Molecular dynamics simulation on devitrification: isothermal devitrification and thermodynamics of PbF2 glasses

The vitrification and devitrification features of lead fluoride are investigated by means of molecular dynamic simulations. The influence of heating rate on the devitrification temperature as well as the dependence of the glass properties on its thermal history, i.e., the cooling rate employed, is identified. As expected, different glasses are obtained when the cooling rates differ. Diffusion coefficient analysis during heating of glass and crystal, indicates that the presence of defects on the glassy matrix favors the transition processes from the ionic to a superionic state, with high mobility of fluorine atoms, responsible for the high anionic conduction of lead fluoride. Nonisothermal and isothermal devitrification processes are simulated in glasses obtained at different cooling rates and structural organizations occurring during the heat treatments are clearly observed. When a fast cooling rate is employed during the glass formation, the devitrification of a single crystal (limited by the cell dimensions) is observed, while the glass obtained with slower cooling rate, allowing relaxations and organization of various regions on the glass bulk during the cooling process, devitrifies in more than one crystalline plane.     

Synthesis and characterisation of the amidine complexes trans-[PtCl(NH3){HNC(NH2)R}2]Cl (R = Me, Ph, CH2Ph) derived from addition of NH3 to the coordinated nitriles in trans-[PtCl2(NCR)2]

The di-nitrile complexes trans-[PtCl₂(NCR)₂] (R = Me, Ph, CH₂Ph) react with an excess of gaseous NH₃ in CH₂Cl₂ at −10 °C to form, in high yield, the corresponding di-amidine complexes trans-[PtCl(NH₃){HNC(NH₂)R}₂]Cl in which also one chlorine ligand has been displaced by NH₃. The ¹H NMR spectra in DMSO showed the formation of different species which were characterized through NOESY, TOCSY and ¹H/¹³C heteronuclear correlations as trans-[Pt(NH₃){HNC(NH₂)R}₂(DMSO)]Cl₂ and trans-[PtCl{HNC(NH₂)R}₂(DMSO)]Cl.     

Trust and relational capital

Trust can be viewed at the same time as an instrument both for an agent selecting the right partners in order to achieve its own goals, and for an agent of being selected from other potential partners in order to establish with them a cooperation/collaboration and to take advantage from the accumulated trust. In this paper we will analyze trust as the agents’ relational capital. Starting from the classical dependence network with potential partners, we introduce the analysis of what it means for an agent to be trusted and how this condition could be strategically used from it for achieving its own goals, that is, why it represents a form of power. The idea of taking another agent’s point of view is especially important if we consider the amount of studies in social science that connect trust with social capital related issues. Although there is a big interest in literature about ‘social capital’ and its powerful effects on the wellbeing of both societies and individuals, often it is not clear enough what is it the object under analysis. Individual trust capital (relational capital) and collective trust capital not only should be disentangled, but their relations are quite complicated and even conflicting. To overcome this gap, we propose a study that first attempts to understand what trust is as capital of individuals. In which sense “trust” is a capital. How this capital is built, managed and saved. In particular, how this capital is the result of the others’ beliefs and goals. Then we aim to analytically study the cognitive dynamics of this object.     

Synthesis and properties of fully conjugated macrocycles composed of m-diethynylene-phenylene-bridged two dibenzofuran,dibenzothiophene and carbazole units

Fully conjugated macrocycles 1a?1c composed of m-diethynylene-phenylene-bridged two dibenzofuran, dibenzothiophene and carbazole units were synthesized via Sonogashira cross coupling reactions under high-diluted condition. These conjugated macrocycles were fully characterized by ¹H NMR, ¹³C NMR, FT-IR, Mass spectroscopies and elemental analysis. Photophysical and redox properties of 1a?1c were investigated by means of UV–vis/fluorescence spectroscopies and cyclic voltammetry, respectively, and those features were compared with those of the corresponding linear phenylethynyldibenzoheterols 11a?11c. Furthermore, their structural and electronic insights were studied by theoretical calculations at the B3LYP/cc-pVDZ//B3LYP/6-31G(d) level of theory.     

