An Experimental Charge Density Study of the N-H+…O− Bonds in a Proton-Transfer System in Comparison with Regular N-H…O and O-H…N Hydrogen Bonds

An experimental charge density study has been carried out on N-H⁺…O⁻ bonds in the proton-transfer compound piperazinium oxalate as well as on the normal O-H…N bonds in the thiodiglycolic acid-4,4′-bipyridine complex, based on X-ray diffraction measurements at 130 K. The results are compared with those of the normal N-H…O bonds in 5-nitrouracil. In spite of the different crystal geometries, the N-H⁺…O⁻ and the N-H…O bonds exhibit similar values of electron density and the associated curvatures at the hydrogen-acceptor bond critical points (BCPs). Surprisingly, the polarization parameters of the two BCPs are comparable (˜20%). The pseudoatomic charge on the protonated N atom (in N-H⁺…O⁻) is, however, much smaller (-0.05 e) in comparison to the unprotonated case (˜ -0.2 e). The O-H…N hydrogen bonds exhibit shorter H…N distances compared to the charged and the uncharged H…O bonds. Accordingly, the electron densities and the curvatures evaluated at the H…N critical points are also much higher.     

Properties of silica/clay filled heavy‐duty truck tire thread formulation

A tire thread formulation for heavy‐duty trucks containing SBR/BR rubber blend and varying proportions of silica/clay fillers including a silane‐coupling agent have been investigated. The various mixes were compounded in a Banbury ‘O’ mixer and vulcanized using the EV‐system. Silica/clay (80/0) served as the control mix. The oscillating disc rheometer (ODR) was used in determination of cure characteristics. Substitution of silica (80 phr) with china clay up to 40 phr increased the cure rate of the rubber blend mixes as well as their maximum torque level (T_max). T_max was observed to be highest at a filler blend ratio of 40/40 phr. Synergism between silica and clay at this filler blend mixture is suggested to be responsible for the observation. The heat buildup was reduced from 43 to 20°C as the clay content increased. Results also showed that the rubber blend compound containing silica/clay (60/20) filler blend in the stated ratio exhibited the best balance of properties in the critical parameters such as the absolute torque level (69.5 dNm), heat buildup (39°C), and abrasion resistance (0.574 mg.loss/1,000 rev). The rate of depreciation of abrasion resistance of rubber blend compound as the clay content increased was found to be 0.035 mg loss/1,000 rev as silica is substituted with one part of china clay phr. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1024–1028, 2004     

Glucose oxidase electrodes of poly(o‐anisidine), poly(o‐toluidine), and their copolymer as biosensors: A comparative study

Thin films of poly(o‐anisidine) (POA), poly(o‐toluidine) (POT), and their copolymer poly(o‐anisidine‐co‐o‐toluidine) (POA‐co‐POT) were electropolymerized in solutions containing 0.1M monomer(s) and 1M H₂SO₄ as an electrolyte through the application of a sequential linear potential scanning rate of 50 mV/s between ?0.2 and 1.0 V versus an Ag/AgCl electrode on a platinum electrode. A simple technique was used to construct glucose sensors through the entrapment of glucose oxidase (GOD) in thin films of POA, POT, and their copolymer POA‐co‐POT, which were electrochemically deposited on a platinum plate in phosphate and acetate buffers. The maximum current response was observed for POA, POT, and POA‐co‐POT GOD electrodes at pH 5.5 and at a potential of 0.60 V (vs Ag/AgCl). The phosphate buffer yielded a fast response in comparison with the acetate buffer in amperometric measurements. The POT GOD electrode showed a fast response and was followed by POA‐co‐POT and POA GOD electrodes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1877–1884, 2004     

Combustion Modes and Mechanisms of High‐Temperature Oxidation of Magnesium in Oxygen

Oxidation and combustion of single magnesium particles in an oxygen–argon mixture is experimentally studied. A diagram of hightemperature oxidation of magnesium is constructed, and a relation between the structural features of the oxide film and macrokinetics of hightemperature oxidation and mechanisms of transition between different oxidation regimes is established.     

Coupling Between Magnetic Exchange and Charge Activation in Cu‐Doped LaFeO3

Material research on perovskite‐type oxides (ABO₃) has been driven by the recognition of their unique properties primarily attributed to the presence of oxygen octahedron (BO₆). Since 2003, the discovery of strong coupling in TbMnO₃ and BiFeO₃ has stimulated new interests in understanding the relationship between magnetic and electric properties in perovskites. In this article, we report our recent work on the magnetic superexchange interaction and charge formation in copper‐doped LaFeO₃ using high‐temperature neutron diffraction and thermoelectric measurements. In situ neutron diffraction measurements show a loss of antiferromagnetic ordering above 450°C. With an increase in Cu content, the (Fe, Cu)‐O bond length decreases and the (Fe, Cu)–O–(Fe, Cu) bond angle increases, which leads to an enhancement of the Fe–O–Fe superexchange interaction. Thermoelectric and electrical measurements show that the formation of electron holes in Cu‐doped LaFeO₃ is a thermally activated process with two distinct regions with a transition temperature near 450°C, in congruence with the magnetic measurements. Our work show that Cu is in 3+ state in La(Fe,Cu)O₃ at room temperature, resulting in the maximum superexchange interaction between Fe³⁺ ions.     

