Luminescence and stability of aqueous thioalkyl acid capped CdSe/ZnS quantum dots correlated to ligand ionization.

The spectroscopic properties of CdSe/ZnS quantum dots (QDs) were observed to change as a function of thioalkyl acid ligand. Experiments were performed using 2, 3, 6, and 11-carbon linear thioalkyl acids, as well as mercaptosuccinic acid (MSA) and dihydrolipoic acid (DHLA). Bathochromic shifts of up to 14 nm in the emission spectra of QDs capped with these ligands were observed. Similarly, hypsochromic or bathochromic shifts up to 7 nm were observed for a specific ligand in acidic or basic solution, respectively. These shifts could be correlated to the number of ionized ligands and the ability of the ligands to act as hole acceptors. It was also found that differences in quantum yield between the ligands were primarily due to variations in radiative decay rate and not nonradiative decay rate. This indicated that different degrees of QD surface passivation were not responsible for the differences, and that the radiative system must be considered as the sum of the ligands and the QD nanocrystal. The stability of QDs capped with mercaptoacetic acid, MSA, and DHLA towards aggregation at low pH was found to correlate with the pK(a) of the ligands. Spectral shifts were also observed during aggregation. Overall, the luminescence of thioalkyl acid capped QDs appears to be a complex function of dielectric constant, electrostatic or hole-acceptor interactions with ionized ligands, and, to a lesser extent, passivation.     

Tuning Optical Properties of Si Quantum Dots by π‐Conjugated Capping Molecules

The absorption and photoluminescence (PL) properties of silicon quantum dots (QDs) are greatly influenced by their size and surface chemistry. Herein, we examined the optical properties of three Si QDs with increasing σ–π conjugation length: octyl‐, (trimethylsilyl)vinyl‐, and 2‐phenylvinyl‐capped Si QDs. The PL photon energy obtained from as‐prepared samples decreased by 0.1–0.3 eV, while the PL excitation (PLE) extended from 360 nm (octyl‐capped Si QDs) to 400 nm (2‐phenylvinyl‐capped Si QDs). A vibrational PL feature was observed in all samples with an energy separation of about 0.192±0.013 eV, which was explained based on electron–phonon coupling. After soft oxidization through drying, all samples showed blue PL with maxima at approximately 410 nm. A similar high‐energy peak was observed with the bare Si QD sample. The changes in the optical properties of Si QDs were mainly explained by the formation of additional states arising from the strong σ–π conjugation and QD oxidation.     

The photophysical studies of a mixture of CdTe quantum dots and negatively charged zinc phthalocyanines

Fluorescence resonance energy transfer (FRET) studies were carried out with quantum dots capped with thioglycolic acid (TGA) and 2-mercaptoethanol (2-ME) and negatively charged phthalocyanines {Zn tetracarboxy (ZnTCPc), Zn octacarboxy (ZnOCPc) and Zn tetrasulfo (ZnTSPc) phthalocyinines} in a 0.1 NaOH:EtOH (50:50) solvent mixture. The best overlap between emission spectra of the donor (QDs) and the absorption spectra of the acceptor (ZnPc derivatives) was observed for TGA capped QDs, very little overlap was obtained for 2-ME QDs. ZnTSPc gave the highest FRET efficiency (0.3), with ZnOCPc and ZnTCPc giving a FRET efficiency of 0.2. The Φ_T values of the MPcs generally decreased in the presence of the QD whereas the triplet lifetimes (τ_T) of the ZnPc derivatives were higher in the presence of QDs.     

Reversible surface electronic traps in PbS quantum dot solids induced by an order-disorder phase transition in capping molecules

The electronic properties of semiconductor quantum dots (QDs) are critically dependent on the nature of the ligand molecules on their surfaces. Here we show the reversible formation of surface electronic trap states in the model system of solid thin films of PbS QDs capped with thiol molecules. As the temperature was increased from cryogenic to room temperature, we discovered a phase transition in the fluorescence spectra from excitonic emission to trap emission. The critical temperature (T(c)) of the phase transition scales with molecular length and in each case is close to the bulk melting temperature of the capping molecules. We conclude that an order-disorder transition in the molecular monolayer above T(c) introduces surface mobility and the formation of a disordered atomic lead layer at the QD/capping molecule interface, leading to electronic trap formation.     

