荧光碳量子点的制备与进展

近年来,碳量子点作为一种新型的纳米材料,具有低细胞毒性、强荧光性、良好的生物相容性以及制备方法简单等特点,在生物传感、药物传递、细胞成像以及分析检测等领域具有潜在的应用价值,而受到人们的广泛关注。在此综述了碳量子点的制备方法、性质以及应用等,并对其发展前景进行了展望。     

基于绿色天然物质合成荧光碳点及其性质和应用综述

由于荧光显微技术、激光技术和纳米技术的快速发展,荧光纳米材料在生物医药研究和应用方面也越来越重要。传统的荧光材料包括小分子、共轭聚合物等,被广泛应用于生物成像、生物标记诊断、荧光检测等领域。20世纪,随着纳米科学的出现,一种新型的荧光材料——量子点开始进入人们的视野。传统的量子点主要由Ⅱ-Ⅵ、Ⅲ-Ⅴ族元素组成(如Cd、Te等),故称为半导体量子点,由于传统半导体量子点的主体为半导体,在生物安全和环境污染方面存在隐患,从而限制了量子点的应用和发展。自2004年首次发现荧光碳点以来,碳点就一直受到国内外学者的广泛关注。碳点一般指尺寸小于10 nm,具有准球形的结构,能稳定发光的一种纳米碳。与其他碳纳米材料相比,碳点具有独特的发光性质,即发光具有尺寸和波长依赖性。同时,碳点发光克服了有机染料发光不稳定、易光漂白等缺点。此外,碳点易制备且原材料来源广泛、价格低廉。碳点的细胞低毒性对于其在生物领域的应用至关重要,因此,受到了研究者的极大重视。由于碳点不含重金属元素,因此不具有无机半导体量子点的高毒性,可应用到生物成像以及荧光靶向定位领域。最近几年更是掀起了以绿色天然物质为碳源合成荧光碳点的研究热潮。合成此类碳点的优势在于其原料廉价、可再生,适合大规模制备,减少了与化学物质的接触,绿色环保。目前主要报道的原料集中在蔬菜、水果,植物花瓣和果实等,大部分天然物质均含有糖类、蛋白质等成分,从而在合成过程中自我钝化形成异元素掺杂碳点,使其光学性能优异并被广泛应用。但目前报道的此类碳点发光主要集中在短波长且荧光量子产率较低,发光机理尚未明确。本文基于绿色天然物质合成的荧光碳点的最新研究进展,总结了此类碳点的主要合成方法、表征方法、性质以及在离子传感、生物传感与检测、生物成像等领域中的应用,分析总结了此类碳点的优点和缺点,最后展望了基于绿色天然物质合成的荧光碳点在药物载体及药物传递、靶向治疗疾病等研究领域的发展方向。     

手性碳量子点的研究进展

手性碳量子点不仅具备手性性质,而且也继承了碳量子点的光致发光、低毒、生物相容性好等优异的性能,在传感器、催化和生物医药等领域展现出了巨大的应用前景。对手性碳量子点的发展历程、合成方法和应用研究进行了综述,并对手性碳量子点的发展和应用进行展望,为未来手性碳量子点的相关应用研究提供参考。     

纳米粒子的生物安全性研究进展

纳米材料具有表面效应、小尺寸效应、量子尺寸效应、宏观量子效应等特殊性质,在社会生产和生活中有广阔的应用前景,其对人体健康及环境的潜在影响已引起科学界及政府部门的关注。综述了大量常见的人工纳米粒子,包括碳纳米材料、纳米氧化物、纳米金属单质等的生物和毒理学国内外研究成果,比较了这些材料的毒理行为,分析了其生物毒性的产生机理,并展望了纳米粒子生物安全性研究的可能方向。     

石墨烯量子点在生物医学中的研究进展

石墨烯量子点是石墨烯超家族的衍生物,与高维度石墨烯相比,具有良好的生物相容性,较低的细胞毒性及较好的化学修饰性。自发现以来,石墨烯量子点的应用领域被逐渐地拓宽。其中石墨烯量子点的生物应用主要包括生物成像、生物传感器、药物运输、基因载体、抗菌抗病毒及肿瘤的光动力治疗研究等。主要介绍了近几年有关石墨烯量子点生物相容性及其在生物医学研究的进展,并对其发展前景进行了展望。     

