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1.
Polyethylene glycol (PEG) surface modified biocompatible InP/ZnS quantum dots (QDs) act as a potential alternative for conventional carcinogenic cadmium‐based quantum dots for in vivo and in vitro studies. Comprehensively, we studied the interaction between a model protein bovine serum albumin (BSA) and PEGylated toxic free InP/ZnS QDs using various spectroscopic tools such as absorption, fluorescence quenching, time resolved and synchronous fluorescence spectroscopic measurements. These studies principally show that tryptophan (Trp) residues of BSA have preferable binding affinity towards PEG‐InP/ZnS QDs surface and a blue shift in Trp fluorescence emission is a signature of conformational changes in its hydrophobic microenvironment. Photoluminescence (PL) intensity of Trp is quenched by ground state complex formation (static quenching) at room temperature. However, InP/ZnS@BSA conjugates become unstable with increasing temperature and PL intensity of Trp is quenched via dynamic quenching by PEG‐InP/ZnS QDs. Experimentally determined thermodynamic parameters for these conjugates have shown spontaneity, entropy driven and exothermic nature of bio‐conjugation. The calculated binding affinity (n ? 1, Hill coefficient) suggest that the affinity of InP/ZnS QDs for a BSA protein is not dependent on whether or not other BSA proteins are already bound to the QD surface. Energy transfer efficiency (E), Trp residue to InP/ZnS QDs distances and energy transfer rate (kT) were all obtained from FÖrster resonance energy.  相似文献   

2.
A highly sensitive fluorescence method for glycoprotein detection has been established based on fluorescence resonance energy transfer (FRET) between CuInS2 quantum dots (QDs) and rhodamine B (RB). Lectins comprise a group of proteins with unique affinities toward carbohydrate structures, so the process of FRET can occur between lectin‐coated QDs (CuInS2 QDs–Con A conjugates, acceptors) and carbohydrate‐coated RB (RB–NH2‐glu conjugates, donors). The fluorescence of lectin‐coated QDs was recovered in the presence of a glycoprotein such as glucose oxidase (GOx) and transferrin (TRF), which significantly reduced the FRET efficiency between the donor and the acceptor. Under optimal conditions, a linear correlation was established between the fluorescence intensity ratio I654/I577 and the TRF concentration over the range of 6.90 × 10‐10 to 3.45 × 10‐8 mol/L, with a detection limit of 2.5 × 10‐10 mol/L. The linear range for GOx is 3.35 × 10‐10 to 6.70 × 10‐8 mol/L, with a detection limit of 1.5 × 10‐10 mol/L. The proposed method was applied to the determination of glycoprotein in human serum and cell‐extract samples with satisfactory results. Furthermore, CuInS2 QDs–Con A conjugates are used as safe and efficient optical nanoprobes in HepG2 cell imaging. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

3.
Dudu Wu  Zhi Chen 《Luminescence》2014,29(4):307-313
Water‐soluble ZnS quantum dots (QDs) modified by mercaptoacetic acid (MPA) were used to determinate quercetin in aqueous solutions by a fluorescence spectroscopic technique. The results showed that the fluorescence of the modified ZnS QDs could be quenched by quercetin effectively in physiological buffer solution. The optimum fluorescence intensity was found to be at incubation time 10 min, pH 7.0 and temperature 25°C. Under the optimal conditions, the detection limit of quercetin was 5.71 × 10‐7 mol/L. Moreover, the quenching mechanism was discussed to be a static quenching procedure, which was proved by the quenching rate constant Kq (1.14 × 1013 L/mol/s). Copyright © 2013 John Wiley & Sons, Ltd. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

4.
Kui‐Yu Yi 《Luminescence》2016,31(4):952-957
Novel CdTe/ZnS quantum dot (QD) probes based on the quenching effect were proposed for the simple, rapid, and specific determination of ammonium in aqueous solutions. The QDs were modified using 3‐mercaptopropionic acid, and the fluorescence responses of the CdTe/ZnS QD probes to ammonium were detected through regularity quenching. The quenching levels of the CdTe/ZnS QDs and ammonium concentration showed a good linear relationship between 4.0 × 10?6 and 5.0 × 10?4 mol/L; the detection limit was 3.0 × 10?7 mol/L. Ammonium contents in synthetic explosion soil samples were measured to determine the practical applications of the QD probes and a probable quenching mechanism was described. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

