Facile Microwave‐Assisted Solid‐Phase Synthesis of Highly Fluorescent Nitrogen–Sulfur‐Codoped Carbon Quantum Dots for Cellular Imaging Applications

Carbon quantum dots (CQDs) have recently attracted significant attention for both their fundamental science and technological applications as a new class of fluorescent zero‐dimensional nanomaterials with a size below 10 nm. However, the reported methods of synthesis were generally less suitable for the large‐scale production of the CQDs with high‐fluorescent quantum yield (QY). In the paper, a novel one‐pot microwave‐assisted drying synthesis approach was presented to prepare CQDs with high QY of 61.3 % for the first time. The production yield of CQDs was 35±3 % in weight. The as‐prepared CQDs were characterized by various techniques such as TEM, AFM, XRD, XPS, FTIR spectroscopy, UV/Vis absorption spectroscopy, and fluorescence spectroscopy. The results showed that the high QY of CQDs was largely attributed to the dual doping of nitrogen and sulphur into CQDs. Such CQDs were then used as live‐cell imaging reagents due to their high QY, good water dispersibility, fine biocompatibility, high photostability, and low cytotoxicity.     

Understanding the Photoluminescence Mechanism of Nitrogen‐Doped Carbon Dots by Selective Interaction with Copper Ions

Doped fluorescent carbon dots (CDs) have drawn widespread attention because of their diverse applications and attractive properties. The present report focusses on the origin of photoluminescence in nitrogen‐doped CDs (NCDs), which is unraveled by the interaction with Cu²⁺ ions. Detailed spectroscopic and microscopic studies reveal that the broad steady‐state photoluminescence emission of the NCDs originates from the direct recombination of excitons (high energy) and the involvement of defect states (low energy). In addition, highly selective detection of Cu²⁺ is achieved, with a detection limit of 10 μm and a dynamic range of 10 μm –0.4 mm . The feasibility of the present sensor for the detection of Cu²⁺ in real water samples is also presented.     

Nitrogen‐Doped Carbon Nanomaterials: Synthesis,Characteristics and Applications

Nonmetallic carbon‐based nanomaterials (CNMs) are important in various potential applications, especially after the emergence of graphene and carbon nanotubes, which demonstrate outstanding properties arising from their unique nanostructures. The pristine graphitic structure of CNMs consists of sp² hybrid C?C bonds and is considered to be neutral in nature with low wettability and poor reactivity. To improve its compatibility with other materials and, hence, for greater applicability, CNMs are generally required to be functionalized effectively and/or doped with heteroatoms in their graphitic frameworks for feasible interfacial interactions. Among the various possible functional/doping elements, nitrogen (N) atoms have received much attention given their potential to fine tune the intrinsic properties, such as the work‐function, charge carrier concentration, surface energy, and polarization, of CNMs. N‐doping improves the surface energy and reactivity with enhanced charge polarization and minimal damage to carbon frameworks. The modified surface energy and chemical activity of N‐doped carbon nanomaterials (NCNMs) can be useful for a broad range of applications, including fuel cells, solar cells, Li‐ion batteries, supercapacitors, chemical catalysts, catalyst supports, and so forth.     

异元素掺杂碳点的制备及其在生物成像中的应用

荧光碳点具有良好的生物相容性和优良的抗光漂白能力,因此碳点在生物荧光成像方面的应用潜力受到广泛关注,但是碳点相对较低的荧光量子产率和缺乏近红外荧光发射的缺陷限制了碳点在荧光成像分析中的应用.随着异元素掺杂对碳点结构和荧光性质的改善,碳点被越来越广泛地用于生物成像.本文对近年来元素掺杂碳点的合成方法、异元素掺杂对碳点光学性质的影响和元素掺杂碳点在成像分析中的进展进行了综述,并对其应用前景进行了展望.     

Electrochemiluminescence of CdSe Quantum Dots Composited with Nitrogen‐Doped Carbon Nanotubes

A nanocomposite of CdSe quantum dots with nitrogen‐doped carbon nanotubes was prepared for enhancing the electrochemiluminescent (ECL) emission of quantum dots. With hydrogen peroxide as co‐reactant, the nanocomposite modified electrode showed a cathodic ECL emission with a starting potential of ?0.97 V (vs. Ag/AgCl) in phosphate buffer solution, which was five‐times stronger than that from pure CdSe quantum dots and three‐times stronger than that from CdSe quantum dots composited with carbon nanotubes. The latter showed a starting potential of ?1.19 V. This result led to a sensitive ECL sensing of hydrogen peroxide with good stability, acceptable reproducibility and a detection limit down to 2.1×10^?7 mol L^?1. Nitrogen‐doped carbon nanotubes could be used as a good material for the construction of sensitive ECL biosensors for chemical and biochemical analysis.     

