A Facile and Rational Method to Tailor the Symmetry of Au@Ag Nanoparticles
2023-03-04, Ni, Bing, Zhou, Jian, Stolz, Levin, Cölfen, Helmut
Precisely controlling the morphologies of plasmonic metal nanoparticles (NPs) is of great importance for many applications. Here, a facile seed-mediated growth method is demonstrated that tailors the morphologies of Au@Ag NPs from cubes/cuboids to chiral truncated cuboids/octahedra, well-defined octahedra, and tetrahedra, via simply increasing the concentrations of AgNO3 and cysteine in the halide surfactant systems. Accordingly, the particle symmetries are also tuned. The method is quite robust where seeds with distinct shapes including irregular ones can all lead to uniform Au@Ag NPs. The evolution of these shapes can be illustrated by a recently proposed symmetry-based kinematic theory (SBKT). Furthermore, SBKT shows a strategy to optimize the preparation of chiral/dissymmetric NPs, and the experimental results confirm such a dissymmetric synthesis strategy. Cuboids and octahedra with corners differently truncated are identified as two different chiral forms. The chirality of the NPs is additionally probed by electrochemistry, where the chiral NPs show enantioselectivity in the oxidation of d- and l-glucose. Altogether, the results gain fundamental insights into tailoring the plasmonic NP morphologies, and also suggest strategies to obtain chiral NPs.
Formation Of Amorphous Iron‐Calcium Phosphate With High Stability
2023, Chen, Song, Liu, Dachuan, Fu, Le, Ni, Bing, Chen, Zongkun, Knaus, Jennifer, Sturm, Elena V., Wang, Bohan, Cölfen, Helmut, Li, Bin
Amorphous iron-calcium phosphate (Fe-ACP) plays a vital role in the mechanical properties of teeth of some rodents, which are very hard, but its formation process and synthetic route remain unknown. Here, we report the synthesis and characterization of an iron-bearing amorphous calcium phosphate in the presence of ammonium iron citrate (AIC). The iron is distributed homogeneously on the nanometer scale in the resulting particles. The prepared Fe-ACP particles can be highly stable in aqueous media, including water, simulated body fluid and acetate buffer solution (pH 4). In vitro study demonstrates that these particles have good biocompatibility and osteogenic properties. Subsequently, Spark Plasma Sintering (SPS) is utilized to consolidate the initial Fe-ACP powders. The results show that the hardness of the ceramics increases with the increase of iron content, but an excess of iron leads to a rapid decline in hardness. Calcium iron phosphate ceramics with a hardness of 4 GPa can be achieved, which is higher than that of human enamel. Furthermore, the ceramics composed of iron-calcium phosphates showed enhanced acid resistance. This study provides a novel route to prepare Fe-ACP, and presents the potential role of Fe-ACP in biomineralization and as starting material to fabricate acid-resistant high-performance bioceramics.
Tuning the Electronic Properties of Mesocrystals
2022-08, Jenewein, Christian, Schupp, Stefan, Ni, Bing, Schmidt-Mende, Lukas, Cölfen, Helmut
Colloidal crystals are arguably one of the most promising candidates when it comes to the fabrication of nanostructured metamaterials. Especially mesocrystals show exciting new properties that emerge from their inherent directional oriented assembly. With this work, the electrical conductivity of well-defined micrometer-sized platinum nanocube-based mesocrystals is demonstrated and tuned through the variation of different capping agents. Herein, a method is presented to reproducibly quantify the intrinsic resistance of individual mesocrystals through electrical nanoprobing and focused ion beam deposition contacting. A thermally activated tunneling mechanism is identified as the main effect for electron propagation. In addition, the mesocrystals are altered through organically linking and mineral bridging the individual nanoparticles. This results in an increase in mesocrystal rigidity and, more importantly, conductivity by seven orders of magnitude while retaining shape, structure, and composition. In addition, these observations are transferred onto multicomponent superstructures in the form of binary mesocrystals. There, it is demonstrated that the electrical properties could be tuned through the ratio of nanoparticles incorporated into a mesocrystalline host system while simultaneously maintaining potential catalytic or superparamagnetic features of the guest particles.
A Symmetry-Based Kinematic Theory for Nanocrystal Morphology Design
2022-05-09, Ni, Bing, Gonzalez-Rubio, Guillermo, Kirner, Felizitas, Zhang, Siyuan, Cölfen, Helmut
The growth of crystalline nanoparticles (NPs) generally involves three processes: nucleation, growth, and shape evolution. Among them, the shape evolution is less understood, despite the importance of morphology for NP properties. Here, we propose a symmetry-based kinematic theory (SBKT) based on classical growth theories to illustrate the process. Based on the crystal lattice, nucleus (or seed) symmetry, and the preferential growth directions under the experimental conditions, the SBKT can illustrate the growth trajectories. The theory accommodates the conventional criteria of the major existing theories for crystal growth and provides tools to better understand the symmetry-breaking process during the growth of anisotropic structures. Furthermore, complex dendritic growth is theoretically and experimentally demonstrated. Thus, it provides a framework to explain the shape evolution, and extends the morphogenesis prediction to cases, which cannot be treated by other theories.
