Charge mediated semiconducting-to-metallic phase transition in molybdenum disulfide monolayer and hydrogen evolution reaction in new 1T′ phase

The phase transition of single layer molybdenum disulfide (MoS2) from semiconducting 2H to metallic 1T and then to 1T′ phases, and the effect of the phase transition on hydrogen evolution reaction (HER) are investigated within this work by density functional theory. Experimentally, 2H-MoS2 has been widely used as an excellent electrode for HER and can get charged easily. Here we find that the negative charge has a significant impact on the structural phase transition in a MoS2 monolayer. The thermodynamic stability of 1T-MoS2 increases with the negative charge state, comparing with the 2H-MoS2 structure before phase transition and the kinetic energy barrier for a phase transition from 2H to 1T decreases from 1.59 to 0.27 eV when 4e– are injected per MoS2 unit. Additionally, 1T phase is found to transform into the distorted structure (1T′ phase) spontaneously. On their activity toward hydrogen evolution reaction, 1T′-MoS2 structure shows comparable hydrogen evolution reaction activity to the 2H-MoS2 structure. If the charge transfer kinetics is taken into account, the catalytic activity of 1T′-MoS2 is superior to that of 2H-MoS2. Our finding provides a possible novel method for phase transition of MoS2 and enriches understanding of the catalytic properties of MoS2 for HER.

Effect of covalent functionalisation on thermal transport across graphene-polymer interfaces

This paper is concerned with the interfacial thermal resistance for polymer composites reinforced by various covalently functionalised graphene. By using molecular dynamics simulations, the obtained results show that the covalent functionalisation in graphene plays a significant role in reducing the graphene-paraffin interfacial thermal resistance. This reduction is dependent on the coverage and type of functional groups. Among the various functional groups, butyl is found to be the most effective in reducing the interfacial thermal resistance, followed by methyl, phenyl and formyl. The other functional groups under consideration such as carboxyl, hydroxyl and amines are found to produce negligible reduction in the interfacial thermal resistance. For multilayer graphene with a layer number up to four, the interfacial thermal resistance is insensitive to the layer number. The effects of the different functional groups and the layer number on the interfacial thermal resistance are also elaborated using the vibrational density of states of the graphene and the paraffin matrix. The present findings provide useful guidelines in the application of functionalised graphene for practical thermal management.

Magnetic nanoparticles boosting the osmotic efficiency of a polymeric FO draw agent: Effect of polymer conformation

Poly sodium acrylate (PSA)-coated Magnetic Nanoparticles (PSA-MNPs) were synthesized as smart osmotic draw agent (SMDA) for water desalination by forward osmosis (FO) process. The PSA-coated MNPs demonstrated significantly higher osmotic pressure (~ 30 fold) as well as high FO water flux (~ 2–3 fold) when compared to their polymer (polyelectrolyte) counterpart, even at a very low concentration of ~ 0.13 wt.% in the draw solution. The PSA polymer chain conformation – coiled to extended – demonstrates a significant impact on the availability of the polymer hydrophilic groups in solution which is the driving force to attain higher osmotic pressure and water flux. When an optimum concentration of the polymer was anchored to a NP surface, the polymer chains assume an extended open conformation making the functional hydrophilic groups available to attract water molecules. This in turn boosts the osmotic pressure and FO water flux of the PSA-MNP draw agents. The low concentration of the PSA-MNP osmotic agent and the associated high water flux enhances the cost-effectiveness of our proposed SMDA system. In addition, easier magnetic separation and regeneration of the SMDA also improves its usability making it efficient, cost-effective and environment-friendly.

Developing starch-based polymer composites

This project aim was to replace petroleum-based plastic packaging materials that pollute the environment, with biodegradable starch-based polymer composites. It was demonstrated that untreated sugar cane bagasse microfibres and unbleached nanofibres significantly improved the physical, mechanical and chemical properties of starch films, while thermal extrusion of starch with alcohol improved the stiffness and the addition of aconitic acid cross-linked the film making it moisture resistant and extensible.

Efficient and bright polymer light emitting field effect transistors

Light emitting field effect transistors (LEFETs) are emerging as a multi-functional class of optoelectronic devices. LEFETs can simultaneously execute light emission and the standard logic functions of a transistor in a single architecture. However, current LEFET architectures deliver either high brightness or high efficiency but not both concurrently, thus limiting their use in technological applications. Here we show an LEFET device strategy that simultaneously improves brightness and efficiency. The key step change in LEFET performance arises from the bottom gate top-contact device architecture in which the source/drain electrodes are semitransparent and the active channel contains a bi-layer comprising of a high mobility charge-transporting polymer, and a yellow-green emissive polymer. A record external quantum efficiency (EQE) of 2.1% at 1000cd/m2 is demonstrated for polymer based bilayer LEFETs.

