Kinetic study of the chlorination of gallium oxide

The kinetics of the chlorination of gallium oxide in chlorine atmosphere was studied between 650 °C and 800 °C. The calculations of the Gibbs standard free energy variation with temperature for the reaction Ga₂O_3(S)+3Cl_{2 (g)}→2GaCl_3(g)+1.5O_{2 (g)} show that direct chlorination is favorable above 850 °C. Thermogravimetric experiments were performed under isothermal and nonisothermal conditions. The effect of temperature, gas flow rate, and Cl₂ partial pressure were studied. The solids were characterized by X-ray diffraction (XRD) and scanning electronic microscopy (SEM). The nonisothermal results showed that chlorination of Ga₂O₃ starts at approximately 650 °C, with a mass loss of 50 pct at 850 °C. The isothermal results between 650 °C and 800 °C indicated that the reaction rate increased with temperature. The correlation of the experimental data with different solid-gas reaction models showed that the results are adequately represented by the model proposed by Shieh and Lee: X=1−{1−b ