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Self-Assembly of Atomically Precise Nanoclusters: From Irregular Assembly to Crystalline Assembly

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A special issue of Nanomaterials (ISSN 2079-4991). This special issue belongs to the section "Nanofabrication and Nanomanufacturing".

Deadline for manuscript submissions: closed (30 June 2023) | Viewed by 28887

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Dr. Rodolphe Antoine

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Institut Lumière Matière UMR 5306, Université Claude Bernard Lyon 1, CNRS, Univ Lyon, F-69100 Villeurbanne, France
Interests: structural and optical properties of isolated biomolecules; structural and optical properties of isolated nanohybrids; bioparticles; liganded nanoclusters; nonlinear optics; mass spectrometry
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Dear Colleagues,

The persistent efforts toward achieving superior properties for assembled nanoscale particles have been held back due to the resulting polydispersity associated with colloidal routes of synthesis. A solution to this limitation seems to have emerged from the advent of ligand protected atomic clusters (often called atomically precise nanoclusters or quantum clusters). In this case, the ligands stabilizing the clusters are highly reactive in nature and thus provide a facile avenue for the “ligand-mediated spatial organization of nanoclusters”. Further, the most important characteristic of nanoclusters, which distinguishes them from other classes of nanomaterials, is that atomic clusters are imbued with structural integrity. Even polydispersed nanoclusters may be purified following regular purification techniques, and the precise chemical formula of the nanoclusters may be deciphered thanks to mass spectrometry. Thus, unlike other forms of nanoscale particles, a dispersion of atomic clusters typically constitutes of structurally and chemically related species. Hence, the perusal of chemical reactions toward achieving complex nanostructures in a controllable manner could yield self-assembled nanoclusters with multiple functions and collective properties, widening their application potential.

This Special Issue on the “Self-Assembly of Atomically Precise Nanoclusters” is intended to provide a unique international forum aimed at covering a broad description of the various approaches developed for assembling atomically precise clusters into higher ordered structures in various dimensions.

Dr. Rodolphe Antoine
Guest Editor

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Keywords

self-organization
metals
gold
ligands
aggregation-induced emission
metal nanoclusters
self-assembly of metal nanoclusters

Published Papers (12 papers)

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Editorial

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3 pages, 188 KiB

Open AccessEditorial

Self-Assembly of Atomically Precise Nanoclusters: From Irregular Assembly to Crystalline Assembly

by Rodolphe Antoine

Nanomaterials 2023, 13(18), 2551; https://0-doi-org.brum.beds.ac.uk/10.3390/nano13182551 - 13 Sep 2023

Viewed by 734

Abstract

(This article belongs to the Special Issue Self-Assembly of Atomically Precise Nanoclusters: From Irregular Assembly to Crystalline Assembly)

Research

Jump to: Editorial, Review

11 pages, 12377 KiB

Open AccessArticle

Fountain Pen-Inspired 3D Colloidal Assembly, Consisting of Metallic Nanoparticles on a Femtoliter Scale

by Sung-Jo Kim, Il-Hyun Lee, Won-Geun Kim, Yoon-Hwae Hwang and Jin-Woo Oh

Nanomaterials 2023, 13(17), 2403; https://0-doi-org.brum.beds.ac.uk/10.3390/nano13172403 - 24 Aug 2023

Cited by 2 | Viewed by 937

Abstract

The 3D colloidal assemblies composed of nanoparticles (NPs) are closely associated with optical properties such as photonic crystals, localized surface plasmon resonance, and surface-enhanced Raman scattering. However, research on their fabrication remains insufficient. Here, the femtoliter volume of a 3D colloidal assembly is shown, using the evaporation of a fine fountain pen. A nano-fountain pen (NPF) with a micrometer-level tip inner diameter was adopted for the fine evaporation control of the ink solvent. The picoliters of the evaporation occurring at the NFP tip and femtoliter volume of the 3D colloidal assembly were analyzed using a diffusion equation. The shape of the 3D colloidal assembly was dependent on the evaporation regarding the accumulation time and tip size, and they exhibited random close packing. Using gold-, silver-, and platinum-NPs and mixing ratios of them, diverse 3D colloidal assemblies were formed. The spectra regarding a localized surface plasmon resonance of them were changed according to composition and mixing ratio. We expect that this could be widely applied as a simple fabrication tool in order to explore complex metamaterials constructed of nanoparticles, as this method is highly flexible in varying the shape as well as composition ratio of self-assembled structures. Full article

