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1.
Luminescent particles of lead carboxymethyl cellulose (Pb(CMC)2) containing salicyl fluorones (THBF), Pb(CMC)2-THBF were synthesized by the sol-gel method, using sodium carboxymethyl cellulose (NaCMC) as precursor and Pb2+ as precipitant. Pb(CMC)2-THBF can emit the intense and stable solid substrate room temperature phosphorescence (SS-RTP) on filter paper. And EDTA can chelate Pb2+ in Pb(CMC)2-THBF, causing it to decompose into aqueous soluble components PbY2-, CMC- and THBF, which can react with Ag+ to form Ag(CMC)2-THBF, causing the decrease of phosphorescence intensity. Based on the facts above, a new method for the determination of trace silver by SS-RTP quenching method was established. The linear range of this method is 8.0-40.0 fg spot(-1) (20.0-100.0 pg ml(-1)), with a detection limit (LD) of 2.2 fg spot(-1) (corresponding to a concentration range of 5.5 x 10(-13) g ml(-1)), and the regression equation of working curve is DeltaI(p) = 12.56 + 0.5527C(Ag+) (fg spot(-1), 0.4 microl spot(-1)), n = 8, r = 0.9992. This method has been applied to the determination of trace silver in human hair and tea sample with satisfactory results. The mechanism of SS-RTP emission is also discussed.  相似文献   

2.
Nitrocellulose membrane-poly (vinyl alcohol)-ionic imprinting (NCM-PVA-I-I) was prepared using Cu2+ as template. The cavity in NCM-PVA-I-I matched Cu2+ very well and the selectivity was high. Cu2+ entered the cavity and then could form ionic association ([Cu2+]·[(Fin)2]) with the anion of fluorescein (Fin) outside the cavity by electrostatic effect. [Cu2+]·[(Fin)2] could emit strong and stable room temperature phosphorescence on NCM-PVA-I-I. Its ΔIp was proportional to the content of Cu2+. Based on the above facts, a new method for the determination of trace copper by solid substrate-room temperature phosphorimetry (NCM-PVA-I-I-SS-RTP, SS-RTP is the abbreviation of solid substrate-room temperature phosphorimetry) using NCM-PVA-I-I technique has been established. The linear range of this method was 2.00-144.00 fg Cu2+ spot−1 (sample volume: 0.40 μL spot−1, corresponding concentration: 5.00-360.00 pg mL−1), and the detection limit calculated by 3Sb/k was 0.43 fg Cu2+ spot−1 (corresponding concentration: 1.1 × 10−12 g mL−1, n = 11). Samples containing 2.00 and 144.00 fg Cu2+spot−1 were measured, respectively, for seven times and R.S.D.s were 3.5% and 4.7%. NCM-PVA-I-I-SS-RTP could combine very well the characteristics of both the high sensitivity of SS-RTP and the high match and selectivity of NCM-PVA-I-I, and it was rapid, accurate, sensitive and with good repeatability. It has been successfully applied to determine trace copper in human hair and tea samples.  相似文献   

3.
Luminescent silicon dioxide nano-particles with size of 20 nm, which containing dibromofluorescein (D) were synthesized by sol-gel method (symbolized by D-SiO2).The particles can emit intense and stable room temperature phosphorescence signal on polyamide membrane when Pb(Ac)2 was used as a heavy atom perturber. The λexmax/λemmax was 457/622 nm. Our research indicated that the specific immune reaction between goat-anti-human IgG antibody labeled with D-SiO2 and human IgG could be carried out on polyamide membrane quantitatively, and the phosphorescence intensity of the particle was enhanced after the immunoreactions. Thus a new method of solid substrate room temperature phosphorescence immunoassay (SS-RTP-IA) for the determination of human IgG was established basing on antibody labeled with the D-SiO2 nanoparticles. The linear range of this method was 0.0624-20.0 pg human IgG spot−1 (corresponding concentration: 0.156-50.0 ng ml−1, the sample volume: 0.40 μl spot−1) with a limit of detection (LD) as 0.018 pg spot−1, and the regression equation of working curve was ΔIp = 7.201 mIgG (pg spot−1) + 82.57. Samples containing 0.156 and 50.0 ng ml−1 of IgG were measured repeatedly for 11 times and R.S.D.s were 4.1 and 3.4%, respectively. Results showed that this method had the merits as sensitive, accurate and precise.  相似文献   