Ultra-flexible nonvolatile memory based on donor-acceptor diketopyrrolopyrrole polymer blends

Flexible memory cell array based on high mobility donor-acceptor diketopyrrolopyrrole polymer has been demonstrated. The memory cell exhibits low read voltage, high cell-to-cell uniformity and good mechanical flexibility, and has reliable retention and endurance memory performance. The electrical properties of the memory devices are systematically investigated and modeled. Our results suggest that the polymer blends provide an important step towards high-density flexible nonvolatile memory devices.

Hole mobility of 3.56 cm2V−1s−1accomplished using more extended dithienothiophene with furan flanked diketopyrrolopyrrole polymer

A highly extended dithienothiophene comonomer building block was used in combination with highly fused aromatic furan substituted diketopyrrolopyrrole for the synthesis of novel donor–acceptor alternating copolymer PDPPF-DTT. Upon testing PDPPF-DTT as a channel semiconductor in top contact bottom gate organic field effect transistors (OFETs), it was found to exhibit p-channel behaviour. The highest hole mobility of 3.56 cm2 V−1 s−1 was reported for PDPPF-DTT. To our knowledge, this is the highest mobility reported so far for the furan flanked diketopyrrolopyrrole class of copolymers using conventional device geometry with straightforward processing.

Single-walled carbon nanotube-based polymer monoliths for the enantioselective nano-liquid chromatographic separation of racemic pharmaceuticals

Many protocols have been used for extraction of DNA from Thraustochytrids. These generally involve the use of CTAB, phenol/chloroform and ethanol. They also feature mechanical grinding, sonication, N2 freezing or bead beating. However, the resulting chemical and physical damage to extracted DNA reduces its quality. The methods are also unsuitable for large numbers of samples. Commercially-available DNA extraction kits give better quality and yields but are expensive. Therefore, an optimized DNA extraction protocol was developed which is suitable for Thraustochytrids to both minimise expensive and time-consuming steps prior to DNA extraction and also to improve the yield. The most effective method is a combination of single bead in TissueLyser (Qiagen) and Proteinase K. Results were conclusive: both the quality and the yield of extracted DNA were higher than with any other method giving an average yield of 8.5 µg/100 mg biomass.

Synthesis of a multimodal molecular imaging probe based on a hyperbranched polymer architecture

Molecular imaging is utilised in modern medicine to aid in the diagnosis and treatment of disease by allowing its spatiotemporal state to be examined in vivo. This study focuses on the development of novel multimodal molecular imaging agents based on hyperbranched polymers that combine the complementary capabilities of optical fluorescence imaging and positron emission tomography-computed tomography (PET/CT) into one construct. RAFT-mediated polymerisation was used to prepare two hydrophilic hyperbranched polymers that were differentiated by their size and level of branching. The multiple functional end-groups facilitated covalent attachment of both near infrared fluorescent dyes for optical imaging, as well as a copper chelator allowing binding of 64Cu as a PET radio nuclei. In vivo multimodal imaging of mice using PET/CT and planar optical imaging was first used to assess the biodistribution of the polymeric materials and it was shown that the larger and more branched polymer had a significantly longer circulation time. The larger constructs were also shown to exhibit enhanced accumulation in solid tumours in a murine B16 melanoma model. Importantly, it was demonstrated that the PET modality gave rise to high sensitivity immediately after injection of the agent, while the optical modality facilitated extended longitudinal studies, thus highlighting how the complementary capabilities of the molecular imaging agents can be useful for studying various diseases, including cancer.

Multimodal polymer nanoparticles with combined 19F magnetic resonance and optical detection for tunable, targeted, multimodal imagingin vivo

Understanding the complex nature of diseased tissue in vivo requires development of more advanced nanomedicines, where synthesis of multifunctional polymers combines imaging multimodality with a biocompatible, tunable, and functional nanomaterial carrier. Here we describe the development of polymeric nanoparticles for multimodal imaging of disease states in vivo. The nanoparticle design utilizes the abundant functionality and tunable physicochemical properties of synthetically robust polymeric systems to facilitate targeted imaging of tumors in mice. For the first time, high-resolution 19F/1H magnetic resonance imaging is combined with sensitive and versatile fluorescence imaging in a polymeric material for in vivo detection of tumors. We highlight how control over the chemistry during synthesis allows manipulation of nanoparticle size and function and can lead to very high targeting efficiency to B16 melanoma cells, both in vitro and in vivo. Importantly, the combination of imaging modalities within a polymeric nanoparticle provides information on the tumor mass across various size scales in vivo, from millimeters down to tens of micrometers.

