Antonios Kelarakis

Formation Mechanism of Carbogenic Nanoparticles with Dual Photoluminescence Emission

We present a systematic investigation of the formation mechanism of carbogenic nanoparticles (CNPs), otherwise referred to as C-dots, by following the pyrolysis of citric acid (CA)-ethanolamine (EA) precursor at different temperatures. Pyrolysis at 180 °C leads to a CNP molecular precursor with a strongly intense photoluminescence (PL) spectrum and high quantum yield formed by dehydration of CA-EA. At higher temperatures (230 °C) a carbogenic core starts forming and the PL is due to the presence of both molecular fluorophores and the carbogenic core. CNPs that exhibit mostly or exclusively PL arising from carbogenic cores are obtained at even higher temperatures (300 and 400 °C, respectively). Since the molecular fluorophores predominate at low pyrolysis temperatures while the carbogenic core starts forming at higher temperatures, the PL behavior of CNPs strongly depends on the conditions used for their synthesis.

Multifunctional Graphene/Platinum/Nafion Hybrids via Ice Templating

We report the synthesis of multifunctional hybrids in both films and bulk form, combining electrical and ionic conductivity with porosity and catalytic activity. The hybrids are synthesized by a two-step process: (a) ice templation of an aqueous suspension comprised of Nafion, graphite oxide, and chloroplatinic acid to form a microcellular porous network and (b) mild reduction in hydrazine or monosodium citrate which leads to graphene-supported Pt nanoparticles on a Nafion scaffold.

Self-Assembly and Hydrogelation of an Amyloid Peptide Fragment

The self-assembly of a fragment of the amyloid beta peptide that has been shown to be critical in amyloid fibrillization has been studied in aqueous solution. There are conflicting reports in the literature on the fibrillization of Abeta (16-20), i.e., KLVFF, and our results shed light on this. In dilute solution, self-assembly of NH 2-KLVFF-COOH is strongly influenced by aromatic interactions between phenylalanine units, as revealed by UV spectroscopy and circular dichroism. Fourier transform infrared (FTIR) spectroscopy reveals beta-sheet features in spectra taken for more concentrated solutions and also dried films. X-ray diffraction and cryo-transmission electron microscopy (cryo-TEM) provide further support for beta-sheet amyloid fibril formation. A comparison of cryo-TEM images with those from conventional dried and negatively stained TEM specimens highlights the pronounced effects of sample preparation on the morphology. A comparison of FTIR data for samples in solution and dried samples also highlights the strong effect of drying on the self-assembled structure. In more concentrated phosphate-buffered saline (PBS) solution, gelation of NH 2-KLVFF-COOH is observed. This is believed to be caused by screening of the electrostatic charge on the peptide, which enables beta sheets to aggregate into a fibrillar gel network. The rheology of the hydrogel is probed, and the structure is investigated by light scattering and small-angle X-ray scattering.

Oriented Arrays of Graphene in a Polymer Matrix by in situ Reduction of Graphite Oxide Nanosheets

Graphite oxideNafion hybrids with a high degree of alignment are cast from aqueous solution in the absence of any external field and reduced in situ by exposure to hydrazine to produce grapheneNafion hybrids (see image). Dramatic enhancement of electrical conductivity indicates sufficient accessibility of the inorganic nanosheets to the reducing agent, through the nanochannels formed by the polymeric ionic domains.

Nanoparticle-coated separators for lithium-ion batteries with advanced electrochemical performance

We report a simple, scalable approach to improve the interfacial characteristics and, thereby, the performance of commonly used polyolefin based battery separators. The nanoparticle-coated separators are synthesized by first plasma treating the membrane in oxygen to create surface anchoring groups followed by immersion into a dispersion of positively charged SiO(2) nanoparticles. The process leads to nanoparticles electrostatically adsorbed not only onto the exterior of the surface but also inside the pores of the membrane. The thickness and depth of the coatings can be fine-tuned by controlling the ζ-potential of the nanoparticles. The membranes show improved wetting to common battery electrolytes such as propylene carbonate. Cells based on the nanoparticle-coated membranes are operable even in a simple mixture of EC/PC. In contrast, an identical cell based on the pristine, untreated membrane fails to be charged even after addition of a surfactant to improve electrolyte wetting. When evaluated in a Li-ion cell using an EC/PC/DEC/VC electrolyte mixture, the nanoparticle-coated separator retains 92% of its charge capacity after 100 cycles compared to 80 and 77% for the plasma only treated and pristine membrane, respectively.

