Novel nanomaterials for bioassay applications represent a rapidly progressing field of nanotechnology and nanobiotechnology. Fence porphyrin wenwen tu moe key laboratory of analytical chemistry for life science, school of chemistry and chemical engineering, nanjing university, nanjing 210093 p. This method offers a larger number of amino functionalities on the surface of cnts and gs so that large number of biological and drug molecules can be attached. Furthermore, the functionalization of graphene is always based on the graphene from previously prepared go, which has multiple oxygencontaining functionalities, such as hydroxyl and carboxyl groups.
Noncovalent functionalization of graphene and graphene oxide for energy materials, biosensing, catalytic, and biomedical applications vasilios georgakilas, jitendra n. Highly selective covalent organic functionalization of. Here we describe a tripodal motif that binds multivalently to graphene. Englert 1, christoph dotzer 1, guang yang 2, martin schmid 3,christianpapp 3, j. Understanding defectstabilized noncovalent functionalization. Here we describe a tripodal motif that binds multivalently to graphene through three. Facile, noncovalent decoration of graphene oxide sheets with nanocrystals ganhua lu 1, shun mao, sungjin park 2, rodney s. An efficient methodology to make stable aqueous solutions of single. In this work, graphene oxide go was covalently functionalized with dmannose mango using mannosylated ethylenediamine. Functionalized single or multiwalled carbon nanotubes are spin coated on copper.
Noncovalent functionalization generally has little e. Chemical functionalization of graphene and its applications. One common approach is to conduct such a functionalization in an organic solvent and to use amyl or isoamyl nitrite to generate the. Electrical properties of covalently functionalized graphene. Covalent functionalization of graphene with reactive. Single and fewlayer bp 2d bp have been obtained by either micromechanical cleavage scotch tape method3 or liquid. Yonghui zhang et al 2010 nanotechnology 21 065201 view the article online for updates and enhancements. Functionalization of graphene can be done by two different methods. Surface properties of extremely thin graphite lamellae pdf. It also prevents the agglomeration of single layer graphene during reduction and maintains the inherent properties of graphene. Noncovalent sidewall functionalization of singlewalled. Pdf noncovalent functionalization of graphene with a ni. Theoretical models of graphene can be built up using simple aromatic molecules.
An investigation into noncovalent functionalization of a singlewalled carbon nanotube and a graphene sheet with protein g. Noncovalent functionalization of graphene with a niii tetraaza14annulene complex royal society of chemistry guidelines to referees research works. The complexity of go makes the derivatization of the oxygenated groups difficult to control. Covalent bonding to graphene a great deal of interest in covalent functionalization of graphene cfgr was generated when.
Covalent polymer functionalization of graphene nanosheets and. Graphene functionalization with organics is expected to be an important step for the development of graphene based materials with tailored electronic properties. Noncovalent and reversible functionalization of carbon. Noncovalent functionalization of carbon nanotubes for highly. Figure 5li bacteria surface adhesion probed with fluorescence microscopy. The functionalization evidence is highlighted using xray photoemission spectroscopy xps, scanning tunneling microscopy stm, scanning xray photoelectron microscopy spem or angle resolved photoemission spectroscopy arpes. Noncovalent functionalization of boron nitride nanotubes in. Carboxyl groups are ubiquitous in graphene based materials. Functionalization an overview sciencedirect topics. Covalent functionalization can enhance graphenes properties including opening its band gap, tuning conductivity, and improving solubility and stability. Surface functionalization of graphene with polymers for.
Tuning the electronic structure and transport properties of. Recently, significant efforts have focused on surface functionalization of graphene to achieve specific properties for various practical applications. The two main methods of cnt functionalization are covalent and noncovalent modifications. In interpreting these numbers, one must, however, consider that several publications on graphene appeared before 2006, e. In this way, a new member of the growing family of 2d materials, named phosphorene,1,2 the all pcounterpart of graphene, was isolated. The initial step is the reduction of graphite with solvated electrons. Functionalization of graphene by electrophilic alkylation of reduced. Covalent bulk functionalization of graphene nature chemistry. Functionalization of graphene with nitrile groups by. Noncovalent functionalization of single wall carbon. The present work reports the noncovalent functionalization of carbon nanomaterials e. The pyrenepcbm moiety was synthesized via a facile esterification reaction, and pyrene was used as an anchoring bridge to link rgo and pcbm. Pdf stable aqueous dispersion of graphene nanosheets. Covalent functionalization of monolayered transition metal.
