (A18C6) was investigated by means of absorption and emission spectrophotometry. Interaction of the alkali metal ions with both fluoroionophores is weak, while alkaline earth metal ions interact strongly causing 50 and 85% quenching of dansyl fluorescence of N-(5-dimethylamine-1-naphthalenesulfonylo)-1,4,7,10,-tetraoxa-13-azacyclopentadecane (A15C5-Dns) and N-(5-dimethylamine-1-naphthalenesulfonylo)-1,4,7,10,13-pentaoxa-16-azacyclooctadecane (A18C6-Dns), respectively. The Cu(2+), Pb(2+) and Al(3+) cations interact very strongly with dansyl chromophore, causing a major change in absorption spectrum of the chromophore and forming non-fluorescent complexes. The Co(2+), Ni(2+), Zn(2+), Mg(2+) cations interact moderately with both fluoroionophores causing quenching of dansyl fluorescence by several percent only.  相似文献   

9.
Tan J  Yan XP 《Talanta》2008,76(1):9-14
We report a simple twisted intramolecular charge transfer (TICT) chromogenic chemosensor for rapid and selective detection of Hg(2+) and Cu(2+). The sensor was composed of an electron-acceptor 4-fluoro moiety and an electron-donor 7-mercapto-2,1,3-benzoxadiazole species where the S together with the 1-N provided the soft binding unit. Upon Hg(2+) and Cu(2+) complexation, remarkable but different absorbance spectra shifts were obtained in CH(3)CN-H(2)O mixed buffer solution at pH 7.6, which can be easily used for naked-eye detection. The sensor formed a stable 2:1 complex with Cu(2+), and both 2:1 and 3:1 complexes with Hg(2+). While alkali-, alkaline earth- and other heavy and transition metal ions such as Na(+), Mg(2+), Mn(2+), Co(2+), Ni(2+), Ag(+), Zn(2+), Pb(2+) and Cd(2+) did not cause any significant spectral changes of the sensor. This finding is not only a supplement to the detecting methods for Hg(2+) and Cu(2+), but also adds new merits to the chemistry of 4,7-substituted 2,1,3-benzoxadiazoles.  相似文献   

10.
1-((E)-(2-((2-nitrobenzyl)(2-((E)-(2-hydroxynaphthalen-1-yl)methyleneamino)ethyl)amino)ethylimino)methyl)naphthalen-2-ol (H(2)L), The new compound featuring two naphthalene units was synthesized and characterized. We find that H(2)L has high selectivity and sensitivity to detect Zn(2+) ion over other metal ions such as Na(+), Ag(+), Cd(2+), Co(2+), Cr(3+), Cu(2+), Hg(2+), Mn(2+), Ni(2+), Fe(3+), and the sensitivity is about 10(-7)M. The fluorescent changes of H(2)L upon the addition of cations Zn(2+) and triethylamine is utilized as an AND logic gate at the molecular level, using Zn(2+) and triethylamine as chemical inputs and the fluorescence intensity signal as output.  相似文献   

11.
A new terphenyl-based macrocycle 5 incorporating phenanthroline as a fluorophore has been designed, synthesized and examined for its recognition ability toward various cations (Pb(2+), Hg(2+), Ba(2+), Cd(2+), Ag(+), Zn(2+), Cu(2+), Ni(2+), Co(2+), K(+), Mg(2+), Na(+) and Li(+)) by UV-vis, fluorescence and NMR spectroscopy. The receptor 5 showed highly selective 'Off-On' fluorescence signaling behavior for Zn(2+) ions in THF. Interestingly, the addition of H(2)PO(4)(-) ions to the [5-Zn] complex regulates the binding site for additional Zn(2+) ions and hence leads to a blue-shifted emission band.  相似文献   

12.
Glassy test strips partially coated with PVC-film including O-donor macrocyclic receptors (L), tetrabromophenolphthalein ethyl ester (TBPE(-)), and a plasticizer sensed Pb(2+) in aqueous solutions by a unique color change. Yellow films successively changed color to green, dark-blue and purple with increases of the Pb(2+) concentration. In contrast with the ordinary "optode", a characteristic absorption band at 525 nm was newly appeared independently of the protonation and deprotonation of HTBPE (yellow to blue). The unique color change occurred only when asymmetric receptors with respect to the basal plane were coupled with Pb(2+). This optical-structural correlation is likely to be induced by the H aggregate of two sets of TBPE(-) in the 1:2 ion-pair, [Pb-L](2+).(TBPE(-))(2). The color change, based on metachromasy, was exclusive for Pb(2+) among common metal cations (Ca(2+), Al(3+), Cd(2+), Zn(2+), Fe(3+), Co(2+), Hg(2+)) and anions (Cl(-), SO(4)(2-), PO(4)(3-), S(2)O(3)(2-)).  相似文献   

