Self‐Assembled Room Temperature Multiferroic BiFeO3‐LiFe5O8 Nanocomposites

Multiferroic materials have driven significant research interest due to their promising technological potential. Developing new room‐temperature multiferroics and understanding their fundamental properties are important to reveal unanticipated physical phenomena and potential applications. Here, a new room temperature multiferroic nanocomposite comprised of an ordered ferrimagnetic spinel α‐LiFe₅O₈ (LFO) and a ferroelectric perovskite BiFeO₃ (BFO) is presented. It is observed that lithium (Li)‐doping in BFO favors the formation of LFO spinel as a secondary phase during the synthesis of Li_xBi_1?xFeO₃ ceramics. Multimodal functional and chemical imaging methods are used to map the relationship between doping‐induced phase separation and local ferroic properties in both the BFO‐LFO composite ceramics and self‐assembled nanocomposite thin films. The energetics of phase separation in Li doped BFO and the formation of BFO‐LFO composites are supported by first principles calculations. These findings shed light on Li's role in the formation of a functionally important room temperature multiferroic and open a new approach in the synthesis of light element doped nanocomposites for future energy, sensing, and memory applications.     

Evidence for alternative exhaled elimination profiles of disinfection by-products and potential markers of airway responses to swimming in a chlorinated pool environment

Chlorine-based disinfectants protect pool water from pathogen contamination but produce potentially harmful halogenated disinfection by-products (DBPs). This study characterized the bioaccumulation and elimination of exhaled DBPs post-swimming and investigated changes in exhaled breath profiles associated with chlorinated pool exposure. Nineteen participants provided alveolar-enriched breath samples prior to and 5, 90, 300, 510, and 600 minutes post-swimming. Known DBPs associated with chlorinated water were quantitated by thermal desorption-gas chromatography-mass spectrometry. Two distinct exhaled DBP elimination profiles were observed. Most participants (84%) reported peak concentrations immediately post-swimming that reduced exponentially. A sub-group exhibited a previously unobserved and delayed washout profile with peak levels at 90 minutes post-exposure. Metabolomic investigations tentatively identified two candidate biomarkers associated with swimming pool exposure, demonstrating an upregulation in the hours after exposure. These data demonstrated a hitherto undescribed exhaled DBP elimination profile in a small number of participants which contrasts previous findings of uniform accumulation and exponential elimination. This sub-group which exhibited delayed peak-exhaled concentrations suggests the uptake, processing, and immediate elimination of DBPs are not ubiquitous across individuals as previously understood. Additionally, non-targeted metabolomics highlighted extended buildup of compounds tentatively associated with swimming in a chlorinated pool environment that may indicate airway responses to DBP exposure.     

Covalent Linkage and Macrocylization Preserve and Enhance Synergistic Interactions in Catalytic Amyloids

The self-assembly of short peptides into catalytic amyloid-like nanomaterials has proven to be a powerful tool in both understanding the evolution of early proteins and identifying new catalysts for practically useful chemical reactions. Here we demonstrate that both parallel and antiparallel arrangements of β-sheets can accommodate metal ions in catalytically productive coordination environments. Moreover, synergistic relationships, identified in catalytic amyloid mixtures, can be captured in macrocyclic and sheet-loop-sheet species, that offer faster rates of assembly and provide more complex asymmetric arrangements of functional groups, thus paving the way for future designs of amyloid-like catalytic proteins. Our findings show how initial catalytic activity in amyloid assemblies can be propagated and improved in more-complex molecules, providing another link in a complex evolutionary chain between short, potentially abiotically produced peptides and modern-day enzymes.     

Investigation of Chlorpyrifos and Its Transformation Products in Fruits and Spices by Combining Electrochemistry and Liquid Chromatography Coupled to Tandem Mass Spectrometry

The identification of transformation products (TPs) of pesticides in food is a crucial task difficult to tackle, due to the lack of standards. In this work, we present a novel methodology to synthesize five main TP standards of the insecticide chlorpyrifos (CPF) and to investigate their occurrence in selected fruits and spices. TPs were electrochemically (EC) synthesized using a boron-doped diamond electrode (BDD) and identified by EC coupled online to mass spectrometry, LC-MS/MS, and high-resolution mass spectrometry. CPF and its TPs were analyzed in the food samples by LC-MS/MS on multiple reaction monitoring (MRM) after dispersive solid-phase extraction. A good recovery of 83–103% for CPF and 65–85% for TPs was obtained. Matrix effects, which cause signal suppression, ranged between 81 to 95% for all targeted analytes. The limit of detection and quantification for CPF were 1.6–1.9 and 4.9–5.7 μg/kg, respectively. Among investigated samples, CPF was determined in fresh lemon (104 μg/kg), fenugreek seed (40 μg/kg), and black pepper (31 μg/kg). CPF content in all samples was lower than the EU maximum residue level (MRL). The most frequently detected TPs were diethylthiophosphate and diethylphosphate. Other TPs, CPF oxon and trichloropyridinol, were also detected. Hence, EC is a versatile tool to synthesize TP standards which enables the determination of contaminants and residues in foodstuffs even if no commercial standards are available.     

