Room temperature synthesis of water-soluble spherical particles of a uniform diameter composed of carbon nanobelts and C60 molecules

doi:10.21203/rs.3.rs-1648116/v2

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Room temperature synthesis of water-soluble spherical particles of a uniform diameter composed of carbon nanobelts and C60 molecules

https://doi.org/10.21203/rs.3.rs-1648116/v2

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A carbon nanobelt (CNB) is a loop of fused benzene rings and in a sense a cutout of a single-walled carbon nanotube. Various types of CNBs have been successfully synthesized in recent years and CNBs have been utilized for the development of practical devices. A C60 molecule is a football shaped fullerene composed of 60 carbon atoms. Patterns and structures formed by atoms, molecules and particles via bottom-up self-assembly are of great interest and importance not only from a scientific point of view but for the design and production of functional materials and devices, the size of which ranges from nano to macroscopic scales. Colloidal particles are commonly used/utilized in mechanical, chemical and biophysical/biochemical/biomedical engineering, where size uniformity and mono dispersibility of the particles in the solvent, particularly in water, become crucial factors. In this study, we investigate secondary structures formed by (6,6)CNBs and C60 molecules, which are dissolved in 1,2-dichlorobenzene. We find that uniform spherical particles are formed by (6,6)CNBs and C60 molecules in 1,2-dichlorobenzene at room temperature via bottom-up self-assembly, setting the molar concentrations of (6,6)CNBs and C60 molecules at appropriate values, and furthermore those particles are monodisperse even in water. The present facile room temperature synthetic methodology may well be applied to the creation of nano/micro structures/materials using basic carbon nano units such as cycloparaphenylene (CPP, carbon nanorings) and fullerenes; e.g., C60, C70 and C59N.

Table 1: Diameter of a particle produced 168 h after the mixture of the two solutions, and the hydrodynamic diameter and zeta potential of a particle dispersed in distilled water.

Diameter^†1

[nm]

Hydrodynamic diameter^†2

[µm]

Zeta potential^†3

[mV]

(7.12 ± 0.63) × 10²

1.30 ± 0.09

- 38.8 ± 0.7

The particles were synthesized setting the ratio of the molar concentration of (6,6)CNBs to that of C₆₀ molecules at 1 : 2 (the concentrations of (6,6)CNBs and C₆₀ molecules were, respectively, 0.35 and 0.70 µmol ml^-1).

^†1The diameter of the particles was measured, targeting at 100 particles from SEM images.

^†2The hydrodynamic diameter of a particle dispersed in distilled water was measured by Zetasizer.

^†3The zeta potential of a particle dispersed in distilled water was measured by Zetasizer.

Synthetic procedure of particles

We developed a facile room temperature methodology for producing particles composed of (6,6)CNBs and C₆₀ molecules. The synthetic procedure is summarized below.

(a) (6,6)CNBs (Tokyo Chemical Industry Co. Ltd.) and C₆₀ molecules (Kanto Chemical Co. Inc.) were individually dissolved in 1,2-dichlorobenzene. The molar concentrations of (6,6)CNBs and C₆₀ molecules dissolved in 1,2-dichlorobenzene are listed in Methods Table 1.

(b) Those two solutions were mixed, adding 2 ml of the solution of C₆₀ molecules dissolved in 1,2-dichlorobenzene to 2 ml of the solution of (6,6)CNBs dissolved in 1,2-dichlorobenzene. The ratio of the molar concentration of (6,6)CNBs to that of C₆₀ was set at 1 : 1, 1 : 1.25, 1 : 1.5, 1 : 1.75, 1 : 2, 1 : 2.25, 1 : 2.5, 1 : 2.75, 1 : 3 and 2 : 1 (see Methods Table 1).

(d) The solvent; i.e., 1,2-dichlorobenzene, was replaced by ethanol 1, 2, 3, 4, 24 and 168 h after the mixture of the two solutions, followed by sonication and centrifugation twice.

(e) The particles separated by centrifugation were dispersed in distilled water, followed by sonication.

Characterization and observation procedure

The following is the characterization and observation procedure.

(a) The absorption spectra by the supernatant of the solution were measured by ultraviolet-visible (UV-Vis) spectroscopy (DU730, Beckman Coulter Inc.).

