Ion clustering in molecular dynamics simulations of sodium iodide solutions

Model systems of sodium iodide dissolved in dimethyl ether or 1,2-dimethoxyethane (glyme) were studied in order to investigate the structural and dynamic properties of ionic solutions in small and polymeric ethers. Full molecular dynamics simulations were performed at a range of different salt concentrations. An algorithm was designed which assigns ions to clusters and then calculates all the terms which contribute to ionic conductivity. In dilute solutions, free ions are the most common ionic species, followed by ion pairs. As the concentration increases, pairs become the most common species, with significant concentrations of clusters with 3 through 6 ions. Changing the solvent from dimethyl ether to glyme significantly decreases the ion clustering due to the chelate effect in which the two oxygens on a solvent stabilize an associated cation. The conductivity in stable systems is shown to be primarily the result of the movement of free ions and the relative movement of ions within neutral pairs. The Nernst-Einstein relation, commonly used in the discussion of polymer electrolytes, is shown to be inadequate to quantitatively describe conductivity in the model systems.

Synthesis and anti-corrosion performance of Adenine-L-Alanine ramification

In this paper, a new amino acid derivative, namely Adenine-L-Alanine ramification (ALAR) was synthesized and investigated as a green corrosion inhibitor for X80 pipeline steel in 0.1 mol/L hydrochloric acid solution using the weight loss, AC impedance, and polarization curve method. The structure of the derivative was characterized by IR and UV–vis spectrum. The weight loss and AC impedance found that the inhibition efficiency increased with the increase in concentration of the inhibitor but decreased with rise in temperature, the corrosion inhibition efficiency attains 91.26% in 8 × 10−2 g/L concentration at 30 °C. The polarization studies showed that the studied amino acid derivative can be used as a corrosion inhibitor. The surface of inhibited and uninhibited specimens was analyzed by scanning electron microscopy and the adsorption of the inhibitor on the mild steel surface obeys Langmuir adsorption isotherm. The quantum chemical descriptors such as the energy of highest occupied molecular orbital, energy of lowest unoccupied molecular orbital were calculated and the inhibition mechanism can be analyzed by the distribution of electrons. Analysis indicated that the inhibitor molecular and empty d orbital of metal forms the coordination bond, covers on the surface of metal, and prevents corrosion reaction.

1-Naphthyl- and mesityltellurium(IV,II) derivatives of small bite chelating organic ligands: effect of steric bulk and intramolecular secondary bonding interaction on molecular geometry and supramolecular association

The synthesis and characterization of unsymmetric diorganotellurium compounds containing a sterically demanding I-naphthyl or
mesitylligand and a small bite chelating organic ligand capable of 1,4-Te···N(O) intramolecular interaction is described. The reaction
of ArTeCl₃ (Ar = I-C_lOH₇, Np; 2,4,6-Me₃C₆H_2' Mes) with (SB)HgCI [SB = the Schiff base, 2-(4,4'-N0₂C₆H₄CH=NC₆H₃-Me)] or a methyl ketone (RCOCH₃) afforded the corresponding dichlorides (SB)ArTeCI₂ (Ar = Np, 1Aa; Mes, 1Ba) or (RCOCH₂)ArTeCl₂ (Ar = Np; R = Ph (2Aa), Me (3Aa), Np (4Aa); Ar = Mes, R = Ph (2Ba)). Reduction of 1Aa and 1Ba by Na₂S₂0₅ readily gave the tellurides (SB)ArTe (Ar = Np (1A), Mes, (1B) but that of dichlorides derived from methylketones was complicated due to partial decomposition to tellurium powder and diarylditelluride (Ar₂Te₂), resulting in poor yields of the corresponding tellurides 2A, 2B and 3A. Oxidation of the isolated tellurides with S0₂Cl₂, Br₂ and I₂ yielded the corresponding dihalides. All the synthesized compounds have been characterized with the help of IR, ¹H, ^l3C, and ¹²⁵Te NMR and in the case of 2Aa, and 2Ba by X-ray crystallography. Appearance of only one ¹²⁵Te signal indicated that the unsymmetric derivatives were stable to disproportionation to symmetric species. Intramolecular 1,4-Te· . ·0 secondary bonding interactions (SBIs) are exhibited in the crystal structures of both the tellurium(IV) dichlorides, 2Aa, and 2Ba. Steric repulsion of the mesityl group in the latter dominates over lone pair-bond pair repulsion, resulting in significant widening of the equatorial C-Te-C angle. This appears to be responsible for the lack of Te· . ·CI involved supramolecular associations in the crystal structure of 2Ba.