Digital PCR Panel for Sensitive Hematopoietic Chimerism Quantification after Allogeneic Stem Cell Transplantation

Accurate and sensitive determination of hematopoietic chimerism is a crucial diagnostic measure after allogeneic stem cell transplantation to monitor engraftment and potentially residual disease. Short tandem repeat (STR) amplification, the current “gold standard” for chimerism assessment facilitates reliable accuracy, but is hampered by its limited sensitivity (≥1%). Digital PCR (dPCR) has been shown to combine exact quantification and high reproducibility over a very wide measurement range with excellent sensitivity (routinely ≤0.1%) and thus represents a promising alternative to STR analysis. We here aimed at developing a whole panel of digital-PCR based assays for routine diagnostic. To this end, we tested suitability of 52 deletion/insertion polymorphisms (DIPs) for duplex analysis in combination with either a reference gene or a Y-chromosome specific PCR. Twenty-nine DIPs with high power of discrimination and good performance were identified, optimized and technically validated. We tested the newly established assays on retrospective patient samples that were in parallel also measured by STR amplification and found excellent correlation. Finally, a screening plate for initial genotyping with DIP-specific duplex dPCR assays was designed for convenient assay selection. In conclusion, we have established a comprehensive dPCR system for precise and high-sensitivity measurement of hematopoietic chimerism, which should be highly useful for clinical routine diagnostics.     

GRADIENT OF THE MECHANICAL MODULUS IN GLASS-EPOXY-METAL JOINTS AS MEASURED BY BRILLOUIN MICROSCOPY

The newly developed Brillouin microscopy is used for the first time to measure in situ the longitudinal elastic stiffness coefficient in the GHz-range inside of glass-epoxy-metal joints as a function of distance from the substrates. Interphases with a local variation of mechanical properties are quantitatively characterized. These interphases possess unexpected widths of tens to hundreds of microns. Inside the interphases, the spatial variation of the longitudinal stiffness coefficient depends on the type of substrate, on the curing conditions for the epoxy and probably on the distribution of internal stresses. The obtained spatial mechanical profiles provide valuable insight into the morphology-driven mechanics of the interphase, but additional information is needed for a full understanding of their physical and chemical origin. The presented results prove the sensitivity of the Brillouin microscopy; the elastic stiffness coefficients are detected with an accuracy in the subpercentage range. The spatial resolution is better than 10 µm.     

Performance of Methanol Oxidation Catalysts with Varying Pt:Ru Ratio as a Function of Temperature

This paper describes the effects of varying the Pt to Ru ratio in carbon-supported catalysts for methanol oxidation as a function of temperature. Previously these effects were studied in isolation, but now it is shown that the composition of a given catalyst as a function of temperature is extremely important for its activity towards methanol oxidation. Platinum rich 3:2 atomic ratio catalysts perform better than a 1:1 catalyst at 25 °C, where only Pt is believed to be active towards methanol dehydrogenation, since this process is a highly thermally activated process on Ru sites. This result is reversed at 65 °C, where the 1:1 catalyst displays much higher currents across the entire range of polarization. This may result from methanol dehydrogenation occurring on both Ru and Pt sites at higher temperatures. At an intermediate temperature, 45 °C, the 3:2 catalyst is seen to perform better at lower current values, while the 1:1 catalyst is superior at higher current densities, with the crossover occurring at 62 A g^–1. As a consequence, when designing fuel cell catalysts, the composition of the catalyst employed should be tailored with respect to the exact operating conditions, in order to promote optimum fuel cell performance.     

Optimization of citrus peels D-limonene extraction using solvent-free microwave green technology

Attention is presently drawn to the development of a new and green alternative technique for the extraction of essential oil from citrus plant materials. This study was aimed at the extracting essential oil from orange and lemon peels using solvent-free microwave method. This process uses microwave-assisted hydro-diffusion technique to extract essential oil from citrus peels. Response surface methodology was used to investigate the effect of microwave power (200–1,000?W) and extraction time (10–40?min) on the essential oil yield. The oil extracted was characterized using Fourier transform infrared radiation (FTIR) and Gas chromatography–mass spectrometry analysis to determine the functional groups and chemical components present, respectively. The optimum yield of extract from orange and lemon peels were 3.7 and 2.0%, respectively at corresponding power of 1,000?W and time of 10?min. The analysis of variance results showed that the resulting models for both orange and lemon peels were significant and microwave power had greater influence on the extraction processes at both linear and quadratic levels. The FTIR analysis revealed prominent functional groups of alkenes that majorly constitute limonene compound at 1,642 and 1,643?cm^?1 for orange and lemon peels, respectively. The present process permits fast and efficient extraction, avoids water and solvent consumption, and allows substantial energy savings.     

Design and characterization of porous mullite based semi-vitrified ceramics

Three porous ceramic composites were prepared from readily available raw materials (kaolin, bauxite, feldspar and kyanite). The porous ceramic formulations were sintered at different temperatures ranging from 1200 to 1400°C. The fired specimens were characterized by determining their porosity, bulk density, flexural strength, thermochemical stability, microstructure, water and mercury permeability. Apparent porosity and bulk density in the range 15.57 ± 1.56–42.73 ± 2.28?vol% and 2.23 ± 0.31–2.68 ± 0.41?g?cm^?3 respectively were obtained after firing. The flexural strength was in the range of 32.31 ± 2.1–74.88 ± 2.57?MPa and the thermal expansion coefficient of 5–9 × 10^?6 C^?1. The values of water permeability were 745.4, 641.45 and 525.91?L/m² h?kPa respectively for PK3, PK4 and PK5. It was found that at high temperature (1400?°C), kyanite particles enhanced the porosity and thermal stability by reducing glass formation and improving crystallization. The presence of the interconnected pores with size between 0.03 and 4.50?µm, the high total volume of pores together with the high flexural strength and thermal stability make the synthesized porous ceramics suitable for high-pressure filtering applications.