skip to main content


Title: 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
Award ID(s):
1748529 1856515 1830886
NSF-PAR ID:
10380453
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  
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
  1. Abstract

    Juices, wines, and extracts from plants contain high concentrations of various chiral compounds such as carboxylic acids or sugars. Several prior studies reported the synthesis of metallic and semiconducting nanoparticles relying on components of complex biological solutions. Herein, we present preparation of chiral CdS and CdSe quantum dots (QDs) using apple juice and red wine via phase transfer ligand exchange. Although both apple juice and red wine contain a complex mixture of chiral and achiral compounds, we have successfully used them for selective induction of predicted chiroptical properties and confirmed L‐malic acid from the apple juice and L‐tartaric acid from the red wine as the chiral inducers. This work illustrates the capability of using complex mixtures to construct chiral QDs with desired chiroptical properties as well as potential of QDs to selectively report a chiral molecule in a complex chiral mixture without the need for elaborate chiral recognition system.

     
    more » « less
  2. 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
  3. Abstract

    The discovery of carbon dots opens a new avenue to the applications of nanomaterials in biosensing and bioimaging. In this work, we develop simple methods to prepare carbon nanoparticles from xylose and to tune the photoluminescence (PL) characteristics of the xylose-derived carbon nanoparticles via the combination of three different processes: hydrothermal carbonization (HTC), annealing at 850 °C and laser ablation (LA) in a NH4OH solution. The HTC-synthesized carbon dots (CDs) exhibit green emission under the 365 nm UV excitation, the annealing of the HTC-synthesized CDs leads to complete loss of the PL characteristics, and the LA processing of the annealed carbon nanoparticles recovers the PL characteristics with blue shift in comparison to the HTC-synthesized CDs under the same UV excitation. the PL characteristics of the HTC-CDs and the LA-CDs are dependent on theπ-π* transition of C-containing surface-functional groups andπ-π* and n-π* transitions of N-containing surface-functional groups, respectively, which are responsible for the difference in the PL characteristics between the HTC-synthesized CDs and the LA-processed CDs. The approaches demonstrated in this work provide a viable method to introduce and tune surface-functional groups on the surface of carbon nanoparticles.

     
    more » « less
  4. 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
  5. Abstract

    The study of different chiral inorganic nanomaterials has been experiencing rapid growth during the past decade, with its primary focus on metals and semiconductors. Ceramic materials can substantially expand the range of mechanical, optical, chemical, electrical, magnetic, and biological properties of chiral nanostructures, further stimulating theoretical, synthetic, and applied research in this area. An ever‐expanding toolbox of nanoscale engineering and self‐organization provides a chirality‐based methodology for engineering of hierarchically organized ceramic materials. However, fundamental discoveries and technological translations of chiral nanoceramics have received substantially smaller attention than counterparts from metals and semiconductors. Findings in this research area are scattered over a variety of sources and subfields. Here, the diversity of chemistries, geometries, and properties found in chiral ceramic nanostructures are summarized. They represent a compelling materials platform for realization of chirality transfer through multiple scales that can result in new forms of ceramic materials. Multiscale chiral geometries and the structural versatility of nanoceramics are complemented by their high chiroptical activity, enantioselectivity, catalytic activity, and biocompatibility. Future development in this field is likely to encompass chiral synthesis, biomedical applications, and optical/electronic devices. The implementation of computationally designed chiral nanoceramics for biomimetic catalysts and quantum information devices may also be expected.

     
    more » « less