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1.
The fluorescence characteristics of 2-methyl naphthalene have been studied in ionic micelles of sodium dodecyl sulphate (SDS) and cetyl trimethyl ammonium bromide (CTAB) and in nonionic micellar medium of p-t-octylphenyl polyethoxyethanol (Triton X-100). The fluorescence quenching of fluorophore by halides and pseudohalide obeys the Stern-Volmer Equation up to a certain concentration of quencher. A quenching sphere of action model has been considered to explain the deviations from Stern-Volmer behaviour. The distribution of quenchers in the micellar phase has been calculated.  相似文献   

2.
A halide-sensitive fluorescence probe was utilized to evaluate the miscibility of fluorocarbon and hydrocarbon surfactants in aqueous micellar systems. The fluorescence of 6-methoxy-N-1,1,2,2-tetrahydroheptadecafluorodecylquinolinium chloride, FC10MQ, was quenched by halide ions dissociated from the surfactant. The fluorescence in micellar solutions showed an initially rapid decay. This suggests that halide ions effectively quench FC10MQ fluorescence at the micellar surface. The subsequent slow decay corresponds to the quenching of FC10MQ fluorescence in the aqueous bulk phase by the free counterions. The Stern-Volmer plots for fluorescence quenching gave a distinct break at the critical micelle concentration of the cationic surfactants. The abrupt increase in fluorescence quenching is attributed to the solubilization of the probe in the micelles. The fluorescence quenching behavior provides direct information about the immiscibility of fluorocarbon and hydrocarbon species in micelles, and the results indicate that almost pure fluorocarbon micelles appear in surfactants mixtures.  相似文献   

3.
Fluorescence quenching of meso-tetrakis-4-sulfonatophenyl (TPPS(4)) and meso-tetrakis-4-N-methylpyridil (TMPyP) porphyrins is studied in aqueous solution and upon addition of micelles of sodium dodecylsulfate (SDS), cetyltrimethylammonium chloride (CTAC), N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS) and t-octylphenoxypolyethoxyethanol (Triton X-100). Potassium iodide (KI) was used as quencher. Steady-state Stern-Volmer plots were best fitted by a quadratic equation, including dynamic (K(D)) and static (K(S)) quenching. K(S) was significantly smaller than K(D). Frequency-domain fluorescence lifetimes allowed estimating bimolecular quenching constants, k(q). At 25 degrees C, in aqueous solution, TMPyP shows k(q) values a factor of 2-3 higher than the diffusional limit. TPPS(4) shows collisional quenching with pH dependent k(q) values. For TMPyP quenching results are consistent with reported binding constants: a significant reduction of quenching takes place for SDS, a moderate reduction is observed for HPS and almost no change is seen for Triton X-100. Similar data were obtained at 50 degrees C. For CTAC-TPPS(4) system an enhancement of quenching was observed as compared to pure buffer. This is probably associated to accumulation of iodide at the cationic micellar interface. The attraction between CTAC headgroups and I(-), and repulsion between SDS and I(-), enhances and reduces the fluorescence quenching, respectively, of porphyrins located at the micellar interface. The small quenching of TPPS(4) in Triton X-100 is consistent with strong binding as reported in the literature.  相似文献   

4.
Micellar effects on luminescense of organic compounds or probes are well established, and here we show that quenching is highly favored in aqueous sodium dodecyl sulfate (SDS) micelles, which concentrate a naphthalene probe and cations of lanthanides, transition metals, and noble metals. Interactions have been studied by steady state and time-resolved fluorescence in examining the fluorescence suppression of naphthalene by metal ions in anionic SDS micelles. The quenching is collisional and correlated with the unit charge and the reduction potential of the metal ion. The rate constants, calculated in terms of local metal ion concentrations, are close to the diffusion control limit in the interior of SDS micelles, where the microscopic viscosity decreases the transfer rate, following the Stokes-Einstein relation.  相似文献   