Bioinspired Stabilization of Amorphous Calcium Carbonate by Carboxylated Nanocellulose Enables Mechanically Robust, Healable, and Sensing Biocomposites
2023, Wu, Wanlin, Lu, Zhixing, Lu, Canhui, Sun, Xunwen, Ni, Bing, Cölfen, Helmut, Xiong, Rui
Nature builds numerous structurally complex composites with fascinating mechanical robustness and functionalities by harnessing biopolymers and amorphous calcium carbonate (ACC). The key to successfully mimicking these natural designs is efficiently stabilizing ACC, but developing highly efficient, biodegradable, biocompatible, and sustainable stabilizing agents remains a grand challenge since anhydrous ACC is inherently unstable toward crystallization in the wet state. Inspired by the stabilized ACC in crustacean cuticles, we report the efficient stabilization ability of the most abundant biopolymer–cellulose nanofibrils (CNFs) for ACC. Through the cooperative stabilizing effect of surface carboxyl groups and a rigid segregated network, the CNFs exhibit long-term stability (more than one month) and achieved a stabilization efficiency of 3.6 and 4.4 times that of carboxymethyl cellulose (CMC) and alginate, respectively, even higher than poly(acrylic acid). The resulting CNF/ACC dispersions can be constructed into transparent composite films with the high strength of 286 MPa and toughness up to 28.5 MJ/m3, which surpass those of the so far reported synthetic biopolymer-calcium carbonate/phosphate composites. The dynamic interfacial interaction between nanocomponents also provides the composite films with good self-healing properties. Owing to their good wet stability, the composite films present high humidity sensitivity for monitoring respiration and finger contact.
A Bioinspired Gelatin–Amorphous Calcium Phosphate Coating on Titanium Implant for Bone Regeneration
2023, Feng, Yanhuizhi, Wu, Di, Knaus, Jennifer, Keßler, Sascha, Ni, Bing, Chen, Zongkun, Avaro, Johnathan, Xiong, Rui, Cölfen, Helmut, Wang, Zuolin
Biocompatible and bio-active coatings can enhance and accelerate osseointegration via chemical binding onto substrates. Amorphous calcium phosphate (ACP) has been shown as a precursor to achieve mineralization in vertebrates and invertebrates under the control of biological macromolecules. This work presents a simple bioinspired Gelatin-CaPO4 (Gel-CaP) composite coating on titanium surfaces to improve osseointegration. The covalently bound Gel-CaP composite is characterized as an ACP-Gel compound via SEM, FT-IR, XRD, and HR-TEM. The amorphous compound coating exhibited a nanometer range thickness and improved elastic modulus, good wettability, and nanometric roughness. The amount of grafted carboxyl groups and theoretical thickness of the coatings are also investigated. More importantly, MC3T3 cells, an osteoblast cell line, show excellent cell proliferation and adhesion on the Gel-CaP coating. The level of osteogenic genes is considerably upregulated on Ti with Gel-CaP coatings compared to uncoated Ti, demonstrating that Gel-CaP coatings possess a unique osteogenic ability. To conclude, this work offers a new perspective on functional, bioactive titanium coatings, and Gel-CaP composites can be a low-cost and promising candidate in bone regeneration.
Self-Assembly of Colloidal Nanocrystals into 3D Binary Mesocrystals
2022-06-21, Ni, Bing, Gonzalez-Rubio, Guillermo, Cölfen, Helmut
Conspectus: Biominerals are unique materials found in many living organisms that often display outstanding functionalities attributed to their mesocrystalline structure. Mesocrystals are nanocrystal superstructures with mutual crystallographic alignment of the building units. One could thus imagine these optimized evolutionary systems as archetypes to fabricate advanced materials. The main advantage of such systems relies on their ability to combine the features of the nanocrystals with those of single crystalline microscopic structures, yielding assemblies with directional, enhanced, and potentially emergent properties. Moreover, fueled by the promises of multifunctional materials with unprecedented and tunable properties, the rational design of mesocrystals assembled from two distinct colloidal nanocrystal ensembles has become a recent focus of research. However, the combination of dissimilar nanocrystals into ordered binary superstructures is still a major scientific challenge due to the nature of the coassembly process.
