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    Supra-materials Nanoarchitectonics
    Supra-materials Nanoarchitectonics
    Supra-materials Nanoarchitectonics
    Ebook625 pages7 hours

    Supra-materials Nanoarchitectonics

    By Katsuhiko Ariga

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    Supra-materials Nanoarchitectonics provides the latest information on design at the nanoscale, presenting a range of the new challenges that arise as the manipulation techniques that work at the macro- and micro-scale do not work at the nanoscale. The term nanoarchitectonics, coined by Japan's National Institute for Materials Science (NIMS), describes the organized interactions required at the nanoscale, replacing the traditional structure-building approach used in materials design.

    Nanoarchitectonics approaches material design via a profound understanding of the interactions between individual nanostructures and their organization. As the nanoarchitectonics paradigm fits well with the discipline of supramolecular chemistry, this book brings together these two approaches to demonstrate the potential of supramolecular nanoarchitectonics in the development of new materials, both at the nano- and macro-scale.

    • Written by the team that coined the term nanoarchitectonics, providing a detailed explanation of the approach and techniques of supramolecular nanoarchitectonics
    • Demystifies materials design via organized interactions at the nanoscale
    • Explains this new paradigm via practical scientific techniques
    LanguageEnglish
    PublisherElsevier Science
    Release dateOct 7, 2016
    ISBN9780323378307
    Supra-materials Nanoarchitectonics

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      Supra-materials Nanoarchitectonics - Katsuhiko Ariga

      Supra-materials Nanoarchitectonics

      Editors

      Katsuhiko Ariga

      Masakazu Aono

      Table of Contents

      Cover image

      Title page

      Copyright

      Contributors

      Preface

      Overview

      Part 1. Nanoarchitectonics of Basics Materials

      Chapter 1. Nanocluster Science

      1.1. Introduction

      1.2. Precise Synthesis

      1.3. Basic Properties

      1.4. Functionalization Methods

      1.5. Summary and Perspective

      Chapter 2. Highly Luminescent Metal Nanocluster Molecules

      2.1. Introduction

      2.2. Au, Ag, and Au-Ag Alloy Nanoclusters

      2.3. Bi Nanoclusters

      2.4. Perspective

      Chapter 3. Biomimetic Morphology Control of Metal Oxides and Their Site-Selective Immobilization

