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1.
Wu SP  Chen YP  Sung YM 《The Analyst》2011,136(9):1887-1891
A sensitive, selective colorimetric Fe(3+) detection method has been developed by using pyrophosphate functionalized gold nanoparticles (P(2)O(7)(4-)-AuNPs). Gold nanoparticles were prepared by reducing HAuCl(4) with sodium borohydride, in the presence of Na(4)P(2)O(7). IR spectra suggested that pyrophosphates were capped on the surface of the gold nanoparticles. Aggregation of P(2)O(7)(4-)-AuNPs was induced immediately in the presence of Fe(3+) ions, yielding a color change from pink to violet. This Fe(3+)-induced aggregation of P(2)O(7)(4-)-AuNPs was monitored using first the naked eye and then UV-vis spectroscopy with a detection limit of 5.6 μM. The P(2)O(7)(4-)-AuNPs bound by Fe(3+) showed excellent selectivity compared to other metal ions (Ca(2+), Cd(2+), Co(2+), Fe(2+), Hg(2+), K(+), Mg(2+), Mn(2+), Na(+), Ni(2+), Pb(2+), and Zn(2+)). The best detection of Fe(3+) was achieved in a pH range from 3 to 9. In addition, the P(2)O(7)(4-)-AuNPs were also used to detect Fe(3+) in lake water samples, with low interference.  相似文献   

2.
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   

3.
A flow injection (FI) on-line precipitation-dissolution was developed for electrothermal atomic absorption spectrometry (ETAAS) determination of (ultra)trace amounts of beryllium in water samples. Beryllium was precipitated quantitatively with NH(4)OH+NH(4)Cl and collected in a knotted tube of Tygon without using a filter, while the other matrix components flowed downstream to waste. The precipitate was dissolved with nitric acid and a sub-sample was collected in a capillary of a sampling arm assembly, to introduce 10 mul volumes into the graphite tube by means of positive displacement with air through a time-based injector. This sequence was timed to synchronize with the previous introduction of 6 mug of Lu (in 20 mul) by the spectrometer autosampler. The effect of a number of possible cations on the beryllium precipitation process was studied. While, the addition of Ba(2+), Sr(2+), Ca(2+), Mg(2+), Mn(2+), Zn(2+), Co(2+) and Ni(2+) did not produce any perceptible precipitate on the reaction coil walls, the addition of Al(3+), Cr(3+) and Fe(3+) produced large precipitated particles. However, their tolerance limit was well above the levels at which theses species are commonly found in most natural waters. The detection limit (3sigma) of 25 ng l(-1) in the sample solution was obtained. The precision of the method, evaluated by ten replicate analyses of solutions containing 20 and 200 pg of beryllium were 4.8 and 4.0% (n=5), respectively. Enrichment factors from 7.0 to 10.3 and from 10.5 to 13.8 were obtained for precipitation times from 25 to 38 s and from 43 to 50 s for waste and tap waters, respectively. These results indicate that the enrichment factor was limited by the interference of some matrix metals which could precipitate as hydroxides (or related species) and be retained in the reaction coil. The integrated system permits fully automated operation, avoiding time-consuming manual work and enhancing the reproducibility and precision of the determination of beryllium. The results obtained for the determination of beryllium in certified reference materials (trace elements in water), together with the good recovery of spiked analytes, demonstrate the applicability of the procedure to the analysis of natural waters.  相似文献   

4.
Two new rhodamine based probes 1 and 2 for the detection of Fe(3+) were synthesized and their selectivity towards Fe(3+) ions in the presence of other competitive metal ions tested. The probe 1 formed a coloured complex with Fe(3+) as well as Cu(2+) ions and revealed the lack of adequate number of coordination sites for selective complexation with Fe(3+). Incorporation of a triazole unit to the chelating moiety of 1 resulted in the probe 2, that displayed Fe(3+) selective complex formation even in the presence of other competitive metal ions like Li(+), Na(+), K(+), Cu(2+), Mg(2+), Ca(2+), Sr(2+), Cr(3+), Mn(2+), Fe(2+), Co(2+), Ni(2+), Zn(2+), Cd(2+), Hg(2+) and Pb(2+). The observed limit of detection of Fe(3+) ions (5 × 10(-8) M) confirmed the very high sensitivity of 2. The excellent stability of 2 in physiological pH conditions, non-interference of amino acids, blood serum and bovine serum albumin (BSA) in the detection process, and the remarkable selectivity for Fe(3+) ions permitted the use of 2 in the imaging of live fibroblast cells treated with Fe(3+) ions.  相似文献   

