The development of a new class of alternative plastics has been encouraged in the past few years due to the serious environmental issues, such as toxicity and carbon dioxide emissions. Hence, the introduction of renewable, biodegradable, and biocompatible materials is becoming critical as substituents of conventional synthetic plastics. To design a new system of novel TEMPO-oxidized cellulose nanofibrils (TOCNs)/graphene oxide (GO) composite, the 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated oxidation was utilized to disintegrate never-dried wood nanofibrillated cellulose (NFC). GO was incorporated through high intensity homogenization and ultrasonication with varying degree of oxidation (0.5X, 1X, and 2X) of NFC and GO percent loadings: 0.4, 1.2, and 2.0wt %. As a result, despite the presence of carboxylate groups and graphene oxide (GO), X-ray diffraction (XRD) test showed the crystallinity of the bio-nanocomposite was not altered. Scanning electron microscopy (SEM) was used to characterize their morphologies. In addition, the thermal stability of TOCN/GO composite decreased upon oxidation level, and dynamic mechanical analysis (DMA) signified strong intermolecular interactions with the improvement in Young's storage modulus, and tensile strength. Fourier transform infrared spectroscopy (FTIR) was employed to see the hydrogen bonds between GO and cellulosic polymer matrix. The oxygen transmission rate (OTR) of TOCN/GO composite decreased. The water vapor permeability (WVP) was not significantly affected by the reinforcement with GO, but the moderate oxidation enhanced the barrier properties. Ultimately, the newly fabricated TOCN/GO composite can be utilized in a wide range of life science applications, such as food and medical industries. / Master of Science / In recent years, petroleum-based polyolefins have been contributing to severe environmental issues. With this in perspective, the development of a new class of alternative plastics has been encouraged. Hence, the introduction of renewable, biodegradable, and biocompatible materials is becoming critical as a substitute for non-degradable synthetic plastics. In this study, a new system of novel cellulose-based plastic composites was designed by incorporating carbon nanofillers at various percent loadings and different degree of surface modification of the plastics. These treatments are the economical way to achieve the targeted properties for industrial applications, exhibiting the obvious improvement in tensile strength due to the strong interaction between nanofillers and cellulose. In addition, water vapor and oxygen barrier properties play significant roles in food packaging since food decay is vulnerable to these two factors. The barrier performance was enhanced by hindering the permeation of oxygen gases, whereas the water vapor permeability was not significantly affected by the reinforcement with carbon nanofillers. Ultimately, the newly fabricated cellulose plastic can be utilized in various applications, especially, such as the pharmaceutical and biomedical areas, packaging for food and goods, and agriculture due to their high availability, sustainability, and biodegradability.

Yes / We report on the predicted structural disruption of an adenosine-binding DNA aptamer adsorbed via noncovalent interactions on aqueous graphene. The use of surface-adsorbed biorecognition elements on device substrates is needed for integration in nanofluidic sensing platforms. Upon analyte binding, the conformational change in the adsorbed aptamer may perturb the surface properties, which is essential for the signal generation mechanism in the sensor. However, at present, these graphene-adsorbed aptamer structure(s) are unknown, and are challenging to experimentally elucidate. Here we use molecular dynamics simulations to investigate the structure and analyte-binding properties of this aptamer, in the presence and absence of adenosine, both free in solution and adsorbed at the aqueous graphene interface. We predict this aptamer to support a variety of stable binding modes, with direct base−graphene contact arising from regions located in the terminal bases, the centrally located binding pockets, and the distal loop region. Considerable retention of the in-solution aptamer structure in the adsorbed state indicates that strong intra-aptamer interactions compete with the graphene−aptamer interactions. However, in some adsorbed configurations the analyte adenosines detach from the binding pockets, facilitated by strong adenosine−graphene interactions.

