Solid-state NMR study of N labelled polyaniline upon reaction with DPPH

The quantitative investigation of the radical scavenging properties of polyaniline (PANI) upon reaction with excess of the stable DPPH radical (a 4:1 ratio of DPPH to aniline units in the polymer) was carried out using ¹⁵N and ¹³C solid state NMR spectroscopy. During the process the polyaniline was oxidised so that the imine content increased from 45 to 65%. The extent of oxidation measured by NMR was confirmed by N1s XPS analysis. However, within a 30 min reaction time, about 85% of the DPPH radicals were scavenged as monitored by the decay in its EPR signal. This is about 20 times greater than the fraction of DPPH required to oxidize PANI from an imine content of 45-65%. An identification of further redox processes is required to explain the high degree of radical scavenging. At the same time, there was no evidence of significant chemical binding or trapping of DPPH in the PANI structure.     

Integrating functional,social, and psychological determinants to explain online social networking usage

People involved in business are increasingly aware of the online social phenomenon and its potential as a marketing tool. Building upon the marketing, social psychology, and information system literature, this study empirically examines a set of functional determinants derived from the technology acceptance model and socio-psychological determinants drawn from the theory of reasoned action and social cognitive theory that may be responsible for the motivations of participants in online social networks. We propose a model by integrating functional, social, and psychological factors in predicting attitude and online social network usage. The survey outcomes from a cross-sectional study among 387 Facebook users in Malaysia support the hypothesised model. This study contributes by extending the cognitive learning theories in predicting online social networking usage. Particularly, this research presents a different perspective on online social networking by exploring the mediating effect of attitude and the moderating role of individual characteristics. This study demonstrates that desirable changes in the perception of functional benefits, self-efficacy, and need for cognition as well as perceptions of social pressure from significant others might lead to corresponding changes in attitude towards online social networking. Results of the study support the model efficacy and predictive ability of the proposed integrative model which may serve as a theoretical foundation for future researchers interested in examining other virtual community engagements such as blogging, online advertising, and online public relations activities.     

Unraveling the Dynamic Nanoscale Reducibility (Ce4+ → Ce3+) of CeOx–Ru in Hydrogen Activation

The interaction of molecular hydrogen with ceria is of important relevance for heterogeneous catalysis related to green chemistry and renewable energy. Here, the complex structural transformations of a well‐defined cerium oxide model catalyst are followed in situ and in real time when exposed to a reactive H₂ environment. By using electron spectromicroscopy and diffraction with chemical and structural sensitivities, it is demonstrated that the transition from CeO₂ to crystalline Ce₂O₃ occurs through a mixture of transient, coexisting phases on the nanoscale. The findings establish a clear relationship between structure and functionality for hydrogen dissociation over ceria(111), bearing profound implications on the nature of the reduction (Ce⁴⁺ → Ce³⁺) and mechanism for H₂ scission.     

Topochemical manipulation of perovskites: low-temperature reaction strategies for directing structure and properties

Topochemical reaction strategies offer an important low-temperature (<500 °C) approach to the conscious manipulation of various inorganic host materials, allowing access to compounds that cannot be prepared by standard high-temperature methods. As the utility of these strategies continues to expand, researchers will be able to more effectively target materials with technologically significant properties. This Progress Report presents recent advances in topochemical reaction strategies as applied to perovskite and perovskite-related compounds. Emphasis is placed on structural modifications and corresponding variations in properties. Additionally, the future prospects of this approach to the rational design of intricate target compounds are discussed.     

Normalization-Based Task Scheduling Algorithms for Heterogeneous Multi-Cloud Environment

Cloud computing is one of the most successful technologies that offer on-demand services through the Internet. However, datacenters of the clouds may not have unlimited capacity which can fulfill the demanded services in peak hours. Therefore, scheduling workloads across multiple clouds in a federated manner has gained a significant attention in the recent years. In this paper, we present four task scheduling algorithms, called CZSN, CDSN, CDN and CNRSN for heterogeneous multi-cloud environment. The first two algorithms are based on traditional normalization techniques, namely z-score and decimal scaling respectively which are hired from data mining. The next two algorithms are based on two newly proposed normalization techniques, called distribution scaling and nearest radix scaling respectively. All the proposed algorithms are shown to work on-line. We perform rigorous experiments on the proposed algorithms using various synthetic as well as benchmark datasets. Their performances are evaluated through simulation run by measuring two performance metrics, namely makespan and average cloud utilization. The experimental results are compared with that of existing algorithms to show the efficacy of the proposed algorithms.     

