Abstract:Hybrid systems consisting of core/shell semiconductor quantum dots (QDs) and organic rylene dyes have been prepared and characterized. Complex formation is mediated by bidentate carboxylate moieties covalently linked to the dye molecules. The complexes were very stable with respect to time (at least months), dilution (sub nM), and precipitation. After preparation in organic solvent, complexes could be easily transferred into water. The strong quenching of QD emission by the dye molecules (transfer efficiencies… Show more
“…Yet, in some recent reports QD have been successfully utilized as acceptors in conjugation with naphthalimide dyes 39 as well as with light harvesting complexes of the photosynthetic apparatus. 40 Although in many cases the energy transfer from the photoexcited QD to a suitable acceptor can be described in the framework of the Forster mechanism, 25,26,41,42 deviations have been reported in the literature. 43,44 For example, the results of time-resolved single particle experiments on QD−perylene bisimide assemblies have been explained by FRET and non-FRET processes.…”
Section: ■ Introductionmentioning
confidence: 99%
“…45 Recently, rylene diimides have proven their potential for use as suitable acceptor dyes in dye−QD conjugates. 42,44,46 In this context, we have established a route for the preparation of very stable dye−QD complexes by furnishing rylene diimides with dicarboxylate anchors. 42 Here, we use a perylene diimide derivative (PDI) which is attached to CdSe/1 ML CdS/3 ML ZnS multishell particles.…”
The dynamics of the photoinduced Forster resonance energy transfer (FRET) in a perylene diimide−quantum dot organic−inorganic hybrid system has been investigated by femtosecond time-resolved absorption spectroscopy. The bidentate binding of the dye acceptor molecules to the surface of CdSe/CdS/ZnS multishell quantum dots provides a well-defined dye-QD geometry for which the efficiency of the energy transfer reaction can be easily tuned by the acceptor concentration. In the experiments, the spectral characteristics of the chosen FRET pair facilitate a selective photoexcitation of the quantum dot donor. Moreover, the acceptor related transient absorption change that occurs solely after energy transfer is utilized for the determination of the energy transfer dynamics. Our time-resolved measurements demonstrate that an increase of the acceptor concentration accelerates the donor−acceptor energy transfer. Considering a Poisson distribution of acceptor molecules per quantum dot, the dependence of the energy transfer rate on its mean value is linear. The results of the presented spectroscopic experiments allow for determining the relative and absolute acceptor/donor ratio in the investigated FRET system without any parameters intrinsic to Forster theory.
■ INTRODUCTIONSemiconductor quantum dots (QD) are nanometer sized luminescent particles with remarkable optical properties. Since the QD dimension is in the range of the Bohr exciton radius, the electronic transition energies become size dependent which leads to a tunability of the absorption and emission properties. 1 QD have received broad and multidisciplinary research interest which ranges from the elucidation of their fundamental photophysical properties such as blinking, 2−5 homogeneous line width, 6−8 and exciton relaxation dynamics 9−12 to the implementation as light absorbers or emitters in photovoltaic devices, 13−16 LEDs, 17−19 and lasers. 20−22 The reduced size of QD inevitably leads to a high surface to volume ratio and consequently to a strong impact of the surface composition on the QD properties. The QD fluorescence quantum yield can be significantly increased by growing an inorganic shell on the core nanoparticles. The stronger fluorescence of core/shell particles is explained by the saturation of surface associated trap states, and fluorescence quantum yields as high as 85% have been observed. 23,24 High photostability together with strong and narrow emission has motivated the application of QD in biological sensing 25−29 and imaging. 30,31 Sensing applications are typically based on the modulation of the QD emission as response to the presence of a target molecule. 28 The modulation can be achieved by quenching mechanisms such as Forster resonance energy transfer (FRET) 25−28,32,33 or charge transfer (CT). 34−38 In QD-based FRET systems the inorganic nanoparticles are predominantly applied as energy donors. Yet, in some recent reports QD have been successfully utilized as acceptors in conjugation with naphthalimide dyes 39 as well as with light harves...