Characterization of quantum dot bioconjugates by capillary electrophoresis with laser-induced fluorescent detection

In this paper, we present a universal, highly efficient and sensitive method for the characterization of quantum dot (QD) bioconjugates based on capillary electrophoresis with laser-induced fluorescent (LIF) detection. We first prepared CdTe QDs in aqueous phase by a chemical route with mercaptopropionic acid as a ligand, and then were coupled to certain proteins using bifunctional linkage reagent or electrostatic attraction. The QD bioconjugates were characterized by capillary electrophoresis with LIF detection. We found that QD bioconjugates were efficiently separated with free QDs by the optimization of buffer pH. Furthermore, we found that ultrafiltration was an effective and simple approach to purify QD conjugates with bovine serum albumin (BSA). Due to their broad absorption spectra and size dependent emission wavelength tunability, QDs can be excited to emit different colour fluorescence using a single wavelength laser source, and therefore, we believe that CE with LIF detection will become a universal and efficient tool for the characterization of QD bioconjugates.     

Facile synthesis of fluorescent quantum dot‐polymer nanocomposites via frontal polymerization

We report an available approach for quickly fabricating CdS QD‐polymer nanocomposites via frontal polymerization (FP). First, we synthesized (3‐mercaptopropyl)‐1‐trimethoxysilane (MPS)‐capped CdS quantum dots (QDs). With these MPS‐capped CdS QDs containing mercapto groups, MPS‐capped CdS QDs can be easily incorporated into a poly(N‐methylolacrylamide) (PNMA) matrix via FP. A variety of features for preparing QD‐polymer nanocomposites, such as initiator concentration and CdS concentration, were thoroughly investigated. The fluorescence properties of QD‐polymer nanocomposites prepared via FP are comparatively investigated on the basis of ultraviolet–visible (UV–vis) spectra and photoluminescence (PL) spectra. Results show that the PL intensity of QD‐polymer nanocomposites prepared via the FP method is superior to that obtained by the traditional batch polymerization (BP) method. In addition, by measuring the changes of PL intensity of the samples immersed in different concentrations of copper acetate solution, we found the QD‐polymer nanocomposites can be ultrasensitive to copper ions. This FP process can be exploited as a facile and rapid way for synthesis QD‐polymer nanocomposites on a large scale, avoiding the fluorescence quenching of nanocrystals during incorporation nanocrystals into polymer matrices. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2170–2177, 2010     

Self‐Assembled Luminescent Quantum Dots To Generate Full‐Color and White Circularly Polarized Light

The design and fabrication of quantum dots (QDs) with circularly polarized luminescence (CPL) has been a great challenge in developing chiroptical materials. We herein propose an alternative to the use of chiral capping reagents on QDs for the fabrication of CPL‐active QDs that is based on the supramolecular self‐assembly of achiral QDs with chiral gelators. Full‐color‐tunable CPL‐active QDs were obtained by simple mixing or gelation of a chiral gelator and achiral 3‐mercaptopropionic acid capped QDs. In addition, the handedness of the CPL can be controlled by the supramolecular chirality of the gels. Moreover, QDs with circularly polarized white light emission were fabricated for the first time by tuning the blending ratio of colorful QDs in the gel. The chirality transfer in the co‐assembly of the achiral QDs with the gelator and the spacer effect of the capping reagents on the QD surface are also discussed. This work provides new insight into the design of functional chiroptical materials.     

