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1.
Core–shell structured quantum dot (QD)–silica fluorescent nanoparticles have attracted a great deal of attention due to the excellent optical properties of QDs and the stability of silica. In this study, core–shell structured CdTe/CdS@SiO2@CdTe@SiO2 fluorescent nanospheres were synthesized based on the Stöber method using multistep silica encapsulation. The second silica layer on the CdTe QDs maintained the optical stability of nanospheres and decreased adverse influences on the probe during subsequent processing. Red‐emissive CdTe/CdS QDs (630 nm) were used as a built‐in reference signal and green‐emissive CdTe QDs (550 nm) were used as a responding probe. The fluorescence of CdTe QDs was greatly quenched by added S2?, owing to a S2?‐induced change in the CdTe QDs surface state in the shell. Upon addition of Cd2+ to the S2?‐quenched CdTe/CdS@SiO2@CdTe@SiO2 system, the responding signal at 550 nm was dramatically restored, whereas the emission at 630 nm remained almost unchanged; this response could be used as a ratiometric ‘off–on’ fluorescent probe for the detection of Cd2+. The sensing mechanism was suggested to be: the newly formed CdS‐like cluster with a higher band gap facilitated exciton/hole recombination and effectively enhanced the fluorescence of the CdTe QDs. The proposed probe shows a highly sensitive and selective response to Cd2+ and has potential application in the detection of Cd2+ in environmental or biological samples.  相似文献   

2.
The use of bacterial cells to produce fluorescent semiconductor nanoparticles (quantum dots, QDs) represents a green alternative with promising economic potential. In the present work, we report for the first time the biosynthesis of CdS QDs by acidophilic bacteria of the Acidithiobacillus genus. CdS QDs were obtained by exposing A. ferrooxidans, A. thiooxidans and A. caldus cells to sublethal Cd2+ concentrations in the presence of cysteine and glutathione. The fluorescence of cadmium-exposed cells moves from green to red with incubation time, a characteristic property of QDs associated with nanocrystals growth. Biosynthesized nanoparticles (NPs) display an absorption peak at 360 nm and a broad emission spectra between 450 and 650 nm when excited at 370 nm, both characteristic of CdS QDs. Average sizes of 6 and 10 nm were determined for green and red NPs, respectively. The importance of cysteine and glutathione on QDs biosynthesis in Acidithiobacillus was related with the generation of H2S. Interestingly, QDs produced by acidophilic bacteria display high tolerance to acidic pH. Absorbance and fluorescence properties of QDs was not affected at pH 2.0, a condition that totally inhibits the fluorescence of QDs produced chemically or biosynthesized by mesophilic bacteria (stable until pH 4.5–5.0). Results presented here constitute the first report of the generation of QDs with improved properties by using extremophile microorganisms.  相似文献   

3.
The effect of equimolar concentrations of Hg2+ and Cd2+ on the whole cell absorption spectra, absorption spectra of the extracted phycocyanin (PC) and fluorescence emission spectra of phycobilisomes (PBS) was investigated in the cells of Anabaena flos-aquae. The PC component of the PBS was found to be extremely sensitive to the Hg2+ rather than the Cd2+ ions. Further, the results showed that Hg2+ and Cd2+ induced decrease in the rate of Hill activity (H2O - DCPIP) was partially restored by the electron donor NH2OH, not by the diphenyl carbazide. Similarly, chlorophyll a fluorescence emission in the presence of metals showed that addition of NH2OH could effectively reverse the metal induced alterations in the fluorescence emission intensity. These results, together, suggested that Hg2+ and Cd2+ caused damage to the photosystems (PS) II reaction center. However, a relatively higher stimulation of the chlorophyll a emission at 695 nm with a red shift of 4.0 nm in the presence of Hg2+, and Cd2+ induced preferential decrease in the emission intensity at 676 nm as compared with the peak at 695 nm were indicative of the differential action of Hg2+ and Cd2+ on the PS II.  相似文献   

