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。     

石墨烯-硒化物量子点复合物的制备与性能研究

利用表面包覆1层吡啶分子的量子点和化学还原性石墨烯通过π-π堆积的方式,制备了石墨烯-量子点(PbSe、ZnSe、CdSe)复合物。包覆在量子点外层的吡啶分子芳香环结构起到桥梁的作用,将石墨烯和量子点π-π堆积起来,同时延伸了石墨烯的共轭结构。通过XRD、UV-Vis、TEM、Raman等表征手段,考察了相应复合物的结构、形成机理与性质。所制石墨烯-量子点复合物能稳定分散于水或极性溶液中,使得此类石墨烯复合物在生物体内具有良好的应用前景。通过循环伏安法对制备的产物进行了电化学性能测试。根据循环伏安曲线,复合物CCG-ZnSe的电容较单纯的CCG、ZnSe有大幅提高。     

石墨烯量子点的制备及在生物传感器中的应用研究进展

石墨烯是由一层碳原子以sp~2杂化轨道按蜂巢晶格排列构成的二维碳纳米材料,由于其超大的平面共轭结构,石墨烯中的π电子具有显著的离域效应。石墨烯具有许多令人惊奇的电子或电学性质,比如室温量子霍尔效应、自选传输性质、极高的载流子迁移率和超低的电阻率以及优异的光学性质和力学性质。然而,与其他绝大多数二维材料不同,较大二维尺寸的石墨烯还具有零带隙的半金属材料特性,限制了石墨烯在光电器件和半导体等领域的应用。因此,如何打开石墨烯的带隙,将其从半金属材料转变为半导体材料,引起了人们的广泛兴趣。目前,已知打开石墨烯带隙的方法主要有两种:一种是对石墨烯进行化学掺杂以破坏其π电子共轭体系;另外一种是基于量子效应,将石墨烯切割成纳米带、纳米筛或量子点。石墨烯量子点(GQDs)是二维平面尺寸小于100 nm的石墨烯片段,因其具有量子限域效应和边界效应而呈现出特殊的物理化学性质,是一种具有带隙的半导体材料。与传统半导体量子点相比,GQDs具有毒性低、水溶性好、化学活性低、生物相容性好以及荧光性质稳定等突出优点。此外,GQDs具有单原子层平面共轭结构和较大的比表面积,同时表面的含氧基团可以为外来分子与之结合提供活性位点,在太阳能电池、光电子器件、生物医药等领域具有广泛的应用前景。GQDs的制备方法主要分为自上而下和自下而上两种方法。自上而下法主要包括强酸氧化法,水热/溶剂热法,电化学氧化法等。该方法的优点是原料来源丰富、制备过程相对简单,制备所得的GQDs表面含有丰富的含氧基团,具有良好的水溶性,易于表面功能化。自下而上方法主要分为可控有机合成和碳化反应。前者可以制备出具有精确碳原子数、大小和形状均一的GQDs,但是制备过程复杂繁琐、反应耗时长且产率较低,而后者所制备的GQDs,其尺寸和结构难以控制,产物具有多分散性。本文全面介绍了石墨烯量子点的各种制备方法,对这些方法的特点进行了评论,同时对重要或新颖方法的反应机理进行了阐述,并且重点介绍了GQDs在生物传感器方面的应用,最后对GQDs的未来研究和发展前景进行了展望。     

石墨烯衍生物在肿瘤治疗方面的研究进展

石墨烯衍生物是利用氧化石墨烯表面的含氧官能团进行化学修饰而形成的复合炭材料。在兼备石墨烯非凡的物理及化学性质基础上,石墨烯衍生物还具有优良的水溶性和生物相容性,从而拓展了石墨烯的应用领域。综述石墨烯衍生物在肿瘤治疗方面的研究进展,主要包括生物成像、纳米载药及光动力疗法,为其在生物医药领域的进一步应用提供了新方法和新思路。     