基于生物质烟灰的碳量子点的制备及性能

分别以河北沧州和山东日照的民居烟道灰为原料,通过酸回流法成功制备了具有良好水溶性和稳定性的碳量子点。高分辨透射电子显微镜观察表明碳量子点为球形颗粒,内核尺寸小于1 nm;傅里叶变换红外光谱仪和X-射线光电子能谱仪研究表明碳量子点表面含有羧基、羟基等有机官能团;拉曼光谱和X-射线衍射测量表明碳量子点结晶性差,内部含有大量缺陷;荧光光谱测量结果表明碳量子点发射黄色荧光,波长大于500 nm且具有较高的荧光量子产率,最高可达3. 83%。结果表明,民居烟道灰有望成为碳量子点制备的新型廉价原料,所获得的黄光发射碳量子点在生物成像等领域具有广阔的应用前景。     

一步法合成特异性pH响应碳量子点及其发光机理研究

本研究利用溶剂热反应, 以柠檬酸为碳源, 甲酰胺和水为混合溶剂, 一步合成氮掺杂碳量子点。研究表明, 所制备的氮掺杂碳量子点具有良好的水溶性和明亮的蓝光发射, 以及典型的依赖于激发光的荧光发射特性。特别的是, 该碳量子点显示出不同于普通碳量子点的、独特的pH响应行为, 除了具有传统的荧光强度随着pH变化的响应行为外, 还表现出在碱性条件下, 产生新的不依赖于激发光的红光发射的性能。通过系统研究碳量子点在不同碱性环境和不同羟基含量溶液中的荧光特性, 结合拉曼光谱、红外、XPS等表征, 分析其化学组成与表面态分子, 探讨了其发光机制, 证实这种特异性pH响应行为是由于在强碱性环境中含有的大量氢氧根结合在碳量子点表面, 从而改变碳量子点的表面状态, 形成新的稳定的发光中心。最后, 通过细胞毒性实验及细胞成像分析表明, 所获得的碳量子点具有低细胞毒性, 并可作为荧光探针应用于细胞成像, 显示其在生物成像领域的潜在应用价值。     

硒化镉量子点的改性及作为生物荧光探针应用研究进展

硒化镉量子点在生物医学等领域有广阔的应用前景,但因其荧光强度低、生物不相容、荧光量子产率低等缺陷而在实际应用上受限。对硒化镉量子点进行有机改性能够达到改善上述缺陷,从而可以拓展其应用范围,例如太阳能电池和活体成像等。基于对硒化镉量子点进行有机改性的优势,综述了近几年来在硒化镉量子点改性的研究进展,包括有机分子改性、核-壳结构改性和低聚物改性。同时,还综述了硒化镉量子点在生物荧光探针领域的最新研究进展,并对未来的发展方向及应用前景作出了展望。     

生物医用量子点材料的研究进展

量子点是一种新型的荧光材料,由于独特的微观结构和物理、化学特性,使其在生物医学领域有广阔的应用前景。通过对近十多年来,有关含重金属的量子点制备技术、应用实例等的现状分析,提出了合成新颖的无重金属量子点即低毒性或生物兼容性量子点的重要意义和迫切性,介绍了合成低毒性或生物兼容性量子点的最新研究现状,并展望了今后的发展前景。     

Ⅱ-Ⅵ型量子点的制备、修饰及其生物应用

根据近10年的研究情况对Ⅱ-Ⅵ型量子点的制备、修饰进行了介绍,分析了量子点制备过程中的优、缺点. 探讨了Ⅱ-Ⅵ量子点在生物应用的最新研究成果,并对其研究前景进行了预测.     

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.     