(b) The structures of the particles were observed by scanning electron microscopy (SEM) (SU8030, Hitachi Ltd.) and transmission electron microscopy (TEM) (2200FS, JEOL Ltd.). The size of the particles was measured, targeting at 100 particles from the SEM images.

(c) The hydrodynamic diameter and zeta potential of the particles dispersed in distilled water were measured by Zetasizer (Nano-ZS, Malvern Panalytical Ltd.).

(d) The precipitation procedure of the particles dispersed in distilled water was observed, and photographed and recorded on videotape. The intensity of the transmitted light of 500 and 600 nm wavelengths through the whole solution confined in a glass container was measured with a spectral photometer (U-3500 Spectrophotometer, Hitachi High-Tech Co.) and the turbidity was defined as \(\left(1-{I}_{trans}/{I}_{in}\right)\times 100 \%\), where \({I}_{in}\) and \({I}_{trans}\) ae, respectively, the intensities of the incident and transmitted light.

(f) The molecular weight of the compounds forming the particles was measured with time-of-flight mass spectrometry (TOF-MS) (autoflex2, Bruker Co.), where (6,6)CNBs are positively charged, whereas C₆₀ molecules are negatively charged.

Methods table

Table 1 Molar concentrations of the solution of CNBs and C₆₀ dissolved in 1,2-dichlorobenzene.

Ratio of the molar concentrations of (6,6)CNBs and C₆₀	Molar concentration of (6,6)CNBs [µmol ml^-1]	Molar concentration of C₆₀ [µmol ml^-1]
1 : 1	0.70	0.70
1 : 1.25	0.70	0.875
1 : 1.5	0.70	1.05
1 : 1.75	0.70	1.225
1 : 2	0.70	1.40
1 : 2.25	0.70	1.575
1 : 2.5	0.70	1.75
1 : 2.75	0.70	1.925
1 : 3	0.70	2.10
2 : 1	1.40	0.70

The molar concentrations of (6,6)CNBs and C₆₀ molecules became half after the mixture of the two solutions.

Data availability

All of the data supporting this work are available from the corresponding author upon reasonable request.

Acknowledgements

We would like to thank Mr Haruyoshi Sato, Ms Hiromi Kawada and Mr Keisuke Yanagisawa, Technical Managers of the Bio-Nano Electronics Research Centre, Toyo University, for their technical support of TEM observation of the particles, interpretation of the TEM images and the measurement of the turbidity of the suspension of the particles dispersed in distilled water.

Author contributions

SC performed experiments, characterizations and data analyses, and drew graphs; SK performed experiments, characterizations, data analyses and computer simulations, and drew graphs; YM performed experiments, characterizations and data analyses; TMi performed experiments; and TMa organized the present research project, raised the fund, carried out data analyses and wrote the manuscript. All the authors checked the manuscript, images and graphs and agreed with the contents of the paper.

Funding

The present research has been financially supported by Toyo University since April 2021.

Competing interests

The authors declare no competing interests.

Additional information

Supplementary information. The online version contains supplementary material available at https://doi.org/10.???????????.