Synchrotron X-ray 2D and 3D elemental imaging of CdSe/ZnS quantum dot nanoparticles in Daphnia magna

The potential toxicity of nanoparticles to aquatic organisms is of interest given that increased commercialization will inevitably lead to some instances of inadvertent environmental exposures. Cadmium selenide quantum dots (QDs) capped with zinc sulfide are used in the semiconductor industry and in cellular imaging. Their small size (<10 nm) suggests that they may be readily assimilated by exposed organisms. We exposed Daphnia magna to both red and green QDs and used synchrotron X-ray fluorescence to study the distribution of Zn and Se in the organism over a time period of 36 h. The QDs appeared to be confined to the gut, and there was no evidence of further assimilation into the organism. Zinc and Se fluorescence signals were highly correlated, suggesting that the QDs had not dissolved to any extent. There was no apparent difference between red or green QDs, i.e., there was no effect of QD size. 3D tomography confirmed that the QDs were exclusively in the gut area of the organism. It is possible that the QDs aggregated and were therefore too large to cross the gut wall.     

Multidentate surface ligand exchange for the immobilization of CdSe/ZnS quantum dots and surface quantum dot-oligonucleotide conjugates

A method for synthesizing multidentate thiol ligands on fused silica surfaces (e.g., optical fibers) was developed for the immobilization of CdSe/ZnS quantum dots (QDs) capped with hydrophilic or hydrophobic ligands. This work was motivated by the poor stability of QDs immobilized via monodentate thiol ligands and the need for stable immobilization strategies in the development of sensor technologies based on QDs. Multi-dentate immobilization was able to withstand washing protocols, and surface ligand exchange occurred via self-assembly through the zinc-metal affinity interaction. Atomic force and scanning electron microscopy images suggested that the QDs were immobilized at high density, approximately 2-4 x 10 (13) cm (-2). It was possible to immobilize one, two, or three colors of QD. Upon immobilization, 1-2 nm bathochromic shifts in the PL spectra were observed. This was attributed to both ligand exchange and the change in local environment. The change in environment was accompanied by a decrease in PL lifetime. Self-assembly of immobilized QD-oligonucleotide and QD-avidin conjugates was also demonstrated. These conjugates were able to hybridize with complementary oligonucleotide and bind biotin, respectively. This versatile immobilization chemistry is an important step in the development of surface-based QD nanosensors. Such technology requires QDs to be immobilized such that they remain accessible to target molecules in solution.     

Reduced ionic contaminations in CdSe quantum dot dispersed ferroelectric liquid crystal and its applications

Octadecylamine capped cadmium selenide quantum dots (CdSe QDs) were dispersed in the ferroelectric liquid crystal (FLC) FELIX 16/100. The QD dispersed FLC system was investigated on the planar anchored cell. Addition of specific concentration of the QDs in the pure FLC induces a new relaxation mode along with the Goldstone relaxation mode. QDs assisted quantum fluctuations are probably responsible for the existence of this new relaxation mode in the QDs dispersed FLC system. The ionic contaminations associated with the FLC materials were trapped on the surface of QDs due to the ion-trapping character of QDs. The trapping of ionic contaminations was confirmed by the a.c. conductivity measurement. The physical properties of the pure and dispersed FLC were carried out as a function of doping concentration of QDs, temperature and frequency.     

Gold nanoparticle-quantum dot-polystyrene microspheres as fluorescence resonance energy transfer probes for bioassays

The paper describes the development of highly sensitive particle-based fluorescence resonance energy transfer (FRET) probes that do not use molecular fluorophores as donors and acceptors. In these probes, CdSe/ZnS luminescent quantum dots (QDs) were capped with multiple histidine-containing peptides to increase their aqueous solubility while maintaining their high emission quantum yield and spectral properties. The peptide-modified QDs (QD-His) were covalently attached to carboxyl-modified polystyrene (PS) microspheres to form highly emitting PS microspheres (QD-PS). Gold nanoparticles (AuNPs) were then covalently attached to the QD-PS surface to form AuNP-QD-PS composite microspheres that were used as FRET probes. Attachment of AuNPs to QD-PS completely quenched the QD emission through FRET interactions. The emission of QD-PS was restored when the AuNPs were removed from the surface by thiol ligand displacement. The new AuNP-QD-PS FRET platform is simple to prepare and highly stable, and it opens many new possibilities for carrying out FRET assays on microparticle-based platforms and in microarrays. The versatility of these assays could be greatly increased by replacing the linkers between the QDs and AuNPs with ones that selectively respond to specific cleaving agents or enzymes.     