      3.1. Introduction

      3.2. Liquid Phase Morphology Control of ZnO

      3.3. Biomimetic Site-Selective Immobilization of Metal Oxides

      3.4. Summary

      Chapter 4. Molecular Surface Arrangement to Control Dynamic Dewettability

      4.1. Introduction

      4.2. Low Contact Angle Hysteresis Surfaces

      4.3. Summary

      Part 2. Nanoarchitectonics of Inorganic Materials

      Chapter 5. Organic-Inorganic Hybrid Nanoarchitecture at Mesoscale

      5.1. Introduction

      5.2. Organic-Inorganic Hybrid Hollow Capsules Prepared by Colloid Templating

      5.3. Self-Assembled Nanohybrid of Magnetic Nanoparticle Clusters With Polysaccharide Nanogels

      5.4. Summary

      Chapter 6. Nanoarchitectonic Metals

      6.1. Introduction

      6.2. Seeded-Mediated Growth Method

      6.3. Galvanic Replacement Method

      6.4. Polyol Method

      6.5. Surfactant-Mediated Method

      6.6. Electrocatalytic Applications

      6.7. Conclusions

      Chapter 7. Functional Layered Compounds for Nanoarchitectonics

      7.1. Introduction

      7.2. Photofunctions of Intercalation Compounds

      7.3. Reconstruction of Nanosheets Into Functional Nanostructures

      7.4. Nanosheets for Soft Materials

      Part 3. Nanoarchitectonics of Bio-Materials and for Biomedicals

      Chapter 8. Engineering DNA Molecules for Morphological Reconfiguration

      8.1. Engineering Static DNA Nanostructures

      8.2. Engineering DNA Nanostructures With Dynamic Morphology

      8.3. Constrained Motion of DNA Nanostructures in Thermodynamic Equilibrium

      8.4. Conclusions

      Chapter 9. Smart Polymers With Nanoarchitectonics

      9.1. Introduction

      9.2. Classification on the Basis of Stimuli

      9.3. Applications of Smart Polymers

      9.4. Conclusions

      Chapter 10. Crystal-Induced Nanoarchitectonics of Organic Polymer Materials

      10.1. Introduction

      10.2. Organic Polymer Materials for Nanoarchitectonics

      10.3. Conclusions

      Chapter 11. Nanoarchitectonics for Cyclodextrin-Mediated Solubilization and Nanoassembly of Therapeutic Agents

      11.1. Supramolecular Manipulation: Nanomedicine With Host–Guest Nanoarchitectonics

      11.2. Cyclodextrin Inclusion Complex Formation Toward Nanoassembled Systems

      11.3. Nanoassembly Control Using a CD Inclusion Complex for PDT Application

      11.4. Summary

      Part 4. Nanoarchitectonics for Energy/Environment

      Chapter 12. Nanoarchitectonics Towards Smart Chemical Sensing

      12.1. Introduction

      12.2. Recent Examples of Chemical Sensing

      12.3. Conclusions

      Chapter 13. Nanoarchitectonics for Energy and Environment

      13.1. Introduction

      13.2. Nanoarchitectonics for Dye-Sensitized Solar Cells

      13.3. Nanoarchitectonics for Bioinspired Catalysis

      13.4. Nanoarchitectonics for Reversible Hydrogen Storage

      13.5. Development of Temperature-Responsive Hydrogel Nanoparticles for Energy-Efficient CO2 Separation

      13.6. Conclusions

      Index

      Copyright

      William Andrew is an imprint of Elsevier

      The Boulevard, Langford Lane, Kidlington, Oxford, OX5 1GB, United Kingdom

      50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States

      Copyright © 2017 Elsevier Inc. All rights reserved.

      No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions.

      This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein).

      Notices

      Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary.

      Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility.

      To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein.

      Library of Congress Cataloging-in-Publication Data

      A catalog record for this book is available from the Library of Congress

      British Library Cataloguing-in-Publication Data

      A catalogue record for this book is available from the British Library

      ISBN: 978-0-323-37829-1

      For information on all William Andrew publications visit our website at https://www.elsevier.com/

      Publisher: Matthew Deans

      Acquisition Editor: Simon Holt

      Editorial Project Manager: Sabrina Webber

      Production Project Manager: Susan Li

      Designer: Greg Harris

      Typeset by TNQ Books and Journals

      Contributors

      K. Cervantes-Salguero,     Tohoku University, Sendai, Miyagi, Japan

      M. Ebara,     National Institute for Materials Science (NIMS), ​Tsukuba, Japan

      K. Eid

      Zhejiang University of Technology, Zhejiang, P.R. China

      Changchun Institute of Applied Chemistry, Changchun, P.R. China

      University of Chinese Academy of Sciences, Beijing, P.R. China

      M.W. England,     National Institute of Advanced Industrial Science and Technology (AIST), Nagoya, Japan

      T. Funaki,     Research Center for Photovoltaics, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki, Japan

      Y. Hoshino,     Kyushu University, Fukuoka, Japan

      A. Hozumi,     National Institute of Advanced Industrial Science and Technology (AIST), Nagoya, Japan

      S. Ishihara,     National Institute for Materials Science, Tsukuba, Japan

      N. Kameta,     Research Institute for Sustainable Chemistry, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki, Japan

      K. Katagiri,     Hiroshima University, Higashihiroshima, Japan

      W. Kurashige,     Tokyo University of Science, Shinjuku-ku, Tokyo, Japan

      J. Labuta,     National Institute for Materials Science, Tsukuba, Japan

      Y. Manaka,     Renewable Energy Research Center, National Institute of Advanced Industrial Science and Technology (AIST), Koriyama, Fukushima, Japan