(This article belongs to the Special Issue Self-Assembly of Atomically Precise Nanoclusters: From Irregular Assembly to Crystalline Assembly)

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13 pages, 5597 KiB

Open AccessArticle

Shape Dependence of Silver-Nanoparticle-Mediated Synthesis of Gold Nanoclusters with Small Molecules as Capping Ligands

by Cheng-Yeh Chang, Yi-Ru Wu, Tzu-Hsien Tseng, Jun-Hao Su, Yu-Shan Wang, Fang-Yi Jen, Bo-Ru Chen, Cheng-Liang Huang and Jui-Chang Chen

Nanomaterials 2023, 13(16), 2338; https://0-doi-org.brum.beds.ac.uk/10.3390/nano13162338 - 14 Aug 2023

Cited by 1 | Viewed by 2469

Abstract

In this study, differently shaped silver nanoparticles used for the synthesis of gold nanoclusters with small capping ligands were demonstrated. Silver nanoparticles provide a reaction platform that plays dual roles in the formation of Au NCs. One is to reduce gold ions and the other is to attract capping ligands to the surface of nanoparticles. The binding of capping ligands to the AgNP surface creates a restricted space on the surface while gold ions are being reduced by the particles. Four different shapes of AgNPs were prepared and used to examine whether or not this approach is dependent on the morphology of AgNPs. Quasi-spherical AgNPs and silver nanoplates showed excellent results when they were used to synthesize Au NCs. Spherical AgNPs and triangular nanoplates exhibited limited synthesis of Au NCs. TEM images demonstrated that Au NCs were transiently assembled on the surface of silver nanoparticles in the method. The formation of Au NCs was observed on the whole surface of the QS-AgNPs if the synthesis of Au NCs was mediated by QS-AgNPs. In contrast, formation of Au NCs was only observed on the edges and corners of AgNPts if the synthesis of Au NCs was mediated by AgNPts. All of the synthesized Au NCs emitted bright red fluorescence under UV-box irradiation. The synthesized Au NCs displayed similar fluorescent properties, including quantum yields and excitation and emission wavelengths. Full article

(This article belongs to the Special Issue Self-Assembly of Atomically Precise Nanoclusters: From Irregular Assembly to Crystalline Assembly)

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16 pages, 75254 KiB

Open AccessEditor’s ChoiceArticle

Electric Field-Induced Nano-Assembly Formation: First Evidence of Silicon Superclusters with a Giant Permanent Dipole Moment

by Fatme Jardali, Jacqueline Tran, Frédéric Liège, Ileana Florea, Mohamed E. Leulmi and Holger Vach

Nanomaterials 2023, 13(15), 2169; https://0-doi-org.brum.beds.ac.uk/10.3390/nano13152169 - 26 Jul 2023

Cited by 1 | Viewed by 958

Abstract

The outstanding properties of silicon nanoparticles have been extensively investigated during the last few decades. Experimental evidence and applications of their theoretically predicted permanent electric dipole moment, however, have only been reported for silicon nanoclusters (SiNCs) for a size of about one to two nanometers. Here, we have explored the question of whether suitable plasma conditions could lead to much larger silicon clusters with significantly stronger permanent electric dipole moments. A pulsed plasma approach was used for SiNC production and surface deposition. The absorption spectra of the deposited SiNCs were recorded using enhanced darkfield hyperspectral microscopy and compared to time-dependent DFT calculations. Atomic force microscopy and transmission electron microscopy observations completed our study, showing that one-to-two-nanometer SiNCs can, indeed, be used to assemble much larger ”superclusters” with a size of tens of nanometers. These superclusters possess extremely high permanent electric dipole moments that can be exploited to orient and guide these clusters with external electric fields, opening the path to the controlled architecture of silicon nanostructures. Full article

(This article belongs to the Special Issue Self-Assembly of Atomically Precise Nanoclusters: From Irregular Assembly to Crystalline Assembly)