纳米铝和石墨烯量子点改性的相变微胶囊的制备及特性

本工作旨在探索石墨烯量子点及纳米铝对改善相变微胶囊热性能、悬浮液物理稳定性等特性的作用。以石蜡为芯材、三聚氰胺-甲醛-尿素树脂为壁材,采用原位聚合法制备了三个相变微胶囊样品,分别为不复合石墨烯量子点及纳米铝的样品、复合1.5%石墨烯量子点的样品、复合1.5%石墨烯量子点及7%(质量分数)纳米铝的样品。通过扫描电镜、粒度仪、热传导系数仪、差示扫描量热仪及静置法分别对相变微胶囊的外观、粒径分布、热导率、热物性以及相变悬浮液物理稳定性进行了表征与分析。结果表明,改性微胶囊成型良好,石墨烯量子点的加入有助于提高微胶囊粒径的均匀性,同时复合石墨烯量子点及纳米铝的微胶囊导热系数提高了254.55%,达到0.78 W/(m·K),包覆率提高至92.65%,且相变悬浮液实现了48 h不分层。     

石墨烯及其衍生物的抗菌性研究进展

该文主要介绍近年来关于石墨烯及其衍生物在抗菌性方面的应用研究进展,包括石墨烯及其衍生物的抗菌性,抗菌性的测定方法对比,以及生物安全性评估等内容。研究表明:石墨烯及其衍生物具有良好的抗菌性和生物相容性,同时也是抗菌活性物质的理想载体。通过剂量调控和化学修饰可以保持石墨烯的优越性,同时又避免其诱发生物毒性,拓宽其在生物医学工程领域的研究与应用。     

石墨烯/量子点复合材料的研究进展

石墨烯/量子点复合材料因其具有优异的性能,近年来已成为国内外研究的热点。着重介绍了石墨烯/量子点复合材料的制备方法和应用进展。     

氮氯共掺杂石墨烯量子点的合成及其对汞离子检测

以果糖、乙二胺、盐酸为原料，采用水热法将N、Cl原子掺杂在石墨烯量子点上，制备出氮氯共掺杂石墨烯量子点(N,Cl-GQDs),利用透射电镜、X射线光电子能谱、紫外-可见吸收光谱、荧光光谱等手段对其结构和性能进行了表征。结果表明：合成的N,Cl-GQDs为分散效果良好的球形，与单独氮掺杂及未掺杂的石墨烯量子点相比，双元素掺杂石墨烯量子点具有更好的光学性能。同时利用电化学发光淬灭原理构建了传感器，实现了对汞离子的检测，计算得出检测限为0.03ng/mL。     

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。     

石墨烯/CdS量子点复合材料的电化学性能研究

原位合成法制备石墨烯/CdS量子点复合材料, 并考察其作为锂离子电池负极材料的电化学性能. 交流阻抗揭示电解质在石墨烯/CdS量子点复合材料表面形成稳定的SEI膜, 首次放电比容量达1264.7mAh/g, 循环20次后可逆容量为888.9mAh/g. 结果显示CdS量子点提高了石墨烯结构的稳定和层间传导性, 从而导致复合材料的电化学性能明显优于单独的石墨烯材料.     

荧光碳点的制备和性质及其应用研究进展

荧光碳点是继碳纳米管、纳米金刚石和石墨烯之后,最受关注的碳纳米材料之一。与传统半导体量子点相比,碳点具有优异的荧光性能、小尺寸特性、良好的生物相容性、低毒性以及表面易于化学修饰等特点,在环境检测、生物成像、药物载体、光催化及电催化技术等领域具有很好的潜在应用价值。总结了碳点合成方法、结构与性能及应用面进展,剖析了目前制约碳点应用发展的瓶颈问题,并展望了其未来的研究发展重点方向。      

Glowing Graphene Quantum Dots and Carbon Dots: Properties,Syntheses, and Biological Applications

The emerging graphene quantum dots (GQDs) and carbon dots (C‐dots) have gained tremendous attention for their enormous potentials for biomedical applications, owing to their unique and tunable photoluminescence properties, exceptional physicochemical properties, high photostability, biocompatibility, and small size. This article aims to update the latest results in this rapidly evolving field and to provide critical insights to inspire more exciting developments. We comparatively review the properties and synthesis methods of these carbon nanodots and place emphasis on their biological (both fundamental and theranostic) applications.     

Emissive ZnO-graphene quantum dots for white-light-emitting diodes

Hybrid nanostructures combining inorganic materials and graphene are being developed for applications such as fuel cells, batteries, photovoltaics and sensors. However, the absence of a bandgap in graphene has restricted the electrical and optical characteristics of these hybrids, particularly their emissive properties. Here, we use a simple solution method to prepare emissive hybrid quantum dots consisting of a ZnO core wrapped in a shell of single-layer graphene. We then use these quantum dots to make a white-light-emitting diode with a brightness of 798?cd?m(-2). The strain introduced by curvature opens an electronic bandgap of 250?meV in the graphene, and two additional blue emission peaks are observed in the luminescent spectrum of the quantum dot. Density functional theory calculations reveal that these additional peaks result from a splitting of the lowest unoccupied orbitals of the graphene into three orbitals with distinct energy levels. White emission is achieved by combining the quantum dots with other emissive materials in a multilayer light-emitting diode.     

