The polymeric characteristics and photoluminescence mechanism in polymer carbon dots: A review

A large amount of emerging research on carbon dots (CDs) has been gradually improving the understanding of their structures, properties and emission mechanism. Distinct from the dominating status of quantum confinement effect in quantum dots, CDs always suffer from the complicated optical properties, deriving from the large differences in raw materials and synthesis methods. The diverse concepts and species puzzle researchers and hinder the further study. Thus, there is an urgent need to unify the definition and clarify the confused relation of CDs. Herein, we classify the raw materials of CDs synthesis into small molecules and polymers, and discuss CDs from the aspects of raw materials. We believe that the polymer-like structures reserved in CDs are universal no matter from the condensation of small molecules or the direct inheritance of polymers. Moreover, many similarities are concluded between CDs and polymers through serious comparisons and enough evidences. The formation processes of CDs are mostly polymerization and the obtained CDs always possess polymeric characteristics, such as abundant reactive functional groups, polydispersity of products, highly crosslinked network structure and other similar properties to non-conjugated fluorescent polymers. Therefore, the new concept, polymer carbon dots (PCDs), is put forward to generalize all kinds of CDs based on the summary of related reports. Besides, the complicated influence factors of photoluminescence (PL) are discussed and mainly classified as molecule state, carbon core state, surface state and crosslink enhanced emission (CEE) effect. In general, this review puts forward PCDs as a unified definition of reported CDs, and summarizes the polymeric characteristics of PCDs from formation process and product properties, as well as simultaneously illustrates the PL mechanism.     

Ratiometric fluorescence detection of mercuric ion based on the nanohybrid of fluorescence carbon dots and quantum dots

A novel nanohybrid ratiometric fluorescence probe comprised of carbon dots (C-dots) and hydrophilic CdSe@ZnS quantum dots (QDs) has been developed by simply mixing the blue-emission C-dots with red-emission carboxylmethyldithiocarbamate modified CdSe@ZnS QDs (GDTC-QDs). The nanohybrid ratiometric fluorescence probe exhibits dual emissions at 436 nm and 629 nm under a single excitation wavelength. Due to the strong chelating ability of GDTC on the surface of QDs to mercuric ion (Hg²⁺), the fluorescence of the GDTC-QDs in the nanohybrid system could be selectively quenched in the presence of Hg²⁺ while the fluorescence of the C-dots remained constant, resulting in an obviously distinguishable fluorescence color evolution (from red to blue) of the nanohybrid system. The detection limit of this method was found to be as low as 0.1 μM. Furthermore, the recovery result for Hg²⁺ in real samples including tap water and lake water by this method was satisfying, suggesting its potential application for Hg²⁺ sensing.     

Study on the fluorescence characteristics of carbon dots

Herein, we prepared water-soluble fluorescent carbon dots with diameter about 1.5 nm from cheap commercial lampblack. These fluorescent carbon nanoparticles are stable toward photobleaching and stable in water for more than half a year without fluorescence decrease. In order to improve its fluorescence properties, we passivated these nanoparticles with bisamino-terminated polyethylene glycol (PEG_1500N). Therefore, both fluorescence quantum yield and lifetime increased after this progress. In addition, the passivated carbon dots were more inert to solvent than the bare one and showed different responses to pH change.     

Long-wavelength (red to near-infrared) emissive carbon dots: Key factors for synthesis,fluorescence mechanism,and applications in biosensing and cancer theranostics

Carbon dots (CDs), as a new member of carbon nanostructures, have been widely applied in extensive fields due to their exceptional physicochemical properties. While, the emissions of most reported CDs are located in the blue to green range under the excitation of ultraviolet or blue light, which severely limits their practical applications, especially in photovoltaic and biological fields. Studies that focused on synthesizing CDs with long-wavelength (red to near-infrared) emission/excitation features (simply named L-w CDs) and exploring their potential applications have been frequently reported in recent years. In this review, we analyzed the key influence factors for the synthesis of CDs with long wavelength and multicolor (containing long wavelength) emissive properties, discussed possible fluorescence mechanism, and summarized their applications in sensing and cancer theranostics. Finally, the existing challenges and potential opportunities of L-w CDs are presented.     

Multicolor, large-area fluorescence sensing through oligothiophene-self-assembled monolayers

We present a new strategy to realize self-assembled monolayers (SAMs) on quartz and silicon with a multicolour fluorescence pattern starting from a single, proton sensitive oligothiophene dye exposed at a defined pH. Fine tuning of the SAMs emission color over the entire visible range, including white, is demonstrated. Finally, integration of SAMs in patterned thin layer cells (TLCs) is exploited to demonstrate cation sensing potential in real devices.     

