functionalization-dispersion-carbon-nanomaterials-using-an

Functionalization and Dispersion of Carbon Nanomaterials Using an Environmentally Friendly Ultrasonicated Ozonolysis Process

Functionalization of carbon nanomaterials is often a critical step that facilitates their integration into larger material systems and devices. In the ...

La Trobe University

The immobilisation efficiency of the complexes of oligonucleotide/poly(L-lysine) on two polymeric carboxy-rich surfaces, i.e. poly(styrene/maleic acid) (PSMA) and poly(styrene/maleic anhydride) (PSMAA), has been investigated using X-ray photoelectron spectroscopy, atomic force microscopy (AFM) and fluorescence-based measurements of DNA attachment. A molecularly thin layer of either electrostatically or covalently (via amide bond) bound poly(L-lysine) allows the 'switching' from COOH-based to NH(2)-based surface functionality. The results indicate that approximately 54-57% and 55-62% of the applied oligonucleotides bind to polymeric surfaces via the route of electrostatic adsorption of poly(L-lysine) and covalent bonding of poly(L-lysine), respectively. This system can be applied conveniently for the detection of nucleic acids in both disposable and reusable biosensors.

Poly(L-lysine)-mediated immobilisation of oligonucleotides on carboxy-rich polymer surfaces.

The adsorption and decomposition pathways of 1-propanethiol on a Ga-rich GaAs(100) surface have been investigated using the techniques of temperature programmed desorption, X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectrometry (TOF-SIMS). 1-Propanethiol adsorbs dissociatively on a clean GaAs(100) surface to form propanethiolate and hydrogen. Further reactions of these species to form new products compete with the recombinative desorption of molecular propanethiol. The C-S bond scission in the propanethiolate results in the formation of propyl species and elemental sulfur. The generation of propene via beta-hydride elimination then follows. In addition, propane and hydrogen form via reductive elimination processes. A recombinative high-temperature propanethiol desorption state is also observed. XPS and TOF-SIMS analyses confirm the presence of sulfur on the GaAs(100) surface following thermal decomposition. This paper discusses the mechanisms by which these products form on the GaAs(100) surface.

Surface reactions of 1-propanethiol on GaAs(100).

The adsorption and covalent immobilization of human immunoglobulin (HIgG) and lysozyme (LYZ) on surface-modified poly(tert-butyl methacrylate) PtBMA films have been evaluated using x-ray photoelectron spectroscopy (XPS), ellipsometry and atomic force microscopy (AFM). Surface modification of PtBMA (UV irradiation) afforded surfaces suitable for both the physical and covalent attachment of proteins. The XPS and ellipsometry results showed good correlation in terms of variable-dense/thickness protein layer formation between physisorbed and covalently bound proteins. The amount of physisorbed HIgG ranged from 23.0 +/- 1.6 ng mm(2) on PtBMA, with corresponding film thicknesses 17.0 +/- 1.2 nm. Covalent immobilization mediated through 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC)/N-hydroxysulfosuccinimide (sulfo-NHS) coupling chemistry, afforded 5.6-8 ng mm(2) of HIgG with a corresponding thickness of 5.9 +/- 0.6 nm on PtBMA. The attachment of LYZ to modified PtBMA surface was similarly translated, where adsorption yielded up to 15 ng mm(2), while covalent immobilization afforded typically 7-8 ng mm(2). The thickness of the adsorbed LYZ protein layer was 11.0 +/- 3.2 nm (PtBMA), suggesting the greater portion of protein adsorbs on surface-modified PtBMA.

A comparative study between the adsorption and covalent binding of human immunoglobulin and lysozyme on surface-modified poly(tert-butyl methacrylate).

Fluoropolymer plasma coatings have been investigated for application as stent coatings due to their chemical stability, conformability, and hydrophobic properties. The challenge resides in the capacity for these coatings to remain adherent, stable, and cohesive after the in vivo stent expansion, which can generate local plastic deformation of up to 25%. Plasma-coated samples have been prepared by a multistep process on 316L stainless steel substrates, and some coated samples were plastically deformed to mimic a stent expansion. Analyses were then performed by X-ray photoelectron spectroscopy (XPS), X-ray photoelectron emission microscopy (X-PEEM), and time-of-flight secondary ion mass spectrometry (TOF-SIMS) to determine the chemical and physical effects of such a deformation on both the coating and the interfacial region. While XPS analyses always showed a continuous coating with no significant effect of the deformation, TOF-SIMS and near-edge X-ray absorption fine structure (derived from X-PEEM) data indicated the presence of a certain density of porosity and pinholes in all coatings as well as sparse fissures and molecular fragmentation in the deformed ones. The smallness of the area fraction affected by the defects and the subtlety of the chemical changes could only be evidenced through the higher chemical sensitivity of these latter techniques.

X-ray photoelectron emission microscopy and time-of-flight secondary ion mass spectrometry analysis of ultrathin fluoropolymer coatings for stent applications.

