Alkali Cation Doping for Improving the Structural Stability of 2D Perovskite in 3D/2D PSCs.

3D/2D hybrid perovskite systems have been intensively investigated to improve the stability of perovskite solar cells (PSCs), whereas undesired crystallization of 2D perovskite during the film formation process could undermine the structural stability of 2D perovskite materials, which causes serious hysteresis of PSCs after aging. This issue is, however, rarely studied. The stability study for 3D/2D hybrid systems to date is all under the one-direction scan, and the lack of detailed information on the hysteresis after aging compromises the credibility of the stability results. In this work, by correlating the hysteresis of the hybrid PSCs with the 2D crystal structure, we find that the prompt 2D perovskite formation process easily induces numerous crystal imperfections and structural defects. These defects are susceptible to humidity attack and decompose the 2D perovskite to insulating long-chain cations and 3D perovskite, which hinder charge transfer or generate charge accumulation. Therefore, a large hysteresis is exhibited after aging the 3D/2D hybrid PSCs in an ambient environment, even though the reverse-scan power conversion efficiency (PCE) is found to be well-preserved. To address this issue, alkali cations, K+ and Rb+, are introduced into the 2D perovskite to exquisitely modulate the crystal formation, which gives rise to a higher crystallinity of 2D perovskite and a better film morphology with fewer defects. We achieved PCE beyond 21% due to the preferable charge transfer process and reduced nonradiative recombination losses. The structural features also bring about impressive moisture stability, which results in the corresponding PSCs retaining 93% of its initial PCE and negligible hysteresis after aging in an ambient atmosphere for 1200 h.

Antibody-Binding, Antifouling Surface Coatings Based on Recombinant Expression of Zwitterionic EK Peptides.

Development of antifouling films which selectively capture or target proteins of interest is essential for controlling interactions at the "bio/nano" interface. However, in order to synthesize biofunctional films from synthetic polymers that incorporate chemical "motifs" for surface immobilization, antifouling, and oriented biomolecule attachment, multiple reaction steps need to be carried out at the solid/liquid interface. EKx is a zwitterionic peptide that has previously been shown to have excellent antifouling properties. In this study, we recombinantly expressed EKx peptides and genetically encoded both surface attachment and antibody-binding motifs, before characterizing the resultant biopolymers by traditional methods. These peptides were then immobilized to organosilica nanoparticles for binding IgG, and subsequently capturing dengue NS1 as a model antigen from serum-containing solution. We found that a mixed layer of a short peptide (4.9 kDa) "backfilled" with a longer peptide terminated with an IgG-binding Z-domain (18 kDa) demonstrated selective capture of dengue NS1 protein down to ∼10 ng mL-1 in either PBS or 20% serum.

Tunable Biogenic Manganese Oxides.

Influence of the conditions for aerobic oxidation of Mn2+(aq) catalysed by the MnxEFG protein complex on the morphology, structure and reactivity of the resulting biogenic manganese oxides (MnOx ) is explored. Physical characterisation of MnOx includes scanning and transmission electron microscopy, and X-ray photoelectron and K-edge Mn, Fe X-ray absorption spectroscopy. This characterisation reveals that the MnOx materials share the structural features of birnessite, yet differ in the degree of structural disorder. Importantly, these biogenic products exhibit strikingly different morphologies that can be easily controlled. Changing the substrate-to-protein ratio produces MnOx either as nm-thin sheets, or rods with diameters below 20 nm, or a combination of the two. Mineralisation in solutions that contain Fe2+(aq) makes solids with significant disorder in the structure, while the presence of Ca2+(aq) facilitates formation of more ordered materials. The (photo)oxidation and (photo)electrocatalytic capacity of the MnOx minerals is examined and correlated with their structural properties.

Investigation of the potential for direct compaction of a fine ibuprofen powder dry-coated with magnesium stearate.