碳点在样品前处理及色谱分离中的应用

碳点（CDs）具有生物相容性好、毒性低、稳定性好等优点,目前已广泛应用于生物成像、传感、光催化等领域。近年来,以CDs为吸附剂和分离材料的样品前处理和色谱分离研究也引起了研究者的极大兴趣。该文对CDs在样品前处理和色谱分离中的应用进行了综述,并对其发展前景进行了展望。     

Lanthanide doped carbon dots as a fluorescence chromaticity-based pH probe

A colorimetric and fluorescent pH probe was designed by doping carbon dots (C-dots) with Eu(III), Tb(III) and 2,6-pyridinedicarboxylic acid (DPA). The resulting nanoparticles were applied as fluorescent indicators for pH values (best detected at excitation/emission wavelengths of 272/545, 614 nm). The pH induced optical effects are due to pH induced variations in energy transfer. The fluorescence of the probe shows a continuous color variation, and a linear change with pH values in the range from 3.0 to 10.0 can be established by using a Commission Internationale de L’Eclairage (CIE) chromaticity diagram. This new kind of pH nanoprobe is more accurate than previously reported pH indicator probes because the pH value can be calculated by using chromaticity coordinates that only depend on the chromaticity. The pH nanoprobe was applied to visualize pH values in human breast adenocarcinoma cells (MCF-7).

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Graphical abstract Carbon dots modified with Eu(III) and Tb(III) complexes of 2,6-pyridinedicarboxylic acid (DPA) were prepared. The doped carbon dots were used as a pH-sensitive nanosensor. The fluorescence chromaticity of the nanoparticles changes with the variation of pH value.

     

Kilogram-scale synthesis of carbon quantum dots for hydrogen evolution,sensing and bioimaging

The development of large-scale synthetic methods for high quality carbon quantum dots (CQDs) is fundamental to their applications. However, the macroscopic preparation and scale up synthetic of CQDs is still in its infancy. Here, we report a facile, green, kilogram-scale synthesis of high quality fluorescent CQDs derived from poplar leaves via a one-step hydrothermal method. Notably, the throughput of CQDs can reach a level up to as high as 1.4975 kg in one pot. The structure and properties of the as-prepared CQDs were assessed through TEM, XRD, XPS and various spectroscopic methods. The obtained high quality CQDs with a photoluminescent quantum yield of 10.64% showed remarkable stability in aqueous media, rich functional groups, high photostability, consistent photoluminescence within biological pH range and low cytotoxicity. On account of these good properties, we demonstrated the multifunctional application to electrocatalytic water splitting, Fe³⁺ sensing and bioimaging. It showed remarkable electrocatalytic activity, Fe³⁺ sensitivity and good biocompatibility. This study provides a green, facile, inexpensive and large-scale method for producing high quality CQDs, which provides application value for large-scale production of CQDs.     

Kilogram-scale synthesis of carbon quantum dots for hydrogen evolution,sensing and bioimaging

A facile, low-cost, green, kilogram-scale synthesis of high quality CQDs were synthesized. The throughput of CQDs is 1.4975 kg in one pot and the as-prepared CQDs have a highly crystalline hexagonal structure with remarkable solubility, stability, and biocompatibility. It showed outstanding electrocatalytic activity, Fe³⁺ sensitivity and good biocompatibility.     

The quenching of the fluorescence of carbon dots: A review on mechanisms and applications

Carbon dots (CDs) possess unique optical properties such as tunable photoluminescence (PL) and excitation dependent multicolor emission. The quenching and recovery of the fluorescence of CDs can be utilized for detecting analytes. The PL mechanisms of CDs have been discussed in previous articles, but the quenching mechanisms of CDs have not been summarized so far. Quenching mechanisms include static quenching, dynamic quenching, Förster resonance energy transfer (FRET), photoinduced electron transfer (PET), surface energy transfer (SET), Dexter energy transfer (DET) and inner filter effect (IFE). Following an introduction, the review (with 88 refs.) first summarizes the various kinds of quenching mechanisms of CDs (including static quenching, dynamic quenching, FRET, PET and IFE), the principles of these quenching mechanisms, and the methods of distinguishing these quenching mechanisms. This is followed by an overview on applications of the various quenching mechanisms in detection and imaging.

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Graphical abstract Schematic representation of the quenching mechanisms of carbon dots (CDs) which include static quenching, dynamic quenching, Förster resonance energy transfer (FRET), photoinduced electron transfer(PET), surface energy transfer (SET), Dexter energy transfer (DET) and inner filter effect (IFE). All these effects can be used to detect and image analytes.

     

Small nanoparticles bring big prospect: The synthesis,modification, photoluminescence and sensing applications of carbon dots

As a new type of carbon-based fluorescent nanomaterials, carbon dots(CDs) are provided with the advantages of small size, excellent photoluminescence(PL) property, easy surface modification, robust stability,good water solubility and biocompatibility, which endow them with great potential in sensing. In this review, we first describe the preparation of CDs from different starting materials via various techniques, and pre-/post-modification strategies to modulate their PL properties. Second, we o...     