5.
Strong luminescence CdS quantum dots (QDs) have been prepared and modified with l-cysteine by a facile seeds-assistant technique in water. They are water-soluble and highly stable in aqueous solution. CdS QDs evaluated as a luminescence probe for heavy and transition metal (HTM) ions in aqueous solution was systematically studied. Five HTM ions such as silver(I) ion, copper(II) ion, mercury(II) ion, cobalt(II) ion, and nickel(II) ion significantly influence the photophysics of the emission from the functionalized CdS QDs. Experiment results showed that the fluorescence emission from CdS QDs was enhanced significantly by silver ion without any spectral shift, while several other bivalent HTM ions, such as Hg(2+), Cu(2+), Co(2+), and Ni(2+), exhibited effective optical quenching effect on QDs. Moreover, an obvious red-shift of emission band was observed in the quenching of CdS QDs for Hg(2+) and Cu(2+) ions. Under the optimal conditions, the response was linearly proportional to the concentration of Ag(+) ion ranging from 1.25 x 10(-7) to 5.0 x 10(-6)molL(-1) with a detection limit of 2.0 x 10(-8)molL(-1). The concentration dependence of the quenching effect on functionalized QDs for the other four HTM ions could be well described by typical Stern-Volmer equation, with the linear response of CdS QDs emission proportional to the concentration ranging from 1.50 x 10(-8) to 7.50 x 10(-7)molL(-1) for Hg(2+) ion, 3.0 x 10(-7) to 1.0 x 10(-5)molL(-1) for Ni(2+) ion, 4.59 x 10(-8) to 2.295 x 10(-6)molL(-1) for Cu(2+) ion, and 1.20 x 10(-7) to 6.0 x 10(-6)molL(-1) Co(2+) ion, respectively. Based on the distinct optical properties of CdS QDs system with the five HTM ions, and the relatively wide linear range and rapid response to HTM ions, CdS QDs can be developed as a potential identified luminescence probe for familiar HTM ions detection in aqueous solution.  相似文献   

6.
Cooperative interactions between metal ions and bivalent tryptophan side chain are identified in water by fluorescence quenching of a designed novel receptor, EDTA-bis(L-tryptophan methyl ester), supplemented by a circular dichroism study; results revealed that the receptor is capable of distinguishing a variety of metal ions on the basis of their abilities in quenching tryptophan fluorescence and the relative magnitude of these interactions is Cu2+ approximately Fe2+ > Co2+ > Ni2+ > Mn2+ > Zn2+ > La3+ > Al3+.  相似文献   

7.
A fluorophotometric method for the determination of anionic surfactant sodium dodecyl sulphate (SDS) was proposed. The method is based on the quenching effect of SDS on the fluorescence of near-infrared (NIR) hydrophobic dye, 2-[4'chloro-7'(3'hexadecyl-2'benzothiazolinylidene)-3',5'-(1',3'-propanediyl)-1',3',5'-heptatriene-1'-yl]-3-ethylbenzothiazolium iodide (dye I) in the presence of Triton X-100. The calibration graph is linear in the concentration range from 0 to 2 x 10(-6) mol L(-1) of SDS with a detection limit (LOD) of 8.3 x 10(-8) mol L(-1). The relative standard deviation for the determination of 7 x 10(-7) mol L(-1) SDS was 4.1%. Recoveries of 95.3-110.3% were found for the addition to 1.0 x 10(-6) mol L(-1) SDS in the analysis of environmental water samples. Preliminary research shows that the fluorescence quenching is due to the formation of dye aggregate facilitated by SDS.  相似文献   

8.
合成了25,27-二羟基-26,28-二{3-[N-(2-萘基)-2-硫代乙酰胺]丙氧基}-5,11,17,23-四叔丁基杯[4]芳烃(2), 并利用荧光光谱考察了其在乙醇-水混合溶液中对Ag+的光谱选择性. 结果表明, 含有S2O2结合位点的探针分子2对Ag+具有良好的选择性. 通过荧光光谱连续滴定测得探针分子2-Ag+体系的猝灭常数为3.39×103 L/mol, 探针分子对Ag+的检出限可达2.34×10-7 mol/L. 在实际的Ag+检测中, 探针分子2具有一定的应用前景.  相似文献   