      Yoshitake Masuda,     National Institute of Advanced Industrial Science and Technology (AIST), Nagoya, Japan

      N. Miyamoto,     Fukuoka Institute of Technology, Fukuoka, Japan

      T.N. Murakami,     Research Center for Photovoltaics, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki, Japan

      S. Murata,     Tohoku University, Sendai, Miyagi, Japan

      M. Naito,     National Institute for Materials Science, Tsukuba, Japan

      Y. Negishi

      Tokyo University of Science, Shinjuku-ku, Tokyo, Japan

      Tokyo University of Science, Noda, Chiba, Japan

      Institute for Molecular Science, Okazaki, Aichi, Japan

      Y. Niihori,     Tokyo University of Science, Shinjuku-ku, Tokyo, Japan

      K. Nobusawa,     Osaka University, Osaka, Japan

      Y. Oaki,     Keio University, Kohoku-ku, Yokohama, Japan

      S. Sharma,     Tokyo University of Science, Shinjuku-ku, Tokyo, Japan

      H.-T. Sun,     Soochow University, Suzhou, People's Republic of China

      H. Wang,     Zhejiang University of Technology, Zhejiang, P.R. China

      L. Wang,     Zhejiang University of Technology, Zhejiang, P.R. China

      S. Yamamoto,     Fukuoka Institute of Technology, Fukuoka, Japan

      Preface

      How can we create functional materials? We do not always have to create totally new stuffs from zero. In our history, a telescope was invented through wise combinations and arrangements of simple glasses and a light bulb was fabricated with bamboo fibers. Materials themselves are important but architecting them into functional systems and materials are much more important. Supra-materials, which are expected to have advanced functions as compared to conventional materials, would be created through architecting various nanomaterials.

      However, fabrication of systems and materials is not always easy in nanoscale regions where uncontrollable fluctuations and unexpected disturbances significantly affect structural formation. Influence of thermal/statistical fluctuations and mutual interactions unavoidably occurs between component atoms, molecules, and materials. Outputs such as materials structures and properties are not simply determined by known inputs. In the nanoscale region, what we try to prepare cannot be simply attained through conventional one-by-one construction strategy. Therefore, synthesis and fabrication of functional materials using nanoscale components have to be a novel concept, nanoarchitectonics.

      A novel terminology, nanoarchitectonics, which means nano  +  architecto  +  nics, was invented in 2000 as a new paradigm of materials science and technology by Masakazu Aono that was introduced at the 1st International Symposium on Nanoarchitectonics Using Suprainteractions in Tsukuba, Japan. Nanoarchitectonics aims at opening a new paradigm of development of materials design and fabrication with the following working principles:

      1. Nanomaterials or nanosystems with functional reliable functions can be constructed by organizing nanoscale parts even with some unavoidable unreliability.

      2. Functions are not always originated only from the individual nanoparts but their interactions may create new functionalities.

      3. Unexpected functionalities can emerge from assembling or organizing a huge number of nanoparts.

      Nanoarchitectonics has begun to spread into many fields including nanostructured materials synthesis, supramolecular assembly, nanoscale structural fabrications, materials hybridizations, materials and structures for energy and environmental sciences, device and physical application, and bio and medical applications.

      In this book entitled, Supra-Materials Nanoarchitectonics, basic materials to various recent hot examples are assembled with classification of (1) Nanoarchitectonics of Basics Materials; (2) Nanoarchitectonics of Inorganic Materials; (3) Nanoarchitectonics of Biomaterials and for Biomedicals; and (4) Nanoarchitectonics for Energy/Environment. Current frontiers and the future of materials science and technology are also discussed in this book.

      Katsuhiko Ariga

      Masakazu Aono

      Overview

      This short chapter provides some overview comments on nanoarchitectonics of materials design and synthesis. It can be used as a certain guidance for this book through showing tiny essences of this book’s contents.

