Bimetallic Nanomaterials: History
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Bimetallic nanomaterials (BMNs) are one kind of innovative nanomaterials, referring to nano-bimetallic alloy, intermetallic compounds, or the combination of two kinds of metallic nanoparticles. Compared with monometallic nanomaterials, BMNs perform similar or even better physical and chemical properties in the medical field. BMNs possess excellent physical and chemical properties, such as easy surface modification, superior photothermal properties, multiple catalytic properties, delicate sensitivity, and good stability. Synthesis methods of bimetallic nanomaterials. The preparation methods of BMNs commonly used for cancer therapy, such as co-reduction method, hydrothermal method, seed-mediated growth method, and electrodeposition method.

 

  • bimetallic nanomaterials
  • synthesis methods
  • physicochemical properties
  • application in tumor therapy

1. Introduction

Generally, doping with the second metal is considered to possess superior performance than monometallic nanomaterials (MMNs), due to the addition of more active sites by the formation of metal polar bonds and irregular arrangement.[1][2] At the same time, the combination of the two metals is more likely to form complex structures with enhanced SPR effects such as hollow structures, porous structures, and core-shell structures.[3] Therefore, regulating the optical, electrical, chemical, and biological properties by controlling their size, shape, and composition during synthesis is particularly important in the study of monometallic nanomaterials (BMNs).[4] In order to achieve the design and effects, many methods have been extensively tested in the past decades. Among them, there is an important problem that the ratio of the two metals and the shape of BMNs are difficult to control.[5] BMNs with controlled composition can be synthesized by co-reduction method and hydrothermal method, and their shapes are mostly spherical and massive. BMNs synthesized by seed-mediated method usually perform complex shapes, while the BMNs obtained by electrodeposition are mostly nanowires and nanofilms. In order to obtain suitable BMNs for cancer therapy, a systematic understanding of the synthesis methods is required.

2. Classification of synthetic methods

2.1. Co-reduction method

Co-reduction is one of the most straightforward and convenient methods to prepare BMNs due to its simple operation, low cost, and short reaction time. Co-reduction, also known as the one-pot method, is usually used when two precursors containing metal elements are mixed, and the metal ions are reduced to form alloys or intermetallic compounds.[6][7] In addition, the BMNs’ morphology and structure can be tailored by the reaction temperature, the addition of surfactants, the reducing agent, and the nature of coordination ligand. Many common BMNs such as gold/silver core-shell structures, gold/silver nanowires, and gold/platinum NPs are synthesized by this method. More sophisticated nanomaterials with special shapes and structures can be synthesized by co-reduction in combination with other methods.[8] 

2.2. Hydrothermal method

Hydrothermal method is another widely used method, which is similar to the co-reduction method. The metal precursors are promoted to decompose and reduce after heating. The hydrothermal method is generally applicable to reactions with lower reduction potentials that are not easily reduced directly. Up to date, some BMNs synthesized from metal precursors with lower reduction potentials have been prepared with this method, such as CuNi,[9][10] Ni-Fe,[11] CoNi,[12] and NiRe.[13] Besides, the hydrothermal method is not only suitable for metal precursors with low reducibility but also widely used in the synthesis of many BMNs (PtCu, PtPd, et al., for instance).[14][15] In a word, the hydrothermal method is simple to operate and easy to synthesize large quantities of BMNs.

2.3. Seed-mediated growth method

Seed-mediated growth has been proven an effective method for synthesizing plasmonic noble metal nanocrystals.[16] This method has been applied in the synthesis of BMNs because the prepared nanocrystals have well-defined morphology, size, and surface composition. Typically, seed-mediated methods play an important role in the preparation of anisotropic metal structures and hierarchical epitaxial core/shell structures.[17][18][19][20] Seed-mediated growth method has emerged in the field of synthesizing BMNs due to simple operation, strong repeatability, and high yield. In particular, the shapes and components of BMNs can be accurately regulated by the seed-mediated method, which is difficult to obtain by other methods. It is believed that this method will be more extensively used in the future.

2.4. Electrodeposition method

Electrodeposition is a simple and inexpensive synthesis method, which is widely used in the synthesis of nanotube, nanoporosity, and nanofilm.[21][22][23] This method is rarely used to produce BMNs for disease treatment, because of its limitations including harsh reaction conditions, low yield, and difficulty to control.

3. Application

BMNs exhibit various and complex morphologies based on spatial arrangements, which are related to abundant physicochemical properties. Common nanomaterials used in disease treatment are mainly manifested as nanospheres, nanorods, nanoclusters, nanostars, and nanoflowers, which have large surface areas and unique optical properties. BMNs with specific morphology and structure can be obtained by different synthesis methods for the treatment of tumor. 

