ABSTRACT
Guanine-quadruplex, consisting of several stacked guanine-quartets (GQs), has emerged as an important category of novel molecular targets with applications from nanoelectronic devices to anticancer drugs. Incorporation of metal cations into a GQ structure is utilized to form stable G-quadruplexes, while formation of a cation-free GQ network has been challenging. Here we report the room temperature (RT) molecular self-assembly of extended pristine GQ networks on an Au(111) surface. An implanted molybdenum atom within the Au(111) surface is used to nucleate and stabilize the cation-free GQ network. Additionally, decoration of the Au(111) surface with 7-armchair graphene nanoribbons (7-AGNRs) enhances the GQ domain size by suppressing the influence of the disordered phase nucleated from Au step edges. Scanning tunneling microscopy/spectroscopy (STM/STS) and density functional theory (DFT) calculations confirm the formation of GQ networks and unravel the nucleation and growth mechanism. Our work, utilizing a hetero-atom doped substrate, provides a facile approach to enhance the stability and domain size of the GQ self-assembly, which would be applicable for other molecular structures.
ABSTRACT
This spotlight discusses intriguing properties and diverse applications of graphene (Gr) and Gr analogs. Gr has brought us two-dimensional (2D) chemistry with its exotic 2D features of density of states. Yet, some of the 2D or 2D-like features can be seen on surfaces and at interfaces of bulk materials. The substrate on Gr and functionalization of Gr (including metal decoration, intercalation, doping, and hybridization) modify the unique 2D features of Gr. Despite abundant literature on physical properties and well-known applications of Gr, spotlight works based on the conceptual understanding of the 2D physical and chemical nature of Gr toward vast-ranging applications are hardly found. Here we focus on applications of Gr, based on conceptual understanding of 2D phenomena toward 2D chemistry. Thus, 2D features, defects, edges, and substrate effects of Gr are discussed first. Then, to pattern Gr electronic circuits, insight into differentiating conducting and nonconducting regions is introduced. By utilizing the unique ballistic electron transport properties and edge spin states of Gr, Gr nanoribbons (GNRs) are exploited for the design of ultrasensitive molecular sensing electronic devices (including molecular fingerprinting) and spintronic devices. The highly stable nature of Gr can be utilized for protection of corrosive metals, moisture-sensitive perovskite solar cells, and highly environment-susceptible topological insulators (TIs). Gr analogs have become new types of 2D materials having novel features such as half-metals, TIs, and nonlinear optical properties. The key insights into the functionalized Gr hybrid materials lead to the applications for not only energy storage and electrochemical catalysis, green chemistry, and electronic/spintronic devices but also biosensing and medical applications. All these topics are discussed here with the focus on conceptual understanding. Further possible applications of Gr, GNRs, and Gr analogs are also addressed in a section on outlook and future challenges.