“…Yet, in some recent reports QD have been successfully utilized as acceptors in conjugation with naphthalimide dyes 39 as well as with light harvesting complexes of the photosynthetic apparatus. 40 Although in many cases the energy transfer from the photoexcited QD to a suitable acceptor can be described in the framework of the Forster mechanism, 25,26,41,42 deviations have been reported in the literature. 43,44 For example, the results of time-resolved single particle experiments on QD−perylene bisimide assemblies have been explained by FRET and non-FRET processes.…”
Section: ■ Introductionmentioning
confidence: 99%
“…45 Recently, rylene diimides have proven their potential for use as suitable acceptor dyes in dye−QD conjugates. 42,44,46 In this context, we have established a route for the preparation of very stable dye−QD complexes by furnishing rylene diimides with dicarboxylate anchors. 42 Here, we use a perylene diimide derivative (PDI) which is attached to CdSe/1 ML CdS/3 ML ZnS multishell particles.…”
The dynamics of the photoinduced Forster resonance energy transfer (FRET) in a perylene diimide−quantum dot organic−inorganic hybrid system has been investigated by femtosecond time-resolved absorption spectroscopy. The bidentate binding of the dye acceptor molecules to the surface of CdSe/CdS/ZnS multishell quantum dots provides a well-defined dye-QD geometry for which the efficiency of the energy transfer reaction can be easily tuned by the acceptor concentration. In the experiments, the spectral characteristics of the chosen FRET pair facilitate a selective photoexcitation of the quantum dot donor. Moreover, the acceptor related transient absorption change that occurs solely after energy transfer is utilized for the determination of the energy transfer dynamics. Our time-resolved measurements demonstrate that an increase of the acceptor concentration accelerates the donor−acceptor energy transfer. Considering a Poisson distribution of acceptor molecules per quantum dot, the dependence of the energy transfer rate on its mean value is linear. The results of the presented spectroscopic experiments allow for determining the relative and absolute acceptor/donor ratio in the investigated FRET system without any parameters intrinsic to Forster theory.
■ INTRODUCTIONSemiconductor quantum dots (QD) are nanometer sized luminescent particles with remarkable optical properties. Since the QD dimension is in the range of the Bohr exciton radius, the electronic transition energies become size dependent which leads to a tunability of the absorption and emission properties. 1 QD have received broad and multidisciplinary research interest which ranges from the elucidation of their fundamental photophysical properties such as blinking, 2−5 homogeneous line width, 6−8 and exciton relaxation dynamics 9−12 to the implementation as light absorbers or emitters in photovoltaic devices, 13−16 LEDs, 17−19 and lasers. 20−22 The reduced size of QD inevitably leads to a high surface to volume ratio and consequently to a strong impact of the surface composition on the QD properties. The QD fluorescence quantum yield can be significantly increased by growing an inorganic shell on the core nanoparticles. The stronger fluorescence of core/shell particles is explained by the saturation of surface associated trap states, and fluorescence quantum yields as high as 85% have been observed. 23,24 High photostability together with strong and narrow emission has motivated the application of QD in biological sensing 25−29 and imaging. 30,31 Sensing applications are typically based on the modulation of the QD emission as response to the presence of a target molecule. 28 The modulation can be achieved by quenching mechanisms such as Forster resonance energy transfer (FRET) 25−28,32,33 or charge transfer (CT). 34−38 In QD-based FRET systems the inorganic nanoparticles are predominantly applied as energy donors. Yet, in some recent reports QD have been successfully utilized as acceptors in conjugation with naphthalimide dyes 39 as well as with light harves...
“…[29][30][31][32][33] For metallic-carrier NPs, the emission of the (ion-sensitive) fluorophore can be quenched, when the fluorophore comes close to the metal surface. [34][35][36][37][38] In either case the fluorescence is influenced by the distance between the NP and the ion-sensitive fluorophore.…”
Ion sensors based on colloidal nanoparticles (NPs), either as actively ion-sensing NPs or as nanoscale carrier systems for organic ion-sensing fluorescent chelators typically require a charged surface in order to be colloidally stable. We demonstrate that this surface charge significantly impacts the ion binding and affects the read-out. Sensor read-out should be thus not determined by the bulk ion concentration, but by the local ion concentration in the nano-environment of the NP surface. We present a conclusive model corroborated by experimental data that reproduces the strong distance-dependence of the effect. The experimental data are based on the capability of tuning the distance of a pH-sensitive fluorophore to the surface of NPs in the nanometer (nm) range. This in turn allows for modification of the effective acid dissociation constant value (its logarithmic form, pK(a)) of analyte-sensitive fluorophores by tuning their distance to the underlying colloidal NPs.
“…There are reports found for the binding of thiol and carboxyl groups on the surface of QDs [16,17,27,28]. So in order to check the presence of functional groups and binding nature of QDs with capping agents, we have done the FT-IR analysis (Fig.…”
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