碳量子点的生物应用:成像、载药与毒性

碳量子点作为一种新型的纳米材料,具有荧光性能优异、尺寸小、毒性低等诸多优势,因而具有良好的应用前景,尤其在生物医学领域有突出的应用价值,近年来引起了科研者们的广泛关注。在介绍碳量子点光学性质的基础上,重点综述了碳量子点在生物成像、诊疗剂应用及碳量子点生物毒性等方面的最新研究进展,并探讨了碳量子点未来的发展方向和前景。     

Graphene Quantum Dots for Optical Bioimaging

Graphene quantum dots (GQDs) have shown great potential in bioimaging applications due to their excellent biocompatibility, low cytotoxicity, feasibility for surface functionalization, physiological stability, and tunable fluorescence properties. This Review first introduces the intriguing optical properties of GQDs that are suitable for biological imaging, and is followed by the GQDs' synthetic strategies. The emergent and latest development methods for tuning GQDs' optical properties are further described in detail. The recent advanced applications of GQDs in vitro, particularly in cell imaging, targeted imaging, and theranostic nanoplatform fabrication, are included. The applications of GQDs for in vivo bioimaging are also covered. Finally, the Review is concluded with the challenges and prospectives that face this nascent yet exciting field.     

Far‐Red to Near‐Infrared Carbon Dots: Preparation and Applications in Biotechnology

As novel fluorescent nanomaterials, carbon dots (CDs) exhibit excellent photostability, good biocompatibility, and high quantum yield (QY). Their superior properties make them promising candidates for biomedical assays and therapy. Among them, the red‐emission (>600 nm) CDs have attracted increasing attention in the past years due to their little damage to the biological matrix, deep tissue penetration, and minimum autofluorescence background of biosamples. This Review, summarizes the recent progress of far‐red to near‐infrared (NIR) CDs from the preparation and their biological applications. The challenges in designing far‐red and NIR CDs and their further applications in biomedical fields are also discussed.     

石墨烯量子点的制备及其生物应用

石墨烯量子点(GQDs)作为石墨烯材料的衍生物, 在兼顾了石墨烯优良特性的同时, 又依靠量子限域效应和边界效应而具备了光致发光(PL)等石墨烯所不具备的性质, 而且在细胞毒性、生物相容性等方面也有更好的表现。近年来, GQDs的制备方法日趋多样化, 通常将其分为Top-down和Bottom-up两种方法。随着GQDs在生物医学领域应用的不断深化, 对其形貌和尺寸控制也提出了更高的要求, 因此本文对Bottom-up法等一些有希望精确控制GQDs形貌和尺寸的方法进行了重点介绍, 并对各种方法的优缺点进行了对比。目前GQDs的生物应用主要包括生物成像、生物传感器、药物输运和抗菌剂等, 本文对其各种应用分别进行了介绍, 并结合各种应用对GQDs的要求给出了制备方法的建议。文章最后还指出了GQDs研究中存在的问题及发展方向。     

含氮石墨烯量子点的制备及其光学性质研究

采用水热法一步合成了含氮石墨烯量子点(NGQDs), 通过原子力显微镜(AFM)、透射电镜(TEM)、X射线光电子能谱(XPS)等对NGQDs的形貌和组成进行表征, 并进一步通过紫外-可见光谱(UV-Vis)、荧光光谱(PL)等手段研究了NGQDs的光学性质。AFM和TEM分析结果表明, NGQDs尺寸约为8.9 nm、厚度为0.6 ~2.0 nm (即1~3个碳原子层)。XPS分析结果表明NGQDs中氮含量约为17%, 且氮元素主要以“吡咯N”形式存在。光谱学实验表明, NGQDs的激发光谱与吸收光谱基本一致, 且其发射光谱与激发波长之间不存在依赖关系。此外, NGQDs的量子产率为~18%, 并随着含氮量的增加而增加, 且其荧光寿命衰变曲线可以被拟合成很好的双指数衰变曲线(τ₁=2.93 ns, τ₂=9.00 ns), 表明NGQDs有两种发色源, 即边缘富有含氧官能团的sp²碳簇和含氮五元环-吡咯环。     

From Graphite to Graphene Oxide and Graphene Oxide Quantum Dots

Many methods have been reported for synthesizing graphene oxide (GO) and graphene oxide quantum dots (GOQDs) where a tedious operational procedure and long reaction time are generally required. Herein, a facile one‐pot solvothermal method that allows selective synthesis of pure GO and pure GOQDs, respectively is demonstrated. What is more, the final product of either GO or differently sized GOQDs can be easily controlled by adjusting the reaction temperatures or reactant ratios, which is also feasible when enlarged to gram scale. The 2.5 nm GOQDs show excellent photoluminescence that can be utilized for bioimaging or distinctive detection of Eu³⁺ and Tb³⁺ from their respective mixtures with other rare earth and/or transition metal ions, at sub‐ppm level.     

Recent Advances on Graphene Quantum Dots: From Chemistry and Physics to Applications

Graphene quantum dots (GQDs) that are flat 0D nanomaterials have attracted increasing interest because of their exceptional chemicophysical properties and novel applications in energy conversion and storage, electro/photo/chemical catalysis, flexible devices, sensing, display, imaging, and theranostics. The significant advances in the recent years are summarized with comparative and balanced discussion. The differences between GQDs and other nanomaterials, including their nanocarbon cousins, are emphasized, and the unique advantages of GQDs for specific applications are highlighted. The current challenges and outlook of this growing field are also discussed.     