4.
Liu JM  Liu ZB  Lu QM  Li FM  Hu SR  Zhu GH  Huang XM  Li ZM  Shi XM 《Analytica chimica acta》2007,598(2):205-213
In the presence of ion perturber LiAc, 4-generation polyamidoamine dendrimers (4G-D) could emit strong and stable room temperature phosphorescence (RTP) signal at on nitrocellulose membrane (NCM), and Triton X-100 could sharply enhance the RTP signal of 4G-D. Triton X-100-4G-D was used to label concanavalin agglutinin (Con A) to get the labeling product Triton X-100-4G-D-Con A. Quantitative specific affinity adsorption (AA) reaction between Triton X-100-4G-D-Con A and α-fetoprotein variant (AFP-V) could be carried out on the surface of NCM, whose product Triton X-100-4G-D-Con A-AFP-V could emit strong and stable RTP and its ΔIp was proportional to the content of AFP-V. According to the facts above, a new affinity adsorption solid substrate-room temperature phosphorimetry (AA-SS-RTP) for the determination of trace AFP-V by Con A labeled with Triton X-100-4G-D was established. Detection limits of this method were 0.23 fg spot−1 (direct method, corresponding concentration: 5.8 × 10−13 g mL−1) and 0.13 fg spot−1 (sandwich method, corresponding concentration: 3.2 × 10−13 g mL−1). It has been successfully applied to determine the content of AFP-V in human serum and forecast human diseases, for its high sensitivity, long RTP lifetime, good repeatability, high accuracy and little background perturbation with at the long wavelength area. Meanwhile, the mechanism for the determination of trace AFP-V using AA-SS-RTP was also discussed.  相似文献   

5.
Clenbuterol hydrochloride (CLB) could catalyze NaIO4 oxidation of eosine Y (R), which caused the room temperature phosphorescence (RTP) signal of R to quench sharply. The ΔIP (=IP2 − IP1, IP2 was RTP intensities of reagent blank and IP1 was RTP intensities of test solution) of the system was directly proportional to the content of CLB. According to that academic thought, a new solid substrate-room temperature phosphorimetry (SS-RTP) for the determination of trace CLB has been established. This method has high sensitivity (detection limit (LD): 0.021 zg spot−1, corresponding concentration: 5.2 × 10−20 g mL−1) and good selectivity (Er = ±5%, interfering species were of no interference). It has been applied to the determination of residual CLB in the practical samples. The results were verified using HPLC and GC/MS methods. The reaction mechanism of catalytic SS-RTP for the determination of residual CLB was also discussed.  相似文献   

6.
Silicon dioxide nano-particles, diameter 50 nm, containing morin (morin–SiO2) have been synthesized by the sol–gel method. They emit strong and stable room-temperature phosphorescence (SS-RTP) on filter paper as substrate, and bismuth can quench the intensity of the SS-RTP. On this basis a new morin–SiO2 solid-substrate room-temperature phosphorescence-quenching method has been established for determination of traces of bismuth. Reduction of phosphorescence intensity (Ip) is directly proportional to the concentration of bismuth in the working range 0.16–14.4 ag spot–1 (sample volume 0.40 L spot–1, corresponding to the concentration range 0.40–36.0 fg mL–1). The regression equation of the working curve is Ip=14.86+5.279×[Bi3+] (ag spot–1) (n=6, r=0.9982). The detection limit of this method is 0.026 ag spot–1 (corresponding to a concentration of 6.5×10–17 g mL–1).This sensitive, reproducible and accurate method has been used for successful analysis of real samples.  相似文献   