Semiconductor quantum dots for in vivo imaging

Quantum dots play an important role in the in vitro, ex vivo, and in vivo optical imaging. Dramatic improvements have been achieved in the aspect of surface modification, biocompatibility, and targeting specificity, which had significant impact on the in vivo applications of quantum dots. This review summarizes the recent advances of quantum dots for in vivo imaging using both non-specific and targeted approaches. The toxicity of cadmium chalcogenide materials and alternative approaches such as the use of doped nanocrystal quantum dots were also discussed. The integration of quantum dots with other imaging techniques is also expected to give rise to a new generation of multifunctional probes for biomedical applications.     

Patterning nanoroads and quantum dots on fluorinated graphene

Using ab initio methods we have investigated the fluorination of graphene and find that different stoichiometric phases can be formed without a nucleation barrier, with the complete “2D-Teflon” CF phase being thermodynamically most stable. The fluorinated graphene is an insulator and turns out to be a perfect matrix-host for patterning nanoroads and quantum dots of pristine graphene. The electronic and magnetic properties of the nanoroads can be tuned by varying the edge orientation and width. The energy gaps between the highest occupied and lowest unoccupied molecular orbitals (HOMO-LUMO) of quantum dots are size-dependent and show a confinement typical of Dirac fermions. Furthermore, we study the effect of different basic coverage of F on graphene (with stoichiometries CF and C₄F) on the band gaps, and show the suitability of these materials to host quantum dots of graphene with unique electronic properties.     

Electronic excited states in bilayer graphene double quantum dots

We report tunneling spectroscopy experiments on a bilayer graphene double quantum dot device that can be tuned by all-graphene lateral gates. The diameter of the two quantum dots are around 50 nm and the constrictions acting as tunneling barriers are 30 nm in width. The double quantum dot features additional energies on the order of 20 meV. Charge stability diagrams allow us to study the tunable interdot coupling energy as well as the spectrum of the electronic excited states on a number of individual triple points over a large energy range. The obtained constant level spacing of 1.75 meV over a wide energy range is in good agreement with the expected single-particle energy spacing in bilayer graphene quantum dots. Finally, we investigate the evolution of the electronic excited states in a parallel magnetic field.     

Sn量子点/石墨烯复合材料的合成及储锂性能

Sn基材料是目前高容量锂离子电池电极材料研究的热点,但循环性能较差阻碍了其大规模应用。以氧化石墨烯为载体,通过化学还原法在载体表面成功均匀负载<10 nm的Sn量子点,合成Sn量子点/石墨烯(SnQds/rGO)复合电极材料。结果表明,Sn质量分数为90wt%的SnQds/rGO复合材料具有良好的综合电化学性能,首次放电容量和库伦效率分别为939 mAh/g和66.6%,经过200次循环后容量可达621 mAh/g,容量保持率为66.1%。小尺寸的Sn量子点与石墨烯复合能够增强电极材料的结构稳定性和降低阻抗,改善电极材料的循环性能和倍率性能,但会导致首次库伦效率有所降低。      

Influence of edge and center oxidation configurations on non-radiative relaxation in graphene quantum dots

Journal of Materials Science: Materials in Electronics - The photoluminescence quantum yield of graphene quantum dots (GQDs) is usually very low because the fast electron–hole recombination...     

Alignment of colloidal graphene quantum dots on polar surfaces

Controlling the orientation of nanostructures with anisotropic shapes is essential for taking advantage of their anisotropic electrical, optical, and transport properties in electro-optical devices. For large-area alignment of nanocrystals, so far orientations are mostly induced and controlled by external physical parameters, such as applied fields or changes in concentration. Herein we report on assemblies of colloidal graphene quantum dots, a new type of disk-shaped nanostructures, on polar surfaces and the control of their orientations. We show that the orientations of the graphene quantum dots can be determined, either in- or out-of-plane with the substrate, by chemical functionalization that introduces orientation-dependent interactions between the quantum dots and the surfaces.