One‐Step Hydrothermal Synthesis of Nitrogen‐Doped Conjugated Carbonized Polymer Dots with 31% Efficient Red Emission for In Vivo Imaging

Carbon dots with long‐wavelength emissions, high quantum yield (QY) and good biocompatibility are highly desirable for biomedical applications. Herein, a green, facile hydrothermal synthesis of highly efficient red emissive nitrogen‐doped carbonized polymer dots (CPDs) with optimal emission at around 630 nm are reported. The red emissive CPDs possess a variety of superior properties including excellent water dispersibility, good biocompatibility, narrow bandwidth emission, an excitation‐independent emission, and high QY (10.83% (in water) and 31.54% (in ethanol)). Further studies prove that such strong red fluorescence is ascribed to the efficient conjugated aromatic π systems and hydrogen bonds of CPDs. And the fluorescence properties of CPDs can be regulated by adjusting the dosage of HNO₃ before the reaction. Additionally, the as‐prepared CPDs are successfully used as a fluorescent probe for bioimaging, both in vitro and in vivo. More importantly, biodistribution results demonstrate that most CPDs and their metabolites are not only excreted in urine but also excreted by hepatobiliary system in a rapid manner. Besides, the CPDs could easily cross the blood brain barrier, which may provide a valuable strategy for the theranostics of some brain diseases through real‐time tracking.     

Solvent‐Controlled Synthesis of Highly Luminescent Carbon Dots with a Wide Color Gamut and Narrowed Emission Peak Widths

Carbon dots (CDs) have tremendous potential applications in bioimaging, biomedicine, and optoelectronics. By far, it is still difficult to produce photoluminescence (PL) tunable CDs with high quantum yield (QY) across the entire visible spectrum and narrow the emission peak widths of CDs close to those of typical quantum dots. In this work, a series of CDs with tunable emission from 443 to 745 nm, quantum yield within 13–54%, and narrowed full width at half maximum (FWHM) from 108 to 55 nm, are obtained by only adjusting the reaction solvents in a one‐pot solvothermal route. The distinct optical features of these CDs are based on their differences in the particle size, and the content of graphitic nitrogen and oxygen‐containing functional groups, which can be modulated by controlling the dehydration and carbonization processes during solvothermal reactions. Blue, green, yellow, red, and even pure white light emitting films (Commission Internationale de L'Eclairage (CIE)= 0.33, 0.33, QY = 39%) are prepared by dispersing one or three kinds of CDs into polyvinyl alcohol with appropriate ratios. The near‐infrared emissive CDs are excellent fluorescent probes for both in vitro and in vivo bioimaging because of their high QY in water, long‐term stability, and low cytotoxicity.     

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.     

Near‐Infrared Excitation/Emission and Multiphoton‐Induced Fluorescence of Carbon Dots

Carbon dots (CDs) have significant potential for use in various fields including biomedicine, bioimaging, and optoelectronics. However, inefficient excitation and emission of CDs in both near‐infrared (NIR‐I and NIR‐II) windows remains an issue. Solving this problem would yield significant improvement in the tissue‐penetration depth for in vivo bioimaging with CDs. Here, an NIR absorption band and enhanced NIR fluorescence are both realized through the surface engineering of CDs, exploiting electron‐acceptor groups, namely molecules or polymers rich in sulfoxide/carbonyl groups. These groups, which are bound to the outer layers and the edges of the CDs, influence the optical bandgap and promote electron transitions under NIR excitation. NIR‐imaging information encryption and in vivo NIR fluorescence imaging of the stomach of a living mouse using CDs modified with poly(vinylpyrrolidone) in aqueous solution are demonstrated. In addition, excitation by a 1400 nm femtosecond laser yields simultaneous two‐photon‐induced NIR emission and three‐photon‐induced red emission of CDs in dimethyl sulfoxide. This study represents the realization of both NIR‐I excitation and emission as well as two‐photon‐ and three‐photon‐induced fluorescence of CDs excited in an NIR‐II window, and provides a rational design approach for construction and clinical applications of CD‐based NIR imaging agents.     