5.
Water‐soluble thioglycolic acid (TGA)‐capped core/shell CdTe/CdS quantum dots (QDs) were synthesized. The interactions of rhein and emodin with TGA‐CdTe/CdS QDs were evaluated by fluorescence and ultraviolet‐visible absorption spectroscopy. Experimental results showed that the high fluorescence intensity of TGA‐CdTe/CdS QDs could be effectively quenched in the presence of rhein (or emodin) at 570 nm, which may have resulted from an electron transfer process from excited TGA‐CdTe/CdS QDs to rhein (or emodin). The quenching intensity was in proportion to the concentration of both rhein and emodin in a certain range. Under optimized conditions, the linear ranges of TGA‐CdTe/CdS QDs fluorescence intensity versus the concentration of rhein and emodin were 0.09650–60 µg/mL and 0.1175–70 µg/mL with a correlation coefficient of 0.9984 and 0.9965, respectively. The corresponding detection limits (3σ/S) of rhein and emodin were 28.9 and 35.2 ng/mL, respectively. This proposed method was applied to determine rhein and emodin in human urine samples successfully with remarkable advantages such as high sensitivity, short analysis time, low cost and easy operation. Based on this, a simple, rapid and highly sensitive method to determine rhein (or emodin) was proposed. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

6.
Core‐shell CdTe/ZnS quantum dots capped with 3‐mercaptopropionic acid (MPA) were successfully synthesized in aqueous medium by hydrothermal synthesis. These quantum dots have advantages compared to traditional quantum dots with limited biological applications, high toxicity and tendency to aggregate. The concentration of Cu2+ has a significant impact on the fluorescence intensity of quantum dots (QDs), therefore, a rapid sensitive and selective fluorescence probe has been proposed for the detection of Cu2+ in aqueous solution. Under optimal conditions, the fluorescence intensity of CdTe/ZnS QDs was linearly proportional to the concentration of Cu2+ in the range from 2.5 × 10–9 M to 17.5 × 10–7 M with the limit of 1.5 × 10–9 M and relative standard deviation of 0.23%. The quenching mechanism is static quenching with recoveries of 97.30–102.75%. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

7.
CdTe quantum dots (QDs) capped with different stabilizers, i.e. thioglycolic acid (TGA), 3‐mercaptopropionic acid (MPA) and glutathione (GSH) were investigated as fluorescent probes for the determination of Cu2+. The stabilizer was shown to play an important role in both the sensitivity and selectivity for the determination of Cu2+. TGA‐capped CdTe QDs showed the highest sensitivity, followed by the MPA and GSH‐capped CdTe QDs, respectively. The TGA‐ and MPA‐capped CdTe QDs were not selective for Cu2+ that was affected by Ag+. The GSH‐capped CdTe QDs were insensitive to Ag+ and were used to determine Cu2+ in water samples. Under optimal conditions, quenching of the fluorescence intensity (F0/F) increased linearly with the concentration of Cu2+ over a range of 0.10–4.0 µg/mL and the detection limit was 0.06 µg/mL. The developed method was successfully applied to the determination of Cu2+ in water samples. Good recoveries of 93–104%, with a relative standard deviation of < 6% demonstrated that the developed simple method was accurate and reliable. The quenching mechanisms were also described. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

8.
High luminescence quantum yield water‐soluble CdTe/ZnS core/shell quantum dots (QDs) stabilized with thioglycolic acid were synthesized. QDs were chemically coupled to fully humanized antivascular endothelial growth factor165 monoclonal antibodies to produce fluorescent probes. These probes can be used to assay the biological affinity of the antibody. The properties of QDs conjugated to an antibody were characterized by ultraviolet and visible spectrophotometry, fluorescent spectrophotometry, sodium dodecyl sulfate–polyacrylamide gel electrophoresis, transmission electron microscopy and fluorescence microscopy. Cell‐targeted imaging was performed in human breast cancer cell lines. The cytotoxicity of bare QDs and fluorescent probes was evaluated in the MCF‐7 cells with an MTT viability assay. The results proved that CdTe/ZnS QD–monoclonal antibody nanoprobes had been successfully prepared with excellent spectral properties in target detections. Surface modification by ZnS shell could mitigate the cytotoxicity of cadmium‐based QDs. The therapeutic effects of antivascular endothelial growth factor antibodies towards cultured human cancer cells were confirmed by MTT assay. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