      Recent advances and new directions for nanoarchitectonics in small scale regions will be described in the former several sections. Functional nanomaterials including colloidal nanoparticles of metals, carbons, semiconductors, and ceramics, which have already become an important class of materials in the current nanotechnology, serve as the minimum objects for building nanoarchitectures.

      Topics in some chapters show the fundamental aspects and amazing properties of nanoclusters of metals or metal-ion-doped molecular crystals. It has been long accepted that representative noble metals, gold and platinum, are metallic, shiny, conductive, and nontarnish materials, but we see the emergent features totally different from their bulk crystals as their sizes are going down into nanoscale. Most of the metal nanoclusters of single nanometers are no longer jewelry; they become high-tech materials with the catalytic, paramagnetic, plasmonic, and photoluminescence properties that are independent of size. Although nucleation and growth of the nanoclusters had been limited to manipulate in special environments such as in vacuo or under high temperature and pressure, the evolution of synthetic techniques allows us to produce a quantity of nanoclusters, and to manipulate them by hand even under ambient conditions. Relationships between their equilibrium structures being dependent on sizes and properties are also demonstrated.

      Nanoarchitectonics can create the free-standing nanocrystals of semiconductors exhibiting the quantum confinement effect. These nanocrystals are frequently denoted as artificial atoms because of their electronic states being described by atomic-like wave functions. The energy quantization enables us to tune optical absorption and emission spectra that are dependent on size of the nanocrystals for each semiconductor. Combination of size-dependent absorption-emission properties and the unique electronic structures makes the nanocrystals key components to fabricate various quantum dot devices including lasers, solar cells, memories, and light-emitting diodes. A fourth topic focuses on the synthesis of well-controlled shapes of ceramics nanocrystals. The nanocrystals are prepared in liquid phase from the viewpoint of green and sustainable technology. The precise control over the nucleation and growth conditions in aqueous media encourages anisotropic growth of nanocrystals to give the unique morphological crystals with acicular, cylindrical, multineedle, sheet-like shapes.

      Further self-assembly of morphologically controlled nanocrystals for their film formation is still one of the exciting and attractive fields in surface science. The prototypes of devices by taking advantage of immense surface area of the nanocrystals are also demonstrated. The fifth topic demonstrates the supramolecular complexes. The final topic showcases the supramolecular self-assembly at surfaces. Since the initial study on surface chemistry focusing the absorption behaviors of small molecules, including oxygen or carbon dioxide, the choice of adsorbates employed has broadened to organic molecules with multiple functionalities over several decades, spawning a field of host–guest chemistry. Diverse substrates of conductors, semiconductors, or insulators are available. Applications of such supramolecular assemblies working as platforms include repellent painting, oil/water separation devices, and molecular sensors by taking advantage of specific molecular recognitions. Again, the present subsection highlights various tiny objects of organics and inorganics with unique properties that serve as the fundamental building blocks for various supramolecular nanoarchitectonics applications.

      The later parts of this book discuss two additional topics: (1) biomaterials and biomedicals; and (2) energy/environmental sciences. Of course these two areas are hot and very important in recent technologies and have attracted attention on the basis of high social demands. Biorelated sections includes DNA, smart polymers, bioinspired materials, and biomedical usages. On the other hand, energy and environmental sections showcase recent hot examples on materials conversion (mainly catalysis), sensing, solar cells, hydrogen storage, and CO2 separation. Although their details are not described in this overview, one can understand the high importance of nanoarchitectonics to practically useful materials fields.

      Naoto Shirahata

      Katsuhiko Ariga

      Part 1

      Nanoarchitectonics of Basics Materials

      Outline

      Chapter 1. Nanocluster Science

      Chapter 2. Highly Luminescent Metal Nanocluster Molecules

      Chapter 3. Biomimetic Morphology Control of Metal Oxides and Their Site-Selective Immobilization

      Chapter 4. Molecular Surface Arrangement to Control Dynamic Dewettability

      Chapter 1

      Nanocluster Science

      S. Sharma¹, W. Kurashige¹, Y. Niihori¹,  and Y. Negishi¹,²,³     ¹Tokyo University of Science, Shinjuku-ku, Tokyo, Japan     ²Tokyo University of Science, Noda, Chiba, Japan     ³Institute for Molecular Science, Okazaki, Aichi, Japan

