Synthesis of AS1411-Aptamer-Conjugated CdTe Quantum Dots with High Fluorescence Strength for Probe Labeling Tumor Cells

In this paper, we report microwave-assisted, one-stage synthesis of high-quality functionalized water-soluble cadmium telluride (CdTe) quantum dots (QDs). By selecting sodium tellurite as the Te source, cadmium chloride as the Cd source, mercaptosuccinic acid (MSA) as the capping agent, and a borate-acetic acid buffer solution with a pH range of 5–8, CdTe nanocrystals with four colors (blue to orange) were conveniently prepared at 100 °C under microwave irradiation in less than one hour (reaction time: 10–60 min). The influence of parameters such as the pH, Cd:Te molar ratio, and reaction time on the emission range and quantum yield percentage (QY%) was investigated. The structures and compositions of the prepared CdTe QDs were characterized by transmission electron microscopy, energy-dispersive X-ray spectroscopy, selective area electron diffraction, and X-ray powder diffraction experiments. The formation mechanism of the QDs is discussed in this paper. Furthermore, AS1141-aptamer-conjugated CdTe QDs in the U87MG glioblastoma cell line were assessed with a fluorescence microscope. The obtained results showed that the best conditions for obtaining a high QY of approximately 87 % are a pH of 6, a Cd:Te molar ratio of 5:1, and a 30-min reaction time at 100 °C under microwave irradiation. The results showed that AS1141-aptamer-conjugated CdTe QDs could enter tumor cells efficiently. It could be concluded that a facile high-fluorescence-strength QD conjugated with a DNA aptamer, AS1411, which can recognize the extracellular matrix protein nucleolin, can specifically target U87MG human glioblastoma cells. The qualified AS1411-aptamer-conjugated QDs prepared in this study showed excellent capabilities as nanoprobes for cancer targeting and molecular imaging.     

基于InP@ZnS QDs/Dured纳米荧光探针的DNA检测

利用巯基丙酸包覆的In P@Zn S量子点(QDs)与Dured构建了一种检测DNA的荧光探针。在该探针中,以环境友好型带负电的In P@Zn S量子点为荧光团,与带正电的Dured通过静电结合,构建了In P@Zn S QDs/Dured纳米荧光探针。通过荧光共振能量转移(FRET)机理,量子点荧光被猝灭;当DNA存在时,Dured与DNA的特异性结合使Dured从In P@Zn S QDs表面脱附,FRET过程被打断,In P@Zn S QDs荧光恢复,以荧光"关-开"方式检测DNA。该探针检测DNA的线性范围为2.0~275.0 ng·L-1,检测限为1.0 ng·L-1,并可用于模拟生物生理条件下的DNA检测。     

Controlling the size of ZnO quantum dots using the dressed photon–phonon-assisted sol–gel method

We developed a sol–gel method using the dressed photon–phonon (DPP) process. DPPs are selectively exited in nanoscale structures at photon energies that are lower than the bandgap energy, which allows one to increase the growth rate of smaller ZnO quantum dots (QDs). Thus, we obtained a smaller size variance of ZnO QDs. The growth rate was proportional to the power of the light used for DPP excitation. The results were confirmed using a rate equation that accounted for the concentration of the sol–gel solution.     

Surface processes during growth of InAs/GaAs quantum dot structures monitored by reflectance anisotropy spectroscopy

The time resolved reflectance anisotropy spectroscopy (RAS) measurement at 4.2 eV was used for the optimization of technological parameters for Stranski–Krastanow quantum dot (QD) formation. TMIn dosage and waiting time following InAs deposition during which QD formation takes place were optimized.RAS measurement helps us to study the MOVPE surface processes such as QD formation, dissolution of In from InAs QDs during the growth of GaAs capping layer or recovery of epitaxial surface from As deficiency, when As partial pressure is increased. We have shown, that the recovery of epitaxial surface from As deficiency is rather a slow process of the order of tens of seconds.We have for the first time observed in situ the mechanism of In atoms migration from QDs during GaAs capping layer growth. First the GaAs layer is formed and then the In migration from QDs follows. These two processes do not start at the same time, the In dissolution is delayed. Conclusions extracted from RAS measurement are in agreement with photoluminescence results.     

