Protein electrochemistry using graphene-based nano-assembly: an ultrasensitive electrochemical detection of protein molecules via nanoparticle-electrode collisions

We describe a new electrochemical detection approach towards single protein molecules (microperoxidase-11, MP-11), which are attached to the surface of graphene nanosheets. The non-covalently functionalized graphene nanosheets exhibit enhanced electroactive surface area, where amplified redox current is produced when graphene nanosheets collide with the electrode.

Atom probe tomography study of the nanoscale heterostructure around an Al20Mn3Cu2 dispersoid in aluminum alloy 2024.

Atom probe tomography (APT) has been used to investigate the surface and sub-surface microstructures of aluminum alloy 2024 (AA2024) in the T3 condition (solution heat treated, cold worked, and naturally aged to a substantially stable condition). This study revealed surface Cu enrichment on the alloy matrix, local chemical structure around a dispersoid Al20Mn3Cu2 particle including a Cu-rich particle and S-phase particle on its external surface. Moreover, there was a significant level of hydrogen within the dispersoid, indicating that it is a hydrogen sink. These observations of the nanoscale structure around the dispersoid particle have considerable implications for understanding both corrosion and hydrogen embrittlement in high-strength aluminum alloys.

Synthesis and preliminary investigations into norbornane-based amphiphiles and their self-assembly

A range of norbornane based amphiphiles, which possess a rigid 'kink' in the centre of amphiphiles, were accessed via a concise four step synthesis. The self-assembly properties of these novel compounds were then investigated and the critical aggregation concentration (CAC), hydrodynamic diameter (DH) by dynamic light scattering (DLS) and their morphology by cryogenic transmission electron microscopy (cryoTEM) and negatively stained transmission electron microscopy (TEM) were determined. These compounds while possessing similar CAC values (50-70 μM) exhibited a wide variety of particle size (60-140 nm) and morphologies, including vesicles, cigar-shaped aggregates and rod-like micelles. Considering the similarities in molecular structure we have proposed that the unique nature of the molecular 'kink' is affecting molecular assembly in which subtle changes in molecular structure have large ramifications on aggregate size and morphology.

RGO/ZnO nanocomposite: an efficient, sustainable, heterogeneous, amphiphilic catalyst for synthesis of 3-substituted indoles in water

A nanocomposite consisting of reduced graphene oxide and zinc oxide nanoparticles (RGO/ZnO) with unique structural features was developed as an efficient, sustainable, amphiphilic, heterogeneous catalyst for the synthesis of various 3-substituted indoles in water. The catalyst was recycled six times without significant loss in catalytic activity. The higher environmental compatibility and sustainability factors such as smaller E-factor and higher atom economy make the present methodology a true green and sustainable process for the synthesis of various biologically important 3-substituted indoles.

Structure and properties of citrate overlayers adsorbed at the aqueous Au(111) interface.

One of the most common means of gold nanoparticle (AuNP) biofunctionalization involves the manipulation of precursor citrate-capped AuNPs via ligand displacement. However, the molecular-level structural characteristics of the citrate overlayer adsorbed at the aqueous Au interface at neutral pH remain largely unknown. Access to atomistic-scale details of these interfaces will contribute much needed insight into how AuNPs can be manipulated and exploited in aqueous solution. Here, the structures of such citrate overlayers adsorbed at the aqueous Au(111) interface at pH 7 are predicted and characterized using atomistic molecular dynamics simulations, for a range of citrate surface densities. We find that the overlayers are disordered in the surface density range considered, and that many of their key characteristics are invariant with surface density. In particular, we predict the overlayers to have 3-D, rather than 2-D, morphologies, with the anions closest to the gold surface being oriented with their carboxylate groups pointing away from the surface. We predict both striped and island morphologies for our overlayers, depending on the citrate surface density, and in all cases we find bare patches of the gold surface are present. Our simulations suggest that both citrate-gold adsorption and citrate-counterion pairing contribute to the stability of these citrate overlayer morphologies. We also calculate the free energy of adsorption at the aqueous Au(111) interface of a single citrate molecule, and compare this with the corresponding value for a single arginine molecule. These findings enable us to predict the conditions under which ligand displacement of surface-adsorbed citrate by arginine may take place. Our findings represent the first steps toward elucidating a more elaborate, detailed atomistic-scale model relating to the biofunctionalization of citrate-capped AuNPs.

Magnetic liquid marbles : Toward “Lab in a Droplet“

Liquid marbles exhibit great potential for use as miniature labs for small-scale laboratory operations, such as experiment and measurement. While important progress has been made recently in exploring their applications as microreactions, “on-line“ measurement of the components inside the liquid still remains a challenge. Herein, it is demonstrated that “on-line“ detection can be realized on magnetic liquid marbles by taking advantage of their unique magnetic opening feature. By partially opening the particle shell, electrochemical measurement is carried out with a miniaturized three-electrode probe and the application of this technique for quantitative measurement of dopamine is demonstrated. Fully opened magnetic liquid marble makes it feasible to detect the optical absorbance of the liquid in a transmission mode. With this optical method, a glucose assay is demonstrated. Moreover, when magnetic particle shell contains low melting point material, e.g., wax, the liquid marble shows a unique encapsulation ability to form a rigid shell after heating, which facilitates the storage of the non-volatile ingredients. These unique features, together with the versatile use as microreactors, enable magnetic liquid marbles to function as a miniature lab (or called “lab in a droplet“), which may find applications in clinical diagnostics, biotechnology, chemical synthesis, and analytical chemistry.