      Abstract

      Small metal clusters have attracted much attention as new functional nanomaterials because they exhibit different physical/chemical properties and functionalities from their corresponding bulk materials. Among these, thiolate-protected metal clusters demonstrate excellent stability, which makes them promising candidates for various applications. The methods used to synthesize these clusters have progressed dramatically over the past several years. Accordingly, a deeper understanding of the stability, geometrical and electronic structures, and physical and chemical properties of these clusters has been gained. In this chapter, we focus on gold clusters and introduce the latest techniques and findings regarding their precise synthesis, stability, electronic and geometrical structures, physical and chemical properties, and functionalization methods.

      Keywords

      Electronic and geometrical structures; Functionalization methods; Physical and chemical properties; Precise synthesis; Stability; Thiolate-protected gold clusters

      Chapter Outline

      1.1 Introduction

      1.2 Precise Synthesis

      1.2.1 Fractionation

      1.2.2 Size Focusing

      1.2.3 Slow Reduction

      1.2.4 Transformation From One Stable Size to Another

      1.3 Basic Properties

      1.3.1 Stability

      1.3.2 Geometrical Structures

      1.3.3 Electronic Structures

      1.3.4 Size-Specific Physical/Chemical Properties

      1.4 Functionalization Methods

      1.4.1 Selection of Ligand Functional Groups

      1.4.2 Heteroatom Doping of the Metal Core

      1.4.3 Control of the Nature of the Au-Ligand Bond

      1.5 Summary and Perspective

      References

      1.1. Introduction

      Small metal clusters up to 2  nm (<∼100  atoms) in size have different geometric and electronic structures from their corresponding bulk metals (Fig. 1.1) [1]. With regard to their geometry, these clusters adopt special atomic arrangements, such as icosahedral structures, to reduce their surface energy, instead of the close packing found in bulk metals. In addition, their electronic structures are not continuous, as in bulk metals, but rather discretized. Owing to these characteristics, small metal clusters exhibit different physical and chemical properties and functionalities from the bulk metal. Furthermore, these properties and functions undergo significant changes depending on the number of constituent atoms in the metal cluster (Fig. 1.1). Metal clusters with these characteristics have attracted much attention as new functional nanomaterials in a wide range of fields, from basic science to applied chemistry.

      Figure 1.1  Metal clusters discussed in this chapter.

      When working with these small metal clusters, it is essential to synthesize clusters with an atomic level of precision so as to gain an understanding of their fundamental nature and to allow for practical applications in nanoscale devices or as catalysts by controlling their functionalities. Numerous studies regarding such precise synthesis have been reported in the case of phosphine-protected metal clusters, beginning in the end of 1960s [2–18]. However, phosphine-protected metal clusters are susceptible to degradation in solution and in the solid state, and this poor stability restricts the applications of these materials [19]. In contrast, thiolate-protected metal clusters [20–61] show high stability both in solution and in the solid state owing to the formation of strong bonds between the metal and the thiolate group. Therefore, in recent years, intensive research has been conducted on thiolate-protected metal clusters. As a result, various precise methods have been established for the synthesis of these clusters. In addition, much knowledge has been gained with respect to their stability, geometrical and electronic structures, and physical and chemical properties. Furthermore, certain guidelines have been established for the functionalization and application of these metal clusters. Thus, the techniques and knowledge necessary to use thiolate-protected metal clusters in various applications have gradually been obtained in recent years. In this chapter, we focus on gold clusters, which are the most-studied type of cluster, and introduce the latest information regarding their precise synthesis as well as their stability, electronic and geometrical structures, physical and chemical properties, and functionalization.