9.
A new optical chemical sensor has been developed for the selective determination of copper(II) ions in aqueous solutions. The reversible sensing system was prepared by incorporating 1-hydrpxy-2-(prop-2'-enyl)-4-(prop-2'-enyloxy)-9,10-anthraquinone (AQ) as a neutral Cu2+-selective fluoroionophore in the plasticized PVC membrane with potassium tetrakis(p-chlorophenyl borate) as an anionic additive. The response of the sensor is based on the fluorescence quenching of AQ by Cu2+ ions. At a pH 5.5, the proposed sensor displays a calibration response for Cu2+ over a wide concentration rang of 1.0 x 10(-2) to 1.0 x 10(-6) M, with a relatively fast response of less than 40 s. In addition to high stability and reproducibility, the sensor shows a unique selectivity towards Cu2+ ion with respect to common co-existing cations. The proposed fluorescence optode was applied successfully to the determination of copper(II) in black tea samples.  相似文献   

10.
A simple assay for the detection of Fe3+ in water by means of fluorescence spectroscopy was developed based on a commercially available reagent, Azomethine-H(A-H), allowing sensing trace levels of Fe3+ with high selectivity over other cations. A significant fluorescence quenching of A-H at 424 nm was found after its binding with Fe3+ in 100% aqueous solution at pH=7.0, while other physiologically relevant metal ions posed little interference. The fluorescence responses can be well described by the modified Stern-Volmer equation. A good linear relationship(R2=0.9904) was observed up to 1.6×10-5 mol/L Fe3+ ions. The detection limit, calculated via the 3σ IUPAC(international union of pure and applied chemistry) criteria, was 1.95×10-7 mol/L. Moreover, the colorimetric and fluorescent response of A-H to Fe3+ can be conveniently detected by the naked eye, providing a facile method for visual detection of Fe3+. The proposed method was used to determine Fe3+ in water samples. Moreover, inverted fluorescence microscopy imaging using human umbilical vein endothelial cells shows that A-H can be used as an effective fluorescent probe for detecting Fe3+ in living cells.  相似文献   

11.
Gilbert E. Tumambac 《Tetrahedron》2004,60(49):11293-11297
The use of anti-1,8-bis(2,2′-diisopropyl-4,4′-diquinolyl)naphthalene, 1, for metal ion-selective fluorescence recognition has been investigated. Employing CuCl2, ZnCl2, FeCl2, and FeCl3 in fluorescence titration experiments of 1 revealed formation of a bluegreen light emitting bimetallic complex. A dramatic red-shift of the fluorescence maximum of 1 and metal ion-selective quenching was observed in the presence of Cu(II), Fe(II), and Fe(III)chlorides in acetonitrile. By contrast, addition of ZnCl2 was found to result in fluorescence enhancement, whereas Cu(I) did not induce any significant fluorescence change of 1. The sensor was found to undergo highly ion-selective fluorescence quenching in aqueous solution. Screening of main group and transition metal ions showed excellent selectivity for FeCl3 even in the presence of competing metal ions.  相似文献   