One‐Pot Green Synthesis of Nitrogen‐Doped Carbon Quantum Dots for Cell Nucleus Labeling and Copper(II) Detection

The doping of nitrogen into carbon quantum dots is vitally important for improved fluorescence performance. However, the synthesis of nitrogen‐doped carbon quantum dots (N‐CQDs) is usually conducted under strong acid and high temperature, which results in environmental pollution and energy consumption. Herein, the N‐CQDs were prepared by a mild one‐pot hydrothermal process. The hydrothermal reaction temperature was adjusted to control the particle size, nitrogen/carbon atomic ratio, and quantum yield. The products were water soluble with a narrow particle size distribution and good dispersion stability over a wide pH range. The N‐CQDs could penetrate into the HeLa cell nucleus without any further functionalization. Moreover, the fluorescence of N‐CQDs could be selectively quenched by Cu²⁺, which suggested applications for the detection of Cu²⁺ in human plasma.     

基于上转换发光的碳量子点制备及应用研究

碳量子点具有易制备、低毒性、化学惰性高、荧光特性稳定等特点,和其他碳纳米材料(如富勒烯、碳纳米管和石墨烯等)一样引起了研究者的广泛关注。本文将从碳量子点的合成、特性、改性和应用等方面进行阐述,并对其受长波长光激发后可发出短波长光的这一上转换发光特性进行重点综述,为今后碳量子点的合成、改性以及应用提供一定的参考。     

新型水溶性多色荧光碳点的制备及细胞成像研究

以鸡蛋清和牛奶分别与葡萄糖进行水热反应,制备水溶性多色荧光碳点,通过膜和柱层析分离纯化,利用透射电子显微镜(TEM)、紫外吸收光谱(UV)、荧光光谱(FL)、红外光谱(FTIR)等技术对所制备碳纳米粒子的粒径大小、吸收光谱、发光性质、表面基团进行表征。将所制备的碳点与小鼠黑色素瘤细胞共孵育,进行细胞成像应用评价。结果表明:制备的两种水溶性荧光碳点平均粒径分别为2.5 nm和4.9 nm,可在紫外灯下发出明亮的荧光,紫外最大吸收波长为250 nm。基于鸡蛋清或牛奶与葡萄糖反应制备的多色荧光碳量子点具有良好水溶性,其荧光光谱最大发射波长分别在410 nm和400 nm处,同时在660~800 nm激发波长范围内具有上转换性质,且荧光发射光谱随着激发光波长的增加发生红移。红外光谱表明存在—COOH、—NH2和—OH基团。细胞成像结果表明,在405 nm或488 nm激光照射下,所制备的碳点在细胞内的荧光成像清晰可见,而且在碳点浓度小于2.5 mg/mL时,均表现出较低的细胞毒性。     

Reduced Carbon Dots versus Oxidized Carbon Dots: Photo‐ and Electrochemiluminescence Investigations for Selected Applications

The study of the composition, morphology, and surface structure of carbon dots (Cdots) is critical to understanding their effect on the photo‐ and electrochemiluminescence (PL and ECL) of Cdots in selected applications. Herein, two kinds of Cdots were prepared with 3‐(3,4‐dihydroxyphenyl)‐L ‐alanine (L ‐DOPA) as precursor. The Cdots prepared by using a carbonization‐extraction strategy have a low oxidation level and are denoted as reduced Cdots (r‐Cdots). The Cdots obtained with a carbonization‐oxidation process are highly oxidized and are denoted as oxidized Cdots (o‐Cdots). The o‐Cdots have a carbon core and oxygen‐containing loose shell, but the r‐Cdots consist mainly of the carbon core. Whereas r‐Cdots have a strong blue PL but no apparent ECL response, o‐Cdots exhibit a relatively weak PL and strong ECL emission. These properties allow for selected applications of the Cdots. The r‐Cdots were used in cell imaging with their high PL emission. The o‐Cdots, with their high ECL efficiencies, were selected to sense Cu²⁺ with Cu²⁺‐inducing ECL quenching in the o‐Cdots/K₂S₂O₈ system. This work provides the possibility to control the composition of Cdots for selected applications and shows a good way to characterize surface traps of Cdots because ECL is characterized by the surface‐state and PL is mainly related to the core‐state in Cdots.     

Red,Green, and Blue Luminescence by Carbon Dots: Full‐Color Emission Tuning and Multicolor Cellular Imaging

A facile approach for preparation of photoluminescent (PL) carbon dots (CDs) is reported. The three resulting CDs emit bright and stable red, green and blue (RGB) colors of luminescence, under a single ultraviolet‐light excitation. Alterations of PL emission of these CDs are tentatively proposed to result from the difference in their particle size and nitrogen content. Interestingly, up‐conversion (UC)PL of these CDs is also observed. Moreover, flexible full‐color emissive PVA films can be achieved through mixing two or three CDs in the appropriate ratios. These CDs also show low cytotoxicity and excellent cellular imaging capability. The facile preparation and unique optical features make these CDs potentially useful in numerous applications such as light‐emitting diodes, full‐color displays, and multiplexed (UC)PL bioimaging.     