4.
High‐quality CdxZn1 – xSe and CdxZn1 – xSe/ZnS core/shell quantum dots (QDs) emitting in the violet–green spectral range have been successfully prepared using hydrothermal methods. The obtained aqueous CdxZn1 – xSe and CdxZn1 – xSe/ZnS QDs exhibit a tunable photoluminescence (PL) emission (from 433.5 nm to 501.2 nm) and a favorable narrow photoluminescence bandwidth [full width at half maximum (FWHM): 30–42 nm]. After coating with a ZnS shell, the quantum yield increases from 40.2% to 48.1%. These CdxZn1 – xSe and CdxZn1 – xSe/ZnS QDs were characterized by transmission electron microscopy, X‐ray diffraction, X‐ray photoelectron spectroscopy and Fourier transform infrared (FTIR) spectroscopy. To further understand the alloying mechanism, the growth kinetics of CdxZn1 – xSe were investigated through measuring the fluorescence spectra and X‐ray diffraction spectra at different growth intervals. The results demonstrate that the inverted ZnSe/CdSe core/shell structure is formed initially after the injection of Cd2+. With further heating, the core/shell structured ZnSe/CdSe is transformed into alloyed CdxZn1 – xSe QDs with the diffusion of Cd2+ into ZnSe matrices. With increasing the reaction temperature from 100 °C to 180 °C, the duration time of the alloying process decreases from 210 min to 20 min. In addition, the cytotoxicity of CdxZn1 – xSe and CdxZn1 – xSe/ZnS QDs were investigated. The results indicate that the as‐prepared CdxZn1 – xSe/ZnS QDs have low cytotoxicity, which makes them a promising probe for cell imaging. Finally, the as‐prepared CdxZn1 – xSe/ZnS QDs were utilized to ultrasensitively and selectively detect Hg2+ ions with a low detection limit (1.8 nM).  相似文献   

5.
Mercury (Hg2+) is a natural element present in foods such as fish, water and soil. Exposure to mercury leads to severe toxic effects on the nervous, digestive, and immune systems. Here, a novel, green, and environmentally friendly fluorescent probe decorated with cysteine/MnO2 quantum dots (Cys@MnO2 QDs) was synthesized. This synthesis was carried out using a simple ultrasound technique with the aid of cysteine for fabricating Cys@MnO2 QDs to estimate Hg levels in fish and water samples. In this morphological study, Cys@MnO2 QDs were fully characterized using high-resolution transmission electron microscopy, zeta potential analysis, fluorescence, ultraviolet–visible and infrared spectroscopy. The fluorescence of the synthesized Cys@MnO2 QDs was significantly quenched by gradually increasing the Hg(II) concentration. The quenching mechanism based on the Hg–S bonds strengthened the utility of the Cys@MnO2 QDs as a novel luminescent nanoprobe. The estimation of Hg was linear in the concentration range 0.7–100.0 ng mL−1 with a limit of quantitation equal to 0.30 ng mL−1. The Cys@MnO2 QDs are fluorescent probes with various benefits such as speed, ease of use, cost- effective, and being environmentally friendly; they are easily applied in food manufacturing and for public health improvement.  相似文献   

