Carbon dots (CDots) exploit unique properties of small carbon nanoparticles, which represent the often under-appreciated zero-dimensional carbon allotrope. The carbon nanoparticles in CDots could be modified by a selected organic chromophore of desired strong red/near-IR absorption in the dot synthesis to obtain a specific type of hybrid CDots. The reported results show that these hybrid CDots derived from the modification of core carbon nanoparticles by selected dyes or other chromophoric species represent a highly versatile and effective platform for CDots of desired optical properties and photoinduced redox characteristics in a by-design fashion.
Fullerene cages are known as being able to participate in radical initiated copolymerization reactions with vinyl monomers for polymer-functionalized fullerenes. In this work, poly(N-vinylcarbazole) (PVK) was selected as a representative of electronic polymers in the functionalization of fullerene C60 by the same copolymerization reaction to yield the PVK-C60. Similarly found was that small carbon nanoparticles could also participate in the same copolymerization reaction for the nanoparticles to be surface-functionalized and -passivated by the attached PVK polymers, which are structurally adhering to the general definition on carbon dots (CDots), thus PVK-CDots. In the comparison between PVK-CDots and PVK-C60, the former was found to be more absorptive and therefore more effective in photon harvesting across the visible spectral region and also brightly fluorescent, orders of magnitude more so than the latter. Similar to the PVK-C60 and C60 cages in general, the PVK-CDots exhibited significant photoinduced electron accepting characteristics and, at the same time, also extraordinary electron donating abilities that are not available to fullerenes. Because fullerene-based composites with electronic polymers including PVK have found significant applications in optoelectronic devices and systems, the prospect of CDots represented by the PVK-CDots for similar purposes is discussed.
Carbon dots (CDots) are characterized by their optical properties including strong absorptions and bright and colorful fluorescence emissions in the visible spectrum and by their photoinduced redox characteristics as both potent electron acceptors and donors. The reported study was for a systematic comparison of CDots from different synthetic approaches based on the use of pre-existing small carbon nanoparticles sourced from pure carbon soot versus the formation of similar nanoparticles in situ via a one-pot thermal carbonization of organic molecular precursors, emphasizing spectroscopic characterizations over the visible spectrum. The results show that the CDots prepared by the latter under sufficiently robust processing conditions are generally no different from those from the former in terms of the observed optical properties and associated photoinduced redox characteristics in the application-wise more meaningful visible spectral region, suggesting a high stability or general applicability of the definition on CDots as surface-passivated small-carbon nanoparticles. Implications of the reported findings to the further understanding and mechanistic explorations of CDots, including the necessity to focus on the core carbon nanoparticles in CDots in such explorations, are highlighted and discussed.
Carbon–TiO2 hybrid dots in different structural configurations were found to exhibit very different optical properties and photoinduced redox characteristics.
Carbon quantum dots (CDots), generally defined as small carbon nanoparticles with various surface passivation schemes, have emerged to represent a rapidly advancing and expanding research field. CDots are known for their bright and colorful fluorescence emissions, where the colorfulness is associated with the emissions being excitation wavelength dependent. In this work, CDots with 2,2'-(ethylenedioxy)bis(ethylamine) (EDA) for surface functionalization were studied systematically by using steady-state and time-resolved fluorescence methods. The observed fluorescence quantum yields are strongly excitation wavelength dependent, and the dependence apparently tracks closely the observed absorption profile of the EDA-CDots, whereas the excitation wavelength dependence of observed fluorescence lifetimes is much weaker, obviously decoupled from the quantum yields. Mechanistically, the presence of two sequential processes immediately following the photoexcitation of CDots leading to fluorescence is used to rationalize these effects, and the experimental results seem better explained by attributing one of the two processes to be primarily responsible for the characteristic excitation wavelength dependence. Significant implications of the mechanistic probing to the understanding of CDots as a new class of quantum dot-like fluorescent nanomaterials are discussed, and so are further challenges and opportunities.
Host–guest carbon dots (G@CDots) represent a new platform in the rapidly advancing and expanding research field of carbon dots, enabling the development of novel carbon hybrid nanostructures of unique properties beyond those of conventional carbon dots.
•Carbon dots as fluorescence quenching probes for nitroaromatics.•Sensitive and quantitative detection at very low concentrations.•The fluorescence quenching dominated by dynamic processes.