Thermally Activated Upconversion Near‐Infrared Photoluminescence from Carbon Dots Synthesized via Microwave Assisted Exfoliation

Upconversion near‐infrared (NIR) fluorescent carbon dots (CDs) are important for imaging applications. Herein, thermally activated upconversion photoluminescence (UCPL) in the NIR region, with an emission peak at 784 nm, which appears under 808 nm continuous‐wave laser excitation, are realized in the NIR absorbing/emissive CDs (NIR‐CDs). The NIR‐CDs are synthesized by microwave‐assisted exfoliation of red emissive CDs in dimethylformamide, and feature single or few‐layered graphene‐like cores. This structure provides an enhanced contact area of the graphene‐like plates in the core with the electron‐acceptor carbonyl groups in dimethylformamide, which contributes to the main NIR absorption band peaked at 724 nm and a tail band in 800–850 nm. Temperature‐dependent photoluminescence spectra and transient absorption spectra confirm that the UCPL of NIR‐CDs is due to the thermally activated electron transitions in the excited state, rather than the multiphoton absorption process. Temperature dependent upconversion NIR luminescence imaging is demonstrated for NIR‐CDs embedded in a polyvinyl pyrrolidone film, and the NIR upconversion luminescence imaging in vivo using NIR‐CDs in a mouse model is accomplished.     

Solid‐State Carbon Dots with Red Fluorescence and Efficient Construction of Dual‐Fluorescence Morphologies

Stable solid‐state red fluorescence from organosilane‐functionalized carbon dots (CDs) with sizes around 3 nm is reported for the first time. Meanwhile, a novel method is also first reported for the efficient construction of dual‐fluorescence morphologies. The quantum yield of these solid‐state CDs and their aqueous solution is 9.60 and 50.7%, respectively. The fluorescence lifetime is 4.82 ns for solid‐state CDs, and 15.57 ns for their aqueous solution. These CDs are detailedly studied how they can exhibit obvious photoluminescence overcoming the self‐quenching in solid state. Luminescent materials are constructed with dual fluorescence based on as‐prepared single emissive CDs (red emission) and nonfluorescence media (starch, Al₂O₃, and RnOCH₃COONa), with the characteristic peaks located at nearly 440 and 600 nm. Tunable photoluminescence can be successfully achieved by tuning the mass ratio of CDs to solid matrix (such as starch). These constructed dual‐fluorescence CDs/starch composites can also be applied in white light‐emitting diodes with UV chips (395 nm), and oxygen sensing.     

Metal ion sensing and light activated antimicrobial activity of aloe-vera derived carbon dots

Carbon dots (CDs) have emerged out as a potential material amongst the carbon family for a wide range of applications including chemical/biological sensing, photocatalysis, bioimaging, etc. The green synthesis of these CDs from natural sources is gaining the significant interest of peer community for their wide utility. Herein, we present a facile one-step pyrolysis method for CDs synthesis from Aloe-Vera extract, which show bright blue luminescence under UV light with a quantum yield of 12.3%. Further, ex-situ morphological, structural and optical characterizations reveal their high quality and excitation independent emission behavior with the presence of carboxyl, hydroxyl functional groups. Furthermore, these CDs were studied for Fe(III) sensing in water without any surface modifications and assessed for their light activated antibacterial activity against E.Coli and Staphylococcus aureus.     

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。     

Facile plasma-induced fabrication of fluorescent carbon dots toward high-performance white LEDs

In this study, we report a facile plasma-induced method to fabricate photoluminescent carbon dots (CDs) using acrylamide as the precursor in few minutes. The Fourier transform infrared spectra, UV–Vis absorption spectra, photoluminescence, fluorescent lifetime, and transmission electron microscopy of the as-prepared CDs were investigated thoroughly. The CDs have a narrow size distribution of 3–4 nm and exhibit strong blue fluorescence with quantum yield of ~6 %. More importantly, we explored the CDs as color converters along with CdTe quantum dots to generate white light-emitting diodes (LEDs) using a UV-LED chip as the excitation light source. Compared with the conventional YAG:Ce phosphor-based white LEDs, this resulted LED emitted white light with a higher color rendering index up to 87, which may find their potential in optoelectronic device.     