12.
Studies of acrylamide quenching of tryptophan (Trp) fluorescence, photochemistry, and photoionization have been conducted. Quenching of Trp fluorescence in aqueous solution by addition of acrylamide in the concentration range 0.0-0.5 M was measured and resulted in a Stern-Volmer quenching constant of KSV = 21 +/- 3 M-1. Photolysis experiments were performed in which Trp was photolyzed at 295 nm in the presence of varying concentrations of acrylamide. The loss of Trp was monitored using reverse-phase high performance liquid chromatography (RP-HPLC) and was observed to follow first order kinetics. Production of N-formylkynurenine (NFK) was observed by RP-HPLC in irradiated Trp samples both in the presence and absence of added acrylamide. In addition, no new photochemical product was detected. This was taken as evidence that acrylamide did not alter the photochemical pathway but just reduced the reaction rate as expected for a physical quenching mechanism. Plotting the reciprocal of photolysis rate constant versus acrylamide concentration produced a Stern-Volmer constant for quenching of Trp photochemistry of KSV = 6 +/- 2 M-1. The KSV values for both fluorescence quenching and photolysis quenching were thus large, implying efficient quenching of both processes by acrylamide. Assuming an excited singlet state lifetime of 2.8 ns, the calculated second-order quenching rate constants for fluorescence and photolysis were kq = 7.5 x 10(9) and 2.1 x 10(9) M-1 s-1 respectively. The possible involvement of photoionization in the photolysis mechanism was investigated by studies of acrylamide quenching of voltage transients produced by xenon flash lamp excitation of Trp at aqueous/teflon or aqueous/mica interfaces.(ABSTRACT TRUNCATED AT 250 WORDS)  相似文献   

13.
The new fluorescent membrane probe Fluorazophore-L, a lipophilic derivative of the azoalkane 2,3-diazabicyclo[2.2.2]oct-2-ene, is employed to study the quenching of alpha-tocopherol (alpha-Toc) by time-resolved fluorescence in the microheterogeneous environments of Triton XR-100 and SDS micelles, as well as POPC liposomes. Fluorazophore-L has a small nonaromatic fluorescent polar headgroup and an exceedingly long-lived fluorescence (e.g., 140 ns in aerated SDS micelles), which is efficiently quenched by alpha-Toc (3.9 x 10(9) M(-1) s(-1) in benzene). Based on solvatochromic effects and the accessibility by water-soluble quenchers, the reactive headgroup of Fluorazophore-L, along with the chromanol group of alpha-Toc, resides at the water-lipid interface, which allows for a diffusion-controlled quenching in the lipidic environments. The quenching experiments represent an immobile or stationary case; that is, interparticle probe or quencher exchange during the excited-state lifetime is insignificant. Different quenching models are used to characterize the dynamics and antioxidant action of alpha-Toc in terms of diffusion coefficients or, where applicable, rate constants. The ideal micellar quenching model is suitable to describe the fluorescence quenching in SDS micelles and affords a pseudo-unimolecular quenching rate constant of 2.4 (+/- 0.4) x 10(7) s(-1) for a single quencher per micelle along with a mean aggregation number of 63 +/- 3. In Triton micelles as well as in unilamellar POPC liposomes, a two-dimensional (lateral) diffusion model is most appropriate. The mutual lateral diffusion coefficient D(L) for alpha-Toc and Fluorazophore-L in POPC liposomes is found to be 1.8 (+/- 0.1) x 10(-7) cm(2) s(-1), about a factor of 2 larger than for mutual diffusion of POPC, but more than 1 order of magnitude lower than a previously reported value. The comparison of the different environments suggests a quenching efficiency in the order benzene > SDS micelles > Triton micelles > POPC liposomes, in line with expectations from microviscosity. The kinetic measurements provide important benchmark values for the modeling of oxidative stress in membranes and other lipidic assemblies. The special case of small lipidic assemblies (SDS micelles), for which the net antioxidant efficacy of alpha-Toc may be lower than expected on the grounds of its diffusional behavior, is discussed.  相似文献   