Yes / We combine single molecule force spectroscopy measurements with all-atom metadynamics simulations to investigate the cross-materials binding strength trends of DNA fragments adsorbed at the aqueous graphite C(0001) and Au(111) interfaces. Our simulations predict this adsorption at the level of the nucleobase, nucleoside, and nucleotide. We find that despite challenges in making clear, careful connections between the experimental and simulation data, reasonable consistency between the binding trends between the two approaches and two substrates was evident. On C(0001), our simulations predict a binding trend of dG > dA ≈ dT > dC, which broadly aligns with the experimental trend. On Au(111), the simulation-based binding strength trends reveal stronger adsorption for the purines relative to the pyrimadines, with dG ≈ dA > dT ≈ dC. Moreover, our simulations provide structural insights into the origins of the similarities and differences in adsorption of the nucleic acid fragments at the two interfaces. In particular, our simulation data offer an explanation for the differences observed in the relative binding trend between adenosine and guanine on the two substrates.

The topic of this thesis is the study of nitrogen functionalities in nitrogen-doped reduced graphene oxide using Raman spectroscopy. Specifically, the project set out to investigate if the Raman active nitrogen-related vibrational modes of graphene can be identified via isotope labelling. Previous studies have used Raman spectroscopy to characterise nitrogen doped graphene, but none has employed the method of isotope labelling to do so. The study was conducted by producing undoped, nitrogen-doped and nitrogen-15-doped reduced graphene oxide and comparing the differences in the first-order Raman spectrum of the samples. Results of this study are inconclusive. However, some indications linking the I band to nitrogen functionalities are found. Also, a hypothetical Raman band denoted I* possibly related to \spt{3} hybridised carbon is introduced in the same spectral area as I. This indication of a separation of the I band into two bands, each dependent on one of these factors could bring clarity to this poorly understood spectral area. As the results of this study are highly speculative, further research is needed to confirm them and the work presented here serves as a preliminary investigation.

For graphene to be a viable platform for nanoscale devices, high quality growth and structures are necessary. This means structuring the SiC surface to prevent graphene from having to be patterned using standard microelectronic processes. Presented in this thesis are new processes aimed at improving the graphene as well as devices based on high quality graphene nanoribbons. Amorphous carbon (aC) corrals deposited prior to graphene growth are demonstrated to control SiC step-flow. SiC steps are shown to be aligned by the presence of the corrals and can increase SiC terrace widths. aC contacts deposited and crystallized during graphene growth are shown as a way to contact graphene without metal lift-off. Observation of the Quantum Hall Effect demonstrates the high quality of the graphene grown alongside the nanocrystalline graphite contacts. Continuing the ballistic transport measurements on sidewall graphene nanoribbons, the invasive probe effect is observed using an atomic force microscope (AFM) based technique that spatially maps the invasive probe effect. Cleaning experiments demonstrate the role of scattering due to resist residues and environmental adsorbates on graphene nanoribbons. Finally, switches based on junctions formed in the graphene nanoribbons are shown as a route toward graphene based devices.