微波一步法制备氮掺杂碳点及其用于多巴胺的检测研究

以柠檬酸为碳源,尿素为氮源,采用微波一步法制备得到稳定性高,水溶性好的蓝色荧光的氮掺杂碳点。并将该氮掺杂碳点经透射电子显微镜(TEM)、原子力显微镜(AFM)、X-射线光电子能谱(XPS)和红外光谱(IR)表征,发现其粒径为0.5～5 nm,平均粒径2.6 nm,富含羟基、羧基和氨基等官能团。在优化实验条件下,多巴胺浓度在2.5～37.5μmol/L范围内与N-CDs的荧光猝灭效率(I_F/I_(F0))呈良好的线性关系,方法的检出限为0.08μmol/L。采用该方法对正常人尿液中的多巴胺进行测定,其加标回收率为99.5%～106%,RSD为1.8%～2.3%,方法准确度高,结果满意。     

Phenyl‐Modified Carbon Nitride Quantum Dots with Distinct Photoluminescence Behavior

A novel type of quantum dot (Ph‐CN) is manufactured from graphitic carbon nitride by “lining” the carbon nitride structure with phenyl groups through supramolecular preorganization. This approach requires no chemical etching or hydrothermal treatments like other competing nanoparticle syntheses and is easy and safe to use. The Ph‐CN nanoparticles exhibit bright, tunable fluorescence, with a high quantum yield of 48.4 % in aqueous colloidal suspensions. Interestingly, the observed Stokes shift of approximately 200 nm is higher than the maximum values reported for carbon nitride based fluorophores. The high quantum yield and the large Stokes shift are related to the structural surface organization of the phenyl groups, which affects the π‐electron delocalization in the conjugated carbon nitride networks and induces colloidal stability. The remarkable performance of the Ph‐CN nanoparticles in imaging is demonstrated by a simple incubation study with HeLa cells.     

氮掺杂碳量子点的制备及其在细胞成像与邻硝基苯酚检测中的应用

以L-瓜氨酸和尿素为前驱体,采用水热法制备了经济、低毒且具有强荧光性能的氮掺杂碳量子点(N-CQDs),并采用透射电子显微镜(TEM)、傅立叶变换红外光谱(FT-IR)、X射线光子能谱(XPS)等表征了N-CQDs的性能。结果表明,该N-CQDs的平均粒径为2.8 nm,量子产率为39.2%,具有良好的水溶性、稳定性和生物相容性,可用于HepG2细胞成像。此外,基于邻硝基苯酚(o-NP)对N-CQDs的荧光猝灭现象,构建了一种用于测定o-NP的高选择性、高灵敏的荧光探针。在o-NP浓度0.083 3～12.0μmol/L范围内,N-CQDs荧光猝灭程度与o-NP浓度呈现良好的线性关系(r²=0.998),检出限(S/N=3)为25.2 nmol/L。该方法已成功用于贵州省万峰湖和顶效河水样中o-NP的检测。     

水热炭化制备碳量子点及其应用

碳量子点作为新兴的“零维”碳纳米材料引起人们广泛的关注。水热炭化法是目前为止应用最广泛的碳量子点合成方法之一。水热炭化合成碳量子点取材广泛、过程简单,其最大的特点是合成的碳量子点表面含有丰富的含氧官能团,水溶性优异,在制备过程中即可对碳量子点进行表面功能化改性。此外,水热法合成的碳量子点具有石墨或无定形结构的碳核。水热碳量子点的结构和性质主要受原料种类及制备条件（水热炭化温度、时间及化学添加剂）的影响,产物在光催化技术、分析检测、活体成像和细胞标记、发光二极管（LED）及药物输送等领域展示出较好应用效果。本文综述了水热碳量子点的制备、性质、形成机理（包括原料的脱水、聚合、炭化及钝化过程）及发光机理（表面缺陷态效应和量子尺寸效应）,并对水热碳量子点的应用进行了总结。最后,对水热碳量子点发展过程中尚待解决的问题进行总结,对其未来的发展方向进行了展望。     

Hot-Tailoring of Carbon Nitride Dots with Redshifted Photoluminescence for Visual Double Text Encryption and Bioimaging