14.
Metal ions are physiologically essential,but excessive metal ions may cause severe risk to plants and animals.Here,we prepared gold nanoclusters(Au NCs) protected by 11-mercaptoundecanoic acid(11-MUA),which have excellent fluorescence properties for the detection of metal ions.The results showed that the copper ions(Cu~(2+)) and iron ions(Fe~(3+)) in the solution have obvious quenching effect on the fluorescence intensity of Au NCs.The detection range of Fe~(3+) was 0.8–4.5 mmol/L(R~2= 0.992) and 4.5–11.0 mmol/L(R~2= 0.997).And Cu~(2+) has a lower linear range(0.1–1.0 mmol/L,R2= 0.993).When EDTA was added into the reaction system,it was observed that the quenching effect of Cu~(2+) and Fe~(3+)on Au NCs showed different phenomenon.Then,the effect of metal ions on the fluorescence of Au NCs was investigated.The selective detection of Cu~(2+) was achieved by EDTA masking of Fe~(3+).In addition,we realized the metal ions detection application of Au NCs in the serum  相似文献   

15.
The effects of several lanthanide(II)(Ln3+)ions(Dy3+,Er3+,Eu3+,Nd3+,Yb3+) on the room-temperature fluorescence spectra of 2-indolecarboxylic acid, 5-indolecarboxylic acid, 5-methoxy-2-indolecarboxylic acid and 3-indoleacetic acid were investigated. It was found that the fluorescence quenching by Ln3+ ions is much more efficient for the acidic compounds than for non-acidic indoles. Stern-Volmer relationships were obtained for most acidic indoles in the Ln3+ concentration range 10?7–10?4 M, with quenching constants ranging between 3 × 103 and 4.6 × 105 l mol?1. A fluorimetric quenching method was developed for the quantitative analysis of binary mixtures of acidic and non-acidic indoles.  相似文献   

16.
Fluorescence quenching of 9,10-dimethyl-3, 4,6,7,9,10-hexahydro-1,8(2H,5H) acridinedione (ADD) dye by N,N-dimethylaniline (DMA) in SDS and CTAB were studied by steady state fluorescence and time resolved techniques. The Stern-Volmer plots for the quenching of ADD by DMA is found to be linear and the Stern-Volmer constant K(SV) depends on the micellar concentration. The fluorescence quenching analysis reveals the binding of DMA with the micelles. The perturbation of the probe on the position of DMA molecule in micelle is inferred in the present investigation. The ADD fluorophore drives the DMA molecule into the non-polar region (core) of the micelle whereas other fluorophores like pyrene and rhodamine6G do not affect the position of DMA. In this report, the importance of the nature of fluorophores in determining the position and association of the quencher molecules in the aggregated systems is being discussed.  相似文献   

17.
In this study the coordination structure and chemistry of Eu(III) and Cm(III) in the ionic liquid C(4)mimTf(2)N (1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) was investigated by time-resolved laser fluorescence spectroscopy (TRLFS). The dissolution of 1 x 10(-2) M Eu(CF(3)SO(3))(3) and 1 x 10(-7) M Cm(ClO(4))(3) in C(4)mimTf(2)N leads to the formation of two species for each cation with fluorescence emission lifetimes of 2.5 +/- 0.2 ms and 1.0 +/- 0.3 ms for the Eu-species and 1.0 +/- 0.3 ms and 300.0 +/- 50 micros for the Cm-species. The interpretation of the TRLFS data indicates a comparable coordination for both the lanthanide and actinide cation in this ionic liquid. The quenching influence of Cu(II) on the fluorescence emission of Eu(III) and Cm(III) was also measured by TRLFS. While Cu(ii) does not quench the Cm(III) fluorescence emission in C(4)mimTf(2)N the Eu(III) fluorescence emission lifetime for both Eu-species in C(4)mimTf(2)N decreases with increasing Cu(II) concentration. Stern-Volmer constants were calculated (k(SV) = 1.54 x 10(6) M(-1) s(-1) and k(SV) = 2.70 x 10(6) M(-1)). By contrast, the interaction of Cu(II) with Eu(III) and Cm(III) in water leads to a quenching of both the lanthanide and actinide fluorescence. The calculated Stern-Volmer constants are 1.20 x 10(4) M(-1) s(-1) for Eu(III) and 1.27 x 10(4) M(-1) s(-1) for Cm(III). The investigations show, while the chemistry of trivalent lanthanides and actinides is similar in an aqueous system it is dramatically different in ionic liquids. This difference in chemical behavior may provide the opportunity for a separation of lanthanides and actinides with regard to the reprocessing of nuclear fuel.  相似文献   