Bright Aggregation‐Induced‐Emission Dots for Targeted Synergetic NIR‐II Fluorescence and NIR‐I Photoacoustic Imaging of Orthotopic Brain Tumors

Precise diagnostics are of significant importance to the optimal treatment outcomes of patients bearing brain tumors. NIR‐II fluorescence imaging holds great promise for brain‐tumor diagnostics with deep penetration and high sensitivity. This requires the development of organic NIR‐II fluorescent agents with high quantum yield (QY), which is difficult to achieve. Herein, the design and synthesis of a new NIR‐II fluorescent molecule with aggregation‐induced‐emission (AIE) characteristics is reported for orthotopic brain‐tumor imaging. Encapsulation of the molecule in a polymer matrix yields AIE dots showing a very high QY of 6.2% with a large absorptivity of 10.2 L g^?1 cm^?1 at 740 nm and an emission maximum near 1000 nm. Further decoration of the AIE dots with c‐RGD yields targeted AIE dots, which afford specific and selective tumor uptake, with a high signal/background ratio of 4.4 and resolution up to 38 µm. The large NIR absorptivity of the AIE dots facilitates NIR‐I photoacoustic imaging with intrinsically deeper penetration than NIR‐II fluorescence imaging and, more importantly, precise tumor‐depth detection through intact scalp and skull. This research demonstrates the promise of NIR‐II AIE molecules and their dots in dual NIR‐II fluorescence and NIR‐I photoacoustic imaging for precise brain cancer diagnostics.     

Realization of solid-state red fluorescence and concentration-induced multicolor emission from N,B co-doped carbon dots

As a new type of luminescent material, carbon dots (CDs) have attracted increased attention for their superior optical properties in recent years. However, solid-state fluorescent CDs, especially with red emission, are still a major challenge. Here, CDs with solid-state red emission were synthesized by co-doping of N and B using the one-step microwave method. The CD powder exhibits excitation-independent solid-state red fluorescence without any dispersion matrices, with optimum solid-state fluorescence wavelength of 623 nm. The hydrogen bonding interaction in CDs is helpful for solid-state fluorescence of CDs. The I_G/I_D value of CDs reaches up to 3.49, suggesting their very high graphitization degree, which is responsible for their red emission. In addition, CDs show the concentration-induced multicolor emission, which is attributed to the decreased energy gap in the high concentrated CD solution. To exploit their concentration-dependent emission, CDs with changing ratio in matrices are applied as a color-converting layer on ultraviolet chip to fabricate multicolor light-emitting diodes with light coordinates of (0.33, 0.38), (0.41, 0.48), (0.49, 0.44), and (0.67, 0.33), which belong to green, yellow, orange, and red light, respectively.     

Synthesis of Carbon Dots with Multiple Color Emission by Controlled Graphitization and Surface Functionalization

Multiple‐color‐emissive carbon dots (CDots) have potential applications in various fields such as bioimaging, light‐emitting devices, and photocatalysis. The majority of the current CDots to date exhibit excitation‐wavelength‐dependent emissions with their maximum emission limited at the blue‐light region. Here, a synthesis of multiple‐color‐emission CDots by controlled graphitization and surface function is reported. The CDots are synthesized through controlled thermal pyrolysis of citric acid and urea. By regulating the thermal‐pyrolysis temperature and ratio of reactants, the maximum emission of the resulting CDots gradually shifts from blue to red light, covering the entire light spectrum. Specifically, the emission position of the CDots can be tuned from 430 to 630 nm through controlling the extent of graphitization and the amount of surface functional groups, ? COOH. The relative photoluminescence quantum yields of the CDots with blue, green, and red emission reach up to 52.6%, 35.1%, and 12.9%, respectively. Furthermore, it is demonstrated that the CDots can be uniformly dispersed into epoxy resins and be fabricated as transparent CDots/epoxy composites for multiple‐color‐ and white‐light‐emitting devices. This research opens a door for developing low‐cost CDots as alternative phosphors for light‐emitting devices.     

柠檬酸碳点荧光油墨的制备及其荧光性能

目的 以柠檬酸碳点为荧光色料,制备水性碳点荧光油墨,为其进一步应用于防伪包装和荧光生物传感器提供参考.方法 首先以柠檬酸为碳源,采用高温热解法制备碳点,然后以所制备的碳点作为荧光色料,以乙醇溶液为连接料,以羧甲基纤维素钠为粘合剂和稳定剂,以聚乙烯吡咯烷酮溶液为表面活性剂,制备水性碳点荧光油墨.结果 高倍透射电镜扫描显示,所得碳点结构规整,具有球形形貌;粒径分布范围为1.2～1.8 nm,且在水溶液中无明显聚集,分布均匀.另外,所制备的碳点在365 nm紫外光激发下发出蓝色光,且其荧光发射光谱表现出明显的激发波长依赖性.基于上述碳点的水性荧光油墨在可见光下呈棕黄色,对普通打印纸表现出良好的润湿性.结论 制备出的荧光油墨具有荧光性能,其荧光发射波长不随激发波长的变化而变化,且油墨对普通打印纸具有良好的润湿性能.该研究结果对生物质碳点荧光油墨在生物传感器和防伪包装等方面的应用具有一定的参考价值.     