基于碳点荧光恢复法测定生物巯基化合物

碳点(CDots)是一种新型荧光纳米材料,Cu2+可以有效猝灭其荧光;而当有生物巯基化合物存在时,碳点-Cu2+体系的荧光可以恢复.基于此原理,我们成功地构建了检测生物体内总巯基化合物的新方法.该方法具有很好的选择性,常见氨基酸和金属离子对谷胱甘肽(GSH)、半胱氨酸(Cys)和高半胱氨酸(Hcy)的检测无影响.最佳实验条件下,谷胱甘肽、半胱氨酸、高半胱氨酸的浓度在6.0×10-6mol/L～1.0×10-4mol/L与相对荧光强度呈线性,R>0.996,检出限为2.0×10-6mol/L.该体系成功用于血清样品中总巯基化合物的检测.     

超声法一步合成生物相容的黄绿色荧光碳点

本文以蜡烛灰为碳源,在强酸环境中超声法一步合成了粒径均匀的荧光碳点（CDs）,粒径（3.47±1.81）nm,在紫外灯照射下发出黄绿色荧光.研究表明,CDs表面带有-OH、C=O和-COOH等官能团,存在sp3杂化和sp2杂化两种碳原子.所合成的碳点具有良好的耐光漂白能力和生物相容性,能潜在地作为黄绿色荧光成像试剂应用于细胞成像.     

Dendronized molecular knots: selective synthesis of various generations,enantiomer separation,circular dichroism

For the first time, knot molecules (of the amide type) are synthesized, which bear one to three dendritic units of various generations at their periphery. They were obtained through two different routes: i) attachment of dendritic wedges to new mono-, di- and trihydroxy functionalized dodecaamide knots that have been obtained by selective debenzylation of oligobenzyloxy substituted knots, or ii) cyclization of already dendron substituted pyridine-2,6-dicarbonyl dichlorides with an "extended diamine" to directly yield the "tri-dendroknots". The derivatization of knot molecules by functional substituents and even large dendritic units is an important advance in the synthesis and property variation of molecular knots. This holds true in particular for substitution of the pyridine units of the knots, whereas the isophthalic acid units seem not to tolerate larger substitutents, as reflected in lower knot yields. These syntheses also demonstrate knots to be accessible indirectly by substitution of the corresponding mono-, di- and tri-functionalized knot skeleton. An advantage of dendritic "decoration" is the control of solubility and chromatographic behaviour of the molecular knots (knotanes). Suggestions are made about the threading mechanism by supramolecular template effects leading to the formation of amide-based molecular knots. The topological chirality of the new "dendroknots" is shown by efficient enantioseparations (separation factor alpha between 1.22 and 1.48). For this purpose (commercially unavailable) chiral column material of the Chiralpak type was used, in which the chiral component is covalently bonded to the silica gel support. The racemate splittings provide additional evidence for the knotted structure, as all other conceivable isomers such as macromonocyclic or catenated dodecaamides would not be chiral. The pure enantiomers obtained exhibit pronounced Cotton effects in their circular dichroism spectra. By comparison with the unsubstituted knot, the absolute configuration (Lambda, Delta) of all new knots is derived.     

Perspectives of magnetic nature carbon dots in analytical chemistry: From separation to detection and bioimaging

Magnetic nature carbon dots (MNCDs) are fast growing materials with extremely unique physico-chemical properties and physiological ability to extend their applications from separation science to detection and bio-/magnetic resonance imaging applications. Recent studies have revealed that the MNCDs are significantly used as promising agents in analytical chemistry for the separation and identification of trace level target analytes. Further, the MNCDs have been used as probes for bioimaging of cells and magnetic resonance imaging (MRI) of tumors. Due to the lack of comprehensive reviews in this emerging field especially MNCDs applications in analytical chemistry, this review may provide quick guide and reference on the MNCDs-based analytical approaches for the separation and detection of trace level analytes, and bio- and MR- imaging of various cells. In this review article, we will summarize the synthetic approaches for the fabrication of MNCDs. The main part of this proposed review is devoted to the tremendous applications of MNCDs (Fe₃O₄@CDs, metal ion (Fe³⁺, Mn²⁺, Co²⁺ and Gd²⁺)-doped CDs, MnO₂@CDs) in analytical chemistry from separation science to detection and bio- and MR imaging. Finally, we will explore the challenges and future prospects of magneto fluorescent carbon dots in biomedical applications.     