6.
Aqueous phase synthesis of CdTe quantum dots (QDs) with surface functionalization for bioconjugation remains the best approach for biosensing and bioimaging applications. We present a facile aqueous phase method to prepare CdTe QDs by adjusting precursor and ligand concentrations. CdTe QDs had photoluminescence quantum yield up to ≈33% with a narrow spectral distribution. The powder X‐ray diffraction profile elucidated characteristic broad peaks of zinc blende cubic CdTe nanoparticles with 2.5–3 nm average crystalline size having regular spherical morphology as revealed by transmission electron microscopy. Infra‐red spectroscopy confirmed disappearance of characteristic absorptions for –SH thiols inferring thiol coordinated CdTe nanoparticles. The effective molar concentration of 1 : 2.5 : 0.5 respectively for Cd2+/3‐mercaptopropionic acid/HTe at pH 9 ± 0.2 resulted in CdTe quantum dots of 2.2–3.06 nm having band gap in the range 2.74–2.26 eV respectively. Later, QD523 and QD601 were used for monitoring staphylococcal enterotoxin B (SEB; a bacterial superantigen responsible for food poisoning) using Forster resonance energy transfer based two QD fluorescence. QD523 and QD601 were bioconjugated to anti‐SEB IgY antibody and SEB respectively according to carbodiimide protocol. The mutual affinity between SEB and anti‐SEB antibody was relied upon to obtain efficient energy transfer between respective QDs resulting in fluorescence quenching of QD523 and fluorescence enhancement of QD601. Presence of SEB in the range 1–0.05 µg varied the rate of fluorescence quenching of QD523, thereby demonstrating efficient use of QDs in the Forster resonance energy transfer based immunosensing method by engineering the QD size. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

7.
In the present work, an improved class of protein functionalized fluorescent 2D Ti3C2 MXene quantum dots (MXene QDs) was prepared using a hydrothermal method. Exfoliated 2D Ti3C2 sheets were used as the starting precursor and transport protein bovine serum albumin (BSA) was used to functionalize the MXene QDs. BSA-functionalized MXene QDs exhibited excellent photophysical property and stability at various physiological parameters. High-resolution transmission electron microscopy analysis showed that the BSA@MXene QDs were quasispherical in shape with a size of ~2 nm. The fluorescence intensity of BSA@MXene QDs was selectively quenched in the presence of Fe3+ ions. The mechanism of fluorescence quenching was further substantiated using time-resolved fluorescence and Stern–Volmer analysis. The sensing assay showed a linear response within the concentration range 0–150 μM of Fe3+ ions with excellent limit of detection. BSA@MXene QDs probe showed good selectivity toward ferric ions even in the presence of other potential interferences. The practical applicability of BSA@MXene QDs was further tested in real samples for Fe3+ ion quantification and the sensor had good recovery rates. The cytotoxicity studies of the BSA@MXene QDs toward the human glioblastoma cells revealed that BSA@MXene QDs are biocompatible at lower doses and showed significant cytotoxicity at higher dosages.  相似文献   

8.
An easy and effective strategy for synthesizing a ratiometric fluorescent nanosensor has been demonstrated in this work. Novel fluorescent BSA–AuNPs@Tb–AMP (BSA, bovine serum albumin; AMP, adenosine 5′‐monophosphate; AuNPs, Au nanoparticles) metal–organic framework (MOF) nanostructures were synthesized by encapsulating BSA–AuNPs into Tb–AMP MOFs for the detection of 2,6‐pyridinedicarboxylic acid (DPA) and Hg2+. DPA could strongly co‐ordinate with Tb3+ to replace water molecules from the Tb3+ center and accordingly enhanced the fluorescence of Tb–AMP MOFs. The fluorescence of BSA–AuNPs at 405 nm remained constant. While the fluorescence of BSA–AuNPs at 635 nm was quenched after Hg2+ was added, the fluorescence of Tb–AMP MOFs remained constant. Accordingly, a ratiometric fluorescence nanosensor was constructed for detection of DPA and Hg2+. The ratiometric nanosensor exhibited good selectivity to DPA over other substances. The F545/F405 linearly increased with increase of DPA concentration in the range of 50 nM to 10 μM with a detection limit as low as 17.4 nM. F635/F405 increased linearly with increase of Hg2+ concentration ranging from 50 nM to 1 μM with a detection limit as low as 20.9 nM. Additionally, the nanosensor could be successfully applied for the determination of DPA and Hg2+ in running water.  相似文献   