7.
A new indole-based fluorescent chemosensor 1 was prepared and its metal ion sensing properties were investigated. It exhibits high sensitivity and selectivity toward Hg2+ among a series of metal ions in H2O-EtOH (7:1, v/v). The association constant of the 1:1 complex formation for 1-Hg2+ was calculated to be 9.57 × 103 M−1, and the detection limit for Hg2+ was found to be 2.25 × 10−5 M. Computational results revealed that 1 and Hg2+ ion formed with a central tetrahedron-coordinated Hg2+.  相似文献   

8.
A fluorescent probe 1 for Hg2+ based on a rhodamine-coumarin conjugate was designed and synthesized. Probe 1 exhibits high sensitivity and selectivity for sensing Hg2+, and about a 24-fold increase in fluorescence emission intensity is observed upon binding excess Hg2+ in 50% water/ethanol buffered at pH 7.24. The fluorescence response to Hg2+ is attributed to the 1:1 complex formation between probe 1 and Hg2+, which has been utilized as the basis for the selective detection of Hg2+. Besides, probe 1 was also found to show a reversible dual chromo- and fluorogenic response toward Hg2+ likely due to the chelation-induced ring opening of rhodamine spirolactam. The analytical performance characteristics of the proposed Hg2+-sensitive probe were investigated. The linear response range covers a concentration range of Hg2+ from 8.0 × 10−8 to 1.0 × 10−5 mol L−1 and the detection limit is 4.0 × 10−8 mol L−1. The determination of Hg2+ in both tap and river water samples displays satisfactory results.  相似文献   

9.
A new fluorescent chemosensor for Hg2+ based on a dansyl amide-armed calix[4]-aza-crown was reported. It exhibits high sensitivity and selectivity toward Hg2+ over a wide range of metal ions in MeCN-H2O (4:1, v/v). The association constant of the 1:1 complex formation for 2-Hg2+ was calculated to be 1.31 × 105 M−1, and the detection limit for Hg2+ was found to be 4.1 × 10−6 mol L−1.  相似文献   

10.
Enriching the surface density of immobilized capture antibodies enhances the detection signal of antibody sandwich microarrays. In this study, we improved the detection sensitivity of our previously developed P-Si (porous silicon) antibody microarray by optimizing concentrations of the capturing antibody. We investigated immunoassays using a P-Si microarray at three different capture antibody (PSA – prostate specific antigen) concentrations, analyzing the influence of the antibody density on the assay detection sensitivity. The LOD (limit of detection) for PSA was 2.5 ng mL−1, 80 pg mL−1, and 800 fg mL−1 when arraying the PSA antibody, H117 at the concentration 15 μg mL−1, 35 μg mL−1, and 154 μg mL−1, respectively. We further investigated PSA spiked into human female serum in the range of 800 fg mL−1 to 500 ng mL−1. The microarray showed a LOD of 800 fg mL−1 and a dynamic range of 800 fg mL−1 to 80 ng mL−1 in serum spiked samples.  相似文献   

11.
The potentiometric response characteristics of mercury ion-selective membrane electrodes based on 2-amino-6-purinethiol (I1) and 5-amino-1, 3, 4-thiadiazole-2-thiol (I2) were described. Ion selectivities were tested for various plasticizers, which were used as solvent mediators to incorporate the ionophores into the membrane. Effects of experimental parameters such as membrane composition, nature and amount of plasticizers and additives, pH and concentration of internal solution on the potential response of Hg2+ electrodes were investigated. The best performance was obtained with the electrode having a membrane composition (w/w) of (I1) (3.17%): PVC (31.7%): DOP (dioctylpthalate) (63.4%): NaTPB (sodium tetraphenylborate) (1.58%). The proposed electrode reveals a Nernstian response over Hg2+ ion in the concentration range of 7.0 × 10−8-1.0 × 10−1 M with limit of detection 4.4 × 10−8 M. The electrode shows good discrimination toward Hg2+ ion with respect to most common cations. It shows a short response time (10 s) for whole concentration range and can be used for 2 months without any considerable divergence in potentials. For evaluation of the analytical applicability, the electrode was used in the determination of Hg2+ ion in different environmental and biological samples. The practical utility of the membrane electrode has also been observed in the presence of surfactants.  相似文献   