The fabrication of carbon dots and their doped forms by top-down chemical cleavage has attracted considerable attention in the efforts to meet the increasing demands for optoelectronic applications ranging from biosensing to electro- and photocatalysis. However, due to strong quantum confinement effects, the size decrease often leads to an increase in the band gap, even in the emission of deep-ultraviolet (DUV) light, which greatly limits their applications. Here, we report a facile hot-tailoring strategy for fabricating carbon nitride nanodots (CNDs) with redshifted intrinsic photoluminescent (PL) emission, compared with the pristine bulk precursor. It has been found that the different leaving abilities of the C,N-containing groups during the pyrolysis stage and the chemical passivation during the liquid-collection stage played vital roles. Due to the redshifted photoluminescence and other attractive features, the as-obtained CNDs were successfully applied in visual double text encryption with higher security and also in bioimaging with photostability superior to traditional dyes. This work highlights the great potential of the hot-tailoring method in modulating carbon-based nanostructures and offsetting band-gap widening as the size decreases.     

The Use of a Microreactor for Rapid Screening of the Reaction Conditions and Investigation of the Photoluminescence Mechanism of Carbon Dots

A microreactor is applied and reported, for the first time, in the field of research of carbon dots (CDs), including rapid screening of the reaction conditions and investigation of the photoluminescence (PL) mechanism. Various carbonaceous precursors and solvents were selected and hundreds of reaction conditions were screened (ca. 15 min on average per condition). Through analyzing the screened conditions, tunable PL emission maxima, from about 330 to 550 nm with respectable PL quantum yields, were achieved. Moreover, the relationship between different developmental stages of the CDs and the PL properties was explored by using the microreactor. The PL emission was observed to be independent of the composition, carbonization extent, and morphology/size of the CDs. This study unambiguously presents that a microreactor could serve as a promising tool for the research of CDs.     

Tunable Photoluminescence Across the Entire Visible Spectrum from Carbon Dots Excited by White Light

Although reports have shown shifts in carbon dot emission wavelengths resulting from varying the excitation wavelength, this excitation‐dependent emission does not constitute true tuning, as the shifted peaks have much weaker intensity than their dominant emission, and this is often undesired in real world applications. We report for the first time the synthesis and photoluminescence properties of carbon dots whose peak fluorescence emission wavelengths are tunable across the entire visible spectrum by simple adjustment of the reagents and synthesis conditions, and these carbon dots are excited by white light. Detailed material characterization has revealed that this tunable emission results from changes in the carbon dots’ chemical composition, dictated by dehydrogenation reactions occurring during carbonization. These significantly alter the nucleation and growth process, resulting in dots with either more oxygen‐containing or nitrogen‐containing groups that ultimately determine their photoluminescence properties, which is in stark contrast to previous observations of carbon dot excitation‐dependent fluorescence. This new ability to synthesize broadband excitable carbon dots with tunable peak emissions opens up many new possibilities, particularly in multimodal sensing, in which multiple analytes and processes could be monitored simultaneously by associating a particular carbon dot emission wavelength to a specific chemical process without the need for tuning the excitation source.     

Photoactivated Fluorescence Enhancement in F,N‐Doped Carbon Dots with Piezochromic Behavior

Photoactivation in CdSe/ZnS quantum dots (QDs) on UV/Vis light exposure improves photoluminescence (PL) and photostability. However, it was not observed in fluorescent carbon quantum dots (CDs). Now, photoactivated fluorescence enhancement in fluorine and nitrogen co‐doped carbon dots (F,N‐doped CDs) is presented. At 1.0 atm, the fluorescence intensity of F,N‐doped CDs increases with UV light irradiation (5 s–30 min), accompanied with a blue‐shift of the fluorescence emission from 586 nm to 550 nm. F,N‐doped CDs exhibit photoactivated fluorescence enhancement when exposed to UV under high pressure (0.1 GPa). F,N‐doped CDs show reversible piezochromic behavior while applying increasing pressure (1.0 atm to 9.98 GPa), showing a pressure‐triggered aggregation‐induced emission in the range 1.0 atm–0.65 GPa. The photoactivated CDs with piezochromic fluorescence enhancement broadens the versatility of CDs from ambient to high‐pressure conditions and enhances their anti‐photobleaching.     

碳量子点的合成与应用

近年来,由于碳纳米材料具有高的催化活性以及好的稳定性等优点,其在科学、工程以及商业领域都得到了广泛的应用。其中新型"零维"碳纳米材料--碳量子点(carbon dots, CDs)具有荧光信号稳定、无光闪烁、激发波长和发射波长可调控等独特的光学性质,以及生物毒性小和生物相容性好等优势,逐渐成为碳纳米材料的研究热点,广泛应用于生物成像、生物细胞标记、传感器、光催化、太阳能电池以及发光元件等领域。本文主要综述了CDs的不同合成方法(包括自上而下法和自下而上法)及其应用。