      1.2. Precise Synthesis

      Thiolate-protected gold clusters [Aun(SR)m] having a defined number of constituent atoms are typically synthesized by one of the following four methods:

      1. High-resolution separation of a mixture composed of various sizes according to the number of constituent atoms (Fig. 1.2A);

      2. Exposure of a mixture composed of various sizes to extreme conditions followed by the collection of only those clusters stable under such conditions (Fig. 1.2B);

      3. Controlling the growth rate of the clusters so as to obtain a uniform chemical composition (Fig. 1.2C);

      4. Replacing the ligands of the cluster with ligands having different bulkiness so as to render clusters with specific chemical composition stable (Fig. 1.2D).

      Hereafter, each of these methods is explained in detail.

      1.2.1. Fractionation

      Aun(SR)m clusters are generally prepared by adding a reducing agent to a solution containing thiol and gold ions [20]. The aggregation of the resultant gold atoms leads to the formation of Aun(SR)m clusters, and the products obtained by this method normally have a distribution in the number of constituent atoms [21,29,62–80]. The high-resolution separation of such a mixture according to the number of atoms is one of the most efficient methods of obtaining Aun(SR)m clusters with well-defined numbers of constituent atoms (Fig. 1.2A) [21,29,62–80].

      Polyacrylamide gel electrophoresis is a highly effective technique for separating hydrophilic thiolate-protected Aun(SR)m clusters [21,62–64,68–72]. Using this method, clusters such as Au10(SG)10, Au15(SG)13, Au18(SG)14, Au22(SG)16, Au22(SG)17, Au25(SG)18, Au29(SG)20, Au33(SG)22, and Au39(SG)24 (SG  =  glutathiolate) have been isolated with high purity (Fig. 1.3A) [62]. On the contrary, fractional precipitation [73,74] and fractional extraction [75–78] have been primarily employed for the separation of hydrophobic ligand-protected Aun(SR)m clusters. In addition to these frequently used conventional methods, in recent years, reverse-phase high-performance liquid chromatography has also proven very effective for the high-resolution separation of both types of Aun(SR)m clusters [65–67,79,80]. Aun(SC12H25)m clusters have been systematically isolated by this method over a wide range of sizes, from Au38(SC12H25)24 to Au∼520(SC12H25)∼130 (Fig. 1.3B) [66]. Thus, several methodologies have been established to date for the fractionation of Aun(SR)m clusters, and precise systematic isolation can be now carried out for Aun(SR)m clusters protected either with hydrophilic or hydrophobic thiolates using these techniques.

      Figure 1.2  Typical methods for the precise synthesis of Au n (SR) m clusters: (A) fractionation, (B) size focusing, (C) slow reduction, and (D) transformation from one stable size to another.

      Figure 1.3  Examples of the precise synthesis of Au n (SR) m clusters: (A) separation of Au n (SG) m clusters by PAGE, (B) separation of Au n (SC 12 H 25 ) m clusters by reverse-phase high-performance liquid chromatography, (C) size focusing into Au 25 (SC 2 H 4 Ph) 18 , (D) size focusing into Au 25 (SG) 18 , (E) precise synthesis of each Au n (SG) m cluster by slow reduction, and (F) transformation from Au 38 (SC 2 H 4 Ph) 24 to Au 36 (SPh- t Bu) 24 . The figures were adapted from Negishi Y, Nobusada K, Tsukuda T. Glutathione-protected gold clusters revisited: bridging the gap between gold(I)-thiolate complexes and thiolate-protected gold nanocrystals. J Am Chem Soc 2005;127:5261–70 with permission. Copyright 2005 American Chemical Society; Negishi Y, Nakazaki T, Malola S, Takano S, Niihori Y, Kurashige W, Yamazoe S, Tsukuda T, H​äkkinen H. A critical size for emergence of nonbulk electronic and geometric structures in dodecanethiolate-protected Au clusters. J Am Chem Soc 2015;137:1206–12 with permission. Copyright 2015 American Chemical Society; Dharmaratne AC, Krick T, Dass A. Nanocluster size evolution studied by mass spectrometry in room temperature Au25(SR)18 synthesis. J Am Chem Soc 2009;131:13604–05 with permission. Copyright 2009 American Chemical Society; Shichibu Y, Negishi Y, Tsukuda T, Teranishi T. Large-scale synthesis of thiolated Au25 clusters via ligand exchange reactions of phosphine-stabilized Au11 clusters. J Am Chem Soc 2005;127:13464–65 with permission. Copyright 2005 American Chemical Society; Yu Y, Chen X, Yao Q, Yu Y, Yan N, Xie J. Scalable and precise synthesis of thiolated Au10−12, Au15, Au18, and Au25 nanoclusters via pH controlled CO reduction. Chem Mater 2013;25:946–52 with permission. Copyright 2013 American Chemical Society; Zeng C, Liu C, Pei Y, Jin R. Thiol ligand-induced transformation of Au38(SC2H4Ph)24 to Au36(SPh-t-Bu)24. ACS Nano 2013;7:6138–45 with permission. Copyright 2013 American Chemical Society.

