An official website of the United States government
Carbon dots (CDots) are generally defined as small-carbon nanoparticles with surface organic functionalization and their classical synthesis is literally the functionalization of preexisting carbon nanoparticles. Other than these “classically defined CDots”, however, the majority of the dot samples reported in the literature were prepared by thermal carbonization of organic precursors in mostly “one-pot” processing. In this work, thermal processing of the selected precursors intended for carbonization was performed with conditions of 200 °C for 3 h, 330 °C for 6 h, and heating by microwave irradiation, yielding samples denoted as CS200, CS330, and CSMT, respectively. These samples are structurally different from the classical CDots and should be considered as “nano-carbon/organic hybrids”. Their optical spectroscopic properties were found comparable to those of the classical CDots, but very different in the related photoinduced antibacterial activities. Mechanistic origins of the divergence were explored, with the results suggesting major factors associated with the structural and morphological characteristics of the hybrids.
more »
« less
Hydrothermal synthesis of chiral carbon dots
Abstract Nanocolloids that are cumulatively referred to as nanocarbons, attracted significant attention during the last decade because of facile synthesis methods, water solubility, tunable photoluminescence, easy surface modification, and high biocompatibility. Among the latest development in this reserach area are chiral nanocarbons exemplified by chiral carbon dots (CDots). They are expected to have applications in sensing, catalysis, imaging, and nanomedicine. However, the current methods of CDots synthesis show often contradictory chemical/optical properties and structural information that required a systematic study with careful structural evaluation. Here, we investigate and optimize chiroptical activity and photoluminescence ofL‐andD‐CDots obtained by hydrothermal carbonization ofL‐andD‐cysteine, respectively. Nuclear magnetic resonance spectroscopy demonstrates that they are formed via gradual dehydrogenation and condensation reactions of the starting amino acid leading to particles with a wide spectrum of functional groups including aromatic cycles. We found that the chiroptical activity of CDots has an inverse correlation with the synthesis duration and temperature, whereas the photoluminescence intensity has a direct one, which is associated with degree of carbonization. Also, our studies show that the hydrothermal synthesis of cysteine in the presence of boric acid leads to the formation of CDots rather than boron nitride nanoparticles as was previously proposed in several reports. These results can be used to design chiral carbon‐based nanoparticles with optimal chemical, chiroptical, and photoluminescent properties.
more »
« less
- PAR ID:
- 10380453
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Chirality
- Volume:
- 34
- Issue:
- 12
- ISSN:
- 0899-0042
- Page Range / eLocation ID:
- p. 1503-1514
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Carbon dots (CDots) are generally defined as small carbon nanoparticles (CNPs) with effective surface passivation, for which the classical synthesis is the functionalization of pre-existing CNPs with organic molecules. However, “dot” samples produced by “one-pot” thermal carbonization of organic precursors are also popular in the literature. These carbonization-produced samples may contain nano-carbon domains embedded in organic matters from the precursors that survived the thermal processing, which may be considered and denoted as “nano-carbon/organic hybrids”. Recent experimental evidence indicated that the two different kinds of dot samples are largely divergent in their photo-induced antibacterial functions. In this work, three representative carbonization-produced samples from the precursor of citric acid–oligomeric polyethylenimine mixture with processing conditions of 200 °C for 3 h (CS200), 330 °C for 6 h (CS330), and microwave heating (CSMT) were compared with the classically synthesized CDots on their photo-induced antiviral activities. The results suggest major divergences in the activities between the different samples. Interestingly, CSMT also exhibited significant differences between antibacterial and antiviral activities. The mechanistic origins of the divergences were explored, with the results of different antimicrobial activities among the hybrid samples rationalized in terms of the degree of carbonization in the sample production and the different sample structural and morphological characteristics.more » « less
-