5.
The catalytic activity for the decomposition of hydrogen peroxide by anion-exchangers modified with metal complexes of thiacalix[4]arenetetrasulfonate (Me(n+)-TCAS[4], Me(n+)=Mn(3+), Mn(2+), Fe(3+), Co(3+), Co(2+), Cu(2+), Zn(2+) and Ni(2+)) was investigated. As a reference, calix[4]arenetetrasulfonate, calix[6]arenehexasulfonate and calix[8]areneoctasulfonate were also examined. Mn(3+)- and Fe(3+)-TCAS[4] on the modified anion-exchangers showed high catalytic activity in alkaline buffer solutions among metal complexes tested. Mn(3+)- and Fe(3+)-TCAS[4] on the modified anion-exchangers exhibited high and constant levels of catalytic activity even after having been used 5 times, and showed catalytic activity in the presence of an excess of H(2)O(2) over Mn(3+)- and Fe(3+)-TCAS[4] on the modified anion-exchangers. Only Mn(3+)-TCAS[4] on the modified anion-exchangers exhibited high catalytic activity at around a neutral pH.  相似文献   

6.
The reaction of [M(CN)(6)](3-) (M = Cr(3+), Mn(3+), Fe(3+), Co(3+)) and [M(CN)(8)](4-/3-) (M = Mo(4+/5+), W(4+/5+)) with the trinuclear copper(II) complex of 1,3,5-triazine-2,4,6-triyltris[3-(1,3,5,8,12-pentaazacyclotetradecane)] ([Cu(3)(L)](6+)) leads to partially encapsulated cyanometalates. With hexacyanometalate(III) complexes, [Cu(3)(L)](6+) forms the isostructural host-guest complexes [[[Cu(3)(L)(OH(2))(2)][M(CN)(6)](2)][M(CN)(6)]][M(CN)(6)]30 H(2)O with one bridging, two partially encapsulated, and one isolated [M(CN)(6)](3-) unit. The octacyanometalates of Mo(4+/5+) and W(4+/5+) are encapsulated by two tris-macrocyclic host units. Due to the stability of the +IV oxidation state of Mo and W, only assemblies with [M(CN)(8)](4-) were obtained. The Mo(4+) and W(4+) complexes were crystallized in two different structural forms: [[Cu(3)(L)(OH(2))](2)[Mo(CN)(8)]](NO(3))(8)15 H(2)O with a structural motif that involves isolated spherical [[Cu(3)(L)(OH(2))](2)[M(CN)(8)]](8+) ions and a "string-of-pearls" type of structure [[[Cu(3)(L)](2)[M(CN)(8)]][M(CN)(8)]](NO(3))(4) 20 H(2)O, with [M(CN)(8)](4-) ions that bridge the encapsulated octacyanometalates in a two-dimensional network. The magnetic exchange coupling between the various paramagnetic centers is characterized by temperature-dependent magnetic susceptibility and field-dependent magnetization data. Exchange between the CuCu pairs in the [Cu(3)(L)](6+) "ligand" is weakly antiferromagnetic. Ferromagnetic interactions are observed in the cyanometalate assemblies with Cr(3+), exchange coupling of Mn(3+) and Fe(3+) is very small, and the octacoordinate Mo(4+) and W(4+) systems have a closed-shell ground state.  相似文献   

7.
2-((Naphthalen-6-yl)methylthio)ethanol (HL) was prepared by one pot synthesis using 2-mercaptoethanol and 2-bromomethylnaphthalene. It was found to be a highly selective fluorescent sensor for Al(3+) in the physiological pH (pH 7.0-8.0). It could sense Al(3+) bound to cells through fluorescence microscopy. Metal ions like Mn(2+), Fe(3+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Ag(+), Cd(2+), Hg(2+), Cr(3+) and Pb(2+) did not interfere. No interference was also observed with anions like Cl(-), Br(-), F(-), SO(4)(2-), NO(3)(-), CO(3)(2-), HPO(4)(2-) and SCN(-). Experimentally observed structural and spectroscopic features of HL and its Al(3+) complex have been substantiated by computational calculations using density functional theory (DFT) and time dependent density functional theory (TDDFT).  相似文献   