Functional Carbon Quantum Dots for Ocular Imaging and Therapeutic Applications

Carbon quantum dots (CDs) are a class of emerging carbonaceous nanomaterials that have received considerable attention due to their excellent fluorescent properties, extremely small size, ability to penetrate cells and tissues, ease of synthesis, surface modification, low cytotoxicity, and superior water dispersion. In light of these properties, CDs are extensively investigated as candidates for bioimaging probes, efficient drug carriers, and disease diagnostics. Functionalized CDs represent a promising therapeutic candidate for ocular diseases. Here, this work reviews the potential use of functionalized CDs in the diagnosis and treatment of eye-related diseases, including the treatment of macular and anterior segment diseases, as well as targeting Aβ amyloids in the retina.     

Carbon Dots,Unconventional Preparation Strategies,and Applications Beyond Photoluminescence

Carbon dots (C‐dots) are generally separated into graphene quantum dots (GQDs) and carbon nanodots (CNDs) based on their respective top‐down and bottom‐up preparation processes. However, GQDs can be prepared by carbonization of small‐molecule precursors as revealed with unconventional preparation strategies. Thus, it is their structures rather than their precursors and preparation strategy that govern whether C‐dots are GQDs or CNDs. Here, the composites, structure, and electronic properties of C‐dots are discussed. C‐dots generally consist of a graphite‐like core and amorphous oxygen‐containing shell. When graphite becomes C‐dots, its conduction and valence bands are separated, and the quantum confinement effect appears. Combined with the light‐harvesting ability inherited from graphite, electrons in the core of C‐dots are transferred from conduction to valence bands, leading to electron–hole pair formation upon light excitation. The photoexcitation activities, such as photovoltaic conversion, photocatalysis, and photodynamic therapy, are influenced by the electronic properties of the core. Different to the semiconductor properties of core, the C‐dot shell is electrochemically active, leading to electrochemiluminescence (ECL). The oxygen‐containing groups in shell can conjugate to functional species for use in imaging and therapy. The applications of C‐dots beyond photoluminescence, including ECL, solar photovoltaics, photocatalysis, and theranostics, are reviewed.     

Microfluidic Synthesis of Ultrasmall Chitosan/Graphene Quantum Dots Particles for Intranasal Delivery in Alzheimer's Disease Treatment

Nanoparticles (NPs) based therapies for Alzheimer's disease (AD) attract interest due to their ability to pass across or bypass the blood-brain barrier. Chitosan (CS) NPs or graphene quantum dots (GQDs) are promising drug carriers with excellent physicochemical and electrical properties. The current study proposes the combination of CS and GQDs in ultrasmall NP form not as drug carriers but as theranostic agents for AD. The microfluidic-based synthesis of the CS/GQD NPs with optimized characteristics makes them ideal for transcellular transfer and brain targeting after intranasal (IN) delivery. The NPs have the ability to enter the cytoplasm of C6 glioma cells in vitro and show dose and time-dependent effects on the viability of the cells. IN administration of the NPs to streptozotocin (STZ) induced AD-like models lead to a significant number of entrances of the treated rats to the target arm in the radial arm water maze (RAWM) test. It shows the positive effect of the NPs on the memory recovery of the treated rats. The NPs are detectable in the brain via in vivo bioimaging due to GQDs as diagnostic markers. The noncytotoxic NPs localize in the myelinated axons of hippocampal neurons. They do not affect the clearance of amyloid β (Aβ) plaques at intercellular space. Moreover, they showed no positive impact on the enhancement of MAP2 and NeuN expression as markers of neural regeneration. The memory improvement in treated AD rats may be due to neuroprotection via the anti-inflammation effect and regulation of the brain tissue microenvironment that needs to be studied.     

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。     

石墨烯量子点/CdS/CdSe共敏化太阳能电池

以三维锐钛矿TiO₂微球为上层光散射层材料, 以商业纳米TiO₂为下层连接材料, 采用刮刀法制备了一种新颖的双层TiO₂薄膜, 并应用于量子点敏化太阳能电池(QDSSC)。其中, 石墨烯量子点(GQDs)采用滴液法引入, CdS/CdSe量子点采用连续离子层吸附法(SILAR)制备。采用场发射扫描电镜、透射电镜、X射线衍射、紫外-可见漫反射光谱及荧光光谱对样品进行表征。实验还制备了CdS/CdSe量子点敏化及石墨烯量子点/CdS/CdSe共敏化太阳能电池, 并研究了石墨烯量子点及CdS不同敏化周期及对电池性能影响。研究结果表明, 石墨烯量子点及CdS不同敏化周期对薄膜的光学性质、电子传输及载流子复合均有较大影响。优选条件下, TiO₂/QGDs/CdS(4)/CdSe电池的光电转换效率为1.24%, 光电流密度为9.47 mA/cm², 显著高于TiO₂/CdS(4)/CdSe电池的这些参数(0.59%与6.22 mA/cm²)。这主要是由于TiO₂表层吸附石墨烯量子点后增强了电子的传输, 减少了载流子的复合。     

Specific Oxygenated Groups Enriched Graphene Quantum Dots as Highly Efficient Enzyme Mimics

Significant progress is achieved for the utilization of graphene quantum dots as enzyme mimics in various biomedical fields recently. Although promising, the biocatalytic performance is far from satisfactory. Here, the rational design and synthesis of specific oxygenated groups enriched graphene quantum dots (o‐GQDs) via a facile oxidation reflux route is reported. These well‐prepared o‐GQDs with uniform size exhibit an ultrahigh peroxidase‐like activity in a wide range of pH values, and their superior performance is verified by using glucose detection as a typical model. Compared with classical nanozymes, these o‐GQDs show multiple times higher enzymatic activity. It is believed that the super facile synthesis strategy can greatly facilitate the practical use of o‐GQDs as enzyme mimics in the future.