Effect of heat-treatment atmosphere on the bond strength of apatite layer on Ti substrate

Objectives
The purpose of this study was to investigate the bond strength of apatite layer on titanium (Ti) substrate coated by biomimetic method and to improve the bonding of apatite layer to Ti substrate by optimizing the alkali heat-treatment process.

Methods
Ti plates pre-treated with an alkali solution of 10 M sodium hydroxide (NaOH) were heat-treated at 600 °C for 1 h at different atmospheres: in air and in vacuum. A dense apatite layer formed on top of the sodium titanate layer after soaking the alkali and heat-treated Ti samples in simulated body fluid (SBF) for up to 3 weeks. The bond strengths of the sodium titanate layer on Ti substrate, and apatite layer on the sodium titanate layer, were measured, respectively, by applying a tensile load. The fracture sites were observed with a scanning electron microscope (SEM).

Results
The apatite layer on the substrate after alkali heat-treatment in air achieved higher bond strength than that on the substrate after alkali heat-treatment in vacuum. It was found that the interfacial structure between the sodium titanate and Ti substrate has a significant influence on the bond strength of the apatite layer.

Significance
It is advised that titanium implants can achieve better osseointegration under load-bearing conditions by depositing an apatite layer in vivo on a Ti surface subjected to alkali and heat-treated in air.

Cleavage of Ru-C(aryl) bond of a four-membered ortho-metalated ruthenium(II) organometallics by mercaptopyrimidine and pyridine-2,6-dicarboxylate ligands: spectroscopic, structural and computational studies

The heterogeneous phase reaction of Ru(η2-RL)(PPh3)2(CO)Cl (1) with 2-mercaptopyrimidine(pymSH) and pyridine-2,6-dicarboxylate(dipic) ligands afforded the complexes of the type Ru(PPh3)(CO)(pymS)2 (2) and Ru(PPh3)2(CO)(dipic) (3) in excellent yield respectively. The chelation of pymS/dipic is attended with the cleavage of Ru-O, Ru-Cl and Ru-C(aryl) bonds and the RL ligand is no longer coordinated with the metal center in the products. The spectral (UV-Vis, IR, 1H NMR) and electrochemical data of the complexes are included. In dichloromethane solution both 2 and 3 display one quasi-reversible RuIII/RuII cyclic voltammetric response with E1/2 in the range 1.15-1.50 V vs Ag/AgCl. Structure determinations of 2 and the solvate 3·CH3CN have revealed distorted octahedral RuCN2S2P coordination sphere for 2 and RuCNO2P2 coordination sphere for 3·CH3CN. For 2 the pairs (P, N), (S, S) and (C, N) define the three trans directions whereas for 3·CH3CN those pairs are (P, P), (C, N) and (O, O). The electronic structures and the absorption spectra of 2 and 3 are also scrutinized by the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) analysis.

Announcement effect on the credit spreads of US dollar Malaysian bonds

We find that international political events have more influence on the changes of bond yield spreads from Malaysian USD issues than domestic events. Significant results are consistent across different issues. The resignation by the former Prime Minister, Dr. Mahathir, however created mix response from the market. Using error correction model, this study also found the monetary policy by Federal Reserve have long term and significant impact on the behaviour of the Malaysian USD issues.

