Epitope mapping using mRNA display and a unidirectional nested deletion library

In vitro selection targeting an anti-polyhistidine monoclonal antibody was performed using mRNA display with a random, unconstrained 27-mer peptide library. After six rounds of selection, epitope-like peptides were identified that contain two to five consecutive, internal histidines and are biased for arginine residues, without any other identifiable consensus. The epitope was further refined by constructing a high-complexity, unidirectional fragment library from the final selection pool. Selection by mRNA display minimized the dominant peptide from the original selection to a 15-residue functional sequence (peptide Cmin: RHDAGDHHHHHGVRQ; K-D = 38 nM). Other peptides recovered from the fragment library selection revealed a separate consensus motif (ARRXA) C-terminal to the histidine track. Kinetics measurements made by surface plasmon resonance, using purified Fab (antigen-binding fragment) to prevent avidity effects, demonstrate that the selected peptides bind with 10- to 75-fold higher affinities than a hexahistidine peptide. The highest affinity peptides (K-D approximate to 10 nM) encode both a short histidine track and the ARRXA motif, suggesting that the motif and other flanking residues make important contacts adjacent to the core polyhistidine-binding site and can contribute > 2.5 kcal/mol of binding free energy. The fragment library construction methodology described here is applicable to the development of high-complexity protein or cDNA expression libraries for the identification of protein-protein interaction domains

High power TiO2 and high capacity Sn-doped TiO2 nanomaterial anodes for lithium-ion batteries

A range of phase-pure anatase TiO2 (∼5 nm) and Sn-doped TiO2 nanoparticles with the formula Ti1-xSnxO2 (where x = 0, 0.06, 0.11 and 0.15) were synthesized using a continuous hydrothermal flow synthesis (CHFS) reactor. Charge/discharge cycling tests were carried out in two different potential ranges of 3 to 1 V and also a wider range of 3 to 0.05 V vs Li/Li+. In the narrower potential range, the undoped TiO2 nanoparticles display superior electrochemical performance to all the Sn-doped titania crystallites. In the wider potential range, the Sn-doped samples perform better than undoped TiO2. The sample with composition Ti0.85Sn0.15O2, shows a capacity of ca. 350 mAh g−1 at an applied constant current of 100 mA g−1 and a capacity of 192.3 mAh g−1 at a current rate of 1500 mA g−1. After 500 charge/discharge cycles (at a high constant current rate of 382 mA g−1), the same nanomaterial anode retains a relatively high specific capacity of 240 mAh g−1. The performance of these nanomaterials is notable, particularly as they are processed into electrodes, directly from the CHFS process (after drying) without any post-synthesis heat-treatment, and they are made without any conductive surface coating

A combinatorial nanoprecursor route for direct solid state chemistry: Discovery and electronic properties of new iron-doped lanthanum nickelates up to La4Ni2FeO10-delta

We describe a simple nanoprecursor route for direct solid-state combinatorial synthesis and discovery of heterometallic materials compositions which are normally difficult to make in a single step. Using a combinatorial robot (incorporating a continuous hydrothermal reactor), co-precipitated nanoprecursors containing different amounts of La, Ni and Fe oxides were made. These samples were divided into two identical cloned libraries, which were heat-treated to bring about solid-state transformations at either 1348 K or 1573 K for 12 h. In each case, experimental conditions were designed to form the corresponding La4Ni3 − xFexO10 phases (x = 0.0–3.0) directly without comminution. Such materials are difficult to make without multiple heating and grinding steps. The heat-treated samples from each library were embedded into a wellplate and analysed by powder X-ray diffraction methods in order to elucidate trends in phase behaviour. Several hitherto unknown phase-pure Ruddlesden Popper type La4Ni3 − xFexO10 compositions were identified and their DC electrical conductivities measured

Comparison of three-dimensional analysis and stereological techniques for quantifying lithium-ion battery electrode microstructures

Lithium-ion battery performance is intrinsically linked to electrode microstructure. Quantitative measurement of key structural parameters of lithium-ion battery electrode microstructures will enable optimization as well as motivate systematic numerical studies for the improvement of battery performance. With the rapid development of 3-D imaging techniques, quantitative assessment of 3-D microstructures from 2-D image sections by stereological methods appears outmoded; however, in spite of the proliferation of tomographic imaging techniques, it remains significantly easier to obtain two-dimensional (2-D) data sets. In this study, stereological prediction and three-dimensional (3-D) analysis techniques for quantitative assessment of key geometric parameters for characterizing battery electrode microstructures are examined and compared. Lithium-ion battery electrodes were imaged using synchrotron-based X-ray tomographic microscopy. For each electrode sample investigated, stereological analysis was performed on reconstructed 2-D image sections generated from tomographic imaging, whereas direct 3-D analysis was performed on reconstructed image volumes. The analysis showed that geometric parameter estimation using 2-D image sections is bound to be associated with ambiguity and that volume-based 3-D characterization of nonconvex, irregular and interconnected particles can be used to more accurately quantify spatially-dependent parameters, such as tortuosity and pore-phase connectivity

Mixed molybdenum and vanadium oxide nanoparticles with excellent high-power performance as Li-ion battery negative electrodes