Intensive dry powder coating (mechanofusion) with tablet lubricants has previously been shown to give substantial powder flow improvement. This study explores whether the mechanofusion of magnesium stearate (MgSt), on a fine drug powder can substantially improve flow, without preventing the powder from being directly compacted into tablets. A fine ibuprofen powder, which is both cohesive and possesses a low-melting point, was dry coated via mechanofusion with between 0.1% and 5% (w/w) MgSt. Traditional low-shear blending was also employed as a comparison. No significant difference in particle size or shape was measured following mechanofusion. For the low-shear blended powders, only marginal improvement in flowability was obtained. However, after mechanofusion, substantial improvements in the flow properties were demonstrated. Both XPS and ToF-SIMS demonstrated high degrees of a nano-scale coating coverage of MgSt on the particle surfaces from optimized mechanofusion. The study showed that robust tablets were produced from the selected mechanofused powders, at high-dose concentration and tablet tensile strength was further optimized via addition of a Polyvinylpyrrolidone (PVP) binder (10% w/w). The tablets with the mechanofused powder (with or without PVP) also exhibited significantly lower ejection stress than those made of the raw powder, demonstrating good lubrication. Surprisingly, the release rate of drug from the tablets made with the mechanofused powder was not retarded. This is the first study to demonstrate such a single-step dry coating of model drug with MgSt, with promising flow improvement, flow-aid and lubrication effects, tabletability and also non-inhibited dissolution rate.

Effect of surface coating with magnesium stearate via mechanical dry powder coating approach on the aerosol performance of micronized drug powders from dry powder inhalers.

The objective of this study was to investigate the effect of particle surface coating with magnesium stearate on the aerosolization of dry powder inhaler formulations. Micronized salbutamol sulphate as a model drug was dry coated with magnesium stearate using a mechanofusion technique. The coating quality was characterized by X-ray photoelectron spectroscopy. Powder bulk and flow properties were assessed by bulk densities and shear cell measurements. The aerosol performance was studied by laser diffraction and supported by a twin-stage impinger. High degrees of coating coverage were achieved after mechanofusion, as measured by X-ray photoelectron spectroscopy. Concomitant significant increases occurred in powder bulk densities and in aerosol performance after coating. The apparent optimum performance corresponded with using 2% w/w magnesium stearate. In contrast, traditional blending resulted in no significant changes in either bulk or aerosolization behaviour compared to the untreated sample. It is believed that conventional low-shear blending provides insufficient energy levels to expose host micronized particle surfaces from agglomerates and to distribute guest coating material effectively for coating. A simple ultra-high-shear mechanical dry powder coating step was shown as highly effective in producing ultra-thin coatings on micronized powders and to substantially improve the powder aerosolization efficiency.

Anti-infective characteristics of a new Carbothane ventricular assist device driveline.

Objectives: Driveline infections are a major complication of ventricular assist device (VAD) therapy. A newly introduced Carbothane driveline has preliminarily demonstrated anti-infective potential against driveline infections. This study aimed to comprehensively assess the anti-biofilm capability of the Carbothane driveline and explore its physicochemical characteristics. Methods: We assessed the Carbothane driveline against biofilm formation of leading microorganisms causing VAD driveline infections, including Staphylococcus aureus, Staphylococcus epidermidis, Pseudomonas aeruginosa and Candida albicans, using novel in vitro biofilm assays mimicking different infection micro-environments. The importance of physicochemical properties of the Carbothane driveline in microorganism-device interactions were analyzed, particularly focusing on the surface chemistry. The role of micro-gaps in driveline tunnels on biofilm migration was also examined. Results: All organisms were able to attach to the smooth and velour sections of the Carbothane driveline. Early microbial adherence, at least for S. aureus and S. epidermidis, did not proceed to the formation of mature biofilms in a drip-flow biofilm reactor mimicking the driveline exit site environment. The presence of a driveline tunnel however, promoted staphylococcal biofilm formation on the Carbothane driveline. Physicochemical analysis of the Carbothane driveline revealed surface characteristics that may have contributed to its anti-biofilm activity, such as the aliphatic nature of its surface. The presence of micro-gaps in the tunnel facilitated biofilm migration of the studied bacterial species. Conclusion: This study provides experimental evidence to support the anti-biofilm activity of the Carbothane driveline and uncovered specific physicochemical features that may explain its ability to inhibit biofilm formation.