Adaptation of pharmaceutical excipients to FDM 3D printing for the fabrication of patient-tailored immediate release tablets

This work aims to employ fused deposition modelling 3D printing to fabricate immediate release pharmaceutical tablets with several model drugs. It investigates the addition of non-melting filler to methacrylic matrix to facilitate FDM 3D printing and explore the impact of (i) the nature of filler, (ii) compatibility with the gears of the 3D printer and iii) polymer: filler ratio on the 3D printing process. Amongst the investigated fillers in this work, directly compressible lactose, spray-dried lactose and microcrystalline cellulose showed a level of degradation at 135°C whilst talc and TCP allowed consistent flow of the filament and a successful 3D printing of the tablet. A specially developed universal filament based on pharmaceutically approved methacrylic polymer (Eudragit EPO) and thermally stable filler, TCP (tribasic calcium phosphate) was optimised. Four model drugs with different physicochemical properties were included into ready-to-use mechanically stable tablets with immediate release properties. Following the two thermal processes (hot melt extrusion (HME) and fused deposition modelling (FDM) 3D printing), drug contents were 94.22%, 88.53%, 96.51% and 93.04% for 5-ASA, captopril, theophylline and prednisolone respectively. XRPD indicated that a fraction of 5-ASA, theophylline and prednisolone remained crystalline whilst captopril was in amorphous form. By combining the advantages of thermally stable pharmaceutically approved polymers and fillers, this unique approach provides a low cost production method for on demand manufacturing of individualised dosage forms.

Photoluminescent carbogenic nanoparticles directly derived from crude biomass

We present an environmentally benign, energy efficient and readily scalable approach to synthesize photoluminescent carbogenic nanoparticles directly from soft tissue biomass. Our approach relies on the pyrolytic decomposition of grass that gives rise to the formation of well-defined nanoparticles. The carbogenic nanoparticles can be readily surface modified, generating a series of highly selective photoluminescent materials that exhibit remarkable stability upon prolonged exposure to aggressive, high-temperature, high-salinity environment.

Nematic and Columnar Ordering of a PEG-Peptide Conjugate in Aqueous Solution

The self-assembly in aqueous solution of a PEG-peptide conjugate is studied by spectroscopy, electron microscopy, rheology and small-angle X-ray and neutron scattering (SAXS and SANS). The peptide fragment, FFKLVFF is based on fragment KLVFF of the amyloid beta-peptide, Abeta(16-20), extended by two hydrophobic phenylalanine units. This is conjugated to PEG which confers water solubility and leads to distinct self-assembled structures. Small-angle scattering reveals the formation of cylindrical fibrils comprising a peptide core and PEG corona. This constrained structure leads to a model parallel beta-sheet self-assembled structure with a radial arrangement of beta sheets. On increasing concentration, successively nematic and hexagonal columnar phases are formed. The flow-induced alignment of both structures was studied in situ by SANS using a Couette cell. Shear-induced alignment is responsible for the shear thinning behaviour observed by dynamic shear rheometry. Incomplete recovery of moduli after cessation of shear is consistent with the observation from SANS of retained orientation in the sample.

Superhydrophilic and solvent resistant coatings on polypropylene fabrics by a simple deposition process

A simple, yet general coating method to plasma treated polymeric substrates is presented. The method is based on electrostatic interactions between the surface functionalized nanoparticles and the charged substrate and leads to stable and solvent resistant multilayer coatings. The coatings render polypropylene (PP) hydrophilic and in the case of PP fabric superhydrophilic. The superhydrophilicity is attributed to the topography and increased roughness of the fabric compared to a planar, smooth substrate.

Micellisation and gelation of diblock copolymers of ethylene oxide and propylene oxide in aqueous solution, the effect of P-block length

The aqueous solution properties of five diblock copolymers prepared by sequential anionic copolymerisation (i.e. E102P37, E104P52, E92P55, E104P60 and E98P73 where E denotes oxyethylene and P denotes oxypropylene) were studied across a wide range of concentration. The techniques used to study micellisation and micellar properties in dilute solution were static and dynamic light scattering, surface tension, and eluent gel-permeation chromatography. The gelation of concentrated solutions was also investigated. As expected, the critical micelle concentration (CMC) was lowered and the association number of the micelles was increased by an increase in P-block length. In contrast, the critical gel concentration was unchanged, consistent with the constant E-block length leading to micelles with essentially identical E-block fringes. Comparison of the CMCs of the diblock copolymers with those of triblock EmPnEm copolymers with the same P-block length shows the diblock copolymers to micellise more efficiently. A similar comparison of the CMCs of the diblock copolymers with those of EmBn copolymer (B denotes oxybutylene) shows the hydrophobicity of a P unit to be one-sixth that of a B unit. The possibility is explored of correlating the limiting association number of a spherical micelle with the hydrophobe block length of its constituent copolymer. Of the five copolymers, only dilute solutions of E98P73 were predominantly micellar at both room temperature and body temperature, and this copolymer must be a prime candidate in any consideration of the potential application of EmPn copolymers in the solubilisation and controlled release of drugs.