In summary, many complex and diverse morphologies can be exhibited in BMNs that indicate the suitable characteristics for tumor therapy, such as good biocompatibility, drug-loading capacity, photothermal and catalytic properties. BMNs have a broad development prospect in tumor therapy by virtue of these abundant morphologies. BMNs have been widely used in biomedical fields, especially in biosensing and imaging, due to their unique catalytic and optical properties. In addition, many studies have shown that BMNs are also promising nanotechnology in cancer therapy.

4. Influence and new progress

In conclusion, the co-reduction method, hydrothermal method, and seed-mediated method have been widely used for the preparation of BMNs suitable for cancer therapy. Especially the seed-mediated method can precisely control the morphology of BMNs to obtain unparalleled properties. Although precise porous BMNs can also be obtained by the electrodeposition method and seed-mediated method, which are difficult to be obtained by other methods. It is exciting that BMNs with delicate structures can be synthesized more conveniently with the assistance of two synthesis methods, such as seed-mediated method and co-reduction, template synthesis and co-reduction.[24] Therefore, it is very important to choose the appropriate method according to the properties and morphology of BMNs.

However, it is still challenging to find suitable synthetic methods from many methods that can be used to produce BMNs for cancer therapy. It has been found that BMNs with zero dimension, such as spheres, rods, stars, and flowers, are usually used in cancer treatment. These structures are usually synthesized by seed-mediated and hydrothermal methods, where the regulation of BMNs' morphology has been well studied. In addition, it is also suggested that the growth pattern and mechanisms of all BMNs can be thoroughly explored by molecular simulation to establish a material library so that nanostructures with specific properties and shapes can be designed more clearly to reply to complex environments and various therapeutic applications.