Localized deoxygenation and direct patterning of graphene oxide films by focused ion beams.

Exposure to controlled doses (~4.65 × 10(-3) to 2.79 × 10(-2) nC/µm(2) ion fluence) of Ga ions via a focused ion beam (FIB) deoxygenates graphene oxide (GO) and increases the electrical conductivity in 100 × 100 µm(2) patches by several orders of magnitude compared to that in unexposed GO. Raman spectra and the carbon/oxygen ratio in exposed areas are indicative of chemically reduced graphene oxide (rGO). This novel FIB-induced conversion technique is harnessed for the direct imprinting of complex micrometer-scale shapes and sub-20-nm lines of rGO in insulating films and flakes of GO establishing the capability of generating features varying in size from approximately tens of nanometers to approximately hundreds of micrometers in a maskless, efficient manner.

Azide photochemistry for facile modification of graphitic surfaces: preparation of DNA-coated carbon nanotubes for biosensing.

A facile, two-step method for chemically attaching single-stranded DNA to graphitic surfaces, represented here by carbon nanotubes, is reported. In the first step, an azide-containing compound, N-5-azido-nitrobenzoyloxy succinimide (ANB-NOS), is used to form photo-adducts on the graphitic surfaces in a solid-state photochemical reaction, resulting in active ester groups being oriented for the subsequent reactions. In the second step, pre-synthesized DNA strands bearing a terminal amine group are coupled in an aqueous solution with the active esters on the photo-adducts. The versatility of the method is demonstrated by attaching pre-synthesized DNA to surfaces of carbon nanotubes in two platforms-as vertically-aligned multi-walled carbon nanotubes on a solid support and as tangled single-walled carbon nanotubes in mats. The reaction products at various stages were characterized by x-ray photoelectron spectroscopy. Two different assays were used to check that the DNA strands attached to the carbon nanotubes were able to bind their partner strands with complementary base sequences. The first assay, using partner DNA strands tethered to gold nanoparticles, enabled the sites of DNA attachment to the carbon nanotubes to be identified in TEM images. The second assay, using radioactively labelled partner DNA strands, quantified the density of functional DNA strands attached to the carbon nanotubes. The diversity of potential applications for these DNA-modified carbon-nanotube platforms is exemplified here by the successful use of a DNA-modified single-walled carbon-nanotube mat as an electrode for the specific detection of metal ions.

Fabrication of a Reusable Carbon Dot/Gold Nanoparticle/Metal-Organic Framework Film for Fluorescence Detection of Lead Ions in Water.

Solid-state sensing platforms are desirable for the development of reusable sensors to promote public health measures such as testing for drinking water contamination. A bioinspired metal-organic framework (MOF)-based material has been developed by imitating metal-protein interactions in biological systems to attain high sensitivity and selectivity to Pb2+ through fluorescence sensing. A zirconium terephthalate-type framework (also known as NH2-UiO-66) was modified with both gold nanoparticles and thiol-functionalized carbon dots to give HS-C/Au(x)/UiO-66 composites with different Au content (x) and were subsequently adapted into films that show extraordinary sensitivity to Pb2+. The HS-C/Au(1.4)/UiO-66 film that consists of 1.4 wt % Au shows a quenching response with the limit of detection of 80 parts per trillion and sustained performance for five cycles. Moreover, the fluorescence response of the HS-C/Au(x)/UiO-66 film to Pb2+ can be reversed from emission quenching to enrichment of fluorescence by increasing the Au content. The performance of the HS-C/Au(x)/UiO-66 film as a solid-state sensor demonstrates its potential for application in reusable sensing devices to ensure public safety from Pb2+ contamination in drinking water.

Green ammonia synthesis using CeO2/RuO2 nanolayers on vertical graphene catalyst via electrochemical route in alkaline electrolyte.

