Transparent and flexible films of new segmented polyurethane nanocomposites incorporated by NH2-functionalized TiO2 nanoparticles

In this work, TiO₂ nanoparticles are surface modified by NH₂-terminated organic moieties arised from 4,4′-methylene diphenyl diisocyanate (MDI). These nanoparticles are incorporated into ether-based segmented polyurethane (SPU) matrix. MDI is utilized as monomer together with poly(tetramethylene oxide) (PTMO) comonomer for preparing the final polymer as well. The NH₂-functionalized TiO₂ nanoparticles are covalently linked to the NCO terminals of the resulting SPU macromolecules during film preparation stage. Therefore, in addition to butylene glycol, these surface modified nanoparticles with enhanced organophilicity could play the role of the second chain extender of NCO-capped SPU macromolecules through formation of urea linkages. Optical and thermal behaviors of the transparent and flexible film (SPU/TiO₂–MDI) is compared with those of unmodified TiO₂ (SPU/TiO₂) and TiO₂-unloaded SPU films. Though the particle loading is only 5 wt.%, incorporation of TiO₂ and TiO₂–MDI nanoparticles into the SPU polymer enhances significantly the light absorption in UV region at 300–400 nm. SEM images of the prepared films clearly show a considerable decrease in particle aggregation for TiO₂–MDI into SPU matrix compared to that of unmodified TiO₂. TG analyses indicate a one-step decomposition pattern with onset temperatures of about 360 and 380 °C for neat SPU and SPU/TiO₂–MDI, respectively. Moreover, DTA thermograms of both nanocomposites show obviously two exothermic phase transitions in the thermal range of 330–440 °C.     

Resistive switching characteristics of ZnO–graphene quantum dots and their use as an active component of an organic memory cell with one diode-one resistor architecture

We investigated the resistive switching characteristics of a polystyrene:ZnO–graphene quantum dots system and its potential application in a one diode-one resistor architecture of an organic memory cell. The log–log I–V plot and the temperature-variable I–V measurements revealed that the switching mechanism in a low-current state is closely related to thermally activated transport. The turn-on process was induced by a space-charge-limited current mechanism resulted from the ZnO–graphene quantum dots acting as charge trap sites, and charge transfer through filamentary path. The memory device with a diode presented a ∼10³ I_ON/I_OFF ratio, stable endurance cycles (10² cycles) and retention times (10⁴ s), and uniform cell-to-cell switching. The one diode-one resistor architecture can effectively reduce cross-talk issue and realize a cross bar array as large as ∼3 kbit in the readout margin estimation. Furthermore, a specific word was encoded using the standard ASCII character code.     

Cell-Free Synthesis of Selenoproteins in High Yield and Purity for Selective Protein Tagging

The selenol group of selenocysteine is much more nucleophilic than the thiol group of cysteine. Selenocysteine residues in proteins thus offer reactive points for rapid post-translational modification. Herein, we show that selenoproteins can be expressed in high yield and purity by cell-free protein synthesis by global substitution of cysteine by selenocysteine. Complete alkylation of solvent-exposed selenocysteine residues was achieved in 10 minutes with 4-chloromethylene dipicolinic acid (4Cl-MDPA) under conditions that left cysteine residues unchanged even after overnight incubation. Gd^III−Gd^III distances measured by double electron–electron resonance (DEER) experiments of maltose binding protein (MBP) containing two selenocysteine residues tagged with 4Cl-MDPA-Gd^III were indistinguishable from Gd^III−Gd^III distances measured of MBP containing cysteine reacted with 4Br-MDPA tags.     

Structural,magnetic, thermal and optical properties of Sn2+ cation doped magnetite nanoparticles

Tin doped nanomagnetites, Sn_xFe_3-xO₄, were synthesized with various concentrations of Sn²⁺ ion (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0) by co-precipitation method. XRD, VSM, TG-DTA, SEM-EDX and UV–Vis were used to characterize and study the structural, magnetic, thermal, and optical properties of Sn_xFe_3-xO₄ nanoparticles. XRD confirmed the presence of cubic structure and spinel phase of tin doped magnetites. The d-spacing, lattice parameter, density, crystallite size and cation distribution were derived from the XRD analysis. The M − H curves exhibited changes in saturation magnetization (M_s), coercive field (H_c), remanent magnetization (M_r) and susceptibility (χ), with increasing concentration of non-magnetic Sn²⁺ ions. Differential thermal analysis was used to study the thermal stability of Sn_xFe_3-xO₄ nanoparticles. The SEM images revealed the surface morphology of the nanoparticles and the EDX spectra showed an increase in the Sn content and a corresponding decrease in the Fe content for the tin doped samples. The optical bandgap was found to be centered at 3.9 eV for the synthesized materials. This systematic study may be the first comprehensive report on synthesis and characterization of tin doped magnetites.     