We focus this Account on the growth of tridimensional (3D) binary mesocrystals and the understanding of the self-assembly of two colloidal nanocrystal ensembles with the ultimate goal to serve as a basis for more rational mesocrystal syntheses in the future. The formation of mesocrystals demands nanocrystals with defined surface faceting, the primary factor influencing their oriented self-assembly. Notably, such a process cannot be successfully afforded without functionalized nanocrystals with high and, in many cases, tunable colloidal stability. Besides, the nature and solvation degree of the surface ligand shell influences the effective shape of the nanocrystals and the kinetics of self-assembly. If the assembly is triggered by reducing the colloidal stability with nonsolvents, 3D single-component mesocrystals are often grown. Here, the different magnitude of the van der Waals attraction forces between nanocrystals with differing compositions, dimensions, and morphologies generally favors the segregation and growth of single component mesocrystals. This phenomenon was illustrated during the successful preparation of 3D binary mesocrystals composed of iron oxide and platinum nanocubes. Although the building blocks possessed comparable sizes and were stabilized by similar ligands, the amount of the second component could only be arbitrarily tuned up to some extent, even when the assembly conditions were rationally optimized to achieve 3D binary mesocrystals. Only a small amount of it was effectively incorporated into the matrix of the initial mesocrystal. The 3D binary mesocrystal growth process demands a delicate control over the size, shape, and surface chemistry of the nanocrystals, the solvent nature, and the self-assembly process. Hence, the improvement of our ability to control the synthesis of 3D binary mesocrystalline materials is critical to exploit their potential toward technological applications in catalysis, energy storage, or structural materials.
How a Facet of a Nanocrystal Is Formed : The Concept of the Symmetry Based Kinematic Theory
2023, Ni, Bing, Gonzalez-Rubio, Guillermo, Cölfen, Helmut
Conventional nanocrystal (NC) growth mechanisms have overwhelmingly focused on the final exposed facets to explain shape evolution. However, how the final facets are formed from the initial nuclei or seeds, has not been specifically interrogated. In this concept paper, we would like to concentrate on this specific topic, and introduce the symmetry based kinematic theory (SBKT) to explain the formation and evolution of crystal facets. It is a crystallographic theory based on the classical crystal growth concepts developed to illustrate the shape evolution during the NC growth. The most important principles connecting the basic NC growth processes and morphology evolution are the preferential growth directions and the properties of kinematic waves. On the contrary, the final facets are just indications of how the crystal growth terminates, and their formation and evolution rely on the NC growth processes: surface nucleation and layer advancement. Accordingly, the SBKT could even be applied to situations where non-faceted NCs such as spheres are formed.
Chiral Seeded Growth of Gold Nanorods Into 4-Fold Twisted Nanoparticles with Plasmonic Optical Activity
2023, Ni, Bing, Mychinko, Mikhail, Gómez-Graña, Sergio, Morales-Vidal, Jordi, Obelleiro-Liz, Manuel, Heyvaert, Wouter, Gonzalez-Rubio, Guillermo, Cölfen, Helmut, Bals, Sara, Liz-Marzán, Luis M.
A robust and reproducible methodology to prepare stable inorganic nanoparticles with chiral morphology might hold the key to the practical utilization of these materials. We describe herein an optimized chiral growth method to prepare 4-fold twisted gold nanorods, where the amino acid cysteine is used as a dissymmetry inducer. Four tilted ridges were found to develop on the surface of single-crystal nanorods upon repeated reduction of HAuCl4 , in the presence of cysteine as the chiral inducer and ascorbic acid as a reducing agent. From detailed electron microscopy analysis of the crystallographic structures, we propose that dissymmetry results from the development of chiral facets in the form of protrusions (tilted ridges) on the initial nanorods, eventually leading to a twisted shape. The role of cysteine is attributed to assisting enantioselective facet evolution, which is supported by density functional theory simulations of the surface energies, modified upon adsorption of the chiral molecule. The development of R-type and S-type chiral structures (small facets, terraces, or kinks) would thus be non-equal, removing the mirror symmetry of the Au NR and in turn resulting in a markedly chiral morphology with high plasmonic optical activity. This article is protected by copyright. All rights reserved.
Eine symmetriebasierte kinematische Theorie für das Design von Nanokristall‐Morphologien
2022-05-09, Ni, Bing, Gonzalez-Rubio, Guillermo, Kirner, Felizitas, Zhang, Siyuan, Cölfen, Helmut
Das Wachstum von kristallinen Nanopartikeln (NP) umfasst im Allgemeinen drei Prozesse: Keimbildung, Wachstum und die Entwicklung der Form. Von diesen Prozessen ist die Formentwicklung trotz der Bedeutung der Morphologie für die Eigenschaften der NP am wenigsten verstanden. Hier beschreiben wir eine symmetriebasierte kinematische Theorie (SBKT) die auf klassischen Wachstumstheorien basiert, um den Prozess zu veranschaulichen. Auf Grundlage des Kristallgitters, der Keim- (oder Kern-) Symmetrie und der bevorzugten Wachstumsrichtungen unter den experimentellen Bedingungen kann die SBKT die Wachstumstrajektorien veranschaulichen. Die Theorie erfüllt die konventionellen Kriterien der wichtigsten bestehenden Theorien für das Kristallwachstum und bietet Werkzeuge zum besseren Verständnis des Symmetriebrechens während des Wachstums anisotroper Strukturen. Darüber hinaus wird das komplexe dendritische Wachstum sowohl theoretisch als auch experimentell nachgewiesen. Damit bietet sie einen Ansatz zur Erklärung der Formentwicklung und erweitert die Vorhersage der Morphogenese auf Fälle, die von anderen Theorien nicht erfasst werden können.