Bifunctional polydopamine@Fe3O4 core-shell nanoparticles for electrochemical determination of lead(II) and cadmium(II).

The present paper has focused on the potential application of the bifunctional polydopamine@Fe3O4 core-shell nanoparticles for development of a simple, stable and highly selective electrochemical method for metal ions monitoring in real samples. The electrochemical method is based on electrochemical preconcentration/reduction of metal ions onto a polydopamine@Fe3O4 modified magnetic glassy carbon electrode at -1.1 V (versus SCE) in 0.1 M pH 5.0 acetate solution containing Pb(2+) and Cd(2+) during 160 s, followed by subsequent anodic stripping. The proposed method has been demonstrated highly selective and sensitive detection of Pb(2+) and Cd(2+), with the calculated detection limits of 1.4×10(-11)M and 9.2×10(-11) M. Under the optimized conditions, the square wave anodic stripping voltammetry response of the modified electrode to Pb(2+) (or Cd(2+)) shows a linear concentration range of 5.0-600 nM (or 20-590 nM) with a correlation coefficient of 0.997 (or 0.994). Further, the proposed method has been performed to successfully detect Pb(2+) and Cd(2+) in aqueous effluent.

A novel spectrofluorometric method for the determination of methiocarb using an amphiphilic p-sulfonatocalix[4]arene.

The characteristics of host-guest complexation between tetrabutyl ether derivatives of p-sulfonatocalix[4]arene (SC4Bu) and methiocarb [3,5-dimethyl-4-(methylthio) phenyl methylcarbamate] were investigated by fluorescence spectrometry. Upon addition of methiocarb, the fluorescence intensity of SC4Bu was quenched regularly and a slight red shift was observed for the maximum emission peak. These results indicated that the SC4Bu-methiocarb complex was formed a 1:1 mole ratio. An association constant of 1.67×10(4) L mol(-1) was calculated by applying a deduced equation. The interaction mechanism of the inclusion complex was discussed. Based on the results, a novel spectrofluorimetric method was described for the determination of methiocarb with a detection limit at 0.05 µg mL(-1). This method is very simple and shows high sensitivity and selectivity. Moreover, the proposed method was successfully applied to the determination of methiocarb in water samples.

Solvent dependent fluorescent properties of a 1,2,3-triazole linked 8-hydroxyquinoline chemosensor: tunable detection from zinc(II) to iron(III) in the CH3CN/H2O system.

A triazole-containing 8-hydroxyquinoline (8-HQ) ether 2 was efficiently synthesized in two steps from the "click" strategy. Compound 2 gave a strong fluorescence (Φ = 0.21) in nonprotic solvent like CH(3)CN, and a weak fluorescence (Φ = 0.06) in protic solvent like water. In water, a more than 100 nm red shift of the fluorescence maximum was observed for compound 2 in comparison with that in CH(3)CN. This fluorescence difference may be attributed to the intermolecular photoinduced proton transfer (PPT) process involving the protic solvent water molecules. Similarly, this intermolecular PPT process was also observed in the high-water-content CH(3)CN aqueous solution (e.g., CH(3)CN/H(2)O = 5/95, v/v). The water content in the CH(3)CN/H(2)O binary solvent mixture greatly affected the fluorescence intensity (e.g., Φ = 0.06 and 0.25 when CH(3)CN/H(2)O = 5/95 and 95/5, v/v, respectively) and emission wavelength. Using this interesting property, by simple variation of the water content in the CH(3)CN aqueous solution, compound 2 was tuned from a selective "turn-on" fluorescent sensor for Zn(2+) (CH(3)CN/H(2)O = 5/95, v/v) to a ratiometric one for Zn(2+) and a selective "turn-off" one for Fe(3+) (CH(3)CN/H(2)O = 95/5, v/v) over a wide range of pH value. In high-water-content (CH(3)CN/H(2)O = 5/95, v/v) aqueous solution compound 2 shows a selective "turn-on" response toward Zn(2+), with a 10-fold enhancement in the fluorescence intensity at 428 nm and a 62 nm blue shift of the emission maximum (490 to 428 nm) due to the inhibition of intermolecular PPT process upon chelating with Zn(2+). However, in a less polar solvent (CH(3)CN/H(2)O = 95/5, v/v) in which compound 2 has high fluorescence (quantum yield =0.25), it shows a ratiometric response toward Zn(2+), with a continuous decrease of the fluorescence intensity at 399 nm and an increase at 423 nm. More interestingly, in this case, it also exhibits a very sensitive, selective, and ratiometric fluorescence quenching in the presence of Fe(3+), with an 81 nm red shift of the emission maximum (399 to 480 nm) in a wide range of pH through a metal ligand charge transfer (MLCT) effect.