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13 pages, 2283 KiB

Open AccessArticle

The Kinetics of Aragonite Formation from Solution via Amorphous Calcium Carbonate

by Simon M. Clark, Vili Grigorova, Bruno Colas, Tamim A. Darwish, Kathleen Wood, Joerg Neuefeind and Dorrit E. Jacob

Nanomaterials 2022, 12(23), 4151; https://0-doi-org.brum.beds.ac.uk/10.3390/nano12234151 - 23 Nov 2022

Cited by 3 | Viewed by 1316

Abstract

Magnesium doped Amorphous Calcium Carbonate was synthesised from precursor solutions containing varying amounts of calcium, magnesium, H₂O and D₂O. The Mg/Ca ratio in the resultant Amorphous Calcium Carbonate was found to vary linearly with the Mg/Ca ratio in the precursor solution. All samples crystallised as aragonite. No Mg was found in the final aragonite crystals. Changes in the Mg to Ca ratio were found to only marginally effect nucleation rates but strongly effect crystal growth rates. These results are consistent with a dissolution-reprecipitation model for aragonite formation via an Amorphous Calcium Carbonate intermediate. Full article

(This article belongs to the Special Issue Self-Assembly of Atomically Precise Nanoclusters: From Irregular Assembly to Crystalline Assembly)

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14 pages, 3727 KiB

Open AccessFeature PaperArticle

Supramolecular Self-Assembly of Atomically Precise Silver Nanoclusters with Chiral Peptide for Temperature Sensing and Detection of Arginine

by Wenjuan Wang, Zhi Wang, Di Sun, Shulin Li, Quanhua Deng and Xia Xin

Nanomaterials 2022, 12(3), 424; https://0-doi-org.brum.beds.ac.uk/10.3390/nano12030424 - 27 Jan 2022

Cited by 22 | Viewed by 3378

Abstract

Metal nanoclusters (NCs) as a new type of fluorescent material have attracted great interest due to their good biocompatibilities and outstanding optical properties. However, most of the studies on metal NCs focus on the synthesis, atomic or molecular assembly, whereas metal NCs ability to self-assemble to higher-level hierarchical nanomaterials through supramolecular interactions has rarely been reported. Herein, we investigate atomic precise silver NCs (Ag₉-NCs, [Ag₉(mba)₉], where H₂mba = 2-mercaptobenzoic acid) and peptide DD-5 were used to induce self-assembly, which can trigger an aggregation-induced luminescence (AIE) effect of Ag₉-NCs through non-covalent forces (H-bond, π–π stacking) and argentophilic interactions [Ag(I)–Ag(I)]. The large Stokes shift (~140 nm) and the microsecond fluorescence lifetime (6.1 μs) indicate that Ag₉-NCs/DD-5 hydrogel is phosphor. At the same time, the chirality of the peptide was successfully transferred to the achiral Ag₉-NCs because of the supramolecular self-assembly, and the Ag₉-NCs/DD-5 hydrogel also has good circularly polarized luminescence (CPL) properties. In addition, Ag₉-NCs/DD-5 luminescent hydrogel is selective and sensitive to the detection of small biological molecule arginine. This work shows that DD-5 successfully induces the self-assembly of Ag₉-NCs to obtain high luminescent gel, which maybe become a candidate material in the fields of sensors and biological sciences. Full article

(This article belongs to the Special Issue Self-Assembly of Atomically Precise Nanoclusters: From Irregular Assembly to Crystalline Assembly)

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13 pages, 3650 KiB

Open AccessArticle

Advancement of Fluorescent and Structural Properties of Bovine Serum Albumin-Gold Bioconjugates in Normal and Heavy Water with pH Conditioning and Ageing

by Bence Fehér, Judith Mihály, Attila Demeter, László Almásy, András Wacha, Zoltán Varga, Imre Varga, Jan Skov Pedersen and Attila Bóta

Nanomaterials 2022, 12(3), 390; https://0-doi-org.brum.beds.ac.uk/10.3390/nano12030390 - 25 Jan 2022

