Generation of Nanoparticles on and within Polymeric Materials.

It is well-established that the structural, morphological and performance characteristics of nanoscale materials critically depend upon the dispersion state of the nanofillers that is, in turn, largely determined by the preparation protocol. In this report, we review synthetic strategies that capitalise on the generation of nanoparticles on and within polymeric materials, an approach that relies on the chemical transformation of suitable precursors to functional nanoparticles synchronous with the build-up of the nanohybrid systems. This approach is distinctively different compared to standard preparation methods that exploit the dispersion of preformed nanoparticles within the macromolecular host and presents advantages in terms of time and cost effectiveness, environmental friendliness and the uniformity of the resulting composites.

Antimicrobial coatings based on amine-terminated graphene oxide and Nafion with remarkable thermal resistance.

We present a novel type of layer-by-layer (LbL) waterborne coating based on Nafion and amine-terminated graphene oxide (GO-NH) that inhibits the growth of and by more than 99% and this performance is not compromised upon extensive thermal annealing at 200 °C. Quartz crystal microbalance (QCM) sensorgrams allow the real time monitoring of the build-up of the LbL assemblies, a process that relies on the strong electrostatic interactions between Nafion (pH = 2.7, = -54.

Resculpting carbon dots via electrochemical etching.

Substantial efforts are directed into exploring the structure-properties relationships of photoluminescent Carbon dots (C-dots). This study unravels a resculpting mechanism in C-dots that is triggered by electrochemical etching and proceeds via extensive surface oxidation and carbon-carbon breakage. The process results in the gradual shrinkage of the nanoparticles and can enhance the quantum yield by more than half order of magnitude compared to the untreated analogues.

Carbon Dots/Iron Oxide Nanoparticles with Tuneable Composition and Properties.

We present a simple strategy to generate a family of carbon dots/iron oxide nanoparticles (C/Fe-NPs) that relies on the thermal decomposition of iron (III) acetylacetonate in the presence of a highly fluorescent carbon-rich precursor (derived via thermal treatment of ethanolamine and citric acid at 180 °C), while polyethylene glycol serves as the passivation agent. By varying the molar ratio of the reactants, a series of C/Fe-NPs have been synthesized with tuneable elemental composition in terms of C, H, O, N and Fe. The quantum yield is enhanced from 6 to 9% as the carbon content increases from 27 to 36 wt%, while the room temperature saturation magnetization is improved from 4.

Towards Red Emissive Systems Based on Carbon Dots.

Carbon dots (C-dots) represent an emerging class of nontoxic nanoemitters that show excitation wavelength-dependent photoluminescence (PL) with high quantum yield (QY) and minimal photobleaching. The vast majority of studies focus on C-dots that exhibit the strongest PL emissions in the blue/green region of the spectrum, while longer wavelength emissions are ideal for applications such as bioimaging, photothermal and photodynamic therapy and light-emitting diodes. Effective strategies to modulate the PL emission of C-dot-based systems towards the red end of the spectrum rely on extensive conjugation of sp domains, heteroatom doping, solvatochromism, surface functionalization and passivation.

A rich gallery of carbon dots based photoluminescent suspensions and powders derived by citric acid/urea.

In this study we demonstrate simple guidelines to generate a diverse range of fluorescent materials in both liquid and solid state by focusing on the most popular C-dots precursors, i.e. the binary systems of citric acid and urea.

Structure-properties relationships in alkaline treated rice husk reinforced thermoplastic cassava starch biocomposites.

The study focuses on structure-properties relationships in thermoplastic cassava starch (TPS) based biocomposites comprising 5-20 wt% of untreated and treated rice husk (RH). Alkaline treatment with 11% w/v NaOH removed the hemicellulose layer of RH as confirmed by Fourier-transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA), and resulted in a larger population of -OH groups exposing on the fibril surface. Consequently, the filler-matrix interactions between treated RH and TPS were enhanced, although Brunauer-Emmett-Teller (BET) surface area analysis indicated that the surface area of treated RH was not increased.

Carbon Dots for Forensic Applications: A Critical Review.

Owing to their superior fluorescence performance, inexpensive synthesis and nontoxic nature, carbon dots (C-dots) are systematically explored in a variety of applications; in this review, we outline and critically discuss recent trends with respect to their potential exploitation in criminal investigation, forensic toxicology and anti-counterfeit interventions. Capitalising on their colour-tuneable behaviour (in the sense that they adopt different colours with respect to the incident radiation), C-dot-based compositions are ideal for the visual enhancement of latent fingerprints, affording improved contrast against multicoloured and patterned backgrounds. As highly sensitive and highly selective optical nanoprobes, C-dots show excellent analytical performance in detecting biological compounds, drugs, explosives, heavy metals and poisonous reactants.

Layer by Layer Antimicrobial Coatings Based on Nafion, Lysozyme, and Chitosan.