Preliminary investigations into the use of a functionalised polymer to reduce diffusion in Fricke gel dosimeters

Purpose A modification of the existing PVA-​FX hydrogel has been made to investigate the use of a functionalised polymer in a Fricke gel dosimetry system to decrease Fe3+ diffusion. Methods The chelating agent, xylenol orange, was chem. bonded to the gelling agent, polyvinyl alc. (PVA) to create xylenol orange functionalised PVA (XO-​PVA)​. A gel was created from the XO-​PVA (20​% w​/v) with ferrous sulfate (0.4 mM) and sulfuric acid (50 mM)​. Results This resulted in an optical d. dose sensitivity of 0.014 Gy-​1, an auto-​oxidn. rate of 0.0005 h-​1, and a diffusion rate of 0.129 mm2 h-​1; an 8​% redn. compared to the original PVA-​FX gel, which in practical terms adds approx. 1 h to the time span between irradn. and accurate read-​out. Conclusions Because this initial method of chem. bonding xylenol orange to polyvinyl alc. has inherently low conversion, the improvement on existing gel systems is minimal when compared to the drawbacks. More efficient methods of functionalising polyvinyl alc. with xylenol orange must be developed for this system to gain clin. relevance.

Polymer encapsulation of magnesium to control biodegradability and biocompatibility

Clinical utility of biodegradable magnesium implants is undermined by the untimely degradation of these materials in vivo. Their high corrosion rate leads to loss of mechanical integrity, peri–implant alkalization and localised accumulation of hydrogen gas. Biodegradable coatings were produced on pure magnesium using RF plasma polymerisation. A monoterpene alcohol with known anti-inflammatory and antibacterial properties was used as a polymer precursor. The addition of the polymeric layer was found to reduce the degradation rate of magnesium in simulated body fluid. The in vitro studies indicated good cytocompatibility of non-adherent THP–1 cells and mouse macrophage cells with the polymer, and the polymer coated sample. The viability of THP–1 cells was significantly improved when in contact with polymer encapsulated magnesium compared to unmodified samples. Collectively, these results suggest plasma enhanced polymer encapsulation of magnesium as a suitable method to control degradation kinetics of this biomaterial.

Wetting, solubility and chemical characteristics of plasma-polymerized 1-isopropyl-4-methyl-1,4-cyclohexadiene thin films

Investigations on the wetting, solubility and chemical composition of plasma polymer thin films provide an insight into the feasibility of implementing these polymeric materials in organic electronics, particularly where wet solution processing is involved. In this study, thin films were prepared from 1-isopropyl-4-methyl-1,4-cyclohexadiene (γ-Terpinene) using radio frequency (RF) plasma polymerization. FTIR showed the polymers to be structurally dissimilar to the original monomer and highly cross-linked, where the loss of original functional groups and the degree of cross-linking increased with deposition power. The polymer surfaces were hydrocarbon-rich, with oxygen present in the form of O–H and C=O functional groups. The oxygen content decreased with deposition power, with films becoming more hydrophobic and, thus, less wettable. The advancing and receding contact angles were investigated, and the water advancing contact angle was found to increase from 63.14° to 73.53° for thin films prepared with an RF power of 10 W to 75 W. The wetting envelopes for the surfaces were constructed to enable the prediction of the surfaces’ wettability for other solvents. The effect of roughness on the wetting behaviour of the films was insignificant. The polymers were determined to resist solubilization in solvents commonly used in the deposition of organic semiconducting layers, including chloroform and chlorobenzene, with higher stability observed in films fabricated at higher RF power.

Fabrication and characterization of RF plasma polymerized thin films from 3,7-dimethyl-1,6-octadien-3-ol for electronic and biomaterial applications

Poly(linalool) thin films were fabricated using RF plasma polymerisation. All films were found to be smooth, defect-free surfaces with average roughness of 0.44 nm. The FTIR analysis of the polymer showed a notable reduction in –OH moiety and complete dissociation of C=C unsaturation compared to the monomer, and presence of a ketone band absent from the spectrum of the monomer. Poly(linalool) were characterised by chain branching and a large quantity of short polymer chains. Films were optically transparent, with refractive index and extinction coefficient of 1.55 and 0.001 (at 500 nm) respectively, indicating a potential application as an encapsulating (protective) coating for circuit boards. The optical band gap was calculated to be 2.82 eV, which is in the semiconducting energy gap region.

Synthesis of radio frequency plasma polymerized non-synthetic Terpinen-4-ol thin films

Recent advancements in the area of organic polymer applications demand novel and advanced materials with desirable surface, optical and electrical properties to employ in emerging technologies. This study examines the fabrication and characterization of polymer thin films from non-synthetic Terpinen-4-ol monomer using radio frequency plasma polymerization. The optical properties, thickness and roughness of the thin films were studied in the wavelength range 200–1000 nm using ellipsometry. The polymer thin films of thickness from 100 nm to 1000 nm were fabricated and the films exhibited smooth and defect-free surfaces. At 500 nm wavelength, the refractive index and extinction coefficient were found to be 1.55 and 0.0007 respectively. The energy gap was estimated to be 2.67 eV, the value falling into the semiconducting Eg region. The obtained optical and surface properties of Terpinen-4-ol based films substantiate their candidacy as a promising low-cost material with potential applications in electronics, optics, and biomedical industries.