9.
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   

10.
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   

11.
“Giant” core/shell quantum dots (g‐QDs) are a promising class of materials for future optoelectronic technologies due to their superior chemical‐ and photostability compared to bare QDs and core/thin shell QDs. However, inadequate light absorption in the visible and near‐infrared (NIR) region and frequent use of toxic heavy metals (e.g., Cd and Pb) are still major challenges for most g‐QDs (e.g., CdSe/CdS) synthesized to date. The synthesis of NIR, heavy metal‐free, Zn‐treated spherical CuInSe2/CuInS2 g‐QDs is reported using the sequential cation exchange method. These g‐QDs exhibit tunable NIR optical absorption and photoluminescence (PL) properties. Transient fluorescence spectroscopy shows prolonged lifetime with increasing shell thickness, indicating the formation of quasi type‐II band alignment, which is further confirmed by simulations. As a proof‐of‐concept, as‐synthesized g‐QDs are used to sensitize TiO2 as a photoanode in a photoelectrochemical (PEC) cell, demonstrating an efficient and stable PEC system. These results pave the way toward synthesizing NIR heavy metal‐free g‐QDs, which are very promising components of future optoelectronic technologies.  相似文献   

12.
Water‐soluble glutathione (GSH)‐capped core/shell CdTe/CdS quantum dots (QDs) were synthesized. In pH 5.4 sodium phosphate buffer medium, the interaction between GSH‐CdTe/CdS QDs and sanguinarine (SA) was investigated by spectroscopic methods, including fluorescence spectroscopy and ultraviolet‐visible absorption spectroscopy. Addition of SA to GSH‐CdTe/CdS QDs results in fluorescence quenching of GSH‐CdTe/CdS QDs. Quenching intensity was in proportion to the concentration of SA in a certain range. Investigation of the quenching mechanism, proved that the fluorescence quenching of GSH‐CdTe/CdS QDs by SA is a result of electron transfer. Based on the quenching of the fluorescence of GSH‐CdTe/CdS QDs by SA, a novel, simple, rapid and specific method for SA determination was proposed. The detection limit for SA was 3.4 ng/mL and the quantitative determination range was 0.2–40.0 µg/mL with a correlation coefficient of 0.9988. The method has been applied to the determination of SA in synthetic samples and fresh urine samples of healthy human with satisfactory results. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

13.
Water‐soluble ZnS:Mn quantum dots (QDs) were synthesized using a hydrothermal method with 3‐mercaptopropionic acid as stabilizer. The optical properties of ZnS:Mn QDs were thoroughly investigated by tuning the doping concentration of Mn2+ and the Zn/S precursor ratio, to obtain an optimal parameter for QDs with excellent fluorescence characteristics. ZnS:Mn QDs excited at only one wavelength, however, which seriously limited their further application. Here, a trace Cd ion was doped into a ZnS host, resulting in QD excitation covering a wide adjustable waveband. Furthermore, when a ZnS shell was coated onto the surface of the ZnCdS:Mn QDs, photoluminescence intensity and stability were further enhanced. After coupling with an anti‐CK 19 antibody, the ZnCdS:Mn/ZnS core/shell QDs were able to function by labeling cancer cells, indicating that they could be considered as a suitable bio‐probe for cells and tissue imaging.  相似文献   

14.
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   

15.
In this study, a high fluorescence sensitivity and selectivity, molecularly imprinted nanofluorescent polymer sensor (MIP@SiO2@QDs) was prepared using a reverse microemulsion method. 2,4,6‐Trichlorophenol (2,4,6‐TCP) was detected using fluorescence quenching. Tetraethyl orthosilicate (TEOS), quantum dots (QDs) and 3‐aminopropyltriethoxysilane (APTS) were used as cross‐linker, signal sources and functional monomer respectively. The sensor (MIP@SiO2@QDs) and the non‐imprinted polymer sensor (NIP@SiO2@QDs) were characterized using infra‐red (IR) analysis, X‐ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The selectivity of MIP@SiO2@QDs was examined by comparing 2,4,6‐TCP with other similar functional substances including 2,4‐dichlorophenol (2,4‐DCP), 2,6‐dichlorophenol (2,6‐DCP) and 4‐chlorophenol (4‐CP). Results showed that MIP@SiO2@QDs had better selectivity for 2,4,6‐TCP than the other compounds. Fluorescence quenching efficiency displayed a good linear response at the 2,4,6‐TCP concentration range 5–1000 μmol/L. The limit of detection (LOD) was 0.9 μmol/L (3σ, n = 9). This method was equally applicable for testing actual samples with a recovery rate of 98.0–105.8%. The sensor had advantages of simple pretreatment, good sensitivity and selectivity, and wide linear range and could be applied for the rapid detection of 2,4,6‐TCP in actual samples.  相似文献   