Chemical bulk functionalization of graphene using graphite as starting material has recently gained significant interest since it allows for i the generation of. Noncovalent functionalization of graphene attaching 6,6. Covalent bulk functionalization of graphene article pdf available in nature chemistry 34. While xps results confirmed the functionalization of graphene with organosilane, fig. Surface functionalization of graphene graphene materials. Singlelayer graphene is a newly available conductive material ideally suited for forming welldefined interfaces with electroactive compounds. Noncovalent functionalization is a simple and economic approach to introduce specific functionalities to the graphene surface. Carbon nanotube chemistry involves chemical reactions, which are used to modify the properties of carbon nanotubes cnts. A new graphene fullerene composite rgopyrenepcbm, in which 6,6phenylc61butyric acid methyl ester pcbm was attached onto reduced graphene oxide rgo via the noncovalent functionalization approach, was reported. Number of manuscripts with graphene in the title posted on the preprint server. Introduction noncovalent functionalization of graphene covalent functionalization of graphene graphene nanoparticles conclusion. By contrast, however, the theoretical work on the subject has been distinctly biased towards understanding the. Noncovalent chiral functionalization of graphene with optically active helical polymers chonglei ren state key laboratory of chemical resource engineering, college of materials science and engineering, beijing university of chemical technology, beijing, 29 china.
At this moment, the name graphene was not commonly used. Suspensions of graphene, prepared from graphite foil by sonochemical exfoliation, have been treated with new nonpolar pyrenebutyric amides. Improved properties of chemically modified graphenepoly. Generally speaking, functionalization of graphene with polymers can be achieved via either covalent or noncovalent interactions. Noncovalent functionalization of graphene request pdf. Graphene is twodimensional monolayers of carbon atoms that arranged in a honeycombed network, and have diverse applications in various field such as nanoelectronics sensors, composite materials, and energy technology. Related content improving gas sensing properties of graphene by introducing dopants and.
To date, the mixing of graphene and functionalized graphene with polymers covers the. Noncovalent functionalization of graphene in suspension. In this account, i summarize some of our new ideas and strategies for the controlled functionalization of graphene for the. Cnts have found applications in nanotechnology, electronics, sensors and biosensors, catalysis, energy conversion storage devices, the delivery field, and in the polymer field to. Decades ago, they were important in conferring cationexchange properties to coal and coalderived chars. Graphene sheets were stably dispersed in water by functionalization with sulfonated polyaniline spani, and the composite film of spanifunctionalized graphene showed improved electrochemical stability and enhanced electrocatalytic activity. Graphene has got considerable attention in both experimental and theoretical fields for its extraordinary properties. Graphene, a material made exclusively of sp2 carbon atoms with its. Chemical functionalization and characterization of graphene.
Manufacturing highquality graphene samples is currently becoming a routine technology rather than a cuttingedge accomplishment of just a few labs, as was the case only a few. Department of chemistry, massachusetts institute of technology, cambridge, massachusetts 029, united states s supporting information s igni. Compared to noncovalent functionalization, covalent strategies lead to go conjugates with a higher stability in biological fluids. Facile, noncovalent decoration of graphene oxide sheets with. Selective organic functionalization of graphene bulk or graphene edges. Introduction to the physical properties of graphene. Synthesis and electrical properties of covalent organic frameworks with heavy chalcogens selma duhovicand mircea dinca. Good solvents and nonsolvents for the dried reduced graphene.
Covalent functionalization is an efficient strategy to render graphene additional properties and overcome its shortcomings such as zero band gap and nondispersibility in solvents. Ruoff, and junhong chen1 1 department of mechanical engineering, university of wisconsinmilwaukee, 3200 n. Tuning the electronic structure and transport properties. Abstract graphene is a 2d sheet of sp2 bonded carbon atoms and tends to aggregate together, due to the strong. To investigate chemical functionalization of graphene nanoribbons section 5 zigzag stripes with widths of 22 and 66. The functionalization or doping of graphene aims at tuning its electronic properties by opening a energy gap, main challenge for possible electronic applications. Functionalization of graphene oxide by tetrazine derivatives. The desired functionalization route is most plausibly followed by a reaction between the generated radical species figure 7, step c, which is based on the addition of aryl radicals to the graphene sheet. Graphene based materials gbms, with graphene, their most known member, at the head, constitute a large family of materials which has aroused the interest of scientists working in different research fields such as chemistry, physics, or materials science, to mention a few, arguably as no other material befo graphene chemistry. Noncovalent sidewall functionalization of singlewalled carbon nanotubes alexander star, yi liu, kevin grant, ludek ridvan, j. Dec 21, 20 despite its great promise, chemical functionalization of go is still in early stage, and novel chemical tools for the modification of go are demanded. Characterization, direct electrochemistry, and amperometric biosensing of graphene by noncovalent functionalization with picket. An aqueous dispersion of reduced graphene was prepared by chemical reduction of graphene oxide in aqueous media and was vacuum filtered to generate reduced graphene sheets.