The credit spread dynamics of Latin American euro issues in international bond markets

This paper investigates two important relationships using the sovereign issues made by major Latin American economies in the international bond market: the determinants of credit spread changes using variables derived from structural and macroeconomic theory and the impact of a default episode on the underlying equilibrium dynamics. We find four significant determinants of credit spread changes: an asset and interest rate factor—consistent with structural models of credit spread pricing; the exchange rate—consistent with macroeconomic determinants and the slope of the yield curve—consistent with a business cycle effect. Also, an intra-regional analysis of sovereign yields reveals a shift in the long-run equilibrium dynamics around the Argentine default on the 23 December 2001.

Effect of surface roughness of Ti, Zr, and TiZr on apatite precipitation from simulated body fluid

Some of the critical properties for a successful orthopedic or dental implant material are its biocompatibility and bioactivity. Pure titanium (Ti) and zirconium (Zr) are widely accepted as biocompatible metals, due to their non-toxicity. While the bioactivity of Ti and some Ti alloys has been extensively investigated, there is still insufficient data for Zr and titanium-zirconium (TiZr) alloys. In the present study, the bioactivity, that is, the apatite forming ability on the alkali and heat treated surfaces of Ti, Zr, and TiZr alloy in simulated body fluid (SBF), was studied. In particular, the effect of the surface roughness characteristics on the bioactivity was evaluated for the first time. The results indicate that the pretreated Ti, Zr and TiZr alloy could form apatite coating on their surfaces. It should be noted that the surface roughness also critically affected the bioactivity of these pretreated metallic samples. A surface morphology with an average roughness of approximately 0.6 microm led to the fastest apatite formation on the metal surfaces. This apatite layer on the metal surface is expected to bond to the surrounding bones directly after implantation.

Microstructures and bond strengths of the calcium phosphate coatings formed on titanium from different simulated body fluids

Calcium phosphate (Ca-P) coatings were deposited on Ti substrates by a biomimetic method from m-SBF and 10× SBF, respectively. Comparative study of microstructures and bond strengths of the Ca-P coatings deposited from those different SBFs was carried out. Effect of the surface roughness of the substrates on the bond strength of the Ca-P coatings was also studied. Scanning electron microscopy (SEM), X-ray diffractometry (XRD), Fourier transformed infrared spectroscopy (FTIR), inductive coupled plasma spectrometry (ICP) and thermogravimetry (TG) were used to characterize the Ca-P coatings. The bond strengths between the coatings and Ti substrates were measured using an adhesive strength test. Results indicated that the ionic concentrations of the SBFs and the surface roughness of the substrate had a significant influence on the formation, morphology and bond strength of the Ca-P precipitates. The induction period of time to deposit a complete Ca-P layer from the m-SBF is much longer, but the Ca-P coating is denser and has higher bond strength than that formed from the 10× SBF. The Ti with a surface roughness of R_a 0.64 µm and R_z 2.81 µm favoures the formation of a compact Ca-P coating from the m-SBF with the highest bond strength of approximately 15.5 MPa.

Psychometric properties of the caregiver assessment of movement participation scale for screening children with development coordination disorders

Using Rasch analysis, the psychometric properties of a newly developed 35-item parent-proxy instrument, the Caregiver Assessment of Movement Participation (CAMP), designed to measure movement participation problems in children with Developmental Coordination Disorder, were examined. The CAMP was administered to 465 school children aged 5–10 years. Thirty of the 35 items were retained as they had acceptable infit and outfit statistics. Item separation (7.48) and child separation (3.16) were good; moreover, the CAMP had excellent reliability (Reliability Index for item = 0.98; Person = 0.91). Principal components analysis of item residuals confirmed the unidimensionality of the instrument. Based on category probability statistics, the original five-point scale was collapsed into a four-point scale. The item threshold calibration of the CAMP with the Movement Assessment Battery for Children Test was computed. The results indicated that a CAMP total score of 75 is the optimal cut-off point for identifying children at risk of movement problems.