Povie, G., Segawa, Y., Nishihara, T., Miyauchi, Y. & Itami, K. Synthesis of a carbon nanobelt. Science 356, 172–175 (2017).
Wegner, H. A. On the Way to Carbon Nanotubes: The first synthesis of an aromatic nanobelt. Angew. Chem. Int. Ed. 56, 10995–10996 (2017).
Lu, X. & Wu, J. After 60 years of feforts: The chemical synthesis of a carbon nanobelt. Chem 2, 610–620 (2017).
Wang, J. & Miao, Q. A tetraazapentacene-pyrene belt: Toward synthesis of N–doped zigzag carbon nanobelts. Org. Lett. 21, 10120–10124 (2019).
Xue, S., Kuzuhara, D., Aratani, N. & Yamada, H. Synthesis of a porphyrin(2.1.2.1) nanobelt and its ability to bind fullerene. Org. Lett. 21, 2069–2072 (2019).
Cheung, K. Y., Gui, S., Deng, C., Liang, H., Xia, Z., Liu, Z., Chi, L. & Miao, Q. Synthesis of armchair and chiral carbon nanobelts. Chem 5, 838–847 (2019).
Bergman, H. M., Kiel, G. R., Handford, R. C., Liu, Y. & Tilley, T. D. Scalable, divergent synthesis of a high aspect ratio carbon nanobelt. J. Am. Chem. Soc. 143, 8619–8624 (2021).
Yu, X., Wang, M., Gagnoud, A., Fautrelle, Y., Moreau, R. & Li, X. Fabrication and electrochemical properties of a graphene-enhanced hierarchical porous network of Fe₃O₄/carbon nanobelts. Electrochimica Acta 248, 150–159 (2017).
Ma, C., Cao, E., Dirican, M., Subjalearndee, N., Cheng, H., Li, J., Song, Y., Shi, J. & Zhang, X. Fabrication, structure and supercapacitance of flexible porous carbon nanobelt webs with enhanced inter-fiber connection. App. Surf. Sci. 543, 148783 (2021).
Cheng, Y., Zhang, Y., Jiang, H., Dong, X., Meng, C. & Kou, Z. Coupled cobalt silicate nanobelt-on-nanobelt hierarchy structure with reduced graphene oxide for enhanced supercapacitive performance. J. Power Sources 448, 227407 (2020).
Kroto, H. W., Heath, J. R., O’Brien, S. C., Curl, R. F. & Smalley, R. E. C₆₀: Buckminsterfullerene. Nature 318, 162–163 (1985).
Parviz, B. A., Ryan, D. & Whitesides, G. M. Using self-assembly for the fabrication of nano-scale electronic and photonic devices. IEEE Trans. Adv. Packag. 26, 233–241 (2003).
Boncheva, M., Bruzewicz, D. A. & Whitesides, G. M. Millimeter-scale self-assembly and its applications. Pure Appl. Chem. 75, 621–630 (2003).
Zhou, Y. & Yan, D. Supramolecular self-assembly of amphiphilic hyperbranched polymers at all scales and dimensions: progress, characteristics and perspectives. Chem. Commun., 1172–1188 (2009).
McCarthy, P. A., Huang, J., Yang, S.-C. & Wang, H.-L. Synthesis and characterization of water-soluble chiral conducting polymer nanocomposites. Langmuir 18, 259–263 (2002).
Foos, E. E., Snow, A. W. & Twigg, M. E. Synthesis and characterization of water soluble gold nanoclusters of varied core size. J. Clust. Sci. 13, 543–552 (2002).
He, B., Ha, Y., Liu, H., Wang, K. & Liew, K. Y. Size control synthesis of polymer-stabilized water-soluble platinum oxide nanoparticles. J. Colloid Interface Sci. 308 105–111 (2007).
Hu, Y., Ge, J., Lim, D., Zhang, T. & Yin, Y. Size-controlled synthesis of highly water-soluble silver nanocrystals. J. Solid State Chem. 181, 1524–1529 (2008).
Zhou, L., Dong, C., Wei, S. H., Feng, Y. Y., Zhou, J. H. & Liu, J. H. Water-soluble soft nano-colloid for drug delivery. Mater. Lett. 63, 1683–1685 (2009).
Krutyakov, Yu. A., Kudrinsky, A. A., Olenin, A. Yu. & Lisichkin, G. V. Synthesis of highly stable silver colloids stabilized with water soluble sulfonated polyaniline. App. Surf. Sci. 256, 7037–7042 (2010).
Cui, Q., Xu, J., Shen, G., Zhang, C., Li, L. & Antonietti, M. Hybridizing carbon nitride colloids with a shell of water-soluble conjugated polymers for tunable full-color emission and synergistic cell imaging. ACS Appl. Mater. Interfaces 9, 43966–43974 (2017).
Chakraborty, B. & Weinstock, I.A. Water-soluble titanium-oxides: Complexes, clusters and nanocrystals. Coord. Chem. Rev. 382, 85–102 (2019).
Sinturel, C., Vayer, M., Mahut, F., Bonnier, F., Chourpa, I. & Munnier, E. Influence of PLGA nanoparticles on the deposition of model water-soluble biocompatible polymers by dip coating. Colloids Surf. A Physicochem. Eng. Asp. 608, 125591 (2021).
Stewart, J. J. P. Optimization of parameters for semiempirical methods V: Modification of NDDO approximations and application to 70 elements. J. Mol. Model. 13, 1173–213 (2007).

No competing interests reported.

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Room temperature synthesis of water-soluble spherical particles of a uniform diameter composed of carbon nanobelts and C60 molecules

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