l-Cysteine-induced photoluminescence enhancement of CdSe/ZnSe quantum dots in aqueous solution

l-Cysteine molecules dramatically enhance the photoluminescence of colloidal CdSe/ZnSe quantum dots (i.e., ^CTAB/TOPOQD). Based on our spectroscopic studies of temporal variations in QD quantum yields as well as the in situ infrared spectral features of QDs, we propose that adsorption and rearrangement of l-cysteine molecules at the QD–water interface induces the observed unusual enhancement of the photoluminescence quantum yield. Upon addition of l-cysteine to the ^CTAB/TOPOQD solution, the adsorption of l-cysteine to the ^CTAB/TOPOQD colloidal particles is driven by the formation of a kinetically favorable intermediate species, which is formed by the coordination of thiol groups to the QD surface Cd atoms. The above species then reacts further to form a thermodynamically stable QD species, which probably involves coordination of both the amine and thiol groups of l-cysteine on the QD surface. Additional comparison studies using ^MPAQD and other small ligands (i.e., l-alanine, l-serine, and MPA) confirmed our proposed mechanism of l-cysteine adsorption at the ^CTAB/TOPOQD–water interfaces. In addition to these adsorption structures, we also propose that the dramatic enhancement of QY observed in this study is probably induced by the rearrangement and structural organization of l-cysteine and CTAB molecules at the QD–water interface, which improves the homogeneity and self-organization of the interfacial molecules.     

Hybrid gold/silica/nanocrystal-quantum-dot superstructures: synthesis and analysis of semiconductor-metal interactions

We report on the synthesis and spectroscopic characterization of well-defined hybrid structures that consist of a gold core overcoated with a silica shell, followed by a dense monolayer of CdSe nanocrystal quantum dots (QDs). The dielectric silica spacer of a controlled thickness provides a simple means for tuning interactions between the QD emitters and the metal core. To illustrate this tunability, we demonstrate switching between QD emission quenching and enhancement by varying the silica shell thickness. Synthetic procedures developed here employ a final step of self-assembly of QDs onto the silica shell performed via simple titration of the QD solution with prefabricated core/shell Au/SiO2 particles. This approach allows us to perform an accurate quantitative analysis of the effect of the metal on the QD emission intensity. One important result of this analysis is that nonuniformity of nonradiative rates across the QD ensemble has a significant effect on both the magnitude and the shell-thickness dependence of the emission enhancement/quenching factors.     

Luminescence temperature antiquenching of water-soluble CdTe quantum dots: role of the solvent

Luminescence temperature antiquenching (LTAQ) is observed for water-soluble CdTe quantum dots (QDs) capped with aminoethanethiol (AET). The efficient exciton emission (quantum efficiency of approximately 40% at 300 K) is quenched almost completely as the QD solutions are cooled to below 230 K and is fully recovered around 270 K upon warming up to room temperature (LTAQ). Temperature-dependent lifetime measurements show that the quenching rate is high, resulting in an on/off behavior. No LTAQ is observed for CdTe QDs capped with aminoundecanethiol (AUT). The LTAQ is explained by the influence of solvent freezing on the surface of the QD core. Freezing of the solvation water molecules surrounding the QD will induce strain in the capping shell, due to the interaction between water and the charged heads of the capping molecules. Short carbon chains (AET) will propagate the strain to the QD surface, creating surface quenching states, whereas long and flexible chains (AUT) will dissipate the strain, thus avoiding surface distortion. Freezing-point depression by the addition of methanol results in a lowering of the transition temperature. Additional support is provided by the size dependence of the LTAQ: smaller particles, with higher local ionic strength due to a higher density of charged NH(3)(+) surface groups, experience a lower transition temperature due to stronger local freezing-point depression.     