Thesis (MSc)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: The goal of this thesis is to investigate the effects of distorting a graphene lattice and connect- ing this distorted graphene sheet to a superconductor. At low energies the possible excitation states in graphene are restricted to two distinct regions in momentum space called valleys. Many electronic applications are possible if one can design a graphene system where excitations can be forced to occupy a single valley in a controllable way. Investigating the spectrum of the distorted graphene sheet reveals that, if the chemical potential is chosen to coincide with a bulk Landau level, the normal-superconductor interface always supports propagating modes in both directions. Excitations from opposite valleys travel in opposite directions along the interface. The spectrum of a distorted graphene sheet terminated by an armchair edge, in contrast, is dis- persionless. We verify this insulating nature of the armchair edge for finite samples by numerical means. Furthermore, we verify previous analytical results pertaining to a graphene sheet with NS interface and an applied perpendicular real magnetic field numerically. In the process, it is shown that considering graphene sheets of perfect width is not necessary, as long as the width a few magnetic lengths away from the interface is well-defined. By then considering a finite graphene sheet, terminated by armchair edges, that is distorted and connected to a superconductor, we find bound states near the NS interface that can be changed by distorting the graphene lattice further. / AFRIKAANSE OPSOMMING: Die doel van hierdie tesis is om die uitwerking van die vervorming van ’n grafeenrooster te ondersoek wanneer die met ’n supergeleier verbind word. By lae energieë word die moontlike opwekkings in grafeen beperk tot twee aparte gebiede van momentumruimte — die sogenaamde valleie. Verskeie elektroniese toepassings is moontlik indien ’n grafeenstelsel ontwerp kan word waar opwekkings slegs ’n enkele vallei beset en die besetting beheer kan word. Deur die spektrum van die vervormde grafeenrooster te ondersoek word daar gevind dat, indien die chemiese potensiaal gekies word om saam te val met ’n Landauvlak, die NS-tussenvlak geleiding in beide rigtings ondersteun. Opwekkings van verskillende valleie beweeg in teenoorgestelde rigtings langs die tussenvlak. Daarteenoor is die spektrum van ’n vervormde grafeenroster met ’n leunstoelrand dispersieloos. Ons bevestig hierdie insulerende gedrag van ’n leunstoelrand vir eindige grafeen- roosters deur middel van ’n numeriese berekening. Verder word vorige analitiese resultate wat verband hou met ’n grafeenrooster met normaal-supergeleiertussenvlakstelsel en loodregte mag- neetveld op die vlak bevestig deur middel van numeriese berekeninge. In die proses word dit ook aangedui dat die grafeenrooster nie ’n perfekte wydte hoef te hˆe nie, solank die wydte goed gedefinieer is vir ’n paar magnetiese lengtes in die omgewing van die tussenvlak. Deur dan die eindige grafeenrooster met leunstoelrande te koppel aan ’n supergeleier word gebonde toe- stande naby aan die NS tussenvalk gevind. Hierdie toestande kan gemanipuleer word deur die grafeenrooster verder te vervorm.

In the first part of this work, we describe a theory of the ground states and charge gaps in the fractional quantum Hall states of graphene. The theory relies on knowledge of these properties for filling fractions smaller than one. Then, by the application of two mapping rules, one is able to obtain these properties for fractional quantum Hall states at arbitrary fillings, by conceiving the quantum Hall ferromagnets as vacua on which correlated electrons or correlated holes are added. The predicted charge gaps and phase transitions between different fractional quantum Hall states are in good agreement with recent experiments. In the second part, we investigate the low energy theory for the neutral Landau level of bilayer graphene. We closely analyze the way different terms in the Hamiltonian transform under the action of particle-hole conjugation symmetries, and identify several terms that are relevant in explaining the lack of such symmetry in experiments. Combining an accurate parametrization of the electronic structure of bilayer graphene with a systematic account of the impact of screening we are able to explain the absence of particle-hole symmetry reported in recent experiments. We also study the energetics of fractional quantum Hall states with coherence between n=0 and n=1 cyclotron quantum numbers, and obtain a general formula to map the two-point correlation function from their well-known counterparts made from only n=0 quantum numbers. Bilayer graphene has the potential for realizing these states which have no analogue in other two-dimensional electron systems such as Gallium Arsenide. We apply this formula to describe the properties of the n=0/n=1 coherent Laughlin state which displays nematic correlations. / text