Carbon dots are small carbon nanoparticles with various surface passivation schemes, in which more effective has been the deliberate chemical functionalization of the nanoparticles for brighter fluorescence emissions, though the synthesis method is more tedious and subject to some limitations in the selection of functionalization molecules. Another more popular synthesis method has been the carbonization of organic species, with the method being more efficient and versatile, but less controllable in the synthesis and for the desired dot structure and performance. In this work, a hybrid approach combining the advantageous characteristics of the two synthesis methods was applied to the preparation of carbon dots with polyethyleneimine (PEI) for surface passivation, where pre-processed and selected small carbon nanoparticles were functionalized with PEI in microwave-induced thermal reactions. The optical absorption and fluorescence emission properties were evaluated, and the results suggested that the carbon dots thus prepared shared the same photoexcited state characteristics with those from the deliberate chemical functionalization, including comparable fluorescence colors and other properties. A further demonstration on the similarity in photoexcited state properties was based on the same visible light-activated bactericidal functions of the PEI-carbon dots as those found in carbon dots from the deliberate chemical functionalization. The advantages and potential limitations of the hybrid approach for more controllable yet versatile and efficient syntheses of carbon dots are highlighted and discussed.
Carbon dots, generally defined as small carbon nanoparticles with various surface passivation schemes, have emerged as a new class of quantum-dot-like nanomaterials, with their optical properties and photocatalytic functions resembling those typically found in conventional nanoscale semiconductors. In this work, carbon dots were evaluated for their photoinduced bactericidal functions, with the results suggesting that the dots were highly effective in bacteria-killing with visible-light illumination. In fact, the inhibition effect could be observed even simply under ambient room lighting conditions. Mechanistic implications of the results are discussed and so are opportunities in the further development of carbon dots into a new class of effective visible/natural light-responsible bactericidal agents for a variety of bacteria control applications.
Small carbon nanoparticles were functionalized by low-molecular weight amino compound 3-ethoxypropylamine (EPA) for ultracompact carbon dots of bright fluorescence emissions. The results from solution-phase NMR characterization support the expected dot structure of carbon nanoparticles surface-attached with EPA species. The optical properties of the EPA-carbon dots share many features with those found in carbon dots of other surface functionalities, but there is an extra absorption shoulder in the blue spectral region, into which the excitation results in much enhanced green fluorescence emissions. The EPA-carbon dots were defunctionalized by gradually removing the EPA species from the carbon nanoparticles, along with spectroscopic characterizations on the samples of different degrees of defunctionalization. The outcomes further confirm the critical role of surface functionalization in the superior optical properties of carbon dots. Results from systematic measurements of fluorescence quantum yields and decays at different excitation wavelengths for the EPA-carbon dots and their gradually defunctionalized samples are presented, and their mechanistic implications are discussed.
Carbon dots of small carbon nanoparticles surface-functionalized with 2,2'-(ethylenedioxy)bis(ethylamine) (EDA) were synthesized, and the as-synthesized sample was separated on an aqueous gel column to obtain fractions of the EDA-carbon dots with different fluorescence quantum yields. As already discussed in the literature, the variations in fluorescence performance among the fractions were attributed to the different levels and/or effectiveness of the surface functionalization-passivation in the carbon dots. These fractions, as well as carbon nanoparticles without any deliberate surface functionalization, were dispersed into poly(vinyl alcohol) (PVA) for composite films. In the PVA film matrix, the carbon dots and nanoparticles exhibited much enhanced fluorescence emissions in comparison with their corresponding aqueous solutions. The increased fluorescence quantum yields in the films were determined quantitatively by using a specifically designed and constructed film sample holder in the emission spectrometer. The observed fluorescence decays of the EDA-carbon dots in film and in solution were essentially the same, suggesting that the significant enhancement in fluorescence quantum yields from solution to film is static in nature. Mechanistic implications of the results, including a rationalization in terms of the compression effect on the surface passivation layer (similar to a soft corona) in carbon dots when embedded in the more restrictive film environment resulting in more favorable radiative recombinations of the carbon particle surface-trapped electrons and holes, and also potential technological applications of the brightly fluorescent composite films are highlighted and discussed.
•Functionalized carbon nanoparticles or carbon dots are quantum dot-like.•Carbon dots now represent a rapidly advancing and expanding research field.•Carbon dots have been investigated extensively for bioimaging and theranostics.•Carbon dots are semiconductor-equivalent in energy conversion applications.
Polymer-coated MWNT assisted capture of bacterial cells of filters.