Cnts can be functionalized to attain desired properties that can be used in a wide variety of applications. Pdf selective organic functionalization of graphene bulk. Noncovalent chiral functionalization of graphene with. Properties of graphene with impurities materials research. We will also analyze how graphene properties are affected by derivatization. The properties of gqds are different from bulk graphene due to the quantum. Edge functionalization of graphene and 2d ccops although graphene has been demonstrated as an attractive candidate for energy applications due to its special structure and unique properties, it is rare for graphene based materials with desirable bulk properties to also possess the necessary surface. The utilization of grown or deposited graphene on solid substrates offers key benefits for functionalization processes, but especially to attain structures with a high level of control for electronics and smart materials. Functionalization of graphene nanosheets affects the totalfree energy of mixture systems, which consists of enthalpic and entropic contributions. T1 noncovalent functionalization of singlewalled carbon nanotubes. The pyrenepcbm moiety was synthesized via a facile esterification reaction, and pyrene was used as an anchoring bridge to link rgo and pcbm components.
Graphene for biosensing in the past 2 years, there have been a significant number of publications reporting graphenebased biosensors, 4,914,27,3542 mainly utilizing the unique chemical. Noncovalent functionalization of graphene oxide and. Noncovalent functionalization of graphene with end. Heatinitiated chemical functionalization of graphene. Surface functionalization of graphene with polymers for enhanced. Wet functionalization of graphene and its applications in. These onedimensional nanostructures reveal exceptional thermal, electrical, mechanical and optical properties, which make them promising candidates for potential applications in various fields. Decoration of exfoliated black phosphorus with nickel.
Graphene oxide quantum dots covalently functionalized pvdf membrane with significantlyenhanced bactericidal and antibiofouling performances. Controlled functionalization of graphene oxide with sodium azide. Analysis of the bulk material was carried out by scanning raman. Nonspecific binding on nanotubes, a phenomenon found with a. Graphene is a novel twodimensional carbon material nobel prize, 2010, which holds the technological promise of replacing or at least supplementing traditional silicon. This chapter deals with the theoretical and experimental aspects of noncovalent functionalization of graphene. This study reports the synthesis and characterizations of a new kind of functionalized graphene. However, only a few double covalent functionalization approaches have been developed so far. Stable dispersion of reduced graphene in various organic solvents was achieved via noncovalent functionalization with amineterminated polymers. Chemical functionalization of graphene enables this material to be processed by solventassisted techniques, such as layerbylayer assembly, spincoating, and filtration.
Functionalization of graphene through selfassembly of a hydrophobic backbone of nafion has been reported by choi et al. The rollup direction is theoretically represented by a pair of defined indices n, m. Noncovalent functionalization of singlewalled carbon nanotubes. Interlayer interactions in graphite and carbon nanotubes. Natural polymers lignin and cellulose derivatives are adsorbed on the graphene surfaceby. The assemblies, in suspension and after deposition on solid supports, were characterized by nmr, absorption, and fluorescence spectroscopy and by transmission electron microscopy, where the welldefined shape and size. Here, we present an exploration of singlewalled carbon nanotubes as a platform for investigating surfaceprotein and proteinprotein binding and developing highly specific electronic biomolecule detectors. Xps c1s and n1s confirmed the functionalization of go through the binding energies at 288. Large surface area, chemical stability, and good biocompatibility are features that make graphene base materials appropriate for use.
Covalent functionalization takes place through a classical chemical reaction as well as by introducing a new chemical function into the graphene monolayer by grafting new functional groups. A versatile approach toward covalent bridges between graphene sheets yuan li, valerie alainrizzo, laurent galmiche, pierre audebert, fabien miomandre, guy louarn, michael bozlar, michael a. The covalent functionalization of graphene on substrates. The reaction sequence that we have developed for the first wet chemical bulk functionalization of graphene is depicted in fig. The graphene functionalization approaches also fall into two classes, namely physical functionalization and the chemical functionalization. N2 singlewalled carbon nanotubes swnts have attracted much attention on account of their potential to be transformed into new materials that can be employed to address a wide range of applications. Here, we demonstrate that the energy st 2014 journal of materials chemistry a hot articles. Graphene, the twodimensional parent structural unit of threedimensional graphite and onedimensional carbon nanotubes 1, 2, has been treated theoretically since decades, with suggestions of numerous applications that would benefit from the predicted unusual electron transport properties of a defectfree extended delocalized aromatic carbon system. The assemblies, in suspension and after deposition on solid supports, were characterized by nmr, absorption, and fluorescence spectroscopy and by transmission electron microscopy, where the welldefined shape and size of an appended 60fulleropyrrolidine. Functionalization of graphene for efficient energy. Noncovalent functionalization of carbon nanotubes for.
The covalent functionalization of graphene represents a main topic in the growing field of. Noncovalent functionalization of graphene sheets by. An investigation into noncovalent functionalization of a. Noncovalent functionalization of boron nitride nanotubes. Covalent functionalization of graphene with organosilane and. The noncovalent functionalization of graphene by small molecule aromatic adsorbates, phenanthrenequinone pq, is investigated systematically by combining electrochemical characterization, highresolution interfacial xray scattering, and ab initio density functional theory calculations. Films of this molecule act as adhesion layers to produce long ribbons of exfoliated graphene 7,8,9.
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