Several nano-sized mixed molybdenum/vanadium oxide monoclinic solid solutions were synthesised using a continuous hydrothermal flow process and studied with a wide range of physical characterization techniques including X-ray photoelectron spectroscopy, X-ray diffraction, transmission electron microscopy and X-ray absorption spectroscopy. The nanomaterials were tested as anodes for Li-ion batteries in the potential range 0.05–3.00 V vs. Li/Li+. Samples with nominal formulas of Mo0.5V0.5O2 and Mo0.33V0.67O2 showed excellent performance, especially at high current rates, due to their highly pseudocapacitive charge storage mechanism. At a specific current of 10 A g−1, Mo0.5V0.5O2 and Mo0.33V0.67O2 showed specific capacities of ca. 200 and 170 mAh g−1, respectively. Mo0.5V0.5O2 also showed good cyclability, with a specific capacity of 480 mAh g−1 after 150 cycles at a specific current of 0.5 A g−1. For cyclic voltammetries conducted at high scan rates, pseudocapacitive charge storage contributed more than 90% to the total charge storage for both samples. The scalability of the synthesis technique and excellent electrochemical performance at high power, make these materials promising as negative electrode active materials for Li-ion batteries

Culture-negative bivalvular endocarditis with myocardial destruction in a patient with systemic lupus erythematosus: a case report

Culture-negative endocarditis has long been associated with systemic lupus erythematosus, but is usually asymptomatic or involves a single valve. We present a patient with destructive culture-negative endocarditis that remains without a microbial etiology despite an exhaustive workup using advanced diagnostic techniques in a patient with systemic lupus erythematosus

Examining the effect of nanosized Mg₀.₆Ni₀.₄O and Al₂O₃ additives on S/polyaniline cathodes for lithium–sulphur batteries

Nanostructured magnesium nickel oxide Mg₀.₆Ni₀.₄O and alumina Al₂O₃ were studied as additives to sulphur/polyaniline (S/PANI) composites via wet ball-milling of sulphur and polyaniline followed by heat treatment. Metal oxide nanoparticles, which have small particle size, porous structure and high specific surface area to volume ratio, are expected to be catalytic for chemical reactions, including electron transfer and are able to adsorb lithium polysulphides. The composites were characterized by SEM and electrochemical methods. Cyclic voltammetry studies suggest that the alumina additive acts differently to the Mg₀.₆Ni₀.₄O. The results suggest that although the alumina additive improves the S/PANI composite performance as a lithium–sulphur battery cathode, the use of Mg₀.₆Ni₀.₄O is more effective

Electrochemical reduction of carbon dioxide on copper-based nanocatalysts using the rotating ring-disc electrode

A continuous hydrothermal flow synthesis method was used to produce copper(I) oxide nanoparticles, which were used as an electrocatalyst for the reduction of CO2. A rotating ring-disc electrode (RRDE) system was used to study the electroreduction processes, including a systematic study (including quantitative NMR analysis) to identify product species formed at the disc and detected at the ring. In 0.5 M KHCO3electrolyte with a pH of 7.1, carbon dioxide was found to be exclusively reduced to formate. In the potential range −0.5 to −0.9 V vs the reversible hydrogen electrode (RHE), an active material/glassy-carbon disc electrode was shown to produce formate, with a maximum Faradaic efficiency of 66% (at −0.8 V vs RHE)

High power Nb-doped Lifelong₄ Li-ion battery cathodes; pilot-scale synthesis and electrochemical properties

High power, phase-pure Nb-doped LiFePO₄ (LFP) nanoparticles are synthesised using a pilot-scale continuous hydrothermal flow synthesis process (production rate of 6 kg per day) in the range 0.01–2.00 at% Nb with respect to total transition metal content. EDS analysis suggests that Nb is homogeneously distributed throughout the structure. The addition of fructose as a reagent in the hydrothermal flow process, followed by a post synthesis heat-treatment, affords a continuous graphitic carbon coating on the particle surfaces. Electrochemical testing reveals that cycling performance improves with increasing dopant concentration, up to a maximum of 1.0 at% Nb, for which point a specific capacity of 110 mAh g⁻¹ is obtained at 10 C (6 min for the charge or discharge). This is an excellent result for a high power cathode LFP based material, particularly when considering the synthesis was performed on a large pilot-scale apparatus

Pilot-scale continuous synthesis of a vanadium-doped LiFePO4/C nanocomposite high-rate cathodes for lithium-ion batteries

A high performance vanadium-doped LiFePO4 (LFP) electrode is synthesized using a continuous hydrothermal method at a production rate of 6 kg per day. The supercritical water reagent rapidly generates core/shell nanoparticles with a thin, continuous carbon coating on the surface of LFP, which aids electron transport dynamics across the particle surface. Vanadium dopant concentration has a profound effect on the performance of LFP, where the composition LiFe0.95V0.05PO4, achieves a specific discharge capacity which is among the highest in the comparable literature (119 mA h g−1 at a discharge rate of 1500 mA g−1). Additionally, a combination of X-ray absorption spectroscopy analysis and hybrid-exchange density functional theory, suggest that vanadium ions replace both phosphorous and iron in the structure, thereby facilitating Li+ diffusion due to Li+ vacancy generation and changes in the crystal structure