Cancer‐Cell‐Phenotype‐Dependent Differential Intracellular Trafficking of Unconjugated Quantum Dots

A diverse array of nanoparticles, including quantum dots (QDs), metals, polymers, liposomes, and dendrimers, are being investigated as therapeutics and imaging agents in cancer diseases. However, the role of the cancer‐cell phenotype on the uptake and intracellular fate of nanoparticles in cancer cells remains poorly understood. Reported here is that differences in cancer‐cell phenotypes can lead to significant differences in intracellular sorting, trafficking, and localization of nanoparticles. Unconjugated anionic QDs demonstrate dramatically different intracellular profiles in three closely related human‐prostate‐cancer cells used in the investigation: PC3, PC3‐flu, and PC3‐PSMA. QDs demonstrate punctated intracellular localization throughout the cytoplasm in PC3 cells. In contrast, the nanoparticles localize mainly at a single juxtanuclear location (“dot‐of‐dots”) inside the perinuclear recycling compartment in PC3‐PSMA cells, where they co‐localize with transferrin and the prostate‐specific membrane antigen. The results indicate that nanoparticle sorting and transport is influenced by changes in cancer‐cell phenotype and can have significant implications in the design and engineering of nanoscale drug delivery and imaging systems for advanced tumors.     

Chemical Redox Modulation of the Surface Chemistry of CdTe Quantum Dots for Probing Ascorbic Acid in Biological Fluids

Most of the fluorescence resonance energy transfer (FRET)‐based sensors employing quantum dots (QDs) usually use organic fluorophores and gold nanoparticles as the quenchers. However, complex processes for the modification/immobilization of the QDs are always necessary, as the generation of FRET requires strict distance between the donor and acceptor. Herein, a simple chemical redox strategy for modulating the surface chemistry of the QDs to develop a QD‐based turn‐on fluorescent probe is reported. The principle of the strategy is demonstrated by employing CdTe QDs with KMnO₄ as the quencher and ascorbic acid as the target analyte. The fluorescence of CdTe QDs is quenched with a blue‐shift upon addition of KMnO₄ due to the oxidation of the Te atoms on the surface of the QDs. The quenched fluorescence of the QDs is then recovered upon addition of ascorbic acid due to the reduction of CdTeO₃/TeO₂ on the surface of the QDs to CdTe. The recovered fluorescence of the QDs increases linearly with the concentration of ascorbic acid from 0.3 to 10 µM . Thus, a novel QD‐based turn‐on fluorescent probe with a detection limit as low as 74 nM is developed for the sensitive and selective detection of ascorbic acid in biological fluids. The present approach avoids the complex modification/immobilization of the QDs involved in FRET‐based sensors, and opens a simple pathway to developing cost‐effective, sensitive, and selective QD‐based fluorescence turn‐on sensors/probes for biologically significant antioxidants.     

量子点在细胞以及体内生物中成像的研究进展

量子点是一种荧光半导体纳米材料,与生物分子结合成一种高亮度而稳定的荧光探针应用于生物成像.通过生物成像可观察量子点标记分子与其靶标的相互作用,实时观测其在活细胞及活体中的运行轨迹,实现对细胞水平及在活体层次的研究.利用这种生物成像技术还可以研究疾病的发生发展过程.介绍了量子点的光学特性,重点综述了量子点在细胞、体内生物成像中的应用,并展望了其发展前景.     

硫化铜量子点的研究进展

硫化铜量子点作为一种p型半导体纳米晶,具有很强的表面等离子体共振效应、低的毒性以及独特的光学和电学性能,在光催化、生物技术、光电转换材料领域受到了极大关注。由于单分散的硫化铜量子点的制备过程复杂,效率较低,并且纯的硫化铜量子点电导率较低,这极大地限制了其在能量存储器件方面的应用。此外,由于硫化铜量子点复杂的能带结构和独特的p型半导体特性,针对硫化铜量子点的光学性能调控尚不成熟。基于此,本文综述了硫化铜量子点在制备方面的研究现状与取得的进展,介绍了硫化铜量子点的能带结构、晶体结构,及其在量子点敏化太阳能电池、光催化降解污染物、肿瘤细胞诊断与治疗等方面的研究进展,并对硫化铜量子点或Cu系量子点更进一步的研究、开发应用提出了几点建议。     

木质素碳量子点在防伪包装中的应用研究

目的 探索木质素碳量子点(CQDs)荧光油墨及其书写式标签、CQDs/聚乙烯醇(PVA)复合荧光薄膜在防伪包装中的应用潜力。方法 以木质素为碳源,采用一锅水热法得到未掺杂碳量子点O-CQDs和硫掺杂碳量子点S-CQDs,并以此为荧光填料,以乙醇、乙二醇和丙三醇的混合液为溶剂,制备荧光油墨及其书写式荧光标签和CQDs/PVA复合荧光薄膜,探索其荧光防伪性能。结果 硫掺杂木质素碳量子点油墨MS-CQDs及其书写标签、PVA复合薄膜在可见光下均无色,在365 nm紫外光照下则呈现强烈的淡蓝色荧光。结论 MS-CQDs书写式称量纸荧光标签及其与PVA的复合薄膜均具有良好的荧光性能,在荧光防伪领域具有良好的应用潜力。     

Monolayer Silane‐Coated,Water‐Soluble Quantum Dots

A one‐step method to produce ≈12 nm hydrodynamic diameter water‐soluble CdSe/ZnS quantum dots (QDs), as well as CdS/ZnS, ZnSe/ZnMnS/ZnS, AgInS₂/ZnS, and CuInS₂/ZnS QDs, by ligand exchange with a near‐monolayer of organosilane caps is reported. The method cross‐links the surface‐bound silane ligands such that the samples are stable on the order of months under ambient conditions. Furthermore, the samples may retain a high quantum yield (60%) over this time. Several methods to functionalize aqueous QD dispersions with proteins and fluorescent dyes have been developed with reaction yields as high as 97%.     