12.
8-Quinolineboronic acid phosphorescent molecular switch (8-QBA-PMS) in the “off” state emitted weak room temperature phosphorescence (RTP) of 8-QBA on the acetylcellulose membrane (ACM) with the perturbation of Pb2+. When 8-QBA-PMS was used to label concanavalin agglutinin (Con A) to form 8-QBA-PMS-Con A based on the reaction between -OH of 8-QBA-PMS and -COOH of Con A, 8-QBA-PMS turned “on” automatically due to its structure change, and RTP of the system increased 2.7 times. Besides, -NH2 of 8-QBA-PMS-Con A could carry out affinity adsorption (AA) reaction with the -COOH of alpha-fetoprotein variant (AFP-V) to form the product Con A-AFP-V-Con A-8-QBA-PMS containing -NH-CO- bond, causing the RTP of the system to further increase. Moreover, the amount of AFP-V was linear to the ΔIp of the system in the range of 0.012-2.40 (fg spot−1). Thus, a new affinity sensitive adsorption solid substrate room temperature phosphorimetry using 8-QBA-PMS as labelling reagent (8-QBA-PMS-AASSRTP) for the determination of AFP-V was proposed with the detection limit (LD) of 9 × 10−15 g mL−1. It had been used to determine AFP-V in human serum with the results agreeing with enzyme-link immunoassay (ELISA), showing promise for the prediction of PHC due to the intimate association between AFP-V and primary hepatocellular carcinoma (PHC). The mechanism of the promethod was also discussed.  相似文献   

13.
Luminescent 50-nm silicon dioxide nanoparticles containing both types of rhodamine 6G (R; particles denoted R-SiO2) were synthesized by the sol–gel method. In the presence of Pb(Ac)2 as a heavy atom perturber the particle can emit the intense and stable room-temperature phosphorescence (RTP) signal of R on a polyamide membrane, with exmax/emmax=470/635 nm for R. Our research indicates that the specific immune reaction between goat-anti-human IgG antibody labeled with R-SiO2 and human IgG can be carried out quantitatively on a polyamide membrane, and the phosphorescence intensity was enhanced after the immunoreaction. Thus a new method for solid-substrate room-temperature phosphorescence immunoassay (SS-RTP-IA) for determination of human IgG was established on the basis of antibody labeled with the nanoparticles containing binary luminescent molecules. The linear range of this method is 0.0624–20.0 pg spot–1 of human IgG (corresponding to a concentration range of 0.156–50.0 ng mL–1, sample volume 0.40 L spot–1). The regression equations of the working curves are Ip=71.27+7.208mIgG (pg spot–1) (r=0.9996). Detection limits calculated as 3Sb/k are 0.022 pg spot–1. Compared with the same IA using fluorescein isothiocyanate (FITC) as the marker the new method was more sensitive and had a wider linear range. After elevenfold replicate measurement RSD are 4.5 and 3.6% for samples containing 0.156 and 50.0 ng mL–1 IgG, respectively. This method is sensitive, accurate, and of high precision.  相似文献   