Detection of DNA Hybridization via Fluorescence Intensity Variations of ZnSe-DNA Quantum Dot Biosensors

ZnSe quantum dots (QDs) that were capped with 11-mercaptoundecanoic acid (MUA) and conjugated to amino-modified ssDNA molecules exhibited variations in fluorescence emission intensity upon hybridization with complementary ssDNA in solution, a phenomenon that can be exploited for rapid detection of free ssDNA sequences. Conjugation of MUA-capped ZnSe QDs to amino-modified ssDNA molecules resulted in increased fluorescence emission intensity and stability at room temperature. Increasing the length of the ssDNA, that was conjugated to the QDs, resulted in increased fluorescence emission intensity up to a length of about 50 nucleotide bases, beyond which the peak emission intensity reached a plateau. Hybridization of QD-ssDNA conjugates with complementary ssDNA, either in free form or bound to QDs from the same population, resulted in additional fluorescence emission intensity amplification. A small red shift was observed when three-dimensional QD-dsDNA-QD structures were formed. The QD-ssDNA sensors with single ssDNA molecule per QD were developed and used for rapid quantitative detection of fully or partially complementary free ssDNA sequences in aqueous solution. Partial hybridization of the QD-ssDNA sensors with short ssDNA targets resulted in smaller QD emission intensity amplification, when compared to full hybridization. A QD-ssDNA sensor containing a sequence corresponding to the hemoglobin beta gene was used to detect and discriminate between free ssDNA targets consisting of a complementary ssDNA sequence and targets containing a single-base mutation that can cause sickle-cell anemia. Such QD-based biosensors can form the basis for rapid separation-free assays that can be used to detect target biomolecules in solution.     

高量子产率水溶性CdTe量子点的制备与表征

以巯基乙酸(HSCH2 COOH,TGA)为稳定剂,在水相中合成高量子产率CdTe量子点(QDs),产率达68%.用紫外.可见分光光度计、荧光分光光度计、红外光谱仪、透射电子显微镜等对制备的样品进行表征.结果表明:CdTe Ods紫外吸收峰及荧光发射峰均随回流时间延长而红移,即粒径在不断增大;荧光发射峰窄而对称,表明QDs分散性好、大小较均一,半峰宽随回流时间延长而逐渐变宽,表明粒径在增大的同时粒径分布范围也变宽;从TEM及紫外.可见光谱推算,可知其粒径约为3 nm;红外光谱图说明作为稳定剂的巯基乙酸对QDs表面起到修饰作用.     

Enhancing the stability and biological functionalities of quantum dots via compact multifunctional ligands

We have designed and synthesized a series of modular ligands based on poly(ethylene glycol) (PEG) coupled with functional terminal groups to promote water-solubility and biocompatibility of quantum dots (QDs). Each ligand is comprised of three modules: a PEG single chain to promote hydrophilicity, a dihydrolipoic acid (DHLA) unit connected to one end of the PEG chain for strong anchoring onto the QD surface, and a potential biological functional group (biotin, carboxyl, and amine) at the other end of the PEG. Water-soluble QDs capped with these functional ligands were prepared via cap exchange with the native hydrophobic caps. Homogeneous QD solutions that are stable over extended periods of time and over a broad pH range were prepared. Surface binding assays and cellular internalization and imaging showed that QDs capped with DHLA-PEG-biotin strongly interacted with either NeutrAvidin immobilized on surfaces or streptavidin coupled to proteins which were subsequently taken up by live cells. EDC coupling in aqueous buffer solutions was also demonstrated using resonance energy transfer between DHLA-PEG-COOH-functionalized QDs and an amine-terminated dye. The new functional surface ligands described here provide not only stable and highly water-soluble QDs but also simple and easy access to various biological entities.     