Intravital Multiphoton Imaging of the Selective Uptake of Water‐Dispersible Quantum Dots into Sinusoidal Liver Cells

Although many studies reporting the organ‐level biodistribution of nanoparticles (NPs) in animals, very few have addressed the fate of NPs in organs at the cellular level. The liver appears to be the main organ for accumulation of NPs after intravenous injection. In this study, for the first time, the in vivo spatiotemporal disposition of recently developed mercaptosuccinic acid (MSA)‐capped cadmium telluride/cadmium sulfide (CdTe/CdS) quantum dots (QDs) is explored in rat liver using multiphoton microscopy (MPM) coupled with fluorescence lifetime imaging (FLIM), with subcellular resolution (～1 μm). With high fluorescence efficiency and largely improved stability in the biological environment, these QDs show a distinct distribution pattern in the liver compared to organic dyes, rhodamine 123 and fluorescein. After intravenous injection, fluorescent molecules are taken up by hepatocytes and excreted into the bile, while negatively charged QDs are retained in the sinusoids and selectively taken up by sinusoidal cells (Kupffer cells and liver sinusoidal endothelial cells), but not by hepatocytes within 3 h. The results could help design NPs targeting the specific types of liver cells and choose the fluorescent markers for appropriate cellular imaging.     

Oxidized Quasi‐Carbon Nitride Quantum Dots Inhibit Ice Growth

Antifreeze proteins (AFPs), a type of high‐efficiency but expensive and often unstable biological antifreeze, have stimulated substantial interest in the search for synthetic mimics. However, only a few reported AFP mimics display thermal hysteresis, and general criteria for the design of AFP mimics remain unknown. Herein, oxidized quasi‐carbon nitride quantum dots (OQCNs) are synthesized through an up‐scalable bottom‐up approach. They exhibit thermal‐hysteresis activity, an ice‐crystal shaping effect, and activity on ice‐recrystallization inhibition. In the cryopreservation of sheep red blood cells, OQCNs improve cell recovery to more than twice that obtained by using a commercial cryoprotectant (hydroxyethyl starch) without the addition of any organic solvents. It is shown experimentally that OQCNs preferably bind onto the ice‐crystal surface, which leads to the inhibition of ice‐crystal growth due to the Kelvin effect. Further analysis reveals that the match of the distance between two neighboring tertiary N atoms on OQCNs with the repeated spacing of O atoms along the c‐axis on the primary prism plane of ice lattice is critical for OQCNs to bind preferentially on ice crystals. Here, the application of graphitic carbon nitride derivatives for cryopreservation is reported for the first time.     

Bilayer PbS Quantum Dots for High‐Performance Photodetectors

Due to their wide tunable bandgaps, high absorption coefficients, easy solution processabilities, and high stabilities in air, lead sulfide (PbS) quantum dots (QDs) are increasingly regarded as promising material candidates for next‐generation light, low‐cost, and flexible photodetectors. Current single‐layer PbS‐QD photodetectors suffer from shortcomings of large dark currents, low on–off ratios, and slow light responses. Integration with metal nanoparticles, organics, and high‐conducting graphene/nanotube to form hybrid PbS‐QD devices are proved capable of enhancing photoresponsivity; but these approaches always bring in other problems that can severely hamper the improvement of the overall device performance. To overcome the hurdles current single‐layer and hybrid PbS‐QD photodetectors face, here a bilayer QD‐only device is designed, which can be integrated on flexible polyimide substrate and significantly outperforms the conventional single‐layer devices in response speed, detectivity, linear dynamic range, and signal‐to‐noise ratio, along with comparable responsivity. The results which are obtained here should be of great values in studying and designing advanced QD‐based photodetectors for applications in future flexible optoelectronics.     

量子点荧光材料在照明和显示领域的研究进展

由于量子点具有发光波长尺寸可调谐、发光峰窄、发光效率高和热稳定性等特点,近年来作为一种新型发光材料受到了越来越多的关注。它们不仅可以在电激发下实现自主发光,还可以在光激发下实现光转换,因此在照明和显示领域具有很广阔的应用前景。总结了用量子点荧光材料制备白光发光二极管的6种方法及其研究进展,还介绍了它们在液晶显示领域的应用,最后讨论了目前量子点荧光粉存在的问题和今后的研究方向。     

PbS量子点/ZnO纳米片复合膜的制备及其光电化学性能

通过两步法合成PbS量子点(QDs)修饰ZnO纳米片复合膜. 首先利用电化学法在掺氟的SnO₂导电玻璃(FTO)上生长ZnO纳米片, 然后在ZnO纳米片上通过逐次化学浴法沉积PbS量子点形成PbS/ZnO复合膜. 利用扫描电子显微镜(SEM)、X射线衍射仪(XRD)详细表征了样品的表面形貌和晶体结构, 并研究了PbS/ZnO复合膜作为量子点敏化太阳能电池光阳极的紫外-可见吸收谱、光电化学性能和表面光电压谱. 对比ZnO纳米片经PbS量子点修饰前后, 发现PbS量子点修饰后光阳极的光吸收和光伏响应均从紫外区拓宽到了可见光区, 同时光电化学性能有了显著提高, 短路电流密度从敏化前的0.1 mA/cm²增加到0.7 mA/cm², 效率由0.04%增加到0.57%. 与单一ZnO纳米片相比, PbS/ZnO复合膜的表面光伏响应强度明显增强, 说明PbS与ZnO之间形成了有利于光生电荷分离的异质结, 从而导致了PbS/ZnO复合膜光电性能的增加.