Long wavelength red fluorescent dyes from 3,5-diiodo-BODIPYs.

Amphiphilic and long wavelength red fluorescent dyes (4 and 7) were prepared from the Sonogashira coupling reactions of 3,5-diiodo-BODIPYs (1 and 6). One of these compounds, BODIPY 7, readily accumulated within human carcinoma HEp2 cells and was found to localize mainly within the endoplasmic reticulum (ER).

[Study on the inclusion behavior of cucurbit [7] uril with methylene blue by spectrofluorometric titrations].

The characteristics of host-guest complexation between cucurbit [7] uril (CB7) and methylene blue (MB) were investigated by fluorescence spectrometry in acetate buffer solution at room temperature. It was found that the fluorescence intensity of methylene blue regularly increased upon the addition of cucurbit [7] uril accompanying with a blue-shift of the position of the emission maximum. The results indicate the formation of complex between CB7 and MB at a 1 : 1 complex stoichiometry and the association constant was calculated by applying a deduced equation. 1H NMR spectra were applied to to complement the fluorescence work to verify the formation of the complex. From the temperature dependence of the equilibrium constants, thermodynamics parametersH andS values were obtained, indicating an enthalpic driving force for complexation. The possible interaction mechanism was also discussed. This work may extend the application range of cucurbit [7] uril in biochemistry and pharmaceutical analysis.

Spectrofluorometric studies on the interaction between oxacalix[6]arene-locked trizinc(II)porphyrins and crystal violet.

A new fluorogenic oxacalix[6]arene bearing three zinc(II) porphyrin groups (1) was prepared. When crystal violet (CV) was bound to 1, fluorescence intensity of 1 was quenched regularly. This indicates that 1 and CV formed a 1:1 complex and the association constant was calculated. The inclusion mechanism was also discussed. This new fluorometric method was developed for rapid determination of CV with a good linearity in the concentration range of 1.40-37.4 micromolL(-1). The method was applied for the determination of CV in synthetic samples successfully.

Spectrofluorimetric study on the inclusion interaction between vitamin K3 with p-(p-sulfonated benzeneazo)calix[6]arene and determination of VK3.

The characteristics of host-guest complexation between p-(p-sulfonated benzeneazo) calix[6]arene (SBC6A) and vitamin K3 (VK3) were investigated by fluorescence spectrometry. A 1:1 stoichiometry for the complexation was established and was verified by Job's plot. An association constant of 4.95 x 10(3)L mol(-1) at 20 degrees C was calculated by applying a deduced equation. The interaction mechanism of the inclusion complex was discussed. It was found that the fluorescence of SBC6A could be remarkably quenched by an appropriate amount of VK3 especially when non-ionic surfactant Triton X-100 existed. According to the obtained results, a novel sensitive spectrofluorimetric method for the determination of VK3 based on supramolecular complex was developed with a linear range of 5.0 x 10(-7) -3.0 x 10(-5)mol L(-1) and a detection limit of 2.0 x 10(-7)mol L(-1). The proposed method was used to determine VK3 in commercial preparations with satisfactory results.

Spectrofluorometric study on the inclusion behavior of p-(p-carboxyl benzeneazo) calix[4]arene with norfloxacin.