High‐performance In–Zn–O thin‐film transistors with a soluble processed ZrO2 gate insulator

Spin‐coated zirconium oxide films were used as a gate dielectric for low‐voltage, high performance indium zinc oxide (IZO) thin‐film transistors (TFTs). The ZrO₂ films annealed at 400 °C showed a low gate leakage current density of 2 × 10^–8 A/cm² at an electric field of 2 MV/cm. This was attributed to the low impurity content and high crystalline quality. Therefore, the IZO TFTs with a soluble ZrO₂ gate insulator exhibited a high field effect mobility of 23.4 cm²/V s, excellent subthreshold gate swing of 70 mV/decade and a reasonable I_on/off ratio of ～10⁶. These TFTs operated at low voltages (～3.0 V) and showed high drain current drive capability, enabling oxide TFTs with a soluble processed high‐k dielectric for use in backplane electronics for low‐power mobile display applications. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Gas‐phase basicity of 2‐furaldehyde

2‐Furaldehyde (2‐FA), also known as furfural or 2‐furancarboxaldehyde, is an heterocyclic aldehyde that can be obtained from the thermal dehydration of pentose monosaccharides. This molecule can be considered as an important sustainable intermediate for the preparation of a great variety of chemicals, pharmaceuticals and furan‐based polymers. Despite the great importance of this molecule, its gas‐phase basicity (GB) has never been measured. In this work, the GB of 2‐FA was determined by the extended Cooks's kinetic method from electrospray ionization triple quadrupole tandem mass spectrometric experiments along with theoretical calculations. As expected, computational results identify the aldehydic oxygen atom of 2‐FA as the preferred protonation site. The geometries of O‐O‐cis and O‐O‐trans 2‐FA and of their six different protomers were calculated at the B3LYP/aug‐TZV(d,p) level of theory; proton affinity (PA) values were also calculated at the G3(MP2, CCSD(T)) level of theory. The experimental PA was estimated to be 847.9 ± 3.8 kJ mol^?1, the protonation entropy 115.1 ± 5.03 J mol^?1 K^?1 and the GB 813.6 ± 4.08 kJ mol^?1 at 298 K. From the PA value, a ΔH°_f of 533.0 ± 12.4 kJ mol^?1 for protonated 2‐FA was derived. Copyright © 2012 John Wiley & Sons, Ltd.     

Reaction of azides with dichloroindium hydride: very mild production of amines and pyrrolidin-2-imines through possible indium-aminyl radicals

Organic azides are easily reduced to the corresponding amines by reaction with dichloroindium hydride under very mild conditions and in a highly chemoselective fashion. Gamma-azidonitriles give rise to outstanding five-membered cyclizations affording pyrrolidin-2-imines. A rationalization of the overall experimental data cannot exclude the occurrence of competitive radical and nonradical pathways, but certain results are, however, soundly consistent with the intermediacy of indium-bound nitrogen-centered radicals. [reaction: see text]     

Stability study of polyacrylic acid films plasma-polymerized on polypropylene substrates at medium pressure

Plasma polymerization of acrylic acid has become an interesting research subject, since these coatings are expected to be beneficial for biomedical applications due to their high surface density of carboxylic acid functional groups. However, the application of these monomers is counteracted by their low stability in humid environments, since a high stability is a required characteristic for almost any biological application. The present work investigates whether it is possible to obtain stable deposits with a high retention of carboxylic acid functions by performing plasma polymerization on polypropylene substrates with a dielectric barrier discharge operating at medium pressure. In order to obtain coatings with the desired properties, the plasma parameters need to be optimized. Therefore, in this paper, the influence of discharge power and location of the substrate in the discharge chamber is examined in detail. The properties of the deposited films are studied using contact angle measurements, X-ray photoelectron spectroscopy, atomic force microscopy and Fourier transform infrared spectroscopy. Moreover, to determine whether the obtained deposits are soluble in water, the coatings are once again analyzed after rinsing in water. This paper will clearly show that stable COOH-rich surfaces can be obtained at high discharge power and close to the monomer inlet, which might open perspectives for future biomedical applications.