18.
A novel, sensitive and convenient determine technology based on the quenching of the fluorescence intensity of functionalized CdS quantum dots by sulfadiazine was proposed. Luminescent CdS semiconductor quantum dots (QDs) modified by thioglycollic acid (TGA) were synthesized with the microwave method. The modified CdS QDs are water-soluble, stable and highly luminescent. The possible mechanism for the reaction was also discussed. When sulfadiazine was added into the CdS QDs colloid solution, the surface of CdS QDs generates the electrostatic interaction in aqueous medium, which induces the quenching of fluorescence emission at 489 nm. Under optimum condition, the fluorescence intensity versus sulfadiazine concentration gave a linear response according Stern-Volmer equation with an excellent 0.9981 correlation coefficient. The linearity range of the calibration curve was 1.2 x 10(-5) to 2.13 x 10(-3) mol L(-1). The limit of detection (3delta) is 8.0 micromol L(-1). The relative standard deviation for five determinations of 0.13 x 10(-3)mol L(-1) sulfadiazine is 1.4%. The concentrations of sulfadiazine injections were determined by the proposed method with a satisfactory result.  相似文献   

19.
Four amphiphilic pyranines in which the acidic hydrogen of pyranine was replaced by an octyl, dodecyl, hexadecyl, and eicosyl group, POCn (n=8, 12, 16, and 20), were prepared, and their spectroscopic properties and aggregation behaviors in water were investigated. The critical micelle concentration (cmc) of the amphiphilic pyranines was found to be relatively large even in POC20 having a long hydrophobic alkyl chain (ca. 3x10(-3) M). 1H NMR studies revealed that POC16 and POC20 exist in the compact structure with the pyranine nucleus wrapped with a long methylene chain in water. As in the case of parent pyranine, the addition of methylviologen (MV2+) to an aqueous solution of POCn resulted in the absorption spectral change and efficient quenching of POCn fluorescence. In the case of POC8 and POC12, these spectral changes induced by the MV2+ addition were thoroughly explained in terms of the formation of the electrostatic complex POCn/MV2+ with a complexation constant of approximately 3x10(4) M(-1). On the other hand, an unexpectedly large dependence of the absorption spectral change, as well as fluorescence quenching, on the total concentration of MV2+ was observed in POC16 and POC20. The Stern-Volmer plot for quenching of the fluorescence of POC16 and POC20 gave a curve deviating largely upward from a straight line. The plot was successfully analyzed by the equation induced by assuming the aggregate formation of the complex POCn/MV2+, which revealed the considerably small cmc values of the complexes, 3.6x10(-7) and 3.6x10(-8) M for POC16/MV2+ and POC20/MV2+, respectively. Experimental evidence in support of the aggregate formation was obtained by 1H NMR and dynamic light scattering studies.  相似文献   

20.
Abstract— The critical micelle concentration (CMC) of a fluorescent detergent may be measured by determining Stern-Volmer quenching parameters as a function of detergent concentration. The CMC's of a cationic detergent, 11-(3-hexyl-l-indolyI)undecyltrimethylamrnoniurn bromide (6-In-ll+), and an anionic detergent, sodium H-(3-hexyI-l-indoiyI) undecyl sulfate (6-In-ll) were determined by this quenching procedure. Quenchers which were predominantly located in the aqueous phase (e.g. Co2+) or in the micellar phase (e.g. benzophenone) were employed. Aqueous phase quenchers are more effective below the CMC and cause a decrease in the long wavelength portion of the fluorescence band of the indole moiety. Quenchers located in the micellar phase are more effective above the CMC and decrease the short wavelength portion of the fluorescence band of the system.  相似文献   

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