Spectrofluorometric titrations have been performed to investigate the inclusion behavior of p-(p-carboxyl benzeneazo) calix[4]arene (CBC4A) with norfloxacin (NFLX) in NaAc-HAc buffer solution (pH=5.0). It was found that the fluorescence intensity of NFLX quenched regularly upon the addition of CBC4A. The results indicated 1:1 complex stoichiometry and an association constant of 8.21 x 10(5) L mol(-1) at 20.0 degrees C were calculated by applying a deduced equation. Job's plot also verified the existence of 1:1 inclusion complex. The proposed interaction mechanism indicates that NFLX goes into (or partially goes into) the cavity of CBC4A with the help of hydrogen bonding and other forces. The various factors (pH value, ionic strength, and surfactants) affecting the inclusion process were examined in details.

The electrochemical behavior and direct determination of tyrosine at a glassy carbon electrode modified with poly (9-aminoacridine).

9-Aminoacridine was firstly immobilized on the surface of a glassy carbon electrode to form a poly (9-aminoacridine) film modified electrode. The results demonstrated that the modified electrode exhibited a high degree of catalytic activity towards the oxidation of tyrosine and can resolve the interference of tryptophan in the determination of tyrosine. Compared with the bare electrode, the peak current had obviously increased, and the peak potential had shifted in a negative direction. Under the optimum conditions, a linear response to tyrosine was observed in the concentration of 1.0 x 10(-6) -2.8 x 10(-3) M, with a correlation coefficient of 0.9987, and a detection limit (S/N = 3) of 1.0 x 10(-7) M. The modified electrode has been successfully applied to determine the concentration of tyrosine in composite amino acid injections; and it displays excellent repeatability and high sensitivity. The proposed sensor has promising features such as ease of fabrication, good reproducibility, high stability and low cost. And most of all, it has good selectivity.

Preparation and property screening of the solid inclusion complex of norfloxacin with p-sulfonated calix[4]arene.

The complexation of norfloxacin (NFLX) by p-sulfonated calix[4]arene (SC4A) in aqueous solution has been studied by fluorescence spectroscopy and 1H NMR spectroscopy. A 1:1 stoichiometry and a 8086 L mol(-1) stability constant of the NFLX-SC4A complex was obtained by spectrofluorometric titrations. The equimolar solid state inclusion complex of NFLX-SC4A was prepared by the co-precipitation method and then characterized by various techniques, including differential scanning calorimetry (DSC), X-ray powder diffractometry (XRD), Fourier-transform infrared analysis (FT-IR) and scanning electron microscopy (SEM). The experimental results of these chemical property screenings confirmed that NFLX and SC4A can form a stable host-guest complex in the solid state, and SC4A appears to function as a complexing and solubilizing agent for NFLX.

Study on the fluorescence behavior of p-sulfonated calix[4,6]arene in cationic surfactant cetyltrimethylammonium bromide solution and its analytical application.

The fluorescence properties of p-sulfonated calix[4,6]arene (SCnA, n=4, 6) in cationic surfactant cetyltrimethylammonium bromide (CTAB) solution were investigated. It was found that the fluorescence intensity of SCnA could be enhanced markedly by an appropriate amount of CTAB. The results indicate the formation of complex between CTAB and SCnA at a 1:1 complex stoichiometry and their association constants were calculated by applying a deduced equation. Based on the obtained results, a new fluorimetric method has been developed for rapid determination of SCnA with a good linearity in the concentration range of 2x10(-7) to 7x10(-6)mol L-1.

Fluorescent quenching method for determination of trace hydrogen peroxide in rain water.

A simple and sensitive fluorescent quenching method for the determination of trace hydrogen peroxide (H(2)O(2)) has been proposed to determine hydrogen peroxide in rain water sample. The method is based on the reaction of H(2)O(2) with 3,3'-diethyloxadicarbocyanine iodide (DI) to form a compound which has no fluorescence in acetate buffer solution (pH 3.09). The maximum emission wavelength of the system is located at 604 nm with excitation at 570 nm. Under the optimal conditions, the calibration graph was obtained between the quenched fluorescence intensity and hydrogen peroxide concentration in the range of 5.0 x 10(-7) to 9.0 x 10(-4) mol L(-1). The proposed method was applied to determine H(2)O(2) in rain water samples, and the result was satisfactory. The mechanism involved in the reaction was also studied.