Dual-modulator broadband infrared Mueller matrix ellipsometry

A broadband mid-infrared Mueller matrix ellipsometer is described based on two photoelastic modulators and a step-scan interferometer. The data are analyzed using a combination hardware-software double Fourier transformation. Obtaining spectra of the Mueller matrix elements requires that the infrared wavelength-dependent retardation amplitude of the modulators be known through calibration and subsequently incorporated into the data processing. The spectroscopic capability of the instrument is demonstrated in transmission and reflection geometries by the measured Mueller matrices of air, an anisotropic quartz crystal, and the ZnSe-water interface, each from 2500-4000 cm^-1.     

Electron tunneling through ultrathin boron nitride crystalline barriers

We investigate the electronic properties of ultrathin hexagonal boron nitride (h-BN) crystalline layers with different conducting materials (graphite, graphene, and gold) on either side of the barrier layer. The tunnel current depends exponentially on the number of h-BN atomic layers, down to a monolayer thickness. Conductive atomic force microscopy scans across h-BN terraces of different thickness reveal a high level of uniformity in the tunnel current. Our results demonstrate that atomically thin h-BN acts as a defect-free dielectric with a high breakdown field. It offers great potential for applications in tunnel devices and in field-effect transistors with a high carrier density in the conducting channel.     

A multi-objective particle swarm optimisation for filter-based feature selection in classification problems

Feature selection has the two main objectives of minimising the classification error rate and the number of features. Based on binary particle swarm optimisation (BPSO), we develop two novel multi-objective feature selection frameworks for classification, which are multi-objective binary PSO using the idea of non-dominated sorting (NSBPSO) and multi-objective binary PSO using the ideas of crowding, mutation and dominance (CMDBPSO). Four multi-objective feature selection methods are then developed by applying mutual information and entropy as two different filter evaluation criteria in each of the proposed frameworks. The proposed algorithms are examined and compared with a single objective method on eight benchmark data sets. Experimental results show that the proposed multi-objective algorithms can evolve a set of solutions that use a smaller number of features and achieve better classification performance than using all features. In most cases, NSBPSO achieves better results than the single objective algorithm and CMDBPSO outperforms all other methods mentioned above. This work represents the first study on multi-objective BPSO for filter-based feature selection.     

Investigation on the Impact of Seasonally Frozen Soil on Seismic Response of Bridge Columns

This paper presents the development of numerical models that investigated the seismic response of a simple two span prototype bridge system during warm and frozen temperatures. Models from both temperature conditions were subjected to a range of seismic intensities to examine the effect of seasonal freezing on the response of the system. Stiffness characteristics were defined using cyclic models of a bridge pier that were previously developed and validated using results from an experimental program on identical full-scale column-foundation units, which were tested during the summer and winter months. Dynamic characteristics of the seismic models were defined using approaches found in the literature. Frozen conditions increased the maximum bending moment and shear force demands for all seismic intensities, with nonlinearity in the column/foundation reducing the difference between the peak responses at higher intensities. At the depth of maximum foundation shear for the frozen model, demand was three times higher than the unfrozen for the 500-year return period and twice during the 2,500-year event. This is significant as one will assume shear is not critical at this location if the effects of frozen conditions are ignored. Apart from the smallest intensity event, increased peak lateral displacements were developed by the warm model down the length of the column and foundation. However, the displacement demand to capacity ratio was higher at the column top for the frozen model, exceeding the capacity during the 2,500-year return period event.     

Fluorographene: a two-dimensional counterpart of Teflon

A stoichiometric derivative of graphene with a fluorine atom attached to each carbon is reported. Raman, optical, structural, micromechanical, and transport studies show that the material is qualitatively different from the known graphene-based nonstoichiometric derivatives. Fluorographene is a high-quality insulator (resistivity >10(12) Ω) with an optical gap of 3 eV. It inherits the mechanical strength of graphene, exhibiting a Young's modulus of 100 N m(-1) and sustaining strains of 15%. Fluorographene is inert and stable up to 400 °C even in air, similar to Teflon.