      1.2.2. Size Focusing

      The fractionation methods noted herein are suitable for the systematic isolation of a series of Aun(SR)m clusters. However, these methods are not conducive to mass production. To synthesize Aun(SR)m clusters with a specific chemical composition on a large scale (∼100  mg), it is necessary to instead achieve a selective synthesis, and size focusing is an effective means of doing so (Fig. 1.2B). Several Aun(SR)m clusters show higher resistance to deterioration in solution [62] or by thiol etching [81–86] than other clusters of the same type. As such, the less stable clusters could be converted into stable clusters when exposed to extreme conditions [81–86]. As an example, when Aun(SR)m clusters (SR  =  SG⁸⁶ or SC2H4Ph⁸³; 25  ≤  n  <  38) are exposed to extreme conditions, unstable Aun(SR)m clusters are transformed into stable Au25(SR)18 clusters. Stable clusters can be precisely synthesized on a large scale with this size-focusing method (Fig. 1.3C and D).

      1.2.3. Slow Reduction

      NaBH4 is typically employed as the reducing agent for the generation of gold atoms, although the mild agent CO can also be used [30,72,87,88]. In the latter case, the gold atoms are generated more slowly and so the Aun(SR)m clusters are also formed at a reduced pace [87,88]. This lower synthesis rate tends to produce more uniform clusters (Fig. 1.2C) and the precise and size-selective synthesis of Aun(SR)m clusters up to Au25(SG)18 has been realized by this method (Fig. 1.3E) [88]. Even when using NaBH4 as the reducing agent, slow reduction can be achieved by controlling the pH of the solution. Au76(4-MEBA)44 (4-MEBA  =  4-(2-mercaptoethyl)benzoic acid) has been synthesized in this manner [89]. However, this method is only applicable to small Aun(SR)m clusters protected by hydrophilic thiolates. It is expected that the size-selective synthetic methods based on this principle are established even for Aun(SR)m clusters protected by hydrophobic thiolates, as well as for large hydrophilic Aun(SR)m clusters.

      1.2.4. Transformation From One Stable Size to Another

      The chemical composition of stable clusters varies depending on the bulkiness of the thiolate functional group [52,90]. Therefore, when the ligand of a stable cluster is replaced with a bulkier thiolate, distortion of the metallic core is induced, resulting in the formation of clusters with a different composition (Fig. 1.2D) [91]. An example is the reaction of phenylethanethiolate (SC2H4Ph)-protected Au38(SC2H4Ph)24 with 4-tert-butylbenzenthiol (SPh-tBu) in solution, which generates Au36(SPh-tBu)24 as the primary product (yield ∼90%) (Fig. 1.3F) [92,93]. This technique enables the synthesis of stable clusters having different chemical compositions from Aun(SC2H4Ph)m or Aun(SCxH2x+1)m (SCxH2x+1  =  alkanethiolate), and Au28(SPh-tBu)20, Au36(SPh-tBu)24, and Au133(SPh-tBu)52 have all been synthesized by this method [92–96].