Spontaneously Splitting Copper Nanowires into Quantum Dots on Graphdiyne for Suppressing Lithium Dendrites

As an emerging carbon allotrope, the controllable growth of graphdiyne has been an important means to explore its unique scientific properties and applications. In this work, the effect of the crystal structure of copper (Cu) on the growth of graphdiyne is systematically studied. It is found that the crystal boundaries are the origin of the reaction activity. The polycrystalline Cu nanowire with many crystal boundaries is spontaneously split into Cu quantum dots (about 3 nm) by the grown graphdiyne. These Cu quantum dots are uniformly dispersed on the graphdiyne, and they block the long-range ordered growth of the graphdiyne. These Cu quantum dots in situ supported on graphdiyne demonstrate high efficiency in inhibiting the growth of lithium dendrites in lithium metal batteries. Based on this interesting finding, the Cu quantum dots anchored on the all-carbon graphdiyne can be prepared on a large scale, and unique applications of Cu quantum dots in electrochemical fields can be implemented.     

Electronic transport properties of coupled quantum dots on carbon nanotubes

We investigate the electronic transport properties of coupled quantum dots, controlled by local gates on carbon nanotubes. The inter-dot coupling can be tuned from weak to strong by changing gate voltages, and oscillates in short and long period with the distance between two gates. We introduce a one-dimensional scattering model to describe the mechanism of the electron transport through the carbon nanotube quantum dots. We show that pi and PI* channels contribute differently to the inter-dot coupling and the transport phase plays a key role in the oscillations of the coupling.     

Multi-band silicon quantum dots embedded in an amorphous matrix of silicon carbide

Silicon quantum dots embedded in an amorphous matrix of silicon carbide were realized by a magnetron co-sputtering process and post-annealing. X-ray photoelectron spectroscopy, glancing x-ray diffraction, Raman spectroscopy and high-resolution transmission electron microscopy were used to characterize the chemical composition and the microstructural properties. The results show that the sizes and size distribution of silicon quantum dots can be tuned by changing the annealing atmosphere and the atom ratio of silicon and carbon in the matrix. A physicochemical mechanism is proposed to demonstrate this formation process. Photoluminescence measurements indicate a multi-band configuration due to the quantum confinement effect of silicon quantum dots with different sizes. The PL spectra are further widened as a result of the existence of amorphous silicon quantum dots. This multi-band configuration would be extremely advantageous in improving the photoelectric conversion efficiency of photovoltaic solar cells.     

碳量子点敏化二氧化钛复合光催化剂的制备与光催化降解苯酚

为了解决二氧化钛光催化剂存在的禁带宽度大和量子效率低的问题,利用具有优异光吸收性能和电子转移能力的碳量子点改性二氧化钛,可以大幅度提高二氧化钛的光催化性能。本文以富勒烯碳灰为原料,利用混酸回流法制备了一种发黄蓝光的碳量子点,然后采用一步水热法将碳量子点负载于二氧化钛制备了复合光催化剂。借助高分辨透射电子显微镜(HRTEM)、傅里叶变换红外光谱(FT-IR)、紫外可见光光谱(UV-vis)、荧光光谱、X射线衍射(XRD)、X射线光电子能谱分析(XPS)等表征手段对碳量子点和复合光催化剂进行表征,并以苯酚作为模拟废水进行光催化降解实验,结果表明,与纯二氧化钛相比,用碳量子点改性的二氧化钛对苯酚的去除率可提高60%,且其具有较好的稳定性与重复使用性,6次循环利用后仍可达到初次的97.8%。     

One-pot synthesis of hydrophilic and hydrophobic fluorescent carbon dots using deep eutectic solvents as designer reaction media

Carbon dots are often synthesized in the presence of a carbon source and passivating agents in which they are crucial for an enhanced fluorescence. The solvent choice and/or combination to be used in the synthesis of these nanoparticles can influence their surface chemical composition, morphology, and fluorescence properties. In this study, highly fluorescent carbon dots were synthesized using deep eutectic solvents of different compositions as green solvent media and doping agent. Resulting carbon dots were then separated by their hydrophilicity/hydrophobicity using a three-phase solvent system (water/acetone/chloroform) and compared with traditional centrifugation-based separation method. Carbon dots with a size below 20 nm and quantum yield reaching 50% were obtained. Many properties of them including surface functional groups, optical, fluorescence, and electric properties were shown to be determined by the deep eutectic solvent composition.     