The electrodeposition of the electrochemiluminescent (ECL) ruthenium complex, bis(2,2'-bipyridyl)(4'-(4-aminophenyl)-2,2'-bipyridyl)ruthenium(II), [Ru(bpy)(2)(apb)](2+), via the in situ formation of a diazonium species from aqueous media is reported. Surface characterization undertaken using X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) determined that the layer is bound to the substrate via azo bonding. The layer displays good ECL activity and is stable over a long period of time. The excellent potential of this system for ECL sensing applications is demonstrated using the well-known ECL coreactant 2-(dibutylamino)ethanol (DBAE) as a model analyte, which can be detected to a level of 10 nM with a linear range between 10(-8) and 10(-4) M.

Highly stable ECL active films formed by the electrografting of a diazotized ruthenium complex generated in situ from the amine.

Artificial neural networks (ANNs) form a class of powerful multivariate analysis techniques, yet their routine use in the surface analysis community is limited. Principal component analysis (PCA) is more commonly employed to reduce the dimensionality of large data sets and highlight key characteristics. Herein, we discuss the strengths and weaknesses of PCA and ANNs as methods for investigation and interpretation of a complex multivariate sample set. Using time-of-flight secondary ion mass spectrometry (ToF-SIMS) we acquired spectra from an antibody and its proteolysis fragments with three primary-ion sources to obtain a panel of 72 spectra and a characteristic peak list of 775 fragment ions. We describe the use of ANNs as a means to interpret the ToF-SIMS spectral data, highlight the optimal neural network design and computational parameters, and discuss the technique limitations. Further, employing Bi3(+) as the primary-ion source, ANNs can accurately classify antibody fragments from the parent antibody based on ToF-SIMS spectra.

Surface Adsorbed Antibody Characterization Using ToF-SIMS with Principal Component Analysis and Artificial Neural Networks.

The development of electrospun ultrafine fibres from biodegradable and biocompatible polymers has created exciting opportunities for biomedical applications. Fibre meshes with high surface area, suitable porosity and stiffness have been produced. Despite desirable structural and topographical properties, for most synthetic and some naturally occurring materials, the nature of the fibre surface chemistry has inhibited development. Hydrophobicity, undesirable non-specific protein adsorption and bacterial attachment and growth, coupled with a lack of surface functionality in many cases and an incomplete understanding of the myriad of interactions between cells and extracellular matrix (ECM) proteins have impeded the application of these systems. Chemical and physical treatments have been applied in order to modify or control the surface properties of electrospun fibres, with some success. Chemical modification using controlled radical polymerization, referred to here as reversible-deactivation radical polymerization (RDRP), has successfully introduced advanced surface functionality in some fibre systems. Atom transfer radical polymerization (ATRP) and reversible addition fragmentation chain transfer (RAFT) are the most widely investigated techniques. This review analyses the practical applications of electrospinning for the fabrication of high quality ultrafine fibres and evaluates the techniques available for the surface modification of electrospun ultrafine fibres and includes a detailed focus on RDRP approaches.

Surface modification of electrospun fibres for biomedical applications: A focus on radical polymerization methods.

Antibody orientation at solid phase interfaces plays a critical role in the sensitive detection of biomolecules during immunoassays. Correctly oriented antibodies with solution-facing antigen binding regions have improved antigen capture as compared to their randomly oriented counterparts. Direct characterization of oriented proteins with surface analysis methods still remains a challenge however surface sensitive techniques such as Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) provide information-rich data that can be used to probe antibody orientation. Diethylene glycol dimethyl ether plasma polymers (DGpp) functionalized with chromium (DGpp+Cr) have improved immunoassay performance that is indicative of preferential antibody orientation. Herein, ToF-SIMS data from proteolytic fragments of anti-EGFR antibody bound to DGpp and DGpp+Cr are used to construct artificial neural network (ANN) and principal component analysis (PCA) models indicative of correctly oriented systems. Whole antibody samples (IgG) test against each of the models indicated preferential antibody orientation on DGpp+Cr. Cross-reference between ANN and PCA models yield 20 mass fragments associated with F(ab')2 region representing correct orientation, and 23 mass fragments associated with the Fc region representing incorrect orientation. Mass fragments were then compared to amino acid fragments and amino acid composition in F(ab')2 and Fc regions. A ratio of the sum of the ToF-SIMS ion intensities from the F(ab')2 fragments to the Fc fragments demonstrated a 50% increase in intensity for IgG on DGpp+Cr as compared to DGpp. The systematic data analysis methodology employed herein offers a new approach for the investigation of antibody orientation applicable to a range of substrates.

Narelle Brack

Department of Chemistry and Physics,
La Trobe Institute for Molecular Science,
Department of Chemistry and Physics, La Trobe Institute for Molecular Science

La Trobe University

Functionalization and Dispersion of Carbon Nanomaterials Using an Environmentally Friendly Ultrasonicated Ozonolysis Process

Narelle Brack

Department of Chemistry and Physics,La Trobe Institute for Molecular Science,Department of Chemistry and Physics, La Trobe Institute for Molecular Science

La Trobe University

Functionalization and Dispersion of Carbon Nanomaterials Using an Environmentally Friendly Ultrasonicated Ozonolysis Process

Department of Chemistry and Physics,
La Trobe Institute for Molecular Science,
Department of Chemistry and Physics, La Trobe Institute for Molecular Science