null (Ed.)Carbon dots were originally found and reported as surface-passivated small carbon nanoparticles, where the effective surface passivation was the chemical functionalization of the carbon nanoparticles with organic molecules. Understandably, the very broad optical absorptions of carbon dots are largely the same as those intrinsic to the carbon nanoparticles, characterized by progressively decreasing absorptivities from shorter to longer wavelengths. Thus, carbon dots are generally weak absorbers in the red/near-IR and correspondingly weak emitters with low quantum yields. Much effort has been made on enhancing the optical performance of carbon dots in the red/near-IR, but without meaningful success due to the fact that optical absorptivities defined by Mother Nature are in general rather inert to any induced alterations. Nevertheless, there were shockingly casual claims in the literature on the major success in dramatically altering the optical absorption profiles of “carbon dots” by simply manipulating the dot synthesis to produce samples of some prominent optical absorption bands in the red/near-IR. Such claims have found warm receptions in the research field with a desperate need for carbon dots of the same optical performance in the red/near-IR as that in the green and blue. However, by looking closely at the initially reported synthesis and all its copies in subsequent investigations on the “red/near-IR carbon dots”, one would find that the “success” of the synthesis by thermal or hydrothermal carbonization processing requires specific precursor mixtures of citric acid with formamide or urea. In the study reported here, the systematic investigation included precursor mixtures of citric acid with not only formamide or urea but also their partially methylated or permethylated derivatives for the carbonization processing under conditions similar to and beyond those commonly used and reported in the literature. Collectively all of the results are consistent only with the conclusion that the origins of the observed red/near-IR optical absorptions in samples from some of the precursor mixtures must be molecular chromophores from thermally induced chemical reactions, nothing to do with any nanoscale carbon entities produced by carbonization.more » « less
-
Chirality, defined as “a mirror image,” is a universal geometry of biological and nonbiological forms of matter. This geometry of molecules determines how they interact during their assembly and transport. With the development of nanotechnology, many nanoparticles with chiral geometry or chiroptical activity have emerged for biomedical research. The mechanisms by which chirality originates and the corresponding synthesis methods have been discussed and developed in the past decade. Inspired by the chiral selectivity in life, a comprehensive and in-depth study of interactions between chiral nanomaterials and biological systems has far-reaching significance in biomedicine. Here, we investigated the effect of the chirality of nanoscale drug carriers, graphene quantum dots (GQDs), on their transport in tumor-like cellular spheroids. Chirality of GQDs (L/D-GQDs) was achieved by the surface modification of GQDs withL/D-cysteines. As anin-vitrotissue model for drug testing, cellular spheroids were derived from a human hepatoma cell line (i.e., HepG2 cells) using the Hanging-drop method. Our results reveal that theL-GQDs had a 1.7-fold higher apparent diffusion coefficient than theD-GQDs, indicating that theL-GQDs can enhance their transport into tumor-like cellular spheroids. Moreover, when loaded with a common chemotherapy drug, Doxorubicin (DOX), via π-π stacking,L-GQDs are more effective as nanocarriers for drug delivery into solid tumor-like tissue, resulting in 25% higher efficacy for cancerous cellular spheroids than free DOX. Overall, our studies indicated that the chirality of nanocarriers is essential for the design of drug delivery vehicles to enhance the transport of drugs in a cancerous tumor.more » « less
-
The commercially acquired aqueous solution of “carbon quantum dots” sample was evaluated by optical absorption and fluorescence emission methods; in reference to aqueous dispersed small carbon nanoparticles and representative carbon dots prepared from chemical functionalization of the carbon nanoparticles. The results suggest a very low content of carbon that is associated with nanoscale carbon particles/domains in the as-supplied sample; and likely significant contamination by dye-like species/mixtures. In the absence of any information on the synthesis and history of the commercial sample, the possible cause of the contamination was illustrated by an example on similar dye formation in the one-pot carbonization synthesis of “red carbon dots” from citric acid–formamide precursor mixtures under too mild processing conditions that were insufficient for the intended carbonization. The negative impacts to the carbon dots research field by the apparent proliferation and now commercial availability of carbon-deficient or even largely carbon-less “carbon quantum dots”, which are more susceptible to dye contamination or dominance, are discussed.more » « less
