The first example of synthesis Au-nanoparticles with amidine derivatives of closo-decaborate anion as stabilizing ligand
https://doi.org/10.17586/2220-8054-2026-17-1-59-68
Abstract
In this work, we report the one-pot aqueous synthesis of AuNPs using novel amidine derivatives of the closo-decaborate anion, functionalized with pendant thiol groups, as combined reducing and stabilizing agents. A comprehensive characterization using transmission electron microscopy (TEM) revealed the formation of nanoparticles with a distinctive and unusual hollow-core/dense-shell architecture, where a gold-rich shell encapsulates a low-Z element core. This unique morphology accounts for the observed absence of a characteristic surface plasmon resonance (SPR) band in the UV-Vis spectra, distinguishing these materials from classical solid-core AuNPs. X-ray photoelectron spectroscopy (XPS) confirmed the covalent attachment of the ligands via Au-S bonds and the integrity of the boron cage on the nanoparticle surface. The synthesis was optimized, establishing a 1:6 (Au:Ligand) molar ratio as ideal for achieving a narrow particle size distribution.
About the Authors
A. A. IvanovaRussian Federation
Arina A. Ivanova
Moscow, 101000
Moscow,119991
A. D. Filippova
Russian Federation
Arina D. Filippova
Moscow, 119991
M. A. Teplonogova
Russian Federation
Maria A. Teplonogova
Moscow, 119991
A. A. Sadovnikov
Russian Federation
Alexey A. Sadovnikov
119991, Moscow
N. A. Selivanov
Russian Federation
Nikita A. Selivanov
Moscow, 119991
A. P. Zhdanov
Russian Federation
Andrey P. Zhdanov
Moscow, 119991
K. Yu. Zhizhin
Russian Federation
Konstantin Yu. Zhizhin
Moscow, 119991
N. T. Kuznetsov
Russian Federation
Nikolay T. Kuznetsov
Moscow, 119991
References
1. Fernandes D.A. Multifunctional gold nanoparticles for cancer theranostics. 3 Biotech, 2024, 14, 267.
2. Tan D.K., Tai Y., Nguyen T.T. Gold nanoparticles for targeting of biomedical applications: A review. Asian J. Chem., 2024, 36 (8), P. 1741–1746.
3. Asih S., Budi S., Katas H. Synthesis and application of gold nanoparticles as antioxidants. Pharmacia, 2024, 71, P. 1–19.
4. Kattumuri V., Katti K., Bhaskaran S., et al. Gum arabic as a phytochemical construct for the stabilization of gold nanoparticles: in vivo pharmacokinetics and X-ray-contrast-imaging studies. Small, 2007, 3 (2), P. 333–341.
5. Nirmala J.G., Rachineni K., Choudhary S., et al. Triphala polyphenols-functionalized gold nanoparticles impair cancer cell survival through induction of tubulin dysfunction. J. Drug Deliv. Sci. Technol., 2021, 61, 102167.
6. Xia Y., Wu X., Zhao J., et al. Three dimensional plasmonic assemblies of AuNPs with an overall size of sub-200 nm for chemo-photothermal synergistic therapy of breast cancer. Nanoscale, 2016, 8 (44), P. 18682–18692.
7. Zhao R., Xiang J., Wang B., et al. Recent advances in the development of noble metal NPs for cancer therapy. Bioinorg. Chem. Appl., 2022, 2022, 2444516.
8. Sakore P., Gaikwad S., Aadil K.R., et al. The theranostic potential of green nanotechnology-enabled gold nanoparticles in cancer: A paradigm shift on diagnosis and treatment approaches. Results Chem., 2024, 7, 101264.
9. Amendola V., Pilot R., Frasconi M., et al. Surface plasmon resonance in gold nanoparticles: a review. J. Phys.: Condens. Matter, 2017, 29 (20), 203002.
10. Huang X., El-Sayed M.A. Gold nanoparticles: Optical properties and implementations in cancer diagnosis and photothermal therapy. J. Adv. Res., 2010, 1 (1), P. 13–28.