Study on the inclusion interaction of p-sulfonated calix[n]arenes with Vitamin K3 using methylene blue as a spectral probe.

The characteristics of host-guest complexation between p-sulfonated calix[n]arene (SCnA, n = 4, 6) and Vitamin K(3) (VK(3)) were investigated by fluorescence spectrometry and absorption spectrometry using methylene blue (MB) as a probe. Interaction with MB and SCnA led to an obvious decrease in fluorescence intensity of MB, accompanying with shifts of emission peaks. Absorption peaks also showed interesting changes; however, when VK(3) was added, fluorescence intensity and absorbance recovered and a slight and slow red shift was observed. The obtained results showed that the inclusion ability of p-sulphonated calix[n]arenes towards VK(3) was the order: p-sulphonated calix[6]arene (SC6A) >p-sulphonated calix[4]arene (SC4A). Relative mechanism was proposed to explain the inclusion process.

A one-dimensional ladder-like coordination polymer: poly[[hexa-aqua-bis(µ-5-nitro-benzene-1,3-dicarboxyl-ato-κO,O',O'')(µ-oxalato-κO,O':O'',O''')diyttrium(III)] trihydrate].

In the crystal structure of the title one-dimensional coordination polymer, [Y(2)(C(8)H(3)NO(6))(2)(C(2)O(4))(H(2)O)(6)]·3H(2)O, each Y(III) ion is bridged to its neighbours by two 5-nitro-benzene-1,3-dicarboxyl-ate (nbdc) dianions and one oxalate dianion (located on an inversion centre) to form a ladder-like polymeric structure. The two carboxylate groups of nbdc assume different modes of coordination, one is chelating whereas the other is monodentate. Three water mol-ecules coordinate to the Y(III) ion to complete an eight-coordinate distorted dodecahedral geometry. The ladder-like polymers are assembled together by hydrogen bonding and π-π stacking [centrio-centriod distance = 3.819 (9) Å] in the crystal structure.

[Preparation and fluorescence properties of calix[4]arene nanoparticle].

Novel organic nanoparticles of calix[4]arene (CN) were prepared by the reprecipitation method under sonication and vigorous stirring. The nanoparticles showed an average diameter of 40 nm characterized by transmission electron microscopy. It was found that the nanoparticles exhibited better fluorescence compared with that of monomer. In weak acidic medium, the relative fluorescence intensity of these nanoparticles could be quenched remarkably with the addition of appropriate amounts of Fe3+. Based on the obtained results, a novel fluorimetric method has been developed for the rapid determination of Fe3+. Under optimal conditions, the linear range of calibration curves was 1.0 x 10(-6) - 2.4 x 10(-5) mol x L(-1) and the detection limit was 3.0 x 10(-7) mol x L(-1). The proposed method was applied to determine Fe3+ in water samples with satisfactory recovery and relative standard deviation.

[Study on the inclusion behavior of p-sulphonatocalix[4]arene with acridine by spectrofluorometric titrations].

p-sulphonatocalix[4] arene (1) was prepared according to the literature, and spectrofluorometric titrations were performed to investigate the inclusion behavior of (1) and acridine in citrate buffer solution (pH 5.92, 0.1 mol x L(-1)) at different temperatures. It was found that in definite concentration range, the emission peak of acridine exhibited a slight red shift and th fluorescence intensity decreased when (1) was added. They form stable host-guest complex, and the stoichiometry of the inclusion complex is 1 : 1. The stability constants of the inclusion complex at 15.0 degrees C, 20.0, 25.0 and 30.0 degrees C were determined as 3.08 x 10(5), 4.45 x 10(4), 2.58 x 10(4) and 8.90 x 10(3), respectively. The thermodynamic parameters of inclusion process, deltaG, deltaH and deltaS, were determined. The experimental results indicated that the inclusion process was an exothermic and enthalpy-driven process. It was found that the stability constants descended when temperature rose. The most probable pattern of the inclusion complex between (1) and acridine was proposed as: acridine partially goes into the cavity of (1), and the protonated N atom and the negatively charged sulphonyl group bond firmly owing to strong electrostatic interaction. With the main contribution of electrostatic interaction and the assistance of Van de Waals and hydrophobic interaction, the host and the guest molecules form 1 : 1 supramolecular complex.