The Role of Electron Localization in Covalency and Electrochemical Properties of Lithium-Ion Battery Cathode Materials

Following the fundamental research conducted by J. B. Goodenough, the important role of electron localization induced by elemental substitution is studied. The size and electron negativity of host and substituting ions are two important factors in tuning material properties such as local structure and transition metal (TM) oxygen covalency. However, another factor, electron localization, which is widely studied in catalyst research but largely overlooked for battery materials, deserves systematic studies. A combined investigation using synchrotronbased X-ray spectroscopy and theoretical calculations is carried out on the Li-Co-Mn-O model system in which the substituting cation Mn⁴⁺, with its 3d³ electronic structure, is used as a promoter for electron localization. Results indicate that electron localization greatly influences the Co O bond by making it less covalent, which increases the delithiation voltage. It is also found that during charge/discharge, electron localization tends to make TM K-edge X-ray absorption near edge spectroscopy (XANES) spectra show a more “rigid shift” behavior while electron delocalization makes the XANES exhibit a “shape change.” It clearly explains why the K-edge XANES data of some TM oxides show no “rigid shift” while the nominal valence states changed. This work highlights the importance of electron localization with guidance for XANES interpretation.     

Vanadium oxide nanotube spherical clusters prepared on carbon fabrics for energy storage applications

Vanadium oxide nanotubes have shown great promise as electrode materials for energy storage devices. In this study, we report the synthesis of V(2)O(5) nanotube (VNT) clusters, which form densely packed radial arrangements of VNTs on high-surface-area carbon fiber fabrics (CF). This was achieved by coating the CF with V(2)O(5) by pulsed laser deposition (PLD). Hydrothermal treatment of the PLD films in the presence of excess intercalated V(2)O(5) results in formation of well-adhered VNT clusters on the CF. The densely packed VNTs have inner and outer diameters and interlayer distances of ~24, ~70, and ~2.4 nm, respectively. Coin cell type supercapacitors (CR2032) were assembled using VNT-CF as the anode material and electrochemical properties were evaluated.     

Water�CGas Shift and CO Methanation Reactions over Ni�CCeO2(111) Catalysts

X-ray and ultraviolet photoelectron spectroscopies were used to study the interaction of Ni atoms with CeO₂(111) surfaces. Upon adsorption on CeO₂(111) at 300 K, nickel remains in a metallic state. Heating to elevated temperatures (500?C800 K) leads to partial reduction of the ceria substrate with the formation of Ni²⁺ species that exists as NiO and/or Ce_1?xNi_xO_2?y. Interactions of nickel with the oxide substrate significantly reduce the density of occupied Ni 3d states near the Fermi level. The results of core-level photoemission and near-edge X-ray absorption fine structure point to weakly bound CO species on CeO₂(111) which are clearly distinguishable from the formation of chemisorbed carbonates. In the presence of Ni, a stronger interaction is observed with chemisorption of CO on the admetal. When the Ni is in contact with Ce⁺³ cations, CO dissociates on the surface at 300 K forming NiC_x compounds that may be involved in the formation of CH₄ at higher temperatures. At medium and large Ni coverages (>0.3 ML), the Ni/CeO₂(111) surfaces are able to catalyze the production of methane from CO and H₂, with an activity slightly higher than that of Ni(100) or Ni(111). On the other hand, at small coverages of Ni (<0.3 ML), the Ni/CeO₂(111) surfaces exhibit a very low activity for CO methanation but are very good catalysts for the water?Cgas shift reaction.     

Microwave irradiation-assisted method for the deposition of adherent oxide films on semiconducting and dielectric substrates

We report a method for the deposition of thin films and thick coatings of metal oxides through the liquid medium, involving the microwave irradiation of a solution of a metal-organic complex in a suitable dielectric solvent. The process is a combination of sol-gel and dip-coating methods, wherein coatings can be obtained on nonconducting and semiconducting substrates, within a few minutes. Thin films of nanostructured ZnO (würtzite) have been obtained on Si(100), glass and polymer substrates, the nanostructure determined by process parameters. The coatings are strongly adherent and uniform over 15 mm × 15 mm, the growth rate ∼ 0.25 μm/min. Coatings of nanocrystalline Fe₂O₃ and Ga₂O₃ have also been obtained. The method is scalable to larger substrates, and is promising as a low temperature technique for coating dielectric substrates, including flexible polymers.