Fluorescent carbon ‘quantum’ dots are generally obtained by deliberate chemical functionalization of carbon nanoparticles or by ‘one-pot’ carbonization processing. For brightly fluorescent carbon dots with optoelectronic polymers, a hybrid approach was developed to use pre-processed and selected carbon nanoparticles as precursor for surface passivation by poly(9-vinylcarbazole) (PVK) in one-pot thermochemical processing, thus taking advantage of the more controllable feature from the deliberate functionalization and also the versatility associated with the one-pot synthesis. The PVK-carbon dots were characterized by optical spectroscopy, microscopy, and other techniques. The broad applicability of the hybrid approach is discussed.
Carbon dots, generally small carbon nanoparticles with various forms of surface passivation, have achieved the performance level of semiconductor quantum dots in the green spectral region, but their absorption and fluorescence in red/near-IR are relatively weaker. Conceptually similar to endofullerenes, host-guest carbon dots were designed and prepared with red/near-IR dyes encapsulated as guest in the carbon nanoparticle core. Beyond the desired enhancement in optical properties, the host-guest configuration may significantly broaden the field of carbon dots.
The specifically synthesized and selected carbon dots of relatively high fluorescence quantum yields were evaluated in their fluorescence labeling of cells. For the cancer cell lines, the cellular uptake of the carbon dots was generally efficient, resulting in the labeling of the cells with bright fluorescence emissions for both one- and two-photon excitations from predominantly the cell membrane and cytoplasm. In the exploration on labeling the live stem cells, the cellular uptake of the carbon dots was relatively less efficient, though fluorescence emissions could still be adequately detected in the labeled cells, with the emissions again predominantly from the cell membrane and cytoplasm. This combined with the observed more efficient internalization of the same carbon dots by the fixed stem cells might suggest some significant selectivity of the stem cells toward surface functionalities of the carbon dots. The needs and possible strategies for more systematic and comparative studies on the fluorescence labeling of different cells, including especially live stem cells, by carbon dots as a new class of brightly fluorescent probes are discussed.
Graphene is known for high thermal and electrical conductivities. In the preparation of neat carbon materials based on graphene, a common approach has been the use of well-exfoliated graphene oxides (GOs) as the precursor, followed by conversion to reduced GOs (rGOs). However, rGOs are more suitable for the targeted high electrical conductivity achievable through percolation but considerably less effective in terms of efficient thermal transport dictated by phonon progression. In this work, neat carbon films were fabricated directly from few-layer graphene sheets, avoiding rGOs completely. These essentially graphenegraphene composites were of a metal-like appearance and mechanically flexible, exhibiting superior thermal and electrical transport properties. The observed thermal and electrical conductivities are higher than 220 W/m.K and 85000 S/m, respectively. Some issues in the further development of these mechanically flexible graphenegraphene nanocomposite materials are discussed and so are the associated opportunities.
Carbon ‘quantum’ dots or carbon dots have emerged as a new class of luminescent nanomaterials. While photoluminescence properties of carbon dots had targeted optical imaging and related usage, their unique excited state redox processes responsible for the luminescence emissions may find potentially significant optoelectronic applications. In this regard, we investigated the electroluminescence properties of the carbon dots integrated into multilayer light emitting diode devices. The devices emitted white light with a slight blue color, visible to naked eyes, thus validating the expectation that carbon dots may potentially serve as a new platform for electroluminescent nanomaterials.
There has been much discussion on the need to develop fluorescent quantum dots (QDs) as ultracompact probes, with overall size profiles comparable to those of the genetically encoded fluorescent tags. In the use of conventional semiconductor QDs for such a purpose, the beautifully displayed dependence of fluorescence color on the particle diameter becomes a limitation. More recently, carbon dots have emerged as a new platform of QD-like fluorescent nanomaterials. The optical absorption and fluorescence emissions in carbon dots are not bandgap in origin, different from those in conventional semiconductor QDs. The absence of any theoretically defined fluorescence color - dot size relationships in carbon dots may actually be exploited as a unique advantage in the size reduction toward having carbon dots serve as ultracompact QD-like fluorescence probes. Here we report on carbon dots of less than 5 nm in the overall dot diameter with the use of 2,2'-(ethylenedioxy)bis(ethylamine) (EDA) molecules for the carbon particle surface passivation. The EDA-carbon dots were found to be brightly fluorescent, especially over the spectral range of green fluorescent protein. These aqueous soluble smaller carbon dots also enabled more quantitative characterizations, including the use of solution-phase NMR techniques, and the results suggested that the dot structures were relatively simple and better-defined. The potential for these smaller carbon dots to serve as fluorescence probes of overall sizes comparable to those of fluorescent proteins is discussed.