      1.3. Basic Properties

      A number of Aun(SR)m clusters have been precisely synthesized to date by the methods described in the previous section [97]. The subsequent study of these clusters has assessed their stability and also their geometrical and electronic structures and physical and chemical properties. In the following sections, we summarize the most recent findings regarding the basic properties of Aun(SR)m clusters.

      1.3.1. Stability

      Upon allowing a series of Aun(SG)m clusters (n  <  25) (Fig. 1.3A) to react with an excess of glutathione, size reduction occurs via etching to generate Au(I)-thiolate oligomers. Although a similar etching reaction will take place in the case of larger Aun(SG)m clusters (25  ≦  n  ≦  39), the size reduction stops at the Au25(SG)18 stage (Fig. 1.4) rather than proceeding to the oligomer [81]. This phenomenon is due to the fact that Au25(SG)18 has especially high stability against etching among the series of Aun(SG)m clusters shown in Fig. 1.3A. Thus, the stability of Aun(SR)m clusters differs greatly depending on their chemical composition. The size-selective synthesis of stable clusters based on the size-focusing technique described in the previous section utilizes this difference in stability among a series of Aun(SR)m clusters.

      Figure 1.4  Comparison of the stability against etching among a series of Au n (SG) m clusters ( n   =   10–39). This figure was adapted from Shichibu Y, Negishi Y, Tsunoyama H, Kanehara M, Teranishi T, Tsukuda T. Extremely high stability of glutathionate-protected Au25 clusters against core etching. Small 2007;3:835–39 with permission. Copyright 2007 Wiley-VCH Publishing.

      The chemical composition of such stable clusters also changes depending on the thiolate functional group employed. As an example, the clusters [Au25(SR)18]−, Au38(SR)24, Au130(SR)50, Au144(SR)60, and Au329(SR)84 are all stable when the chemical composition is Aun(SC2H4Ph)m or Aun(SCxH2x+1)m [62,65,76,77,98,99]. In contrast, clusters such as Au28(SPh-tBu)20, Au36(SPh-tBu)24, and Au133(SPh-tBu)52 are stable when SPh-tBu is used as the ligand [92–96]. Others, such as [Au23(Sc-C6)16]–, are stable when the ligand is c-hexanethiolate (Sc-C6) [100]. These clusters are stabilized by geometric factors, electronic factors, or both, even though the number of Au atoms and thiolate ligands varies significantly for each [97,101].

      1.3.2. Geometrical Structures

      Until 2007, it had been believed that Aun(SR)m clusters have a geometrical structure in which the gold core is covered by thiolates. Since then, however, several Aun(SR)m clusters have been shown by single crystal X-ray structural analysis to have a gold core covered by the multiple -S(R)[-Au-S(R)-]x staples (x  =  1-4) (Fig. 1.5) [37,92–96,100,102–105]. Based on the geometrical structures determined for Aun(SR)m clusters to date, it can be assumed that almost all Aun(SR)m clusters have this type of core–shell structure in small cluster regions [97].

      In addition, the gold core structure has been found to vary depending on the bulkiness of the ligand. In the case of Aun(SC2H4Ph)m and Aun(SCxH2x+1)m clusters, clusters with sizes below Au144(SR)60 have a gold core based on an icosahedral or a Marks decahedral structure (Fig. 1.5A and B) [102–105]. When the cluster size exceeds Au144(SR)60, the core transitions to one based on a face-centered cubic (fcc) structure, just as in bulk Au [66,67]. In contrast, small Aun(SR)m clusters having a gold core with an fcc structure can be synthesized in the case of Aun(SPh-tBu)m and Aun(Sc-C6)m, both of which employ ligands having bulky functional groups (Fig. 1.5C and D) [92–96,100]. The use of the adamantine thiolate ligand (S-Adm), which has a functional group of even greater bulkiness, results in the production of a Au38S2(S-Adm)20 cluster with a gold core based on a bcc structure [106]. It is likely that the continued design of new thiolates for use as ligands will lead to the synthesis of Aun(SR)m clusters having core structures different from those of any of the previously reported clusters.

      Figure 1.5  Crystal structures of [Au

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