Dielectric Properties of Colossal-Dielectric-Constant Na1/2La1/2Cu3Ti4O12 Ceramics Prepared by Spark Plasma Sintering

In the current study, we report on the dielectric behavior of colossal-dielectric-constant Na_1/2La_1/2Cu₃Ti₄O₁₂ (NLCTO) ceramics prepared by mechanochemical synthesis and spark plasma sintering (SPS) at 850 °C, 900 °C, and 925 °C for 10 min. X-ray powder diffraction analysis showed that all the ceramics have a cubic phase. Scanning electron microscope observations revealed an increase in the average grain size from 175 to 300 nm with an increase in the sintering temperature. SPS NLCTO ceramics showed a room-temperature colossal dielectric constant (>10³) and a comparatively high dielectric loss (>0.1) over most of the studied frequency range (1 Hz–40 MHz). Two relaxation peaks were observed in the spectra of the electrical modulus and attributed to the response of grain and grain boundary. According to the Nyquist plots of complex impedance, the SPS NLCTO ceramics have semiconductor grains surrounded by electrically resistive grain boundaries. The colossal dielectric constant of SPS NLCTO ceramics was attributed to the internal barrier layer capacitance (IBLC) effect. The high dielectric loss is thought to be due to the low resistivity of the grain boundary of SPS NLCTO.     

Gas by-products of CF3I under AC partial discharge

This paper presents the decomposition by-products of trifluro-iodo-methane and their relative proportions in the gas phase under the occurrence of partial discharge. The experiment was performed in the presence of water vapor from 250 to 400 ppm under a non-uniform electric field configuration. The experimental results reveal that the by-products of C₂F₆, C₂F₄, C₂F₅I with the amount of 1300, 200, and 55 (CH₃I) ppm, respectively, were produced for a cumulative charge of 161 mC. Other by-products, such as C₃F₈, CHF₃, C₃F₆ CH₃I were obtained at less than 30 ppm C₂F₆ was the dominant gas by-product of trifluro-iodo-methane suffering partial discharge.     

n-Type GaAs/AlGaAs heterostructure detector with a 3.2 THz threshold frequency

Terahertz detection using the free-carrier absorption requires a small internal work function of the order of a few millielectron volts. A threshold frequency of 3.2 THz (93 microm or approximately 13 meV work function) is demonstrated by using a 1 x 10(18) cm(-3) Si-doped GaAs emitter and an undoped Al(0.04)Ga(0.96)As barrier structure. The peak responsivity of 6.5 A/W, detectivity of 5.5 x 10(8) Jones, and quantum efficiency of 19% were obtained at 7.1 THz under a bias field of 0.7 kV/cm at 6 K, while the detector spectral response range spans from 3.2 to 30 THz.     

Short time synthesis of high quality carbon nanotubes with high rates by CVD of methane on continuously emerged iron nanoparticles

We report the variation of yield and quality of carbon nanotubes (CNTs) grown by chemical vapor deposition (CVD) of methane on iron oxide-MgO at 900-1000 °C for 1-60 min. The catalyst was prepared by impregnation of MgO powder with iron nitrate, dried, and calcined at 300 °C. As calcined and unreduced catalyst in quartz reactor was brought to the synthesis temperature in helium flow in a few minutes, and then the flow was switched to methane. The iron oxide was reduced to iron nanoparticles in methane, while the CNTs were growing.TEM micrographs, in accordance with Raman RBM peaks, indicate the formation of mostly single wall carbon nanotubes of about 1.0 nm size. High quality CNTs with I_G/I_D Raman peak ratio of 14.5 are formed in the first minute of CNTs synthesis with the highest rate. Both the rate and quality of CNTs degrades with increasing CNTs synthesis time. Also CNTs quality sharply declines with temperature in the range of 900-1000 °C, while the CNTs yield passes through a maximum at 950 °C. About the same CNTs lengths are formed for the whole range of the synthesis times. A model of continuous emergence of iron nanoparticle seeds for CNTs synthesis may explain the data. The data can also provide information for continuous production of CNTs in a fluidized bed reactor.     