14.
A diffusive gradient in thin films technique (DGT) was combined with liquid chromatography (LC) and cold vapor atomic fluorescence spectrometry (CV-AFS) for the simultaneous quantification of four mercury species (Hg2+, CH3Hg+, C2H5Hg+, and C6H5Hg+). After diffusion through an agarose diffusive layer, the mercury species were accumulated in resin gels containing thiol-functionalized ion-exchange resins (Duolite GT73, and Ambersep GT74). A microwave-assisted extraction (MAE) in the presence of 6 M HCl and 5 M HCl (55 °C, 15 min) was used for isolation of mercury species from Ambersep and Duolite resin gels, respectively. The extraction efficiency was higher than 95.0% (RSD 3.5%). The mercury species were separated with a mobile phase containing 6.2% methanol + 0.05% 2-mercaptoethanol + 0.02 M ammonium acetate with a stepwise increase of methanol content up to 80% in the 16th min on a Zorbax C18 reverse phase column. The LODs of DGT–MAE–LC–CV-AFS method were 38 ng L−1 for CH3Hg+, 13 ng L−1 for Hg2+, 34 ng L−1 for C2H5Hg+ and 30 ng L−1 for C6H5Hg+ for 24 h DGT accumulation at 25 °C.  相似文献   

15.
The diffusive gradients in thin films (DGT) technique, utilizing resin gel with ion-exchange resin Duolite GT73 and new ion-exchange resin Ambersep GT74, was investigated for the accumulation of four mercury species (Hg2+, CH3Hg+, C2H5Hg+, C6H5Hg+). The diffusion coefficients of mercury species in agarose gel calculated on the basis of Fick’s Law were mercury species-specific. The diffusion coefficients of Hg2+ and CH3Hg+ at 25 °C (9.07 ± 0.23 × 10−6 cm2 s−1 and 9.06 ± 0.30 × 10−6 cm2 s−1, respectively) were very similar, but the diffusion coefficients of C2H5Hg+ (6.87 ± 0.23 × 10−6 cm2 s−1) and C6H5Hg+ (3.86 ± 0.19 × 10−6 cm2 s−1) were significantly lower. Influence of experimental conditions (pH, selected cations, chlorides and humic substance) on mercury species accumulation by DGT was studied. The DGT technique was applied to river water spiked with mercury species.  相似文献   

16.
Shi L  Song W  Li Y  Li DW  Swanick KN  Ding Z  Long YT 《Talanta》2011,84(3):900-904
A new sensing molecule 8-hydroxyquinoline ferrocenoate (Fc-Q) which combines ferrocene and 8-hydroxyquinoline moieties was synthesized and applied as a multi-channel sensor for the detection of Hg2+ ion. Fc-Q can coordinate with Hg2+ to give colorimetric, fluorescent and electrochemical responses. Upon complexation with Hg2+ ion, the characteristic absorption peak is red-shifted (Δλ = 45 nm), the fluorescent intensity is quenched at 303 nm, and the oxidation peak is cathodic shifted (ΔE1/2 = −149 mV). Quantitatively analyzed Hg2+ ions at the range of ppb level could be achieved by electrochemical response. For the practical application of sensing Hg2+ in real world water, Fc-Q modified screen-printed carbon electrodes were obtained for facile, sensitive, and on-site analysis of Hg2+.  相似文献   

17.
We report the synthesis of a novel bistriazene, 4,4′-bis(3-(4-phenylthiazol-2-yl)triazenyl)biphenyl (BPTTBP), and its highly sensitive color reaction with Hg2+. The new reagent was synthesized in good yield by coupling 2-amino-4-phenylthiazole with 4,4′-biphenyldiamine bisdiazonium salt. Using a blend of surfactants N-cetylpyridinium chloride (CPC) and polyethylene glycol n-octanoic phenyl ether (OP) as a micelle sensitizer, the red colored reagent assembles with Hg2+ in pH 9.8 borate buffer according to a 1:1 stoichiometry, forming a blue oligomeric/polymeric chelating complex with a high apparent stability constant (1.1 × 108 M−1). Whereas the maximum absorption of reagent occurs at 510 nm with an extinct coefficient of 1.35 × 104 M−1 cm−1, the complex absorbs at 611 nm, with an apparent extinct coefficient of 1.04 × 105 M−1 cm−1. Beer's law is obeyed in the range of 0-15 μg/25 mL Hg2+, and Sandell's sensitivity is 1.92 × 10−3 μg/cm2. In the presence of thiourea and Na4P2O7 as masking agents, the method was found free from interferences of foreign ions commonly occurring with mercury. The optimized protocol has been successfully applied to spectrophotometric determination of mercury in waste water samples. The features of the new reagent associated with its special structure were discussed, and an unprecedented “domino effect” was proposed to account for its unique chelating stoichiometry with Hg2+.  相似文献   