Synthesis and modulation of the optical properties of carbon quantum dots using microwave radiation

Abstract

Carbon quantum dots have exhibited highly fluorescent characteristics as nanomaterials. Soluble in water and easily synthesized by multiple simple techniques, there are immense fabrication possibilities by permuting their properties via changing precursors, synthesis route, reaction parameters, etc. As economic and environment-friendly seed material, they are being viewed as an alternative to conventional fluorescent materials in myriad of applications including displays, cancer detection, drug delivery carriers in biomedicine, absorbing material in photovoltaics, etc. In this work, the hydrophilic carbon quantum dots were synthesized from the aqueous solution of citric acid and urea through microwave radiation for varying heat durations. The method is facile, faster and friendly to the environment without any need for high temperature and complicated chemical techniques. It was observed that the bandgap of the fabricated carbon quantum dots and its optical properties namely absorbance, photoluminescence enhanced with an increase in exposure of samples to heat up to an optimum limit, owing to the increase in density of states. However, further exposure to heat for longer duration degraded the absorbance and bandgap while photoluminescence gets saturated. Stokes’ shift revealed that all the synthesized carbon quantum dots possess stable emission. This was reconfirmed from consistent emission peak positions under varying excitation in the samples. The absorbance and PL spectrum exhibited by the synthesized dots makes it a suitable material for boosting the performance of organic solar cell.     

碳量子点的合成和应用

近几年,碳量子点作为纳米碳材料中的一颗新星,引起了人们广泛的关注。碳量子点除了具有优秀的光学性质,还有良好的水溶性、低毒性、环境友好、成本低等优点。自从碳量子点被发现以来,人们发现了多种多样的合成碳量子点的方法,主要有电化学法、化学烧蚀法、激光法和微波法等。由于碳量子点具有许多优点,被广泛应用于很多领域,特别是在光催化、生物成像、化学传感等方面。本文介绍了碳量子点的主要合成方法和主要应用。     

三色碳点荧光防伪油墨的制备与性能研究

目的 通过优化碳点合成方法和油墨配方,制备一种具有优良防伪效果和印刷适性的环保丝网印刷油墨。方法 以邻苯二胺为碳源,水或乙醇为溶剂,采用溶剂(水)热法制备红色和黄色碳点。以柠檬酸钠和碳酸氢铵为碳源和氮源制备蓝色碳点,并对三色碳点的结构组成和光学性质进行表征和分析。以三色碳点作为荧光颜料,选择乙醇或水作为溶剂,水性环氧树脂或聚丙烯酸树脂作为连接料,通过实验获得最佳配比,制备三色荧光防伪油墨。结果 三色碳点均具有较为均匀的尺寸,在365 nm紫外光激发下分别发射725 nm的红色荧光、450 nm的蓝色荧光和570 nm的黄色荧光,且rCDs、bCDs和yCDs的荧光量子产率分别为56.63%、64.37%和78.26%。通过对pH、细度、黏度等性能测试,该荧光防伪油墨各项印刷适性指标良好。结论 通过优化碳点合成方法可控调节荧光发射光谱,制备出具有较宽的紫外吸收带、较窄的发射光谱带、荧光量子产率高的三色碳点。以此碳点作为荧光颜料可以制备出印刷适性良好的水性油墨,满足荧光防伪印刷的要求。     

PEI-CDs复合物的制备及其在药物传输中的应用研究

癌症是21世纪威胁人类健康的三大杀手之一。目前,治疗癌症的药物由于缺乏靶向性和选择性对正常细胞和组织也会造成严重损害。靶向性载药体系的构建是解决这一难题的关键。碳点(Cardon dots,CDs)是近年来发展起来的一种新型荧光纳米材料,因其具有无毒性、优良的生物兼容性、良好的发光性能等优点,在肿瘤标记及药物的靶向输送中具有重大的应用潜力。本实验以枸杞为碳源,采用水热法制备碳量子点,通过静电作用将聚乙烯亚胺(PEI)修饰在碳量子点表面,形成PEI-CDs复合物,在室温下通过物理吸附的手段使盐酸阿霉素(Dox)组装到PEI-CDs复合物表面,形成PEI-CDs-Dox型荧光载药系统,并对该载药体系进行体外释放模拟实验。实验结果表明,阿霉素的负载显著增强了碳点复合物的荧光性能,24 h释放率可达90%,随着药物的释放,体系的荧光强度逐渐下降,据此可以将其进一步应用于细胞靶向成像及药物靶向监测。