9.
Water dispersible zinc sulfide quantum dots (ZnS QDs) with an average diameter of 2.9 nm were synthesized in an environment friendly method using chitosan as stabilizing agent. These nanocrystals displayed characteristic absorption and emission spectra having an absorbance edge at 300 nm and emission maxima (λ emission) at 427 nm. Citrate-capped silver nanoparticles (Ag NPs) of ca. 37-nm diameter were prepared by modified Turkevich process. The fluorescence of ZnS QDs was significantly quenched in presence of Ag NPs in a concentration-dependent manner with K sv value of 9 × 109 M−1. The quenching mechanism was analyzed using Stern–Volmer plot which indicated mixed nature of quenching. Static mechanism was evident from the formation of electrostatic complex between positively charged ZnS QDs and negatively charged Ag NPs as confirmed by absorbance study. Due to excellent overlap between ZnS QDs emission and surface plasmon resonance band of Ag NPs, the role of energy transfer process as an additional quenching mechanism was investigated by time-resolved fluorescence measurements. Time-correlated single-photon counting study demonstrated decrease in average lifetime of ZnS QDs fluorescence in presence of Ag NPs. The corresponding F?rster distance for the present QD–NP pair was calculated to be 18.4 nm.  相似文献   

10.
Tm3+:LaF3 nanocrystals were synthesized with hydrothermal technique. Local‐field effect on the radiative relaxation rate was studied in the system of Tm3+:LaF3 nanocrystals immersed in several liquid media. The fluorescence lifetime was measured. It was found that the fluorescence decay presented the characteristics of second‐order exponential decay, for which the contribution from the ions inside the nanocrystal and ions at the interface of the nanocrystal were distinguished. Investigating the experimental results with proposed models, we found that the surface effect had to be eliminated. For rare earth doped LaF3 nanocrystals, real‐cavity model well explains the influence of surrounding medium on the fluorescence relaxation rate. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

11.
Cysteamine (CA)‐capped CdTe quantum dots (QDs) (CA–CdTe QDs) were prepared by the reflux method and utilized as an efficient nano‐sized fluorescent sensor to detect mercury (II) ions (Hg2+). Under optimum conditions, the fluorescence quenching effect of CA–CdTe QDs was linear at Hg2+ concentrations in the range of 6.0–450 nmol/L. The detection limit was calculated to be 4.0 nmol/L according to the 3σ IUPAC criteria. The influence of 10‐fold Pb2+, Cu2+ and Ag+ on the determination of Hg2+ was < 7% (superior to other reports based on crude QDs). Furthermore, the detection sensitivity and selectivity were much improved relative to a sensor based on the CA–CdTe QDs probe, which was prepared using a one‐pot synthetic method. This CA–CdTe QDs sensor system represents a new feasibility to improve the detection performance of a QDs sensor by changing the synthesis method. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

12.
Here we report a facile one‐pot method for the preparation of high‐quality CdSe nanocrystals (NCs) in aqueous solution under an air atmosphere. Compared with the traditional use of NaHSe or H2Se, the more stable sodium selenite is utilized as the Se source for preparing highly luminescent CdSe nanocrystals. By using mercaptosuccinic acid (MSA) as the capping agent and borate–citrate acid as the buffering solution, CdSe nanocrystals with high quantum yield (up to 70%) have been synthesized conveniently. The influence of different experimental parameters, such as the pH of the precursor solution, the molar ratio of Cd2+ to Na2SeO3 and Cd2+ to MSA on the CdSe nanocrystals, has been systematically investigated. The prepared CdSe NCs were spherical with a size of ~ 5 nm. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

13.
Mn2+‐doped CdTe quantum dots (QDs) were synthesized directly via a facile surface doping strategy in aqueous solution. The best optical property emerged when the added amount of Mn2+ was 5% compared to Cd2+ in the CdTe nanoparticles and the reaction temperature was 60 °C. The fluorescence and magnetic properties of the QDs were studied. The as‐prepared Mn2+‐doped CdTe QDs have high quantum yield (48.13%) and a narrow distribution with an average diameter of 3.7 nm. The utility of biological imaging was also studied. Depending on the high quantum yield, cells in culture were illuminated and made more distinct from each other compared to results obtained with normal QDs. They also have a prominent longitudinal relaxivity value (r1 = 4.2 mM?1s?1), which could indicate that the Mn2+‐doped CdTe QDs can be used as a potential multimodal agent for fluorescence and magnetic resonance imaging. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