Silver nanoparticles prepared by gamma irradiation across metal-organic framework templates

In this study, we demonstrate for the first time the successful fabrication of well-dispersed ultrafine silver nanoparticles inside metal-organic frameworks through a single step gamma irradiation at room temperature. HKUST-1 crystals are soaked in silver nitrate aqueous solution and irradiated with a Cobalt 60 source across a range of irradiation doses to synthesize highly uniformly distributed silver nano-particles. The average size of the silver nanoparticles across the Ag@HKUST-1 materials is found to vary between 1.4 and 3 nm for dose exposures between 1 and 200 kGy, respectively. The Ag@HKUST-1 hybrid crystals exhibit strong surface plasmon resonance and are highly durable and efficient catalytic materials for the reduction of 4-nitrophenol to 4-aminophenol (up to 14.46 × 10-3 s-1 for 1 kGy Ag@HKUST-1). The crystals can be easily recycled for at least five successive cycles of reaction with a conversion efficiency higher than 99.9%. The gamma irradiation is demonstrated to be an effective and environmental friendly process for the synthesis of nano-particles across confined metal-organic frameworks at room temperature with potential applications in environmental science.

Strain-responsive polyurethane/PEDOT:PSS elastomeric composite fibers with high electrical conductivity

It is a challenge to retain the high stretchability of an elastomer when used in polymer composites. Likewise, the high conductivity of organic conductors is typically compromised when used as filler in composite systems. Here, it is possible to achieve elastomeric fiber composites with high electrical conductivity at relatively low loading of the conductor and, more importantly, to attain mechanical properties that are useful in strain-sensing applications. The preparation of homogenous composite formulations from polyurethane (PU) and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) that are also processable by fiber wet-spinning techniques are systematically evaluated. With increasing PEDOT:PSS loading in the fiber composites, the Young's modulus increases exponentially and the yield stress increases linearly. A model describing the effects of the reversible and irreversible deformations as a result of the re-arrangement of PEDOT:PSS filler networks within PU and how this relates to the electromechanical properties of the fibers during the tensile and cyclic stretching is presented. Conducting elastomeric fibers based on a composite of polyurethane (PU) and PEDOT:PSS, produced by a wet-spinning method, have high electrical conductivity and stretchability. These fibers can sense large strains by changes in resistance. The PU/PEDOT:PSS fiber is optimized to achieve the best strain sensing. PU/PEDOT:PSS fibers can be produced on a large scale and integrated into conventional textiles by weaving or knitting. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Achieving outstanding mechanical performance in reinforced elastomeric composite fibers using large sheets of graphene oxide

A simple fiber spinning method used to fabricate elastomeric composite fibers with outstanding mechanical performance is demonstrated. By taking advantage of the large size of as-prepared graphene oxide sheets (in the order of tens of micrometers) and their liquid crystalline behavior, elastomeric composite fibers with outstanding low strain properties have been fabricated without compromising their high strain properties. For example, the modulus and yield stress of the parent elastomer improved by 80- and 40-fold, respectively, while maintaining the high extensibility of ∼400% strain inherent to the parent elastomer. This outstanding mechanical performance was shown to be dependent upon the GO sheet size. Insights into how both the GO sheet size dimension and dispersion parameters influence the mechanical behavior at various applied strains are discussed.

Design, characterization and application of a novel mono-layer pin-microvalve for microfluidic devices

Valves are one of the key components in microfluidic devices to control the fluid flow. In this paper we introduce a novel manual pin-valve which can operate in both analogue (partially close) and digital (on/off) states. We also demonstrate implementation of this pin-valve in a hydrodynamic flow focusing (HFF) device. © The Royal Society of Chemistry 2014.

Ultrafine PDMS fibers: Preparation from in situ curing-electrospinning and mechanical characterization

Polydimethylsiloxane (PDMS) fibers with unexpected elasticity were prepared by a modified core-shell electrospinning method using a commercially-available liquid PDMS precursor (Sylgard 184) and polyvinylpyrrolidone (PVP) as core and sheath materials, respectively. The liquid PDMS precursor was crosslinked in situ to form a solid core when the newly-electrospun core-sheath nanofibers were deposited onto a hot-plate electrode collector. After dissolving the PVP sheath layer off the fibers, net PDMS fibers showed larger average diameter than core-sheath fibers, with an average diameter around 1.35 μm. The tensile properties of both single fibers and fibrous mats were measured. Single PDMS fibers had a tensile strength and elongation at break of 6.0 MPa and 212%, respectively, which were higher than those of PDMS cast film (4.9 MPa, 93%). The PDMS fiber mat had larger elongation at break than the single PDMS fibers, which can be drawn up to 403% their original length. Cyclic loading tests indicated a Mullin effect on the PDMS fiber mats. Such a superior elastic feature was attributed to the PDMS molecular orientation within fibers and the randomly-orientated fibrous structure. Highly-elastic, ultrafine PDMS fibers may find applications in strain sensors, biomedical engineering, wound healing, filtration, catalysis, and functional textiles. © The Royal Society of Chemistry 2014.