The electrochemical synthesis of ammonia at ambient temperature and pressure has the potential to replace the conventional process for the production of ammonia. However, the low ammonia yield and poor long-term stability of catalysts for the synthesis of ammonia hinders the application of this technology. Herein, we endeavored to tackle this challenge by synthesizing 3-D vertical graphene (VG) on Ni foam via a one-step, low-temperature plasma process, which offered high conductivity and large surface area. Subsequently, the vertical graphene on Ni foam was loaded with nanolayers of ruthenium oxide (RuO2, ∼2 nm) and cerium oxide (CeO2, <20 nm) nanoparticles via magnetron sputtering. The incorporation of nanoparticle layers (RuO2 and CeO2/RuO2) on VG significantly increased the NH3 yield in KOH electrolyte. Finally, the performance and long-term stability of this composite material were successfully demonstrated by the addition of CeO2/RuO2 nanolayers on the VG electrocatalyst. The catalyst achieved an excellent performance with a high ammonia synthesis yield of 50.56 µg mgtotal cat.-1 h-1 (1.11 × 10-10 mol cm-2 s-1) during the performance evaluation period of 36 h. This observation was also verified by density functional theory calculation, where CeO2 exhibited the best catalytic performance compared to RuO2 and pristine graphene.

One-step method for generating PEG-like plasma polymer gradients: chemical characterization and analysis of protein interactions.

In this work we report a one-step method for the fabrication of poly(ethylene glycol) PEG-like chemical gradients, which were deposited via continuous wave radio frequency glow discharge plasma polymerization of diethylene glycol dimethyl ether (DG). A knife edge top electrode was used to produce the gradient coatings at plasma load powers of 5 and 30 W. The chemistry across the gradients was analyzed using a number of complementary techniques including spatially resolved synchrotron source grazing incidence FTIR microspectroscopy, X-ray photoelectron spectroscopy (XPS) and synchrotron source near edge X-ray absorption fine structure (NEXAFS) spectroscopy. Gradients deposited at lower load power retained a higher degree of monomer like functionality as did the central region directly underneath the knife edge electrode of each gradient film. Surface derivatization experiments were employed to investigate the concentration of residual ether units in the films. In addition, surface derivatization was used to investigate the reactivity of the gradient films toward primary amine groups in a graft copolymer of poly (L-lysine) and poly(ethylene glycol) (PLL-g-PEG copolymer) which was correlated to residual aldehyde, ketone and carboxylic acid functionalities within the films. The protein adsorption characteristics of the gradients were analyzed using three proteins of varying size and charge. Protein adsorption varied and was dependent on the chemistry and the physical properties (such as size and charge) of the proteins. A correlation between the concentration of ether functionality and the protein fouling characteristics along the gradient films was observed. The gradient coating technique developed in this work allows for the efficient and high-throughput study of biomaterial gradient coating interactions.

Interactions of lens care with silicone hydrogel lenses and effect on comfort.

PURPOSE: The purpose of this study was to investigate the effect of lens care products on short-term subjective and physiological performance silicone hydrogel lenses. METHODS: Ten subjects wore either lotrafilcon B or galyfilcon A silicone hydrogel contact lenses soaked in a lens care product containing either Polyquad/Aldox or PHMB or control lenses inserted directly from the pack. Subjects wore the lenses for 6 h. Ocular comfort (graded on a 1 to 10 scale) and ocular physiology were assessed. Unworn but soaked lenses were analyzed for metrological changes, release of excipients into phosphate buffered saline, and changes to their surface chemical composition. RESULTS: None of the lens metrology measures or clinically observed conjunctival or limbal redness changed. Corneal staining was significantly (p < 0.008) raised, albeit to low levels, after 6 h wear for either lens type when soaked in the PHMB solution compared with the control lens (lotrafilcon B 0.4 to 0.9 ± 0.7 to 0.4 vs. 0.1 to 0.4 ± 0.3 to 0.5; galyfilcon A 0.2 to 0.3 ± 0.2 to 0.4 vs. 0.0 ± 0.0). For lotrafilcon B lenses, there were decreases in comfort (p = 0.002), increases in burning/stinging (p = 0.002) after 1 h of wear, and increases in lens awareness on lens insertion (p = 0.0001) when soaked in PHMB. However, lotrafilcon B lenses soaked in Polyquad/Aldox showed increases in burning/stinging after 1 and 6 h (p < 0.008) of lens wear. For galyfilcon A lenses, most significant (p ≤ 0.002) changes to symptomatology occurred after soaking in Polyquad/Aldox solution. More PHMB was released from lotrafilcon B lenses, and more MPDS material was released from galyfilcon A lenses. The surface of galyfilcon A lenses changed but irrespective of lens solution type, whereas the changes to the lens surface was dependent on solution type for lotrafilcon B lenses. CONCLUSIONS: Lens care products can change corneal staining and comfort responses during wear. These changes may be associated with release of material soaked into lenses or changes to the lens surface composition.