14.
A novel assay for oxytetracycline hydrochloride (OTC) based on fluorescence quenching was developed from the interaction between functionalized cadmium telluride quantum dots (CdTe QDs) and OTC. Optimum conditions for the detection of OTC were found after investigating all factors. Under optimum conditions, luminescence of CdTe nanocrystals (λex = 365 nm, λem = 562 nm) was quenched by OTC in a concentration‐dependent manner best described by a modified Stern‐Volmer type equation. Good linearity was obtained with a regression coefficient of 0.9999 in the range of 1.34 ~ 13.4 x 10‐5 mol/L and a limit of detection of 3.08 x 10‐7 mol/L. In addition, the quenching mechanism was also established. The results imply that the close proximity of OTC‐CdTe was driven by electrostatic attraction and the resulting effective electron transfer from OTC to QDs could be responsible for fluorescence quenching of CdTe‐QDs. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

15.
Construction of fluorescent probes for zinc ion (Zn2+) and cadmium ion (Cd2+) is significant for the safety of humans. However, the discriminating recognition of Zn2+ and Cd2+ by a single probe remains challenging owing to their similar properties. Herein, a novel deoxycholic acid derivative containing 8-hydroxyquinoline fluorophore has been facilely synthesized through click chemistry to form a clamp-like probe. Using its perfect bonding cavity from 1,2,3-triazole and quinoline, this molecule showed favorable solvent-dependent fluorescent responses and distinguished Zn2+ and Cd2+ in different solvents. In ethanol aqueous solution, it displayed good selectivity and ratiometric fluorescence to Zn2+ with 30 nm spectroscopic red-shifts. In acetonitrile aqueous solution, it exhibited good selectivity and ratiometric fluorescence to Cd2+ with 18 nm spectroscopic red-shifts. Moreover, the unique microstructural features of the probe in assembly were used to reflect its recognition processes. Due to its merits of low detection limit and instant response time, the probe was utilized for sensing Zn2+ and Cd2+ in water, beer and urine with high accuracy. Meanwhile, this probe served as a handy tool and was employed to obtain inexpensive test strips for the prompt and semiqualitative analysis of Zn2+ and Cd2+ with the naked eye.  相似文献   

16.
In this study, we demonstrated a highly sensitive, selective, and reversible chemosensor for Hg2+ determination. This chemosensor was synthesized by direct condensation of thymin‐1‐ylacetic acid with zinc tetraaminoporphyrin, which has a porphyrin core as the fluorophore and four thymine (T) moieties as the specific interaction sites for Hg2+. The probe (4T‐ZnP) exhibited split Soret bands with a small peak at 408 nm and a strong band at 429 nm in a dimethylformamide/H2O (7/3, v/v) mixed solvent as well as a strong emission band at 614 nm. Upon the addition of Hg2+, the probe displayed strong fluorescence quenching due to the formation of T‐Hg2+‐T complexes. With the aid of the fluorescence spectrometer, the chemosensor in the dimethylformamide/H2O (7/3, v/v) mixed solvent (0.3 μM) exhibited a detection limit of 6.7 nM. Interferences from other common cations, such as Co2+, K+, Sn2+, Zn2+, Cu2+, Ni2+, Mn2+, Na+, Ca2+, Mg2+, Pb2+, and Cd2+, associated with Hg2+ analysis were effectively inhibited. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