11. Wu C.-Y., Hsieh H.-H., Chang T.-Y., et al. Development of MRI-detectable boron-containing gold nanoparticle-encapsulated biodegradable polymeric matrix for boron neutron capture therapy (BNCT). Int. J. Mol. Sci., 2021, 22, 8050.
12. Ready A.D., Nelson Y.A., Torres Pomares D.F., Spokoyny A.M. Redox-active boron clusters. Acc. Chem. Res., 2024, 57, P. 1310–1324.
13. Ohta K. Basic organic and inorganic chemistry of boron clusters and its application to drug discovery. Yakugaku Zasshi, 2022, 142 (8), P. 855–863.
14. Soriano-Urs´ua M.A. Boron applications in prevention, diagnosis and therapy for high global burden diseases. Inorganics, 2023, 11 (9), 358.
15. Hirose K., Konishi T., Tanaka H., et al. Boron neutron capture therapy using cyclotron-based epithermal neutron source and borofalan (10B) for recurrent or locally advanced head and neck cancer (JHN002): An open-label phase II trial. Radiother. Oncol., 2021, 155, P. 182–187.
16. Fujikawa Y., Kawabata S., Tsujino K. et al. Chordoma Treatment with Boron Neutron Capture Therapy (BNCT): Experimental Insights. Proceedings, 2024, 95 (1), 13.
17. Licitra L., Orlandi E., Bossi P., et al. Developing a trial design to establish BNCT as clinical application: insight for the national italian center for oncological hadrontherapy (CNAO). Health Technol., 2024, 14 (5), P. 1037–1041.
18. Zhizhin K.Yu., Zhdanov A.P., Kuznetsov N.T. Derivatives of closo-decaborate anion [B10H10]2− with exo-polyhedral substituents. Russ. J. Inorg. Chem., 2010, 55 (14), P. 2089–2127.
19. Williams D.B.G., Lawton M. Drying of Organic Solvents: Quantitative evaluation of the efficiency of several desiccants. J. Org. Chem., 2010, 75, P. 8351–8354.
20. Zhdanov A.P., Bykov A.Yu., Kubasov A.S., et al. Hydrolysis of nitrilium derivatives of the closo-decaborate anion [2-B10H9(N≡CR)]−. Russ. J. Inorg. Chem., 2017, 62, P. 468–475.
21. Avdeeva V.V., Malinina E.A., Kuznetsov N.T. Boron cluster anions and their derivatives in complexation reactions. Coord. Chem. Rev., 2022, 469, 214636.
22. Gobbo P., Biesinger M.C., Workentin M.S. Facile synthesis of gold nanoparticle (AuNP)–carbon nanotube (CNT) hybrids through an interfacial michael addition reaction. Chem. Commun., 2013, 49, 2831.
23. Gobbo P., Novoa S., Biesinger M.C., Workentin M.S. Interfacial strain-promoted alkyne–azide cycloaddition (I-SPAAC) for the synthesis of nanomaterial hybrids. Chem. Commun., 2013, 49, 3982.
24. Liu Y.-S., Ray K.G., Jørgensen M., et al. Nanoscale Mg–B via surfactant ball milling of MgB2: morphology, composition, and improved hydrogen storage properties. J. Phys. Chem. C, 2020, 124, P. 21761–21771.
25. Saldin V.I., Ignat’eva L.N., Nikolenko Yu.M., et al. Thermal conversions of chitosanium dodecahydro-closo-dodecaborate. Russ. J. Inorg. Chem., 2010, 55, P. 1221–1227.
Review
For citations:
Ivanova A.A., Filippova A.D., Teplonogova M.A., Sadovnikov A.A., Selivanov N.A., Zhdanov A.P., Zhizhin K.Yu., Kuznetsov N.T. The first example of synthesis Au-nanoparticles with amidine derivatives of closo-decaborate anion as stabilizing ligand. Nanosystems: Physics, Chemistry, Mathematics. 2026;17(1):59-68. https://doi.org/10.17586/2220-8054-2026-17-1-59-68
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