Unsymmetrically Substituted Nickel Triazatetra-Benzcorrole and Phthalocynanine Complexes: Conjugation to Quantum Dots and Applications as Fluorescent “Turn ON” Sensors

We report on the design and application of fluorescent nanoprobes based on the covalent linking of _L-glutathione-capped CdSe@ZnS quantum dots (QDs) to newly synthesized unsymmetrically substituted nickel mercaptosuccinic acid triazatetra-benzcorrole (3) and phthalocyanine (4) complexes. Fluorescence quenching of the QDs occurred on conjugation to complexes 3 or 4. The nanoprobes were selectively screened in the presence of different cations and Hg²⁺ showed excellent affinity in “turning ON” the fluorescence of the nanoprobes. Experimental results showed that the sensitivity of QDs-4 towards Hg²⁺ was much higher than that of QDs-3 nanoprobe. The mechanism of reaction has been elucidated based on the ability of Hg²⁺ to coordinate with the sulphur atom of the Ni complex ring and apparently “turn ON” the fluorescence of the linked QDs.     

CdSe/ZnSe/ZnS多壳层结构量子点的制备与表征

展示了一种简捷的多壳层量子点合成路线。在含有过量Se源的CdSe体系中直接注入Zn源,"一步法"合成了CdSe/ZnSe量子点;进一步以CdSe/ZnSe为"核",表面外延生长ZnS壳层制备了核/壳/壳结构CdSe/ZnSe/ZnS量子点。相对于以往报道的多壳层结构量子点的制备方法,该方法通过减少壳层的生长步骤有效地简化了实验操作,缩短了实验周期,同时减少对原料的损耗。对量子点进行高温退火处理,能够大幅提高CdSe/ZnSe/ZnS量子点的发光量子产率。透射电镜、XRD以及光谱研究表明:所制备的量子点接近球形,核与壳层纳米晶均为闪锌矿结构,最终获得的CdSe/ZnSe/ZnS量子点的光致发光量子产率达到53％。为了实现量子点的表面生物功能化,通过巯基酸进行了表面配体交换修饰,使量子点表面具有水溶性的羧基功能团,并且能够维持较高的光致发光量子产率。     

Successful growth of two different quantum dots on one substrate

We report the successful growth of ZnSe and ZnTe quantum dots (QDs) embedded in ZnS on GaAs substrate. These QDs have good optical properties and show quantum confinement effect. High-resolution electron scanning microscope studies show that these QDs are grown in Volmer–Weber mode. It is found that the size of the QDs is controlled by the growth duration. When the growth time is short, high density of QDs could be fabricated, but with a long growth time the small QDs get together to form a large cluster. We also show that with this growth method it is possible to grow both ZnSe quantum and ZnTe QDs on one substrate at the same time. For this dual QDs system, two peaks corresponding to the emission from the ZnSe dots (3.0 eV, blue–violet) and ZnTe dots (2.6 eV, green–blue) could be observed at the same time in the photoluminescence measurement.     

On the relation between the operators of physical quantities of a nonrigid molecule and the symmetry of its equilibrium configurations

Molecules recognizing biomarkers of diseases (monoclonal antibodies (monoABs)) are often too large for biomedical applications, and the conditions that are used to bind them with nanolabels lead to disordered orientation of monoABs with respect to the nanoparticle surface. Extremely small nanoprobes, designed via oriented conjugation of quantum dots (QDs) with single-domain antibodies (sdABs) derived from the immunoglobulin of llama and produced in the E. coli culture, have a hydrodynamic diameter less than 12 nm and contain equally oriented sdAB molecules on the surface of each QD. These nanoprobes exhibit excellent specificity and sensitivity in quantitative determination of a small number of cells expressing biomarkers. In addition, the higher diffusion coefficient of sdABs makes it possible to perform immunohistochemical analysis in bulk tissue, inaccessible for conventional monoABs. The necessary conditions for implementing high-quality immunofluorescence diagnostics are a high specificity of labeling and clear differences between the fluorescence of nanoprobes and the autofluorescence of tissues. Multiphoton micros-copy with excitation in the near-IR spectral range, which is remote from the range of tissue autofluorescence excitation, makes it possible to solve this problem and image deep layers in biological tissues. The two-photon absorption cross sections of CdSe/ZnS QDs conjugated with sdABs exceed the corresponding values for organic fluorophores by several orders of magnitude. These nanoprobes provide clear discrimination between the regions of tumor and normal tissues with a ratio of the sdAB fluorescence to the tissue autofluorescence upon two-photon excitation exceeding that in the case of single-photon excitation by a factor of more than 40. The data obtained indicate that the sdAB-QD conjugates used as labels provide the same, or even better, quality as the “gold standard” of immunohistochemical diagnostics. The developed nanoprobes are expected to find wide application in high-efficiency imaging of tumor and multiparameter diagnostics.     