17.
In this study, fluorescent silver nanoclusters (Ag NCs) were synthesized using denatured fish sperm DNA as the template. In contrast to other methods, this method did not use artificial DNA as the template. After their reaction with denatured fish sperm DNA, Ag+ ions were reduced by NaBH4 to form Ag NCs. The Ag NCs showed a strong fluorescence emission at 650 nm when excited at 585 nm. The fluorescence intensity increased fourfold at pH 3.78, controlled with Britton–Robinson buffer solution. The fluorescence of the Ag NCs was quenched in the presence of trace mercury ions (Hg2+) in a weakly acidic medium and nitrogen atmosphere. The extent of the fluorescence quenching of Ag NCs strongly depends on the Hg2+ ion concentration over a linear range from 2.0 nmol L?1 to 3.0 μmol L?1. The detection limit (3σ/k) for Hg2+ was 0.7 nmol L?1. Thus, a sensitive and rapid method was developed for the detection of Hg2+ ions.  相似文献   

18.
A facile method was developed for the preparation of water soluble β‐Cyclodextrin (β‐CD)‐modified CdSe quantum dots (QDs) (β‐CD‐QDs) by directly replacing the oleic acid ligands on the QDs surface with β‐CD in an alkaline aqueous solution. The as‐prepared QDs show good stability in aqueous solution for several months. Oxoanions, including phosphoric acid ion, sulphite acid ion and carbonic acid ion, affect the fluorescence of β‐CD‐QDs. Among them, H2PO4 exhibited the largest quenching effect. For the polyprotic acids (HO)3AO, the effect of acidic anions on the fluorescence of β‐CD‐QDs was in the order: monoanion (HO)2AO2 > dianion (HO)AO32– >> trianion AO43–. After photoactivation for several days in the presence of anions at alkaline pH, the β‐CD‐QDs exhibited strong fluorescence emission. The effect of various heavy and transition metal ions on the fluorescence properties of the β‐CD‐QDs was investigated further. It was found that Ag+, Hg2+ and Co2+ have significant quenching effect on the fluorescence of the β‐CD‐QDs. The Stern–Volmer quenching constants increased in the order: Hg2+ < Co2+ <Ag+. The adsorption model of metal ions on β‐CD‐QDs was explored. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

19.
In this study, CdS quantum dots (QDs) capped with mercaptosuccinic acid (MSA) were prepared in one step. The size, shape, component and spectral properties of MSA‐capped CdS QDs were characterized by transmission electron microscopy (TEM), photoluminescence (PL) and infrared (IR) spectrometry. The results showed that the prepared QDs with an average diameter of 6 nm have favorable fluorescence, which is greatly influenced by the pH of the environment. The interaction of some heavy metal ions including Ag+, Hg2+, Cu2+, Ni2+ and Co2+ with MSA‐capped CdS QDs was investigated in different buffering pH media. Based on the fluorescence quenching of the QDs in the presence of each of the metal ions, the feasibility of their determinations was examined according to the Stern–Volmer equation. The investigations showed that Hg(II) ions can be determined in the presence of many co‐existing metal ions at a buffering pH of 5. This method was satisfactorily applied to the measurement of Hg(II) ions in some environmental samples. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

20.
In this paper, based on the fluorescence of carbon quantum dots (CQDs) quenched by mercury ions (Hg2+) and the nonresponse of Hg2+ to rhodamine B fluorescence, a dual emission ratio fluorescence sensor was constructed to realize the quantitative detection of Hg2+. Under excitation at 365 nm, the fluorescence spectrum showed double emission peaks at 437 nm and 590 nm, corresponding to the fluorescence emissions of CQDs and rhodamine B, respectively. This method quantitatively detected Hg2+ based on the linear relationship between the ratio of the intensities of the two emission peaks F437/F590 and the concentration of Hg2+. The detection range was 10–70 nM, and the limit of detection (S/N = 3) was 3.3 nM. In addition, this method could also realize the qualitative and semiquantitative detection of Hg2+ according to the fluorescence colour change of the probe under ultraviolet light. After various evaluations, the method could be successfully applied to the quantitative and visual detection of Hg2+ in tap water, and demonstrated excellent selectivity, anti-interference performance, and repeatability of the method.  相似文献   

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