Distortion-free single point imaging of multi-layered composite sandwich panel structures

The results of a magnetic resonance imaging (MRI) investigation concerning the effects of an aluminum honeycomb sandwich panel on the B1 and B0 fields and on subsequent image quality are presented. Although the sandwich panel structure, representative of an aircraft composite material, distorts B0 and attenuates B1, distortion-free imaging is possible using single point (constant time) imaging techniques. A new expression is derived for the error caused by gradient field distortion due to the heterogeneous magnetic susceptibility within a sample and this error is shown not to cause geometric distortion in the image. The origin of the B0 distortion in the sample under investigation was also examined. The graphite-epoxy 'skin' of the panel is the principal source of the B0 distortion. Successful imaging of these structures sets the stage for the development of methods for detecting moisture ingress and degradation within composite sandwich structures.     

Cytotoxicity of Shear Exfoliated Pnictogen (As,Sb, Bi) Nanosheets

The experimental achievement of phosphorene, which exhibits superior electronic, physical, and optical properties has spurred recent interest in other Group 15 elemental 2D nanomaterials such as arsenene, antimonene, and bismuthene. These unique and superior properties of the pnictogen nanosheets have spurred intensive research efforts and led to the discovery of their diversified potential applications; for instance, optical Kerr material, photonic devices, pnictogen-decorated microfibers, high-speed transistors, and flexible 2D electronics. Previous studies have mainly been dedicated to study the synthesis, properties, and applications of the heavy pnictogens nanosheets; however, the toxicological behaviour of these nanosheets has yet to be established. Herein, the cytotoxicity study of pnictogen nanosheets (As, Sb, and Bi) was conducted over 24 h of incubation with various concentrations of test materials and adenocarcinoma human lung epithelial A549 cells. After the treatment period, the remaining cell viabilities were obtained through absorbance measurements with WST-8 and MTT assays. These findings demonstrate that the toxicity of pnictogen nanosheets decreases down Group 15, whereby arsenic nanosheets are considered to be the most toxic, whereas bismuth nanosheets induce low cytotoxicity. The findings of this study constitute an important initial step towards enhancing our understanding of the toxicological effects of pnictogen nanosheets in light of their prospective commercial applications.     

Macrocyclic Cr3+, Mn2+ and Fe3+ complexes of a mimic SOD moiety: Design,structural aspects,DFT, XRD,optical properties and biological activity

A novel SOD-like macrocycle “H₂DPD” and its trivalent chromium, iron and divalent manganese complexes have been isolated and characterized using the conventional tools. The macrocycle was prepared by 2:2 condensation of P-phenylenediamine with 5,5-dimethyl1,3-cyclohexanedione. IR and electronic spectral data suggested that H₂DPD coordinates to the metal ion as N₄ tetradentate donor with two Cl⁻ occupying the remaining two sites of the distorted octahedron. XRD spectrum of Cr³⁺ complex indicated that the complex crystallizes in a face-centered monoclinic structure with lattice parameters: a = 10.9380 Å; b = 12.4870 Å; c = 12.4600 Å, α = γ = 90° and β = 111.430 with space group P 1 21/c 1 (14). The energy gap (E_HOMO-E_LUMO), molecular electrostatic potential map (EPM) of title compounds, bond length, bond angle, as well as global and local reactivity were estimated using DFT method. The E_g values obtained from electronic spectra of Cr³⁺, Mn²⁺ and Fe³⁺ complexes were found to be 1.284, 1.220 and 1.138 eV, respectively which are in accordance with those evaluated by DFT revealing semiconductor nature. Also, the thermal degradation of all title compounds was carried out and the kinetic parameters were evaluated using Coats-Redfern and Horowitz-Metzger equations. Moreover, the compounds have screened for antibacterial as well as superoxide mimic activities. Cr³⁺ complex exhibited the most significant potent activity against all bacterial strains. With respect to SOD-like activity, the macrocycle showed the most remarkable SOD-like activity comparable to the standard drug, ascorbic acid.     