Graphene has recently become the focus of enormous attention for experimentalists and theorists alike mainly due to its unique electronic properties. However, the limited way in which one can control these properties is a major obstacle for device applications. The unifying theme of this thesis is to propose and thoroughly justify ways to control the electronic properties of graphene and carbon nanotubes by light or static electric and magnetic fields and to harness these properties for optoelectronic applications. A linearly polarized excitation is shown to create a strongly anisotropic distribution of photoexcited carriers in graphene, where the momenta of photoexcited carriers are aligned preferentially normal to the polarization plane. This effect offers an experimental tool to generate highly directional photoexcited carriers which could assist in the investigation of "direction-dependent phenomena" in graphene-based nanostructures. The depolarization of hot photoluminescence is used to study relaxation processes in graphene, both free standing and grown on silicon carbide. This analysis is extended to include the effect of a magnetic field, thereby allowing one to obtain the momentum relaxation times of hot electrons. The analysis of momentum alignment in the high frequency regime shows that a linearly polarized excitation allows the spatial separation of carriers belonging to different valleys. Quasi-metallic carbon nanotubes are considered for terahertz applications. They are shown to emit terahertz radiation when a potential difference is applied across their ends and their spontaneous emission spectra have a universal frequency and bias voltage dependence. It is shown that the same intrinsic curvature which opens the gap in the quasi-metallic carbon nanotube energy spectrum also allows optical transitions in the terahertz range. The exciton binding energy in narrow-gap carbon nanotubes is calculated and found to scale with the band gap and vanishes as the gap decreases, even in the case of strong electron-hole attraction. Therefore, excitonic effects should not dominate in narrow-gap nanotubes. Contrary to widespread belief, it is shown that full confinement is possible for zero-energy states in pristine graphene. The exact analytical solutions for the zero-energy modes confined within a smooth one-dimensional potential V = α/ cosh (βx) are presented. This potential provides a good fit for the potential profiles of top-gated graphene structures. It is shown that there is a threshold value of the characteristic potential strength α/β for which the first mode appears, in striking contrast to the non-relativistic case. A relationship between the characteristic strength and the number of modes within the potential is found. An experimental setup is proposed for the observation of these modes. The proposed geometry could be utilized in future graphene-based devices with high on/off current ratios.

The solid acid catalyst of the Keggin-type 12-tungstophosphoric acid (H3PW12O40, HPW) is supported on partially reduced graphene oxide (PRGO) nanosheets for acid-catalyzed reactions. HPW is a new class of catalyst with a good thermal stability and high Bronsted acidity in order to replace common mineral acids. However, it has low specific surface area (1-5 m2/g). Therefore, the possibility of PRGO as a catalytic support for HPW is investigated due to its high surface area (2630 m2/g) and good thermal stability. The synthesis of HPW-GO catalyst is prepared using microwave and laser irradiation without using any chemical reducing agents. The HPW-GO catalysts are characterized by Ultraviolet-visible spectroscopy (UV-Vis), Fourier Transform Infrared Spectroscopy (FT-IR), Raman Spectroscopy, X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction (XRD) techniques, and Transmission Electron Microscopy (TEM). Also, the surface acidity is measured by a non-aqueous titration of n-butyl amine. Furthermore, the application for catalysts is tested by three acid-catalyzed reactions: Esterification, Friedel-Crafts acylation, and Pechmann condensation. The greatest acidity for the microwave irradiation method is with the loading of 85 wt% HPW-GO and 60wt% HPW-GO for laser irradiation. The results observed provide an excellent opportunity for PRGO as a catalytic support for HPW for acid-catalyzed reactions.

This thesis presented the study of carbon-based materials for ultra-sensitive molecular sensing. Reduced Graphene Oxide (rGO), a 2-dimensional one-atomic layer thick carbon material, had the advantage of low-cost, aqueous and industrial-scalable production route. Using rGO as the transducer platform could potentially lower the cost of sensors down to a few dollars per chip. However, there were still limitations in rGO that prevented its widespread usage as a biosensor transducer or in electronics: its low electrical conductivity and large electrical deviations. This thesis was structured to understand and solve these problems for transducer application. The thesis could be broken down into 3 parts: The first part of the thesis presented the critical review of the background and limitations of graphene research, followed by the background and importance of biosensor developments for the detection of sweat sodium ions and circulatory Interleukin-6 proteins. The second part of the thesis tested the hypothesis that the rGO limitations could be eliminated to create a highly sensitive biosensor transducer via (A) improving rGO synthesis (B) pristine Carbon Nanotubes-rGO hybrid film and (C) growth of rGO. The mechanism of ultra-large graphene oxide synthesis and graphene oxide growth was also elucidated in this section. The third part of the thesis then presented the fabrication and test of the practical and homogenous carbon-based biosensor using the transducer synthesized earlier. The thesis showed that through proving the hypothesis correct, it enabled the synthesis of an all organic sodium ion sensor with integrated pump and an ultra-sensitive interleukin-6 bio-sensor. Both of these novel sensors were able to detect the respective molecules in their physiological ranges.