8.
Hashemi P  Noresson B  Olin A 《Talanta》1999,49(4):825-835
Adsorption properties of a fast iminodiacetate-agarose adsorbent, IDA-Novarose, with a capacity of 120-140 mumol/ml were studied for preconcentration of eight transition elements. A FIA-ICP-AES system was used in the study. It was shown that 0.3 ml of the adsorbent, packed in a column, can quantitatively accumulate Cr(3+), Mn(2+), Fe(3+), Co(2+), Ni(2+), Cu(2+), Zn(2+) and Cd(2+) from standard solutions in the pH range between 4 and 8 at high loading flow rates (10-80 ml/min). The rate of adsorption was studied in batch experiments and found to be fast and equal for the divalent metal ions but relatively slow for accumulation of Cr(3+) and Fe(3+). On-line buffering of acidified samples improved the accumulation of metal ions from synthetic samples spiked with humic acid. Quantitative uptakes were observed for most of the studied metals. The accumulation of Cr(3+) was found to be quite sensitive to the ionic strength and some loss of inert complexes of Fe(3+) was also observed. The method was applied to the analysis of certified riverine water (SLRS-3), a tap water and a lake water. With few exceptions the results obtained by ICP-AES after preconcentration agreed well with the certified concentrations and results found by ICP-MS.  相似文献   

9.
Aldimine 4 bearing a 2-quinolyl group was prepared by aza-Wittig reaction between the triphenyliminophosphorane derived from the 1,1'-diazidoferrocene and 2-formylquinoline. However, aldimine 5, bearing a pyrene ring, was prepared using the most reactive tributyliminophosphorane derivative and the corresponding 1-formylpyrene. On the other hand, formation of aldimine 8 involves a tandem process, Staudinger reaction/intramolecular aza-Wittig reaction, by using directly 1,1'-diazidoferrocene and 2-(diphenylphosphonyl)benzaldehyde. Aldimine 4 behaves as chemosensor molecule for Ni(2+), Zn(2+), Cd(2+), Hg(2+) and Pb(2+) cations through two different channels: electrochemical (ΔE(1/2) = 222-361 mV) and chromogenic (Δλ = 122-153 nm), which can be used for the "naked eye" detection of these metal cations. Aldimine 5 behaves as a highly selective redox (in CH(3)CN) and fluorescent (in CH(3)Cl-DMF) probe for Hg(2+) metal cations even in the presence of a large excess of the other metal cations tested. Aldimine 8 displays electrochemical affinity (ΔE(1/2) = 60-288 mV) to Li(+), Ca(2+), Mg(2+), Zn(2+) and Pb(2+) metal cations, with the phosphorus oxide functionality as a binding site. From the (1)H NMR titration data as well as DFT calculations, different tentative binding modes have been established, for these structurally related ferrocenyl derivatives.  相似文献   

10.
The possibility of using a sulphonated aromatic organic complexing agent-Xylenol Orange-for separation of metal ions on the macroreticular anion-exchanger Amberlyst A-26 has been investigated. The dependence of retention on pH was determined by the batch method for Al(3+), Cr(3+), Mn(3+), Fe(3+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Ga(3+), Rh(3+) Cd(2+), In(3+), Ir(3+), and Pb(2+). The selectivity differences make possible the separation of some of these metal ions. The following mixtures, of practical importance, have been separated: Al(3+)-In(3+), Ga(3+)-In(3+) Zn(2+)-In(3+), Cu(2+)-Mn(2+), in various ratios. The method has been applied to analysis of Ga-In alloy.  相似文献   