13.
A new monostyryl boron dipyrromethene derivative (MS1) appended with two triazole units indicates the presence of Hg(2+) among other metal ions with high selectivity by color change and red emission. Upon Hg(2+) binding, the absorption band of MS1 is blue-shifted by 29 nm due to the inhibition of the intramolecular charge transfer from the nitrogen to the BODIPY, resulting in a color change from blue to purple. Significant fluorescence enhancement is observed with MS1 in the presence of Hg(2+); the metal ions Ag(+), Ca(2+), Cd(2+), Co(2+), Cu(2+), Fe(2+), Fe(3+), K(+), Mg(2+), Mn(2+), Ni(2+), Pb(2+), and Zn(2+) cause only minor changes in the fluorescence of the system. The apparent association constant (K(a)) of Hg(2+) binding in MS1 is found to be 1.864 × 10(5) M(-1). In addition, fluorescence microscopy experiments show that MS1 can be used as a fluorescent probe for detecting Hg(2+) in living cells.  相似文献   

14.
New pentaquinone derivatives 5 and 8 having rhodamine moieties have been designed and synthesized that undergo through-bond energy transfer (TBET) in the presence of Hg(2+) ions among the various cations (Cu(2+), Pb(2+), Fe(2+), Fe(3+), Zn(2+), Ni(2+), Cd(2+), Co(2+), Ag(+), Ba(2+), Mg(2+), K(+), Na(+), and Li(+)) tested in mixed aqueous media.  相似文献   

15.
The synthesis, optical and electrochemical properties, and X-ray characterization of two thiazole derivatives capped by ferrocenyl groups (5 and 7) and their model compounds with one ferrocenyl, either at 2 or 5 position of the mono- or bis-thiazolyl rings (3, 9, 11, and 14), are presented. Bisferrocenyl thiazole 5 forms the mixed-valence species 5*+ by partial oxidation which, interestingly, shows an intramolecular electron-transfer phenomenon. Moreover, the reported heteroaromatic compounds show selective ion-sensing properties. Thus, ferrocenylthiazoles linked across the 5 position of the heteroaromatic ring are selective chemosensors for Hg2+ and Pb2+ metal ions; 5-ferrocenylthiazole 3 operates through two channels, optical and redox, for Hg2+ and only optical for Pb2+, whereas 1,1'-bis(thiazolyl)ferrocene 14 is only an optical sensor for both metal ions. Moreover, complex 3 behaves as an electrochemically induced switchable chemosensor because of the low metal-ion affinity of the oxidized 3*+ species. On the other hand, ferrocenylthiazole 9, in which the heterocyclic ring and the ferrocene group are linked across the 2 position, is a selective redox sensor for Hg2+ metal ions, and it responds optically, as does bis(thiazolyl)ferrocene 11, to a narrow range of cations (Zn2+, Cd2+, Hg2+, Ni2+, and Pb2+). Finally, bis(ferrocenyl)thiazole 5 is a dual optical and redox sensor for Zn2+, Cd2+, Hg2+, Ni2+, and Pb2+, whereas bis(ferrocenyl) compound 7, bearing a bis(thiazole) unit as a bridge, is only a chromogenic sensor for Zn2+, Cd2+, Hg2+, Ni2+, and Pb2+. The experimental data and conclusions about both the electronic and ion-sensing properties are supported by DFT calculations which show, in addition, an unprecedented intramolecular electron-transfer reorganization after the first one-electron oxidation of compound 5.  相似文献   

16.
Spirobenzopyrans bearing monoazathiacrown ethers and noncyclic analogues were synthesized, and their ion-responsive photochromism depending on the dual metal ion interaction with the crown ether and the phenolate anion moieties was examined using alkali and alkaline-earth metal ions, Ag(+), Tl(+), Pb(2+), Hg(2+), and Zn(2+). The prepared spirobenzopyrans showed a selective binding ability to Mg(2+) and Ag(+) with negative and positive photochromism, respectively. Among the metal ions, only Ag(+) facilitated photoisomerization to the corresponding merocyanine form. Depending on the ring size of the monoazathiacrown ether moieties, soft metal ions such as Hg(2+) and Ag(+) showed significant shifts in the UV-vis absorption spectra, while hard metal ions such as Mg(2+), Zn(2+), and Pb(2+) did not afford any meaningful shift. This result reflects that the monoazathiacrown ether and phenolate anion moieties prefer soft and hard metal ions, respectively. Therefore, the Mg(2+) and Ag(+) selectivities are mainly derived from the phenolate anion and monoazathiacrown ether moieties, respectively. On the other hand, a spirobenzothiapyran bearing 3,9-dithia-6-monoazaundecane showed a remarkable selectivity to Ag(+).  相似文献   