Announcement effect on the credit spreads of US dollar Malaysian bonds

The main purpose of this paper is to extend the empirical research on the behavior of credit spreads on the USD denominated Malaysian bonds. We find that international political events have more influence on the changes of bond yield spreads from Malaysian USD issues than domestic events. Significant results are consistent across different issues. However, the resignation by the former Prime Minister, Dr Mahathir Mohamad, created a mixed response from the market. Using an error correction model, this study also found that the monetary policy by the US Federal Reserve has a long-term and significant impact on the behavior of the Malaysian USD issues. This study also provides further evidence that the current theoretical framework is sufficient to explain changes in the credit spread of bonds issued by the emerging market.

Volatility linkages and spillovers in stock and bond markets : some international evidence

This study investigates the transmission of market-wide volatility between the equity markets and bond markets of Japan, Germany, the U. K., and the U. S. To measure the volatility transmission, the BEKK- a decomposition approach to the multivariate GARCH (1,1) model, is used to examine the cross-market contemporaneous effect of information arrival. Our results suggest that within the domestic cross markets, the volatility transmission is undirectional from the stock market to the bond market. Evidence from international cross-market analysis is mixed, with strong evidence on volatility spillover among these international stock markets, but weak evidence between international stock and bond markets. In addition, there are significant bi-directional volatility transmissions between stock markets in Germany and the U. K., and between Germany and the U. S. The volatility transmissions among these markets suggest that the international diversification of bonds is not prevalent.

Volatility transmissions between stock and bond markets : evidence from Japan and the U.S.

This study attempts to investigate the transmission of market-wide volatility between the equity markets and bond markets of Japan and the U.S. To measure the volatility transmission, the BEKK (Baba, Engle, Kraft and Kroner, 1990) method, a decomposition approach of the multivariate GARCH (1,1) model, is used to examine the cross-market contemporaneous effect of information arrival. The time series analysis provides evidence to the long-run phenomena of causality in conditional variances of paired assets within the local and international markets. Within various pairings, some evidence of bi-directional volatility transmissions such as informational linkages have been observed. Our empirical results suggest that within the domestic cross markets, the volatility transmission is unidirectional from the stock market to the bond market. Evidence from international cross-market analysis is mixed, with strong evidence on volatility spillover among these international stock markets, but weak evidence between international stock and bond markets. In addition, there are significant directional volatility transmissions between DJI index and FTSE100 index, and between DJI index and DAX200 index. The volatility transmission between these two markets indicates that the international diversification of bonds is not prevalent.

Volatility transmission between stock and bond markets : evidence from US and Australia

This paper investigates the cross-market informational dependence between these assets under disparate interest rate conditions of the U.S and Australia. With conditional variance as a proxy for volatility, we use the BEKK – a matricular decomposition of the bivariate GARCH (1,1) model to examine the cross-market contemporaneous effect of information arrival. Applying the model to the stock and bond indices of both countries, we find evidence of volatility spillover, thereby supporting the notion of informational dependence between each market

The effect of coordinating and non-coordinating additives on the transport properties in ionic liquid electrolytes for lithium batteries

In the present study we expand our analysis of using two contrasting organic solvent additives (toluene and THF) in an ionic liquid (IL)/Li NTf 2 electrolyte. Multinuclear Pulsed-Field Gradient (PFG) NMR, spin-lattice (T1) relaxation times and conductivity measurements over a wide temperature range are discussed in terms of transport properties and structuring of the liquid. The conductivity of both additive samples is enhanced the most at low temperatures, with THF slightly more effective than toluene. Both the anion and lithium self-diffusivity are enhanced in the same order by the additives (THF > toluene) while that of the pyrrolidinium cation is marginally enhanced. 1H spin-lattice relaxation times indicate a reasonable degree of structuring and anisotropic motion within all of the samples and both 19F and 7Li highlight the effectiveness of THF at influencing the lithium coordination within these systems.