Cited by 1 | Viewed by 2057

Abstract

The red-emitting fluorescent properties of bovine serum albumin (BSA)–gold conjugates are commonly attributed to gold nanoclusters formed by metallic and ionized gold atoms, stabilized by the protein. Others argue that red fluorescence originates from gold cation–protein complexes instead, not gold nanoclusters. Our fluorescence and infrared spectroscopy, neutron, and X-ray small-angle scattering measurements show that the fluorescence and structural behavior of BSA–Au conjugates are different in normal and heavy water, strengthening the argument for the existence of loose ionic gold–protein complexes. The quantum yield for red-emitting luminescence is higher in heavy water (3.5%) than normal water (2.4%), emphasizing the impact of hydration effects. Changes in red luminescence are associated with the perturbations of BSA conformations and alterations to interatomic gold–sulfur and gold–oxygen interactions. The relative alignment of domains I and II, II and III, III and IV of BSA, determined from small-angle scattering measurements, indicate a loose (“expanded-like”) structure at pH 12 (pD ~12); by contrast, at pH 7 (pD ~7), a more regular formation appears with an increased distance between the I and II domains, suggesting the localization of gold atoms in these regions. Full article

(This article belongs to the Special Issue Self-Assembly of Atomically Precise Nanoclusters: From Irregular Assembly to Crystalline Assembly)

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9 pages, 2024 KiB

Open AccessArticle

Ligand Effects on Intramolecular Configuration, Intermolecular Packing, and Optical Properties of Metal Nanoclusters

by Sainan Wu, Xiao Wei, Hao Li, Honglei Shen, Jiaojiao Han, Xi Kang and Manzhou Zhu

Nanomaterials 2021, 11(10), 2655; https://0-doi-org.brum.beds.ac.uk/10.3390/nano11102655 - 09 Oct 2021

Cited by 3 | Viewed by 2312

Abstract

Surface modification has served as an efficient approach to dictate nanocluster structures and properties. In this work, based on an Ag₂₂ nanocluster template, the effects of surface modification on intracluster constructions and intercluster packing modes, as well as the properties of nanoclusters or cluster-based crystallographic assemblies have been investigated. On the molecular level, the Ag₂₂ nanocluster with larger surface steric hindrance was inclined to absorb more small-steric chlorine but less bulky thiol ligands on its surface. On the supramolecular level, the regulation of intramolecular and intermolecular interactions in nanocluster crystallographic assemblies rendered them CIEE (crystallization-induced emission enhancement)-active or -inactive nanomaterials. This study has some innovation in the molecular and intramolecular tailoring of metal nanoclusters, which is significant for the preparation of new cluster-based nanomaterials with customized structures and enhanced performances. Full article

(This article belongs to the Special Issue Self-Assembly of Atomically Precise Nanoclusters: From Irregular Assembly to Crystalline Assembly)

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Review

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23 pages, 5683 KiB

Open AccessReview

Viewing Aggregation-Induced Emission of Metal Nanoclusters from Design Strategies to Applications

by Tingting Li, Haifeng Zhu and Zhennan Wu

Nanomaterials 2023, 13(3), 470; https://0-doi-org.brum.beds.ac.uk/10.3390/nano13030470 - 24 Jan 2023

Cited by 8 | Viewed by 2598

Abstract

Aggregation-induced emission (AIE)-type metal nanoclusters (NCs) represent an innovative type of luminescent metal NCs whose aggregates exhibit superior performance over that of individuals, attracting wide attention over the past decade. Here, we give a concise overview of the progress made in this area, from design strategies to applications. The representative design strategies, including solvent-induction, cation-induction, crystallization-induction, pH-induction, ligand inheritance, surface constraint, and minerals- and MOF-confinement, are first discussed. We then present the typical practical applications of AIE-type metal NCs in the various sectors of bioimaging, biological diagnosis and therapy (e.g., antibacterial agents, cancer radiotherapy), light-emitting diodes (LEDs), detection assays, and circularly polarized luminescence (CPL). To this end, we present our viewpoints on the promises and challenges of AIE-type metal NCs, which may shed light on the design of highly luminescent metal NCs, stimulating new vitality and serving as a continuous boom for the metal NC community in the future. Full article

(This article belongs to the Special Issue Self-Assembly of Atomically Precise Nanoclusters: From Irregular Assembly to Crystalline Assembly)

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17 pages, 1455 KiB

Open AccessReview

Ultrasmall-in-Nano: Why Size Matters

by Ryan D. Mellor and Ijeoma F. Uchegbu

Nanomaterials 2022, 12(14), 2476; https://0-doi-org.brum.beds.ac.uk/10.3390/nano12142476 - 19 Jul 2022