Synthesis of stable dispersion of ZnO quantum dots in aqueous medium showing visible emission from bluish green to yellow

Aqueous dispersion of 4-8 nm size stable ZnO quantum dots (QDs) exhibiting luminescence in the visible region have been synthesized by a simple solution growth technique at room temperature. Silica has been used as capping agent to control the particle size as well as to achieve uniform dispersion of QDs in aqueous medium. X-ray diffractometer (XRD) analysis reveals formation phase pure ZnO particles having wurzite (hexagonal) structure. Atomic force microscope (AFM) images show that the particles are spherical in shape, having average crystalline sizes ∼4, 5.5 and 8 nm for samples prepared at pH values of 10, 12 and 14, respectively. From the optical absorption studies, the band gap energy of QDs is found to be blue shifted as compared to bulk ZnO (3.36 eV) due to the quantum confinement effect and is consistent with the band gap calculated by using effective-mass approximation model. The photoluminescence (PL) observed in these QDs has been attributed to the presence of defect centers.     

Synthesis,COSMO-RS analysis and optical properties of surface modified ZnS quantum dots using ionic liquids

Zinc sulfide (ZnS) quantum dots (QDs) were synthesized using the microwave assisted ionic liquid (MAIL) route. Three ionic liquids (ILs), namely, 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]BF₄]), trihexyl(tetradecyl) phosphonium bis(trifluoromethanesulfonyl) amide ([P_6,6,6,14][TSFA]) and trihexyl(tetradecyl) phosphonium chloride ([P_6,6,6,14][Cl]) were used in this study. The size and structure of the QDs were characterized by high-resolution transmission electron microscopy (HR-TEM) and selected area electron diffraction (SAED) pattern, respectively. The synthesized QDs were of wurtzite crystalline structure with size less than 5 nm. The QDs were more uniformly distributed while using the phosponium based ILs as a reaction medium during synthesis. The optical properties were investigated by UV–vis absorption and photoluminescence (PL) emission spectroscopy. The optical properties of QDs showed the quantum confinement effect in their absorption and the effect of cation and anion structural moiety was observed on their bandedge emission. The QDs emission intensity was measured higher for [P_6,6,6,14][Cl] due to their better dispersion as well as high charge density of Cl anion. The capability of the ILs in stabilizing the QDs was interpreted by density functional theory (DFT) computations. The obtained results are in good agreement with the theoretical prediction.     

Intrinsic and Mn doped InAs quantum dots studied at the atomic scale by cross-sectional scanning tunneling microscopy

Cross-sectional Scanning Tunneling Microscopy (X-STM) is an ideal tool to study the structural properties of semiconductor nanostructures, such as InAs self-assembled quantum dots (QDs) and the properties of individual doping atoms at the atomic scale. The technique allows for a precise determination of the size, shape and composition of overgrown semiconductor nanostructures which can be part of a (complex) multilayer structure. In this paper we discuss our recent results on InAs QD structures that were capped by various methods in order to control their size and shape. We will show that the capping process does strongly affect the final QD structure and thus forms a very important step in the dot formation process. Recently people have started to investigate magnetically doped QDs. We have used our X-STM technique to study the incorporation of single Mn-impurities in InAs/GaAs QDs.     