11.
Chen Z  Adams MA 《Talanta》1998,47(3):779-786
A flow injection analysis of Ca(2+) and Mg(2+) using indirect potentiometric detection in natural waters is proposed, where Ca(2+) or Mg(2+) are injected into a buffer carrier containing phosphate, resulting in the formation of Ca(3)(PO(4))(2) or Mg(3)(PO(4))(2). The consequent reduction in free phosphate in the carrier solution is detected using a metallic cobalt wire electrode. Indirect electrode response was used and the experimental conditions affecting electrode response were optimized. Responses were linear in the concentration range 5x10(-4) to 5x10(-3) M with a detection limit of 1x10(-5) M in 20 mM phosphate buffer at pH 8.0. The relative standard derivation at 1 mM of Ca(2+) and Mg(2+) were 3.9 and 3.7% (n=10), respectively. EGTA and 8-hydroxyquinoline were used as the masking agents for Ca(2+) and Mg(2+), respectively. Concentrations of Ca(2+) and Mg(2+) in natural waters were successfully determined by the proposed method.  相似文献   

12.
本文用ab initio研究了簇合物HeLi^n^+(n=0, 1)的几何构型和成键性质。在MP2(FULL)/6-31G**, 水平优化所得LeLi^+的平衡键长为0.2062nm, 与实验值0.205nm十分吻合。比较了HeLi^+(X^1∑^+和a^3∑^+), HeLi(X^2∑^+和a^4II)以及HLi(X^1∑^+)的稳定性, 计算了HeLi^+基态的相关能, 势能曲线和垂直激发态光谱。计算采用了6-31G**, 6-311G**,6-311G(2df, 2pd), 6-311G(3df, 2pd)和6-311+G(3df, 2pd)基组; 采用的方法包括MP2(FULL), MP4, MCSCF, MRSDCI, CCD和ST4CCD。计算表明, 同价HeLi^n^+中激发态的离解能均远比基态的大, 其中HeLi^+(a^3∑^+)的离解能最高(60.49kj/mol),说明激发态是稳定束缚态。HeLi^+基态比等电子体HLi分子基态的稳定性小得多。HeLi^+由A^1∑^+到B^1II的垂直跃迁(3σ→1π)振子强度较大而垂直跃迁能较小。  相似文献   

13.
The behavior of a modified carbon paste electrode (CPE) for nickel determination by anodic adsorptive stripping voltammetry (AAdsSV) was studied. The electrode was built incorporating the Dowex 50W x 12 (H(+) form) ion exchanger to a Nujol-graphite base paste. Ni(2+) was preconcentrated on the electrode surface in open circuit conditions, with the reduction (-1300 mV)/reoxidation step carried out in HCl solution (pH 3). During deposition time (5 min), the hydrogen evolution did not present obstacle in the quantification of nickel. For 12 min of accumulation and 5 min of deposition, nickel can be quantified up to 600 mug l(-1). The detection limit was 0.005 mug l(-1) at a linear potential scan rate of 200 mV s(-1). Interferences from Hg(2+) and Ag(2+) up to a concentration of 1 and 0.6 mg l(-1), respectively, were eliminated with the aid of the anion exchanger Dowex-2 (mesh 200-400) which was added to the sample in the preconcentration step. The tolerance for some metal ions such as Cu(2+), Cd(2+), Fe(3+), Zn(2+), Co(2+) and Pb(2+) was improved in the same way. The method was applied for the determination of nickel in samples of tap and mineral water. At the concentration level of 50 mug l(-1) of Ni (2+), the results were in good agreement with those obtained using Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES). For a Ni(2+) concentration of 5 mug l(-1), the results obtained showed better accuracy than those obtained by ICP-AES.  相似文献   

14.
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   

15.
Parent 1-silaadamant-1-yl (1+) and a series of mono-beta-silyl-substituted- (2-Me+, 2-F+, 2-Cl+, 2-Br+), bis-beta-silyl-substituted- (3-Me+), and tris-beta-silyl-substituted (4-Me+)-1-silaadamant-1-yl cations were studied by the DFT method at the B3LYP/6-31G(d,p) level and by GIAO NMR at the B3LYP/ 6-31G(d,p)//B3LYP/6-31G(d,p) level. The geometries, relative energies, NMR chemical shifts, and charge distribution in the bridgehead silylium ions are discussed and compared. The magnitude of the beta-silyl effect (the Si-C-Si+ hyperconjugation) is gauged as a function of structure. Related model studies on the silabicyclo[2.2.2]octyl (5+, 6+, 5a+, and 6a+), silanorbornyl (7+ and 8+), and silacyclohexyl cations (9+ and 10+) were carried out in which the effect of beta-silyl substitution on geometry, stability, and NMR chemical shifts was probed. The acyclic model Me3Si-CH2-Si+(Me)2 (11+) was used to gauge the influence of the twist angle between the p-orbital at Si+ and the C-Si bond on relative stability and on the changes in the 29Si NMR chemical shifts. Finally, interaction of 1+ with H2O and MeOH and 2-Me+ with H2O was also examined. The resulting optimized structures (12+, 13+, and 14+) and the computed NMR chemical shifts are most compatible with the formation of silaoxonium ions.  相似文献   