Composition and concentration-dependent photoluminescence of nitrogen-doped carbon dots

Photoluminescent carbon dots have received significant research interest in recent years owing to their extraordinary optical properties, biocompatibility, and versatile functionalities. Nitrogen-doping is a widely used strategy for enhancing the photo-electronic functionalities of carbon dots. However, there is a lack of systematic study on the composition and concentration-dependency emission behaviour of N-doped carbon dots in the literature. In this study, multicolour carbon dots (CDs) having different degree of nitrogen doping were synthesized by varying the molar ratio of citric acid to urea in the precursor via hydrothermal treatment. The effects of nitrogen doping on chemical, optical, and electronic properties of CDs were characterized using various techniques including transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared (FTIR); fluorescence and absorption spectroscopy; fluorescence lifetime and Hall effect measurements. Three main emissive centres were recognized in concentration-dependent fluorescence study of N-CDs which can be ascribed to molecular type of fluorescence, core emission, and mid-gap nitrogen states on the edge/surface of CDs. A plausible mechanism in relation to the obtained results is proposed. This work provides insights on the opto-electro-tunability of CDs via N-doping.     

胶体量子点多色LED的设计、制备和表征

量子点LED采用胶体量子点为LED发光层,通过调节量子点的尺寸可以制作出覆盖可见以及近红外光谱的量子点LED(QD-LED),而且量子点LED器件发出的光谱范围很窄(光谱半高宽可达30 nm).为了研究不同发光颜色的QD-LED器件特性,本文采用具有523 nm和608 nm发光波长的CdSe/ZnS核壳型量子点为发光层、poly-TPD为空穴传输层、ZnO为电子传输层,制备了量子点红光和绿光LED并讨论了器件的相关特性.这些结果对量子点LED在飞机驾驶舱以及医疗器械照明方面的应用提供了参考,但要满足商业化的需求其寿命、亮度以及效率还需要进一步的提高.     

Excitation‐Dependent Photoluminescence from Single‐Carbon Dots

Carbon dots (CDs) are carbon‐based fluorescent nanoparticles that can exhibit excitation‐dependent photoluminescence (PL) “tunable” throughout the entire visible range, interesting for optoelectronic and imaging applications. The mechanism underlying this tunable emission remains largely debated, most prominently being ascribed to dot‐to‐dot variations that ultimately lead to excitation‐dependent ensemble properties. Here, single‐dot spectroscopy is used to elucidate the origin of the excitation‐dependent PL of CDs. It is demonstrated that already single CDs exhibit excitation‐dependent PL spectra, similar to those of the CD ensemble. The single dots, produced by a facile one‐step synthesis from chloroform and diethylamine, exhibit emission spectra with several characteristic peaks differing in emission peak position and spectral width and shape, indicating the presence of distinct emission sites on the CDs. Based on previous work, these emission sites are related to the sp² subregions in the carbon core, as well as the functional groups on the surface. These results confirm that it is possible to integrate and engineer different types of electronic transitions at the nanoscale on a single CD, making these CDs even more versatile than organic dyes or inorganic quantum dots and opening up new routes toward light‐emission engineering.     

Assignment of Core and Surface States in Multicolor-Emissive Carbon Dots

It is important to reveal the luminescence mechanisms of carbon dots (CDs). Herein, CDs with two types of optical centers are synthesized from citric acid in formamide by a solvothermal method, and show high photoluminescence quantum yield reaching 42%. Their green/yellow emission exhibits pronounced vibrational structure and high resistance toward photobleaching, while broad red photoluminescence is sensitive to solvents, temperature, and UV–IR. Under UV–IR, the red emission is gradually bleached due to the photoinduced dehydration of the deprotonated surface of CDs in dimethyl sulfoxide, while this process is hindered in water. From the analysis of steady-state and time-resolved photoluminescence and transient absorption data together with density functional theory calculations, the green/ yellow emission is assigned to conjugated sp²-domains (core state) similar to organic dye derivatives stacked within disk-shaped CDs; and the broad red emission—to oxygen-containing groups bound to sp²-domains (surface state), whereas energy transfer from the core to the surface state can happen.     