In situ growth of three-dimensional graphene coatings on arbitrary-shaped micro/nano materials and its mechanism studies

In the past decade, there have been great advances in the controllable growth of two-dimensional (2D) graphene sheets. However, the preparation of 3D structured graphene such as graphene coatings on arbitrary-shaped micro/nano materials still remains a formidable challenge. Herein, we have proposed a general strategy for the in situ growth of 3D graphene coatings on the micro/nano particles with arbitrary shapes. Inspired by the CVD growth mechanism of 2D graphene sheets on the bulk metal substrates, we have in situ constructed a nanometer-thick catalytic interface on the micro/nano particle surface by introducing a trace amount of transition metal salts and solid carbon sources with strictly-controlled content and ratio. Growth of 3D graphene coatings is accomplished through a solid-state reaction. Under the catalysis of the in situ formed catalytic interface consisting of highly-ordered metal nanoislands, the nano-thick amorphous carbon layer which arousing from the pyrolysis of carbon sources can be effectively transformed into a continuous and uniform graphene coating throughout the material surface based on a “dissolution–precipitation” mechanism. 3D graphene coatings have been successfully grown on lithium iron phosphate, silver, copper and silicon particles. The growth mechanism of the 3D graphene coatings has been studied in detail and a growth model is also proposed.     

Utilizing sensor data to model students’ creativity in a digital environment

While creativity is essential for developing students’ broad expertise in Science, Technology, Engineering, and Math (STEM) fields, many students struggle with various aspects of being creative. Digital technologies have the unique opportunity to support the creative process by (1) recognizing elements of students’ creativity, such as when creativity is lacking (modeling step), and (2) providing tailored scaffolding based on that information (intervention step). However, to date little work exists on either of these aspects. Here, we focus on the modeling step. Specifically, we explore the utility of various sensing devices, including an eye tracker, a skin conductance bracelet, and an EEG sensor, for modeling creativity during an educational activity, namely geometry proof generation. We found reliable differences in sensor features characterizing low vs. high creativity students. We then applied machine learning to build classifiers that achieved good accuracy in distinguishing these two student groups, providing evidence that sensor features are valuable for modeling creativity.     

Preparation and physical properties of the layered niobate Cu0.5Nb3O8: Application to photocatalytic hydrogen evolution

The new layered niobate Cu_0.5Nb₃O₈ is synthesized by soft chemistry in aqueous electrolyte via Cu²⁺→H⁺ exchange between copper nitrate and HNb₃O₈·H₂O. The characterization of the exchanged product is made by means of thermal gravimetry, chemical analysis, X-ray diffraction and IR spectroscopy. Thermal analysis shows a conversion to anhydrous compound above 500 °C. The oxide displays a semiconductor like behavior; the thermal variation of the conductivity shows that d electrons are strongly localized and the conduction is thermally activated with activation energy of 0.13 eV. The temperature dependence of the thermopower is indicative of an extrinsic conductivity; the electrons are dominant carriers in conformity with an anodic photocurrent. Indeed, the Mott–Schottky plot confirms n-type conduction from which a flat band potential of −0.82 V_SCE, an electronic density of 8.72×10¹⁹ m⁻³ and a depletion width of 4.4 nm are determined. The upper valence band, located at ~5.8 eV below vacuum is made up predominantly of Cu²⁺: 3d with a small admixture of O²⁻: 2p orbitals whereas the conduction band consists of empty Nb⁵⁺: 5s level. The energy band diagram shows the feasibility of the oxide for the photocatalytic hydrogen production upon visible light (29 mW cm⁻²) with a rate evolution of 0.31 mL g⁻¹ min⁻¹.     

Impact behavior and fractographic study of carbon nanotubes grafted carbon fiber-reinforced epoxy matrix multi-scale hybrid composites

Carbon nanotubes are the most promising reinforcement for high performance composites. Multiwall carbon nanotubes were directly grown onto the carbon fiber surface by catalytic thermal chemical vapor deposition technique. Multi-scale hybrid composites were fabricated using the carbon nanotubes grown fibers with epoxy matrix. Morphology of the grown carbon nanotubes was investigated using field emission scanning electron microscopy and transmission electron microscopy. The fabricated composites were subjected to impact tests which showed 48.7% and 42.2% higher energy absorption in Charpy and Izod impact tests respectively. Fractographic analysis of the impact tested specimens revealed the presence of carbon nanotubes both at the fiber surface and within the matrix which explained the reason for improved energy absorption capability of these composites. Carbon nanotubes presence at various cracks formed during loading provided a direct evidence of micro crack bridging. Thus the enhanced fracture strength of these composites is attributed to stronger fiber–matrix interfacial bonding and simultaneous matrix strengthening due to the grown carbon nanotubes.