Luminescent amphiphilic nanogels by terpyridine-Zn(II) complexation of polymeric micelles

In this work, we investigated terpyridine (tpy)/Zn(II) complexation for the crosslinking of polymeric micelles of the branched poly(ethylene oxide)–poly(propylene oxide) block copolymer Tetronic® 1107 (T1107) in water and produce physically stable amphiphilic luminescent nanogels. Nanoparticles displayed a size of 235 ± 25 and 318 ± 57 nm before and after Zn(II) crosslinking, respectively, as measured by dynamic light scattering. High-resolution scanning electron microscopy analysis revealed the multimicellar nature of the crosslinked nanoparticles. In addition, Zn(II) complexation prevented nanoparticle disassembly after extreme dilution below the critical micellar concentration and reduced the minimum concentration required for the reverse thermal gelation of concentrated aqueous T1107 systems. The cell compatibility and uptake were initially assessed in the murine macrophage cell line RAW 264.7. Results showed that complexation increases the cell compatibility of the nanoparticles with respect to the non-complexed counterparts. In addition, non-crosslinked nanoparticles accumulated in the cell membrane, while the complexed ones were internalized, as observed by confocal laser scanning fluorescence microscopy. Then, the antiproliferative activity of the crosslinked nanoparticles was confirmed in the rhabdomyosarcoma cell line Rh30; their inhibitory concentration 50 (IC₅₀) being 101 μg/mL (6.7 μM). Finally, the encapsulation and release of the hydrophobic antiretroviral efavirenz was characterized in vitro. Complexation slightly reduced the release kinetics with respect to the pristine nanoparticles. Overall results demonstrate the promise of this simple modification strategy to produce amphiphilic nanogels with a set of advantageous physicochemical, optical, and biological properties.     

Photo-recycling the Sacrificial Electron Donor: Towards Sustainable Hydrogen Evolution in a Biphasic System

H₂ may be evolved biphasically using a polarised liquid|liquid interface, acting as a “proton pump”, in combination with organic soluble metallocenes as electron donors. Sustainable H₂ production requires methodologies to recycle the oxidised donor. Herein, the photo-recycling of decamethylferrocenium cations (DcMFc⁺) using aqueous core-shell semiconductor CdSe@CdS nanoparticles is presented. Negative polarisation of the liquid|liquid interface is required to extract DcMFc⁺ to the aqueous phase. This facilitates the efficient capture of electrons by DcMFc⁺ on the surface of the photo-excited CdSe@CdS nanoparticles, with hydrophobic DcMFc subsequently partitioning back to the organic phase and resetting the system. TiO₂ (P25) and CdSe semiconductor nanoparticles failed to recycle DcMFc⁺ due to their lower conduction band energy levels. During photo-recycling, CdS (on CdSe) may be self-oxidised and photo-corrode, instead of water acting as the hole scavenger.     

Hierarchical Bayesian autoregressive models for large space–time data with applications to ozone concentration modelling

Increasingly large volumes of space–time data are collected everywhere by mobile computing applications, and in many of these cases, temporal data are obtained by registering events, for example, telecommunication or Web traffic data. Having both the spatial and temporal dimensions adds substantial complexity to data analysis and inference tasks. The computational complexity increases rapidly for fitting Bayesian hierarchical models, as such a task involves repeated inversion of large matrices. The primary focus of this paper is on developing space–time autoregressive models under the hierarchical Bayesian setup. To handle large data sets, a recently developed Gaussian predictive process approximation method is extended to include autoregressive terms of latent space–time processes. Specifically, a space–time autoregressive process, supported on a set of a smaller number of knot locations, is spatially interpolated to approximate the original space–time process. The resulting model is specified within a hierarchical Bayesian framework, and Markov chain Monte Carlo techniques are used to make inference. The proposed model is applied for analysing the daily maximum 8‐h average ground level ozone concentration data from 1997 to 2006 from a large study region in the Eastern United States. The developed methods allow accurate spatial prediction of a temporally aggregated ozone summary, known as the primary ozone standard, along with its uncertainty, at any unmonitored location during the study period. Trends in spatial patterns of many features of the posterior predictive distribution of the primary standard, such as the probability of noncompliance with respect to the standard, are obtained and illustrated. Copyright © 2012 John Wiley & Sons, Ltd.