Study on the inclusion behavior of p-sulphonatocalix[4]arene with 9-amino-acridine by spectrofluorometric titrations.

Spectrofluorometric titrations have been performed to investigate the inclusion behavior of p-sulphonatocalix[4]arene (SC4A) and 9-amino-acridine (AA) in citrate buffer solution (pH 5.92). It was found that the fluorescence intensity of AA quenched regularly upon the addition of SC4A. The proposed interaction mechanism between SC4A and AA indicates that AA partially goes into the cavity of SC4A with the help of strong electrostatic interaction and hydrogen bonding, which formed by the protonated N atom and the amino groups of AA bonding with sulphonyl groups of SC4A, respectively. The inclusion ratio was 1:1 and the inclusion constant was 1.84 x 10(5) L mol(-1) at 25.0 degrees C.

Spectrofluorimetric study on the inclusion interaction between lomefloxacin and p-sulfonated calix[4]arene and its analytical application.

The characteristics of host-guest complexation between p-sulfonated calix[4]arene (SC4A) and lomefloxacin (LMFX) were investigated by fluorescence spectrometry. A 1:1 stoichiometry for the complexation was established and an association constant of 6.48x10(4) l mol-1 at 25 degrees C was calculated by applying a deduced equation. The interaction mechanism of the inclusion complex was discussed and the various factors affecting the inclusion process were examined in detail. It was found that an appropriate amount of cationic surfactant cetyltrimethylammonium bromide (CTAB) can remarkably enhance the fluorescence intensity of the supramolecular complex system. Based on the obtained results, a novel sensitive spectrofluorimetric method for the determination of lomefloxacin based on supramolecular complex was developed with a linear range of 0.01-3.0 microg ml-1 and a detection limit of 0.008 microg ml-1, for the first time. The method was applied for the determination of lomefloxacin in pharmaceutical preparations successfully.

[Highly sensitive spectrofluorimetric determination of trace amounts of nitrite with N-(1-naphthyl) ethylenediamine].

A simple and sensitive fluorescence quenching method for the determination of trace nitrite was developed. The method is based on the reaction of NED with nitrite in acidic medium to form a new compound, which has weak fluorescence. The linear range was 1.07-214.0 microg x L(-1) with a 3sigma detection limit of 0.069 microg x L(-1) under the optimum experimental conditions. This proposed method has been applied to the determination of trace amounts of NO2- in tap water and lake water without extraction.

Preparation of fluorescent polyvinyl alcohol keto-derivatives nanoparticles and selective determination of chromium(VI).

A novel fluorescent polyvinyl alcohol keto-derivatives nanoparticle (PVAK) has been prepared in one-step method. The nanoparticles has excitation and emission maxima at 349 and 462 nm, respectively. Based on the fluorescence quenching of PVAK by Cr(VI), we established a simple and selective fluorimetric method for the determination of Cr(VI) without separation of Cr(III) in water. The reaction conditions between Cr(VI) and PVAK were investigated in detail. Furthermore, the reaction mechanism between PVAK and Cr(VI) was also discussed. Under optimal experimental conditions, a limit of detection of 0.02 microg mL(-1) was achieved. The calibration curve was linear over the concentration range 0.1-13.2 microg mL(-1) with a correlation coefficient of 0.9987. The proposed method has been applied to the selective quantification of Cr(VI) in synthetic samples and waste-water samples with the satisfactory results.