Fluorocarbon Plasma Gas Passivation Enhances Performance of Porous Silicon for Desorption/Ionization Mass Spectrometry.

Desorption/ionization on porous silicon mass spectrometry (DIOS-MS) is shown to be a powerful technique for the sensing of low-molecular-weight compounds, including drugs and their metabolites. Surface modification of DIOS surfaces is required to increase analytical performance and ensure stability. However, common wet chemical modification techniques use fluorosilanes, which are less suitable for high-throughput manufacturing and analytical repeatability. Here, we report an alternative, rapid functionalization technique for DIOS surfaces using plasma polymerization (ppDIOS). We demonstrate the detection of drugs, metabolites, pesticides, and doping agents, directly from biological matrices, with molecular confirmation performed using the fragmentation capabilities of a tandem MS instrument. Furthermore, the ppDIOS surfaces were found to be stable over a 162 day period with no loss of reproducibility and sensitivity. This alternative functionalization technique is cost-effective and amenable to upscaling, ensuring avenues for the high-throughput manufacture and detection of hundreds of analytes across various applications while still maintaining the gold-standard clinical technique using mass spectrometry.

Three-Dimensional Hierarchical Porous Nanotubes Derived from Metal-Organic Frameworks for Highly Efficient Overall Water Splitting.

Effective design of bifunctional catalysts for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is important but remains challenging. Herein, we report a three-dimensional (3D) hierarchical structure composed of homogeneously distributed Ni-Fe-P nanoparticles embedded in N-doped carbons on nickel foams (denoted as Ni-Fe-P@NC/NF) as an excellent bifunctional catalyst. This catalyst was fabricated by an anion exchange method and a low-temperature phosphidation of nanotubular Prussian blue analogue (PBA). The Ni-Fe-P@NC/NF displayed exceptional catalytic activity toward both HER and OER and delivered an ultralow cell voltage of 1.47 V to obtain 10 mA cm-2 with extremely excellent durability for 100 h when assembled as a practical electrolyser. The extraordinary performance of Ni-Fe-P@NC/NF is attributed to the abundance of unsaturated active sites, the well-defined hierarchical porous structure, and the synergistic effect between multiple components. Our work will inspire more rational designs of highly active non-noble electrocatalysts for industrial energy applications.

Electrochemical oxidation disinfects urban stormwater: Major disinfection mechanisms and longevity tests.

Although electrochemical oxidation (ECO) has shown excellent potential for disinfecting wastewater and surface waters, its application on urban stormwater has been rarely tested. In order to improve stormwater ECO design, this paper explores the major inactivation processes using Boron Doped Diamond (BDD) and titanium Dimensional Stable Anodes (DSA). Both BDD and DSA showed comparable disinfection rates. The mechanism study suggested that BDD relied on hydroxyl radical and the presence of chloride ions, while DSA disinfected stormwater mainly via the production of free­chlorine. A deterioration study carried out at a catchment in Melbourne, showed a steady performance for BDD and revealed that DSA's performance degraded with time, likely linked to the high operational voltage required for specific chemistry of stormwater. Scanning Electron Microscopes and an Energy Dispersive X-ray Detector tests confirmed elemental losses occurred on the DSA surface, together with an aluminium/silicon coating layer potentially sourced from the stormwater clayish sediments. Furthermore, disinfection by-products in electrochemical disinfected stormwater using either BDD or DSA were at least one order of magnitude lower than the Australia Drinking Water Guidelines limits. The mechanism and long-term study demonstrated that careful anode selection is required as some anodes will deteriorate in stormwater matrices faster than others.