Temperature-dependent energy transfer in cadmium telluride quantum dot solids

Efficiently luminescing colloidal CdTe quantum dots (QDs) were used for the preparation of monodispersed and mixed size QD solids. Luminescence spectra and decay times of the QD emission were measured as a function of temperature to study energy transfer (ET) processes in the QD solids. In the luminescence decay curves of the emission of the largest QDs (acceptors), a rise time of the luminescence signal is observed due to energy transfer from smaller QDs. Both the rise time (a measure for the energy transfer rate) and the luminescence decay time lengthen upon cooling. This is explained by the decreased dipole strength of the excitonic emission of the QDs in the solid due to the presence of a singlet and a lower lying triplet level. Studies of energy transfer in heteronuclear QD solids reveal that single-step ET dominates.     

A quantum dot-lucigenin probe for Cl-

In this work, the first chloride ion sensor based on QD-lucigenin nanoparticles is reported. The mechanism uses the ability of semiconductor QDs to engage in short range exchange processes, leading to fluorescence changes. An acridinium dication (lucigenin) which is an electron acceptor, was self-assembled on the surface of negative charged QDs (capped with mercaptopropionic acid). Mutual quenching of the lucigenin and QD were observed. From a sphere of action, Perrin-type model, exchange was estimated to occur over a range of the order of 2 nm. The possibility of spin-orbit coupling (SOC) or electron transfer between the QD and the lucigenin dication (Luc(2+)) is discussed. The radical cation Luc(+*) was not identified, but electron transfer from the QD conduction band to the Luc(2+), then electron transfer back, from the Luc(+*) to the QD valence band, could lead to mutual quenching, without build up of Luc(+*) . SOC between the QD and lucigenin, with or without charge transfer being involved, can also account for the results obtained. Lucigenin is also a chloride-sensitive indicator dye, with a sensing mechanism based on SOC. In the QD-MPA-lucigenin conjugate luminescence is restored by adding chloride ion. Thus, the presence of chloride is transduced into an enhancement of the luminescence of QDs. Using this operating principle, a chloride ion sensor based on CdSe-ZnS core-shell QD nanoparticles, showed a very good linearity in the range 1-250 mM, with a detection limit 0.29 mM and a RSD of 2.5% (n = 10). In a study of interferences, the chloride sensitive QDs showed good selectivity to most of the other anions tested. The versatility of the system was also demonstrated in terms of fluorescent emission wavelength, which could be selected across a wide range through choice of QDs. Examples are shown for lambda(max) = 500, 540 and 620 nm. The results from samples mimicking physiological conditions suggested very good applicability in the determination of chloride ion in physiological samples.     

CdTe/CdS量子点的Ⅰ-Ⅱ型结构转变与荧光性质

制备了壳层厚度可以精确控制的CdTe/CdS核壳量子点, 利用紫外-可见吸收光谱、光致发光光谱、透射电镜和时间分辨光谱等技术, 分析了CdS壳层厚度对CdTe量子点的荧光量子产率和光谱结构的影响规律. 发现了不同于CdSe/CdS, CdSe/ZnS, CdTe/ZnS等核壳量子点的荧光峰展宽、大幅度红移以及荧光寿命大幅度增加现象. 根据能带的位置关系, 随着CdS厚度的增加, CdTe从Ⅰ型结构逐渐过渡到Ⅱ型核壳结构. 对于Ⅱ型CdTe/CdS核壳量子点, 不仅存在CdTe核区导带电子与价带空穴间的直接复合, 还存在CdS壳层导带电子与CdTe核价带空穴界面处的间接复合, 发光机制的变化导致荧光峰的展宽、明显红移和荧光寿命的增加. 当壳层过厚时, 壳层表面新引入的缺陷会阻碍荧光寿命和量子产率的进一步提高.