The study focuses on the development of a new family of layer-by-layer coatings comprising Nafion, lysozyme and chitosan to address challenges related to microbial contamination. Circular dichroism was employed to gain insights on the interactions of the building blocks at the molecular level. Quartz crystal microbalance tests were used to monitor in real time the build-up of multilayer coatings, while atomic force microscopy, contact angle and surface zeta potential measurements were performed to assess the surface characteristics of the multilayer assemblies.

Facile Fluorescence "Turn on" Sensing of Lead Ions in Water via Carbon Nanodots Immobilized in Spherical Polyelectrolyte Brushes.

Heavy metal detection has become very important for the protection of water resource. In this work, a novel controllable probe is presented for the sensitive detection of Pb in aqueous solutions. The probe was synthesized via the immobilization of surface functionalized carbon dots (named as CAEA-Hs) into the shell of the spherical polyelectrolyte brushes (SPB).

Dramatic photoluminescence quenching in carbon dots induced by cyclic voltammetry.

This study focuses on the structural rearrangements and the photoluminescent behavior of pyrolytically derived carbon dots when subjected to a series of cyclic voltammetry sweeps. Although the electrical signals involved are not pronounced, multiple electrochemical cycling results in a progressive suppression of the photoluminescence, so that after 42 sweeps the intensity is reduced by one order of magnitude. At the same time, the fluorescence component stemming from the organic fluorophores is blue-shifted, while the contribution of the carbogenic cores is red-shifted.

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.

Carbogenically coated silica nanoparticles and their forensic applications.

Carbogenically coated silica nanoparticles (C-SiO2) exhibit color-tunability and carry great promise for two important forensic applications. First, the C-SiO2 nanopowders are ideal for fingerprint development, yielding strong contrast against multicoloured and patterned backgrounds. Second, spontaneous nanoparticle aggregation leads to non-duplicable, inexpensive nanotags that can support sustainable technologies to combat counterfeiting.

Carbon dot based nanopowders and their application for fingerprint recovery.

The incorporation of a minor amount of carbogenic nanoparticles into powder compositions imparts remarkable colour-tuneability, without compromising the flowability. In a proof-of-concept demonstration we report the use of these hybrid nanopowders for the visual enhancement of latent fingerprints where they effectively resolve issues arising from poor contrast against multi-coloured or patterned backgrounds.

Self-suspended permanent magnetic FePt ferrofluids.

We present the synthesis and characterization of a new class of self-suspended ferrofluids that exhibit remanent magnetization at room temperature. Our system relies on the chemisorption of a thiol-terminated ionic liquid with very low melting point on the surface of L10 FePt nanoparticles. In contrast, all types of ferrofluids previously reported employ either volatile solvents as the suspending media or superparamagnetic iron oxide nanoparticles (that lacks permanent magnetization) as the inorganic component.

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.

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.

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.

Nafion as cosurfactant: solubilization of nafion in water in the presence of Pluronics.

Incorporation of Nafion to aqueous solutions of Pluronics adversely impacts micellization due to extensive Nafion/copolymer interactions. Light scattering and zeta potential measurements provide evidence for the formation of sizable and stable Nafion/copolymer complexes, in expense of the neat copolymer micelles. At high copolymer concentrations, the overall interaction diagram of Nafion/copolymer reflects the competitive action of the release of packing constraints due to micellar destabilization induced by Nafion on one hand and the gelator nature of the Nafion on the other.

Interactions of an anionic surfactant with poly(oxyalkylene) copolymers in aqueous solution.

The interactions of sodium dodecyl sulfate (SDS) with poly(ethylene oxide)/poly(alkylene oxide) (E/A) block copolymers are explored in this study. With respect to the specific compositional characteristics of the copolymer, introduction of SDS can induce fundamentally different effects to the self-assembly behavior of E/A copolymer solutions. In the case of the E(18)B(10)-SDS system (E = poly(ethylene oxide) and B = poly(butylene oxide)) development of large surfactant-polymer aggregates was observed.

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.

Interactions of bovine serum albumin with ethylene oxide/butylene oxide copolymers in aqueous solution.

The interactions of bovine serum albumin (BSA) with three ethylene oxide/butylene oxide (E/B) copolymers having different block lengths and varying molecular architectures is examined in this study in aqueous solutions. Dynamic light scattering (DLS) indicates the absence of BSA-polymer binding in micellar systems of copolymers with lengthy hydrophilic blocks. On the contrary, stable protein-polymer aggregates were observed in the case of E 18B 10 block copolymer.

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.

Polymer-surfactant vesicular complexes in aqueous medium.

The introduction of ionic single-tailed surfactants to aqueous solutions of EO(18)BO(10) [EO = poly(ethylene oxide), BO = poly(1,2-butylene oxide), subscripts denote the number of repeating units] leads to the formation of vesicles, as probed by laser scanning confocal microscopy. Dynamic light scattering showed that the dimensions of these aggregates at early stages of development do not depend on the sign of the surfactant head group charge. Small-angle X-ray scattering (SAXS) analysis indicated the coexistence of smaller micelles of different sizes and varying polymer content in solution.