16.
For detection of phenolic compounds in environmental water samples we propose an amperometric biosensor based on tyrosinase immobilized in titania sol-gel. The analytical characteristics toward catechol, p-cresol, phenol, p-chlorophenol, and p-methylcatechol were determined. The linear range for catechol determination was 2.2 x 10(-7)-1.3 x 10(-5) mol L(-1) with a limit of detection of 9 x 10(-8) mol L(-1) and sensitivity 2.0 x 10(3) mA mol(-1) L. The influence of sample matrix components on the electrode response was studied according to Plackett-Burman experimental design. The potential interferents Mg(2+), Ca(2+), HCO3(-), SO4(2-), and Cl(-), which are usually encountered in waters, were taken into account in the examination. Cu(2+) was also taken into account, because CuSO(4) is sometimes added to a water sample, as a preservative, before determination of phenolic compounds. It was found that among the ions tested only Mg(2+) and Ca(2+) did not directly affect the electrode response. The developed biosensor was used for determination of catechol in spring and surface water samples using the standard addition method.  相似文献   

17.
A method for quantitative extraction of zinc with potassium ethyl xanthate into carbon tetrachloride is described. The optimum conditions are: pH 5-6 and Zn(II) to reagent ~1:8 mole ratio. The effects of other ions on the extraction of Zn(2+) have been investigated, and its separation from As(3+), Pb(2+), Cu(2+) and Fe(3+)is described. The possibility of repeated use of the solvent (still loaded with xanthate after the zinc has been stripped) for further extractions (after addition of a little extra xanthate) has been explored. Various stripping agents have been examined, and the optimum conditions found.  相似文献   

18.
The behavior of selenocystine (SeCyst) alone or in the presence of various metal ions (Bi(3+), Cd(2+), Co(2+), Cu(2+), Cr(3+), Ni(2+), Pb(2+), and Zn(2+)) was studied using differential pulse voltammetry (DPV) over a wide pH range. Voltammetric data matrices were analyzed using chemometric tools recently developed for nonlinear data: pHfit and Gaussian Peak Adjustment (GPA). Under the experimental conditions tested, no evidence was found for the formation of metal complexes with Bi(3+), Cu(2+), Cr(3+), and Pb(2+). In contrast, SeCyst formed electroinactive complexes with Co(2+) and Ni(2+) and kinetically inert but electroactive complexes with Cd(2+) and Zn(2+). Titrations with Cd(2+), Co(2+), Ni(2+), and Zn(2+) produced data that were reasonably consistent with the formation of stable 1:1 M(SeCyst) complexes.  相似文献   

19.
An efficient fluorescent Al(3+) receptor, N-(2-hydroxy-1-naphthalene)-N'-(2-(2-hydroxy-1-naphthalene)amino-ethyl)-ethane-1,2-diamine (L) has been synthesized by the condensation reaction between 2-hydroxy naphthaldehyde and diethylenetriamine. High selectivity and affinity of L towards Al(3+) in ethanol (EtOH) as well as in HEPES buffer at pH 7.4, makes it suitable to detect intracellular Al(3+) with fluorescence microscopy. Metal ions, viz. Li(+), Na(+), K(+), Mg(2+), Ca(2+), Mn(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Ag(+), Cd(2+), Hg(2+) and Pb(2+) do not interfere. The lowest detection limit for Al(3+) is 3.0 × 10(-7) M and 1.0 × 10(-7) M in EtOH and HEPES buffer respectively.  相似文献   

20.
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