Core-spun carbon nanotube yarn supercapacitors for wearable electronic textiles

Linear (fiber or yarn) supercapacitors have demonstrated remarkable cyclic electrochemical performance as power source for wearable electronic textiles. The challenges are, first, to scale up the linear supercapacitors to a length that is suitable for textile manufacturing while their electrochemical performance is maintained or preferably further improved and, second, to develop practical, continuous production technology for these linear supercapacitors. Here, we present a core/sheath structured carbon nanotube yarn architecture and a method for one-step continuous spinning of the core/sheath yarn that can be made into long linear supercapacitors. In the core/sheath structured yarn, the carbon nanotubes form a thin surface layer around a highly conductive metal filament core, which serves as current collector so that charges produced on the active materials along the length of the supercapacitor are transported efficiently, resulting in significant improvement in electrochemical performance and scale up of the supercapacitor length. The long, strong, and flexible threadlike supercapacitor is suitable for production of large-size fabrics for wearable electronic applications.

An improved understanding of the dispersion of multi-walled carbon nanotubes in non-aqueous solvents

The homogeneous and stable dispersion of carbon nanotubes (CNTs) in solvents is often a prerequisite for their use in advanced materials. Dispersion procedures, reagent concentration as well as the interactions among reagent, defective CNTs and near-perfect CNTs will affect the resulting CNT dispersion properties. This study, for the first time, presents a detailed comparison between two different approaches for dispersing CNTs. The results enhance our understanding of the interactions between surfactant, defective CNTs and near-perfect CNTs and thus provide insight into the mechanism of CNT dispersion. Dispersions of "as-produced" short multi-walled carbon nanotubes (MWCNTs) in N,N-dimethylformamide were prepared by two different surfactant (Triton X-100) assisted methods: ultrasonication and ultrasonication followed by centrifugation, decanting the supernatant and redispersing the precipitate. Visual observation and UV-visible spectroscopy results showed that the latter method produce a more stable dispersion with higher MWCNT content compared to dispersions produced by ultrasonication alone. Transmission electron microscopy and Raman spectroscopic investigations revealed that the centrifugation/ decanting step removed highly defective nanotubes, amorphous carbon and excess surfactant from the readily re-dispersible near-perfect CNT precipitate. This is contrary to other published findings where the dispersed MWCNTs were found in the supernatant. Thermogravimetric analysis showed that 95 % of Triton X-100 was removed by centrifugation/decanting step, and the remainder of the Triton X-100 molecules is likely randomly adsorbed onto the MWCNT surface. Infrared spectral analysis suggests that the methylene groups of the polyoxyethylene (aliphatic ether) chains of the residual Triton X-100 molecules are interacting with the MWCNTs. © 2014 Springer Science+Business Media.

Biocompatibility of transition metal-substituted cobalt ferrite nanoparticles

Transition metals of copper, zinc, manganese, and nickel were substituted into cobalt ferrite nanoparticles via a sol-gel route using citric acid as a chelating agent. The microstructure and elemental compositions of the nanoparticles were characterized using scanning electron microscopy combined with energy dispersive X-ray spectroscopy. The particle size of the nanoparticles was investigated using particle size analyzer, and the zeta potentials were measured using zeta potential analyzer. The phase components of the synthesized transition metal-substituted cobalt ferrite nanoparticles were studied using Raman spectroscopy. The biocompatibility of the nanoparticles was assessed using osteoblast-like cells. Results indicated that the substitution of transition metals strongly influences the physical, chemical properties, and biocompatibility of the cobalt ferrite nanoparticles. © 2014 Springer Science+Business Media.

Annihilation electrogenerated chemiluminescence of mixed metal chelates in solution : Modulating emission colour by manipulating the energetics

We demonstrate the mixed annihilation electrogenerated chemiluminescence of tris(2,2′-bipyridine)ruthenium(ii) with various cyclometalated iridium(iii) chelates. Compared to mixed ECL systems comprising organic luminophores, the absence of T-route pathways enables effective predictions of the observed ECL based on simple estimations of the exergonicity of the reactions leading to excited state production. Moreover, the multiple, closely spaced reductions and oxidations of the metal chelates provide the ability to finely tune the energetics and therefore the observed emission colour. Distinct emissions from multiple luminophores in the same solution are observed in numerous systems. The relative intensity of these emissions and the overall emission colour are dependent on the particular oxidized and reduced species selected by the applied electrochemical potentials. Finally, these studies offer insights into the importance of electronic factors in the question of whether the reduced or oxidized partner becomes excited in annihilation ECL. This journal is