18.
The compound Cs2Hg2USe5 was obtained from the solid-state reaction of U, HgSe, Cs2Se3, Se, and CsI at 1123 K. This material crystallizes in a new structure type in space group P2/n of the monoclinic system with a cell of dimensions a=10.276(6) Å, b=4.299(2) Å, c=15.432(9) Å, β=101.857(6) Å, and V=667.2(6) Å3. The structure contains layers separated by Cs atoms. Within the layers are distorted HgSe4 tetrahedra and regular USe6 octahedra. In the temperature range of 25-300 K Cs2Hg2USe5 displays Curie-Weiss paramagnetism with μeff=3.71(2) μB. The compound exhibits semiconducting behavior in the [010] direction; the conductivity at 298 K is 3×10−3 S/cm. Formal oxidation states of Cs/Hg/U/Se may be assigned as +1/+2/+4/− 2, respectively.  相似文献   

19.
Measurements of Pb isotope ratios in ice containing sub-pg g−1 concentrations are easily compromised by contamination, particularly where limited sample is available. Improved techniques are essential if Antarctic ice cores are to be analysed with sufficient spatial resolution to reveal seasonal variations due to climate. This was achieved here by using stainless steel chisels and saws and strict protocols in an ultra-clean cold room to decontaminate and section ice cores. Artificial ice cores, prepared from high purity water were used to develop and refine the procedures and quantify blanks. Ba and In, two other important elements present at pg g−1 and fg g−1 concentrations in Polar ice, were also measured. The final blank amounted to 0.2 ± 0.2 pg of Pb with 206Pb/207Pb and 208Pb/207Pb ratios of 1.16 ± 0.12 and 2.35 ± 0.16, respectively, 1.5 ± 0.4 pg of Ba and 0.6 ± 2.0 fg of In, most of which probably originates from abrasion of the steel saws by the ice. The procedure was demonstrated on a Holocene Antarctic ice core section and was shown to contribute blanks of only ∼5%, ∼14% and ∼0.8% to monthly resolved samples with respective Pb, Ba and In concentrations of 0.12 pg g−1, 0.3 pg g−1 and 2.3 fg g−1. Uncertainties in the Pb isotopic ratio measurements were degraded by only ∼0.2%.  相似文献   

20.
Naphthalimide derivative (compound 1) containing hydrophilic hexanoic acid group was synthesized and used to recognize Hg2+ in aqueous solution. The fluorescence enhancement of 1 is attributed to the formation of a complex between 1 and Hg2+ by 1:1 complex ratio (K = 2.08 × 105), which has been utilized as the basis of fabrication of the Hg2+-sensitive fluorescent chemosensor. The comparison of this method with some other fluorescence methods for the determination of Hg2+ indicated that the method can be applied in aqueous solution rather than organic solution. The analytical performance characteristics of the proposed Hg2+-sensitive chemosensor were investigated. The chemosensor can be applied to the quantification of Hg2+ with a linear range covering from 2.57 × 10−7 to 9.27 × 10−5 M and a detection limit of 4.93 × 10−8 M. The experiment results show that the response behavior of 1 toward Hg2+ is pH independent in medium condition (pH 4.0–8.0). Most importantly, the fluorescence changes of the chemosensor are remarkably specific for Hg2+ in the presence of other metal ions, which meet the selective requirements for practical application. Moreover, the response of the chemosensor toward Hg2+ is fast (response time less than 1 min). In addition, the chemosensor has been used for determination of Hg2+ in hair samples with satisfactory results, which further demonstrates its value of practical applications.  相似文献   

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