Self-Assembly Self-Assembly of Organic Building Blocks with Directly Exfoliated Graphene to Fabricate Di- and Tricomponent Hybrids Pengyao Xing, [a, b] Linyi Bai, [a] Hongzhong Chen, [a] Phoebe Huijun Tham, [a] Aiyou Hao, [b] and Yanli Zhao* [a, c] Abstract: In this work, we developed a strategy to fabricate self-assembled aggregates encapsulating graphene from direct exfoliation of graphite. Naphthalene-anhydride-ap- pended glutamic acid (NG) and pyrene-appended glutamic acid (PG) were utilized to exfoliate graphite to generate few- layer graphene in basic aqueous media. Acidification-trig- gered self-assembly of PG could encapsulate graphene sheets to give graphene@microsheet hybrids. Melamine (Mm) was introduced to induce the morphological transfor- mation of PG from microsheets to twisted fibers with colum- nar packing. In the presence of graphene, this transforma- tion allowed the fabrication of twisted-fiber-encapsulated graphene (graphene@twist fiber). Tricomponent hybrids were also built up via in situ preparation of gold nanoparti- cles (AuNPs) on the negatively charged surface of few-layer graphene during the self-assembly process. This study pres- ents an approach to construct directly exfoliated graphene- based hybrids through self-assembly. 1. Introduction Supramolecular self-assembly has been developed as a power- ful strategy to construct aggregates from the nanoscale to macroscale. [1] Multi-dimensional materials such as zero-dimen- sional (0D) micelles or nanovesicles, 1D fibers, 2D sheets, and 3D networks prepared from supramolecular self-assembly are attracting more and more attention. Extraordinary properties of self-assembled materials like shape memory, self-healing, and stimuli-responsiveness rely on their dynamic nature. [2] Noncovalent forces including p–p stacking, hydrogen bonding, electrostatic, hydrophilic–hydrophobic, and van der Waals in- teractions hold the building blocks together to give supra- molecular aggregates. Among these interactions, the hydrogen bonding interaction is a widely investigated weak force due to its directional feature, which enables the formation of highly ordered molecular arrangements. Thus, it plays a vital role in designing hydrogel and chiral amplification systems. [3] Amino acid and short-peptide-based building blocks possess multiple hydrogen-bonding sites, exhibiting many superior advantages over other building blocks. [4] By regulating their hydrogen- bonding interaction between amides and carboxylic acid groups, self-assembly behavior can be achieved to meet re- quirements. [5] An important feature of such self-assembled ag- gregates is their capability to serve as matrixes to embed inor- ganic nanomaterials, forming organic–inorganic hybrids. [6] For example, nanomaterials like silica, metal nanoparticles, carbon- based materials, clay nanosheets, and polyoxometalate clusters have been combined with organic substrates to generate com- posites, [7] showing promising applications in supercapacitors, catalysis, sensors, and photovoltaics. A character of the organ- ic–inorganic hybrids is that the stability of inorganic nanomate- rials would be enhanced after being trapped within organic substrates. These hybrids could be categorized into two dis- tinct classes according to the nature of interfaces between or- ganic and inorganic components. [7a] In class I, organic and inor- ganic components are linked by noncovalent interactions, while for class II, they are bridged by strong chemical bonds. With exceptional mechanical, optical and electronic proper- ties, graphene and its derivatives including graphene oxide (GO) and reduced graphene oxide (RGO) show important ap- plications in conducting materials, photovoltaics, and biomed- icine. [8] The combination with organic compounds allows gra- phene to achieve more functions and capabilities such as en- hanced biocompatibility and water solubility. [9] Through a non- covalent pathway, organic compounds with aromatic domains [a] P. Xing, + L. Bai, + H. Chen, P.H. Tham, Prof. Y. Zhao Division of Chemistry and Biological Chemistry School of Physical and Mathematical Sciences Nanyang Technological University 21 Nanyang Link, 637371 (Singapore) E-mail : zhaoyanli@ntu.edu.sg Homepage: www.ntu.edu.sg/home/zhaoyanli [b] P. Xing, + Prof. A. Hao School of Chemistry and Chemical Engineering and Key Laboratory of Colloid and Interface Chemistry of Ministry of Educa- tion Shandong University Jinan 250100 (P.R. China) [c] Prof. Y. Zhao School of Materials Science and Engineering Nanyang Technological University 50 Nanyang Avenue, 639798 (Singapore) [ + ] These authors contributed equally to this work. Supporting information and ORCID(s) from the author(s) for this article are available on the WWW under http://dx.doi.org/10.1002/cnma.201500095. ChemNanoMat 2015, 1, 517 – 527 # 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 517 Full Paper DOI: 10.1002/cnma.201500095