Misfit dislocations in nanocomposites with quantum dots,nanowires and their ensembles

We review theoretical concepts and experimental results on the physics of misfit dislocations in nanocomposite solids with quantum dots (QDs) and nanowires (quantum wires). Special attention is paid to thermodynamic theoretical models of formation of misfit dislocations in QDs and nanowires, including composite core–shell nanowires. The effects of misfit dislocations on the film growth mode during heteroepitaxy and phase transitions in QD systems are analysed. Experimental results and theoretical models of the ordered spatial arrangement of QDs growing on composite substrates with misfit dislocation networks are discussed. The influence of subsurface dislocations in composite substrates on the nucleation of QDs and nanowires on the substrate surface is considered. Models of misfit strain relaxation and dislocation formation in nanofilms on compliant substrates are also reviewed.     

Thermodynamic analysis of the shape, anisotropy and formation process of InAs/InP(0 0 1) quantum dots and quantum sticks grown by metalorganic vapor phase epitaxy

This study describes the origin of the size and shape anisotropy of InAs/InP(0 0 1) quantum dots (QDs) grown by metalorganic vapor phase epitaxy (MOVPE). The geometry of the QDs is determined by carefully analyzing transmission electron microscopy (TEM) images. An analytical model adapted to our QD geometry is used to understand the formation mechanism of the QDs, and to describe the origin of their size dispersion. A shape transition from QDs to elongated quantum sticks (QS) is observed under As-poor growth conditions. This transition, driven by thermodynamics, is clearly described by our model.     

The influence of the quantum dot/polymethylmethacrylate composite preparation method on the stability of its optical properties under laser radiation

Photoluminescent semiconductor nanocrystals, quantum dots (QDs), are nowadays one of the most promising materials for developing a new generation of fluorescent labels, new types of light-emitting devices and displays, flexible electronic components, and solar panels. In many areas the use of QDs is associated with an intense optical excitation, which, in the case of a prolonged exposure, often leads to changes in their optical characteristics. In the present work we examined how the method of preparation of quantum dot/polymethylmethacrylate (QD/PMMA) composite influenced the stability of the optical properties of QD inside the polymer matrix under irradiation by different laser harmonics in the UV (355 nm) and visible (532 nm) spectral regions. The composites were synthesized by spin-coating and radical polymerization methods. Experiments with the samples obtained by spin-coating showed that the properties of the QD/PMMA films remain almost constant at values of the radiation dose below ~10 fJ per particle. Irradiating the composites prepared by the radical polymerization method, we observed a monotonic increase in the luminescence quantum yield (QY) accompanied by an increase in the luminescence decay time regardless of the wavelength of the incident radiation. We assume that the observed difference in the optical properties of the samples under exposure to laser radiation is associated with the processes occurring during radical polymerization, in particular, with charge transfer from the radical particles inside QDs. The results of this study are important for understanding photophysical properties of composites on the basis of QDs, as well as for selection of the type of polymer and the composite synthesis method with quantum dots that would allow one to avoid the degradation of their luminescence.     

Stranski–Krastanov growth of InGaN quantum dots emitting in green spectra

Self-assembled InGaN quantum dots (QDs) were grown on GaN templates by metalorganic chemical vapor deposition. 2D–3D growth mode transition through Stranski–Krastanov mode was observed via atomic force microscopy. The critical thickness for In_0.67Ga_0.33N QDs was determined to be four monolayers. The effects of growth temperature, deposition thickness, and V/III ratio on QD formation were examined. The capping of InGaN QDs with GaN was analyzed. Optimized InGaN quantum dots emitted in green spectra at room temperature.     

以巯基丙酸为稳定剂的水溶性CdTe量子点的水热合成及表征

以巯基丙酸(MPA)为稳定剂,采用水热合成方法在160 ℃下合成水溶性CdTe量子点。研究了不同反应时间及反应前驱体溶液的不同pH值对合成的CdTe量子点光学性质的影响。结果表明:所制得的CdTe量子点的荧光发射波长在510~661 nm范围内连续可调,并且CdTe量子点的光学性质强烈地依赖于反应前驱体溶液的pH值,最佳pH值为9。透射电子显微镜和X射线衍射分析表明所制备的CdTe量子点的形状接近于球形,粒径分布较均匀。与回流方法制备的水溶性量子点相比,高温条件下的水热合成方法简单,反应时间短,CdTe量子点生长速度快,100 min就可生长到3.5 nm,并且所制得的CdTe量子点荧光强度高,稳定性好,荧光量子产率也较高,最高可达44.6%。     