Cited by 17 | Viewed by 2118

Abstract

Gold nanoparticles (AuNPs) are continuing to gain popularity in the field of nanotechnology. New methods are continuously being developed to tune the particles’ physicochemical properties, resulting in control over their biological fate and applicability to in vivo diagnostics and therapy. This review focuses on the effects of varying particle size on optical properties, opsonization, cellular internalization, renal clearance, biodistribution, tumor accumulation, and toxicity. We review the common methods of synthesizing ultrasmall AuNPs, as well as the emerging constructs termed ultrasmall-in-nano—an approach which promises to provide the desirable properties from both ends of the AuNP size range. We review the various applications and outcomes of ultrasmall-in-nano constructs in vitro and in vivo. Full article

(This article belongs to the Special Issue Self-Assembly of Atomically Precise Nanoclusters: From Irregular Assembly to Crystalline Assembly)

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28 pages, 62029 KiB

Open AccessReview

Self-Assembled Metal Nanoclusters: Driving Forces and Structural Correlation with Optical Properties

by Sarita Kolay, Dipankar Bain, Subarna Maity, Aarti Devi, Amitava Patra and Rodolphe Antoine

Nanomaterials 2022, 12(3), 544; https://0-doi-org.brum.beds.ac.uk/10.3390/nano12030544 - 05 Feb 2022

Cited by 29 | Viewed by 4287

Abstract

Studies on self-assembly of metal nanoclusters (MNCs) are an emerging field of research owing to their significant optical properties and potential applications in many areas. Fabricating the desired self-assembly structure for specific implementation has always been challenging in nanotechnology. The building blocks organize themselves into a hierarchical structure with a high order of directional control in the self-assembly process. An overview of the recent achievements in the self-assembly chemistry of MNCs is summarized in this review article. Here, we investigate the underlying mechanism for the self-assembly structures, and analysis reveals that van der Waals forces, electrostatic interaction, metallophilic interaction, and amphiphilicity are the crucial parameters. In addition, we discuss the principles of template-mediated interaction and the effect of external stimuli on assembly formation in detail. We also focus on the structural correlation of the assemblies with their photophysical properties. A deep perception of the self-assembly mechanism and the degree of interactions on the excited state dynamics is provided for the future synthesis of customizable MNCs with promising applications. Full article

(This article belongs to the Special Issue Self-Assembly of Atomically Precise Nanoclusters: From Irregular Assembly to Crystalline Assembly)

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21 pages, 4011 KiB

Open AccessReview

Controlling the Chemistry of Nanoclusters: From Atomic Precision to Controlled Assembly

by Srestha Basu, Anumita Paul and Rodolphe Antoine

Nanomaterials 2022, 12(1), 62; https://0-doi-org.brum.beds.ac.uk/10.3390/nano12010062 - 27 Dec 2021

Cited by 10 | Viewed by 3488

Abstract

Metal nanoclusters have gained prominence in nanomaterials sciences, owing to their atomic precision, structural regularity, and unique chemical composition. Additionally, the ligands stabilizing the clusters provide great opportunities for linking the clusters in higher order dimensions, eventually leading to the formation of a repertoire of nanoarchitectures. This makes the chemistry of atomic clusters worth exploring. In this mini review, we aim to focus on the chemistry of nanoclusters. Firstly, we summarize the important strategies developed so far for the synthesis of atomic clusters. For each synthetic strategy, we highlight the chemistry governing the formation of nanoclusters. Next, we discuss the key techniques in the purification and separation of nanoclusters, as the chemical purity of clusters is deemed important for their further chemical processing. Thereafter which we provide an account of the chemical reactions of nanoclusters. Then, we summarize the chemical routes to the spatial organization of atomic clusters, highlighting the importance of assembly formation from an application point of view. Finally, we raise some fundamentally important questions with regard to the chemistry of atomic clusters, which, if addressed, may broaden the scope of research pertaining to atomic clusters. Full article

(This article belongs to the Special Issue Self-Assembly of Atomically Precise Nanoclusters: From Irregular Assembly to Crystalline Assembly)

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