This entry is adapted from the peer-reviewed paper 10.3390/molecules27248712

References

  1. Sytwu, K.; Vadai, M.; Dionne, J.A. Bimetallic nanostructures: combining plasmonic and catalytic metals for photocatalysis. Adv. Phys.-X 2019, 4, 1619480. He, J.H.; Ichinose, I.; Kunitake, T.; Nakao, A.; Shiraishi, Y.; Toshima, N. Facile fabrication of Ag-Pd bimetallic nanoparticles in ultrathin TiO2-gel films: nanoparticle morphology and catalytic activity. J. Am. Chem. Soc. 2003, 125, 11034-11040.
  2. He, J.H.; Ichinose, I.; Kunitake, T.; Nakao, A.; Shiraishi, Y.; Toshima, N. Facile fabrication of Ag-Pd bimetallic nanoparticles in ultrathin TiO2-gel films: nanoparticle morphology and catalytic activity. J. Am. Chem. Soc. 2003, 125, 11034-11040.
  3. Zhang, H.; Jin, M.S.; Xia, Y.N. Enhancing the catalytic and electrocatalytic properties of Pt-based catalysts by forming bimetallic nanocrystals with Pd. Chem. Soc. Rev. 2012, 41, 8035-8049.
  4. Somu, P.; Paul, S. Protein assisted one pot controlled synthesis of monodispersed and multifunctional colloidal silver‑gold alloy nanoparticles. J. Mol. Liq. 2019, 291, 111303.
  5. Scaria, J.; Nidheesh, P.V.; Kumar, M.S. Synthesis and applications of various bimetallic nanomaterials in water and wastewater treatment. J. Environ. Manage. 2020, 259, 110011.
  6. Chiu, T.H.; Liao, J.H.; Gam, F.; Wu, Y.Y.; Wang, X.P.; Kahlal, S.; Saillard, J.Y.; Liu, C.W. Hydride-containing eight-electron Pt/Ag superatoms: structure, bonding, and multi-nmr studies. J. Am. Chem. Soc. 2022, 144, 10599-10607.
  7. Hu, Y.; Zhang, A.Q.; Li, H.J.; Qian, D.J.; Chen, M. Synthesis, study, and discrete dipole approximation simulation of Ag-Au bimetallic nanostructures. Nanoscale Res. Lett. 2016, 11, 1701751.
  8. Joo, J.H.; Kim, B.H.; Lee, J.S. Synthesis of gold nanoparticle-embedded silver cubic mesh nanostructures using AgCl nanocubes for plasmonic photocatalysis. Small 2017, 13, 1701751.
  9. Radwan, A.B.; Paramparambath, S.; Cabibihan, J.J.; Al-Ali, A.K.; Kasak, P.; Shakoor, R.A.; Malik, R.A.; Mansour, S.A.; Sadasivuni, K.K. Superior non-invasive glucose sensor using bimetallic CuNi nanospecies coated mesoporous carbon. Biosensors-Basel 2021, 11, 463.
  10. Motlak, M.; Barakat, N.; El-Deen, A.G.; Hamza, A.M.; Obaid, M.; Yang, O.B.; Akhtar, M.S.; Khalil, K.A. NiCu bimetallic nanoparticle-decorated graphene as novel and cost-effective counter electrode for dye-sensitized solar cells and electrocatalyst for methanol oxidation. Appl. Catal. A-Gen. 2015, 501, 41-47.
  11. Gai, C.; Zhang, F.; Yang, T.X.; Liu, Z.G.; Jiao, W.T.; Peng, N.N.; Liu, T.T.; Lang, Q.Q.; Xia, Y. Hydrochar supported bimetallic Ni-Fe nanocatalysts with tailored composition, size and shape for improved biomass steam reforming performance. Green Chem. 2018, 20, 2788-2800.
  12. Wei, L.G.; Chen, W.; Jia, C.Y.; Wang, D.; Li, M.; Dong, Y.L.; Song, W.N.; Liu, L.L.; Yang, Y.L. Facile synthesis of CoNi bimetallic nanoparticle decorated reduced graphene oxide as efficient and low-cost counter electrode for dye-sensitized solar cells. JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY 2019, 19, 7790-7798.
  13. Wei, Z.J.; Cheng, Y.R.; Chen, M.T.; Ye, Y.H.; Liu, Y.X. Design of low-loaded nire bimetallic catalyst on N-doped mesoporous carbon for highly selective deoxygenation of oleic acid to n-heptadecane. Korean J. Chem. Eng. 2022, 39, 1753-1761.
  14. Xu, B.; Zhang, Z.C.; Wang, X. Formamide: an efficient solvent to synthesize water-soluble and sub-ten-nanometer nanocrystals. Nanoscale 2013, 5, 4495-4505.
  15. Habibi, A.H.; Hayes, R.E.; Semagina, N. Evaluation of hydrothermal stability of encapsulated PdPt@SiO2 catalyst for lean CH4 combustion. Appl. Catal. A-Gen. 2018, 556, 129-136.
  16. Feng, J.; Xu, D.D.; Yang, F.; Chen, J.X.; Wu, C.; Yin, Y.D. Surface engineering and controlled ripening for seed-mediated growth of Au islands on Au nanocrystals. Angew. Chem.-Int. Edit. 2021, 60, 16958-16964.
  17. Scala, A.; Neri, G.; Micale, N.; Cordaro, M.; Piperno, A. State of the art on green route synthesis of gold/silver bimetallic nanoparticles. Molecules 2022, 27, 1134.
  18. Orouji, A.; Abbasi-Moayed, S.; Ghasemi, F.; Hormozi-Nezhad, M.R. A wide-range pH indicator based on colorimetric patterns of gold@silver nanorods. Sens. Actuator B-Chem. 2022, 358, 131479.
  19. Zhang, Q.F.; Jing, H.; Li, G.G.; Lin, Y.; Blom, D.A.; Wang, H. Intertwining roles of silver ions, surfactants, and reducing agents in gold nanorod overgrowth: pathway switch between silver underpotential deposition and gold-silver codeposition. Chem. Mat. 2016, 28, 2728-2741.
  20. Xue, C.; Millstone, J.E.; Li, S.Y.; Mirkin, C.A. Plasmon-driven synthesis of triangular core-shell nanoprisms from gold seeds. Angew. Chem.-Int. Edit. 2007, 46, 8436-8439.
  21. Wang, D.; Wu, Z.; Li, F.X.; Gan, X.P.; Tao, J.M.; Yi, J.H.; Liu, Y.C. A combination of enhanced mechanical and electromagnetic shielding properties of carbon nanotubes reinforced Cu-Ni composite foams. Nanomaterials 2021, 11, 1772.
  22. Simunkova, H.; Lednicky, T.; Whitehead, A.H.; Kalina, L.; Simunek, P.; Hubalek, J. Tantalum-based nanotube arrays via porous-alumina-assisted electrodeposition from ionic liquid: formation and electrical characterization. Appl. Surf. Sci. 2021, 548, 149264.
  23. Katarkar, A.S.; Pingale, A.D.; Belgamwar, S.U.; Bhaumik, S. Experimental study of pool boiling enhancement using a two-step electrodeposited Cu-GNPs nanocomposite porous surface with R-134a. J. Heat Transf.-Trans. Asme 2021, 143, 121601.
  24. Wang, C.Y.; Chen, D.P.; Sang, X.H.; Unocic, R.R.; Skrabalak, S.E. Size-dependent disorder-order transformation in the synthesis of monodisperse intermetallic PdCu nanocatalysts. Acs Nano 2016, 10, 6345-6353.
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