Differential functionalisation of the internal and external surfaces of carbon-stabilised nanoporous silicon.

We report the first method to introduce differential functionalities in the interior pore walls and exterior surface of highly stable thermally hydrocarbonised porous silicon (THCpSi) films. The approach exploits the hydrophobicity of the hydrosilylated THCpSi to, first, selectively functionalise the external surface, and subsequently derivatise the hydrophobic internal pore walls.

Morphology and surface properties of high strength siloxane poly(urethane-urea)s developed for heart valve application.

A series of siloxane poly(urethane-urea) (SiPUU) were developed by incorporating a macrodiol linked with a diisocyanate to enhance mixing of hard and soft segments (SS). The effect of this modification on morphology, surface properties, surface elemental composition, and creep resistance was investigated. The linked macrodiol was prepared by reacting α,ω-bis(6-hydroxyethoxypropyl) poly(dimethylsiloxane)(PDMS) or poly(hexamethylene oxide) (PHMO) with either 4,4'-methylenediphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), or isophorone diisocyanate (IPDI). SiPUU with PHMO-MDI-PHMO and PHMO-IPDI-PHMO linked macrodiols showed enhanced creep resistance and recovery when compared with a commercial biostable polyurethane, Elast-Eon™ 2A. Small and wide-angle X-ray scattering data were consistent with significant increase of hydrogen bonding between hard and SS with linked-macrodiols, which improved SiPUU's tensile stress and tear strengths. These SiPUU were hydrophobic with contact angle higher than 101° and they had low water uptake (0.7%·w/w of dry mass). They also had much higher siloxane concentration on the surface compared to that in the bulk. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 107B: 112-121, 2019.

Fiber with Butterfly Wings: Creating Colored Carbon Fibers with Increased Strength, Adhesion, and Reversible Malleability.

Colored and color-changing materials are central to perception and interaction in nature and have been exploited in an array of modern technologies such as sensors, visual displays, and smart materials. Attempts to introduce color into carbon fiber materials have been limited by deleterious impacts on fiber properties, and the extension of colored fibers toward "smart composites" remains in its infancy. We present carbon fibers incorporating structural color, similar to that observed on the surface of soap bubbles and various insects and birds, by modifying the fiber surface through in situ polymerization grafting. When dry, the treated fibers exhibit a striking blue color, but when exposed to a volatile solvent, a cascade of colors across the visible light region is observed as the film first swells and then shrinks as the solvent evaporates. The treated fibers not only possess a unique color and color-changing ability but also can be reversibly formed into complex shapes and bear significant loads even without being encased in a supporting polymer. The tensile strength of treated fibers shows a statistically significant increase (+12%), and evaluation of the fiber-to-matrix adhesion of these polymers to an epoxy resin shows more than 300% improvement over control fibers. This approach creates a new platform for the multifaceted advance of smart composites.

Effect of Bovine Serum Albumin Treatment on the Aging and Activity of Antibodies in Paper Diagnostics.

Paper and cellulosic films are used in many designs of low-cost diagnostics such as paper-based blood grouping devices. A major issue limiting their commercialization is the short stability of the functional biomolecules. To address this problem, the effect of relative humidity (RH) and bovine serum albumin (BSA) on the antibody bioactivity and the surface chemical composition of a paper blood typing biodiagnostic were studied. An IgM blood typing antibody was physisorbed from solution onto paper - with or without BSA pretreatment, and aged for periods up to 9 weeks under various conditions with a series of RH. The blood typing efficiency of the antibodies and the substrate surface chemical composition were analyzed by image analysis and X-ray photoelectron spectroscopy (XPS), respectively. This study tests two hypotheses. The first is that the hydroxyl groups in paper promote antibody denaturation on paper; the second hypothesis is that proteins such as BSA can partially block the hydroxyl groups within paper, thus preserving antibody bioactivity. Results show that high RH is detrimental to antibody longevity on paper, while BSA can block hydroxyl groups and prolong antibody longevity by almost an order of magnitude-regardless of humidity. This study opens up new engineering concepts to develop robust and marketable paper diagnostics. The simplest is to store paper and antibody based diagnostics in moisture proof packages.