Multicolor carbon dots with concentration-tunable fluorescence and solvent-affected aggregation states for white light-emitting diodes

Multicolor emissive carbon dots (M-CDs) have tremendous potential applications in manifold fields of bioimaging, biomedicine and light-emitting devices. Until now, it is still difficult to produce fluorescence tunable CDs with high quantum yield across the entire visible spectra. In this work, a type of M-CDs with concentration-tunable fluorescence and solvent-affected aggregation states was synthesized by solvothermal treatment of citric acid (CA) and 1-(2-pyridylazo)-2-naphthol (PAN) and the formation mechanism was monitored by different reaction time and raw material ratio. The fluorescence spectra of M-CDs in organic solvents can range from 350 to 750 nm by adjusting the concentration. M-CDs possess different aggregation states in water and organic solvents, accompanied by different fluorescence emission, which is attributed to the different surface states of various component CDs in M-CDs. Moreover, the obtained products can be uniformly dispersed into polymethylmethacrylate (PMMA) solutions as well as epoxy resins to fabricate transparent CDs/PMMA films and CDs/epoxy composites, which can effectively prevent the aggregation and produce multicolor and white light-emitting diodes (WLED). In addition, the prepared WLED with Commission Internationale de L’Eclairage (CIE) of (0.29, 0.31) by using M-CDs/epoxy resin as packages, demonstrating the M-CDs exhibit potential applications for light-emitting devices.

     

Orange‐Emissive Carbon Quantum Dots: Toward Application in Wound pH Monitoring Based on Colorimetric and Fluorescent Changing

Monitoring of wound pH is critical for interpreting wound status, because early identification of wound infection or nonhealing wounds is conducive to administion of therapies at the right time. Here, novel orange‐emissive carbon quantum dots (O‐CDs) are synthesized via microwave‐assisted heating of 1,2,4‐triaminobenzene and urea aqueous solution. The as‐prepared O‐CDs exhibit distinctive colorimetric response to pH changing, and also display pH‐sensitive fluorescence. Benefiting from the response of O‐CDs over a wound‐relevant pH range (5–9), medical cotton cloth is selected to immobilize O‐CDs through hydrogen bond interactions, the resultant O‐CDs‐coated cloth with emission at 560 nm shows a high response to pH variation in the range of 5–9 via both fluorescence and visible colorimetric changes. Moreover, the sensitivity of fluorescence to pH is capable of establishing an analytical mode for determining pH value. Further, the O‐CDs‐based pH indicator possesses not only superior biocompatibility and drug compatibility but also excellent resistance leachability and high reversibility. Importantly, the usage of O‐CDs‐coated cloth to detect pH is free from the interference of blood contamination and long‐term storage, thus providing a valuable strategy for wound pH monitoring through visual response and quantitative determination.     

Fluorescent carbon dots with two absorption bands: luminescence mechanism and ion detection

Herein, we report the synthesis of carbon dots (CDs) with two characterized absorption bands but without excitation wavelength-dependent fluorescence via a one-step hydrothermal method. The structure of CDs was characterized using X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, Fourier transform infrared, and UV–Vis spectroscopy. The structure and photoluminescence of CDs vary significantly with different raw materials and preparation methods, and the mechanism of luminescence is not clear yet. Hence, we studied the luminescence mechanism behind two characterized absorption bands of CDs using fluorescence quenching method with ninhydrin and several ions as quenchers. The influence of the surface groups of CDs on its photoluminescence properties was also discussed. Ninhydrin and a variety of other ions exhibited different quenching effects on the fluorescence emissions which obtained at the two absorption bands of CDs. Combining with the structure characterization results, it can be concluded that the emission wavelength is mainly determined by the carbon core, while the excitation wavelength is determined by the surface nitrogen-containing groups. (The excitation at 234 nm might be due to the Schiff base structure, while the excitation at 345 nm was mainly due to the amide structure.) Furthermore, based on the interaction of NO₂^? with the surface nitrogen-containing groups of CDs, a quantitative detection method of NO₂^? using CDs was proposed in our study. CDs exhibited high selectivity for NO₂^? at pH 1.6 with good linearity to NO₂^? concentration in the range of 1–10 μM.