16.
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   

17.
Significant quenching of fluorescence from CdSe/ZnS nanocrystal quantum dots (QDs) coated with mercaptoundecanoic ligands has been realized by copper nanoparticles (NPs). (a) Static quenching in the electrostatic association between the CdSe/ZnS QDs and cetyltrimethylammonium bromide-coated Cu NPs and (b) dynamic quenching of the same nanocrystals by polyvinylpyrrolidone-coated Cu NPs were studied. In both cases, the quenching of fluorescence from the CdSe/ZnS nanocrystals is sensitive to nanomolar concentrations of the copper NPs, and the quenching efficiency increases as spectral overlap between the CdSe/ZnS emission and the copper nanoparticle absorption increases. This suggests that the observed quenching is a result of energy transfer processes. These findings open new avenues for the utilization of Cu NPs in energy transfer-based applications.  相似文献   

18.
With high theoretical energy density, rechargeable metal–gas batteries (e.g., Li–CO2 battery) are considered as one of the most promising energy storage devices. However, their practical applications are hindered by the sluggish reaction kinetics and discharge product accumulation during battery cycling. Currently, the solutions focus on exploration of new catalysts while the thorough understanding of their underlying mechanisms is often ignored. Herein, the interfacial electronic interaction within rationally designed catalysts, ZnS quantum dots/nitrogen‐doped reduced graphene oxide (ZnS QDs/N‐rGO) heterostructures, and their effects on transformation and deposition of discharge products in the Li–CO2 battery are revealed. In this work, the interfacial interaction can both enhance the catalytic activities of ZnS QDs/N‐rGO heterostructures and induce the nucleation of discharge products to form a homogeneous Li2CO3/C film with excellent electronic transmission and high electrochemical activities. When the batteries cycle within a cutoff specific capacity of 1000 mAh g?1 at a current density of 400 mA g?1, the cycling performance of the Li–CO2 battery using a ZnS QDs/N‐rGO cathode is over 3 and 9 times than those coupled with a ZnS nanosheets (NST)/N‐rGO cathode and a N‐rGO cathode, respectively. This work provides comprehensive understandings on designing catalysts for Li–CO2 batteries as well as other rechargeable metal–gas batteries.  相似文献   

19.
Development of the fluorescent pH detection method is promising due to the sensitivity, easy operation, and low‐cost, etc. However, traditional organic fluorophores have still some disadvantages such as the tedious preparation and purification as well as low photostability and water solubility, which limits the rapid detection application. Semiconductor quantum dots (QDs) have recently risen to prominence as an alternative for organic fluorophores in fluorescence analysis by virtue of their convenient synthesis and superior optical properties. In this study, we report on sodium 4‐mercaptophenolate functionalized CdSe/ZnS QDs (denoted as ?OPhS‐QDs), which can serve as a selective “on–off” fluorescence probe for aqueous media pH. ?OPhS‐QDs exhibit strong fluorescence in near neutral medium. As a Lewis organic base, ?OPhS‐ moieties on QDs surface easily binds to proton under acidic conditions to yield 4‐mercaptophenol capped QDs (i.e. HOPhS‐QDs), which acts as an efficient hole trapper. As a result, the QDs photoluminescence (PL) is switched off. Under optimal conditions, the present probe exhibits a good linear relationship between fluorescence response and pH values in the pH range 3.0–5.2. Furthermore, the present probe exhibits a high selectivity for proton over other common cations and has been successfully used for pH detection in real water samples.  相似文献   

20.
Ning Liu  Ping Yang 《Luminescence》2014,29(6):566-572
Hybrid SiO2‐coated CdTe/CdSe quantum dots (QDs) were prepared using CdTe/CdSe QDs prepared by hydrothermal synthesis. A CdSe interlayer made CdTe/CdSe cores with unique type II heterostructures. The hybrid SiO2‐coated CdTe/CdSe QDs revealed excellent photoluminescence (PL) properties compared with hybrid SiO2‐coated CdTe QDs. Because of the existence of spatial separations of carriers in the type II CdTe/CdSe core/shell QDs, the hybrid QDs had a relatively extended PL lifetime and high stability in phosphate‐buffered saline buffer solutions. This is ascribed to the unique components and stable surface state of hybrid SiO2‐coated CdTe/CdSe QDs. During the stabilization test in phosphate‐buffered saline buffer solutions, both static and dynamic quenching occurred. The quenching mechanism of the hybrid QDs was not suited with the Stern–Volmer equation. However, the relative stable surface of CdTe/CdSe QDs resulted in lower degradation and relative high PL quantum yields compared with hybrid SiO2‐coated CdTe QDs. As a result, hybrid SiO2‐coated CdTe/CdSe QDs can be used in bioapplications. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

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