17.
Mercury is one of the most toxic heavy metals present in the environment. In this study, a highly sensitive and specific monoclonal antibody (mAb)-based indirect competitive enzyme-linked immunosorbent assay (ELISA) for the determination of Hg(2+) was developed. A new bifunctional ligand, 6-mercaptonicotinic acid (MNA), which contains a pyridine ring bearing a carboxylic group and a mercapto group, was selected for the preparation of immunogen. After immunization of mice and performing the hybridoma technique, the obtained mAb was characterized for its binding affinity and selectivity for Hg(2+). Based on this novel mAb, an ELISA was established. At optimal experimental conditions, the standard curve of the ELISA for Hg(2+) was constructed in concentration range of 0.1-100 ng mL(-1). The values of IC(50) and LOD of the assay were found to be 1.12 and 0.08 ng mL(-1). The cross-reactivity was lower than 2% with MNA, CH(3)Hg, and CH(3)Hg-MNA and was 11.5% and 4.4% for Hg(+) and Au(3+), respectively. No cross-reactivity was found with other metal ions such as Cu(2+), Sn(2+), Ni(2+), Mn(2+), Pb(2+), Zn(2+), Cd(2+), Fe(2+), Co(2+), Mg(2+), Ca(2+), and anions such as Cl(-), NO(3)(-), NO(2)(-), HCO(3)(-), F(-), and SO(4)(2-), indicating that the assay displays not only high sensitivity but also high selectivity. Different kinds of samples including water, milk, green vegetable, kelp, facial cleanser, and night cream were spiked with Hg(2+) and the extracts were analyzed by ELISA. Acceptable recovery rates of 80.0-113.0% and coefficients of variation of 1.9-18.6% were obtained. A linear relationship between ELISA and cold-vapor atomic fluorescence spectroscopy (CV-AFS) as indicated by a correlation coefficient of 0.97 for liquid samples (water samples) and 0.98 for other samples was obtained. The proposed mAb-based ELISA provides a feasible analytical method for highly sensitive and specific, fast, simple, and accurate determination of uncomplexed trace Hg(2+) in environmental and food samples.  相似文献   

18.
Sheng R  Wang P  Gao Y  Wu Y  Liu W  Ma J  Li H  Wu S 《Organic letters》2008,10(21):5015-5018
A coumarin-based colorimetric chemosensor 1 was designed and synthesized. It exhibits good sensitivity and selectivity for the copper cation over other cations such as Zn(2+), Cd(2+), Pb(2+), Co(2+), Fe(2+), Ni(2+), Ag(+), and alkali and alkaline earth metal cations both in aqueous solution and on paper-made test kits. The change in color is very easily observed by the naked eye in the presence of Cu(2+) cation, whereas other metal cations do not induce such a change. The quantitative detection of Cu(2+) was preliminarily examined.  相似文献   

19.
Ciszewski A 《Talanta》1985,32(11):1051-1054
The determination of trace levels of thallium in bismuth and bismuth salts by differential pulse anodic-stripping voltammetry has been made possible by using a surfactant as an electrochemical masking agent, in addition to a complexing agent. In 0.2M EDTA at pH 4.5 as supporting electrolyte in the absence of surfactant, bismuth at concentrations below 10(-4)M does not interfere. When the electrolyte also contains tetrabutylammonium ions at 0.01 M concentration, bismuth can be tolerated at concentrations up 0.05M, and the height of the thallium peak is unaffected. It is thus possible to determine 1 nM Tl(I) in the presence of 0.05M Bi(III), i.e., Tl at the 1 x 10(-6)% level in bismuth. The precision of the determination and the recovery are satisfactory. Neither an 800-fold ratio of Cu(II) nor a 10(7)-fold ratio of Pb(II) to Tl(I) interferes in the determination. Other cations such as Zn(2+), Cd(2+), In(3+), Hg(2+), Fe(3+), Sb(3+) and Sn(4+) in 10(4)-fold molar ratio to Tl(I) have no effect on the determination. Thallium has been determined in bismuth metal and in bismuth nitrate of various degrees of purity.  相似文献   

20.
Zhang JR  Huang WT  Xie WY  Wen T  Luo HQ  Li NB 《The Analyst》2012,137(14):3300-3305
Coupling T base with Hg(2+) to form stable T-Hg(2+)-T complexes represents a new direction in detection of Hg(2+). Here a graphene oxide (GO)-based fluorescence Hg(2+) analysis using DNA duplexes of poly(dT) that allows rapid, sensitive, and selective detection is first reported. The Hg(2+)-induced T(15)-(Hg(2+))(n)-T(15) duplexes make T(15) unable to hybridize with its complementary A(15) labelled with 6'-carboxyfluorescein (FAM-A(15)), which has low fluorescence in the presence of GO. On the contrary, when T(15) hybridizes with FAM-A(15) to form double-stranded DNA because of the absence of Hg(2+), the fluorescence largely remains in the presence of GO. A linear range from 10 nM to 2.0 μM (R(2) = 0.9963) and a detection limit of 0.5 nM for Hg(2+) were obtained under optimal experimental conditions. Other metal ions, such as Al(3+), Ag(+), Ca(2+), Ba(2+), Mg(2+), Zn(2+), Mn(2+), Co(2+), Pb(2+), Ni(2+), Cu(2+), Cd(2+), Cr(3+), Fe(2+), and Fe(3+), had no significant effect on Hg(2+) detection. Moreover, the sensing system was used for the determination of Hg(2+) in river water samples with satisfactory results.  相似文献   

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