近红外波段InAs量子点结构与光学特性

采用分子束外延技术,分别在480,520℃的生长温度下,制备了淀积厚度2.7ML的InAs/GaAs量子点。用原子力显微镜对样品进行形貌测试和统计分布。结果表明,在相应的生长温度下,量子点密度分别为8.0×10¹⁰,5.0×10⁹cm^-2,提高生长温度有利于获得大尺寸的量子点,并且量子点按高度呈双模分布。结合光致发光谱的分析,在480℃的生长条件下,最近邻量子点之间的合并导致了量子点尺寸的双模分布;而在525℃的生长温度下,In偏析和InAs解析是形成双模分布的主要原因。     

半导体红外量子点发展现状与前景

半导体量子点具有独特的光学与电学性质,特别是红外量子点良好的光稳定性和生物相容性等优点使其在光电器件、生物医学等领域受到广泛关注。综述了吸收或发射光谱位于红外波段的量子点在激光、能源、光电探测以及生物医学等方面的应用现状与前景,归纳了适用于红外量子点材料的制备方法,并对比了不同方法在应用中的优势。半导体红外量子点材料选择丰富、应用形式多样:InAs量子点被动锁模激光器在1.3 μm波长处产生7.3 GHz的近衍射极限脉冲输出;InAs/GaAs量子点双波长激光器可泵浦产生0.6 nW的THz波;PbS量子点掺杂光纤放大器可在1.53 μm中心波长处实现10.5 dB光增益,带宽160 nm;CdSeTe量子点敏化太阳能电池、异质结Si基量子点太阳能电池的总转换效率可达8%和14.8%;胶质HgTe量子点制成的量子点红外探测器(QDIP)可实现3 μm~5 μm中波红外探测,Ge/Si量子点可实现3 μm~7 μm红外探测;CdTe/ZnSe核壳量子点可用于检测DNA序列的损伤与突变。半导体红外量子点上述应用形式的发展,将进一步促进红外光电系统向高效、快速、大规模集成的方向演进,也将极大地促进临床医学中活体成像检测的应用推广。     

Stability and luminescence properties of CsPbBr3/CdSe/Al core-shell quantum dots

To improve the stability and luminescence properties of CsPbBr₃ QDs, we proposed a new core-shell structure for CsPbBr₃/CdSe/Al quantum dots (QDs). By using a simple method of ion layer adsorption and a reaction method, CdSe and Al were respectively packaged on the surface of CsPbBr₃ QDs to form the core-shell CsPbBr₃/CdSe/Al QDs. After one week in a natural environment, the photoluminescence quantum yields of CsPbBr₃/CdSe/Al QDs were greater than 80%, and the PL intensity remained at 71% of the original intensity. Furthermore, the CsPbBr₃/CdSe/Al QDs were used as green emitters for white light-emitting diodes (LEDs), with the LEDs spectrum covering 129% of the national television system committee (NTSC) standard color gamut. The core-shell structure of QDs can effectively improve the stability of CsPbBr₃ QDs, which has promising prospects in optoelectronic devices.     

Procedures for Controlling the Size, Structure and Optical Properties of CdS Quantum Dots during Synthesis in Aqueous Solution

We report an easy approach for the synthesis of CdS Quantum Dots (CdS QDs) with high luminescence and temporal stability through the reaction of Cd²⁺ and S^2- in the presence of mercaptoacetic acid (MAA) as a capping reagent in aqueous medium, under normal pressure and room temperature. The influence of several experimental variables, including temperature, pH, the Cd/S ratio and the Cd/MAA ratio, on the optical properties of the QDs obtained was studied systematically. The experimental results indicate that these variables play an important role in determining the size and state of the surface of the nanoparticles, and hence their luminescent properties and temporal stability. The general aspects of nanocrystal nucleation and growth in the synthesis of nanocrystals were studied. The best conditions for the synthesis of nanoparticles of high quality are also reported. The CdS nanocrystals obtained exhibited a narrow PL band, with reproducible room-temperature quantum yields.