Bio-safety assessment of carbon quantum dots,N-doped and folic acid modified carbon quantum dots: A systemic comparison

The carbon quantum dots(CQDs) and their functionalized materials are promising in biomedical field because of their unique properties;meanwhile,a growing concern has been raised about the potential toxicity of these modified materials in biosystem.In this study,we synthesized original CQDs and two common functionalized CQDs including N-doped CQDs(NCQDs) and folic acid-modified CQDs(FACQDs),and compared the toxicity and biocompatibility with each other in vitro and in vivo.L929,C6 and normal cell MDCK were selected to detect the adverse reaction of these materials in vitro.No acute toxicity or obvious changes were noted from in vitro cytotoxicity studies with the dose of these CQD materials increasing to a high concentration at 1 mg/mL.Among these materials,the FA-CQDs show a much lower toxicity.Moreover,in vivo toxicity studies were performed on the nude mice for 15 days.The experimental animals in 10 or 15 mg/kg groups were similar with animals treated by phosphate buffer solution(PBS) after 15 days.The results of the multifa rious biochemical parameters also suggest that the functionalized products of CQDs do not influence the biological indicators at feasible concentration.Our findings in vitro and in vivo through toxicity tests demonstrate that CQDs and their modified materials are safe for future biological applications.     

Langmuir-Blodgett thin films of quantum dots: synthesis, surface modification, and fluorescence resonance energy transfer (FRET) studies

We describe herein studies on as-prepared hydrophobic ZnS-CdSe quantum dots (QDs) at the air-water interface. Surface pressure-area (pi-A) isotherms have been used to study the monolayer behavior. Uniform, lamellar multilayer thin films of QDs were deposited by the Langmuir-Blodgett (LB) technique. The role of two different surfactant systems commonly employed in the synthesis of these QDs (trioctylphosphine oxide-octadecylamine (TOPO-ODA) system and trioctylphosphine oxide-tetradecylphosphonic acid (TOPO-TDPA) system) on the monolayer behavior and the quality of thin films produced has been investigated. The thin films were characterized by quartz crystal microgravimetry (QCM), contact angle measurements, fluorescence spectroscopy, and transmission electron microscopy (TEM). These QD films were further modified by an amphiphilic polymer, poly(maleic anhydride-alt-1-tetradecene) (PMA). The hydrophobic interaction between the polymers and the surfactants attached to the QDs drove the self-assembly process. The carboxylic acid functional groups in the polymer were also used to immobilize avidin. We have demonstrated a proof of concept for the biosensing strategy wherein the avidin-coated QD films attracted biotinylated gold nanoparticles, resulting in fluorescence resonance energy transfer (FRET) quenching of the thin films.     

Femtosecond fluorescence dynamics and molecular interactions in a water-soluble nonlinear optical polymeric dye

The excited state dynamics of a water-soluble polymeric dye poly(S-119) was investigated using femtosecond time-resolved fluorescence upconversion. Multi-exponential relaxation of fluorescence was observed for poly(S-119) in picosecond and sub-picosecond time ranges. The azo-chromophore of the functionalized polymeric dye Sunset Yellow was used as a model compound for detailed investigations of intermolecular interactions. Excited state decay of this azo-dye can be described by a two-exponential decay law with time-constants of 0.48 ps and 1 ps. Fluorescence anisotropy decay was investigated for both systems. The difference in excited state dynamics between the polymeric dye and the azo-chromophore is explained in terms of inter-molecular interactions resulting in intra-chain aggregate formation.     

Determination of DNA based on fluorescence quenching of terbium doped carbon dots

This work describes the preparation of carbon dots doped with terbium(III) (Tb-CDs) via a hydrothermal method, starting from terbium ion and ethylenediamine. The size, composition and spectral properties of the Tb-CDs were characterized by transmission electron microscopy, infrared spectra, and fluorescence spectra. The results show that doping of the CDs with Tb(III) reduces the particle size and results in more uniform particles, while fluorescence (at excitation/emission peaks of 380/475 nm) is strongly enhanced. The interaction between Tb-CDs and ct-DNA results in fluorescence quenching of Tb-CDs. The findings were exploited to design a quenchometric method for the determination of ct-DNA. The signal drops linearly in the 80 ng·mL^?1 to 50 μg·mL^?1 ct-DNA concentration range, and the detection limit is 53 ng·mL^?1. The method was applied to the determination of ct-DNA in spiked samples and gave satisfactory results. The possible fluorescence quenching mechanism (which is mainly static) was investigated using the Stern–Volmer equation and thermodynamic equations.

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Graphical abstract A kind of carbon dots doped with terbium(III) (Tb-CDs) were prepared via a hydrothermal method, using terbium ion and ethylenediamine as precursor. Doping with Tb(III) reduced the particle size of CDs and results in uniform particle size and stronger fluorescence. The interaction between the Tb-CDs and dsDNA results in quenching of the fluorescence of Tb-CDs and can be applied to determination of dsDNA.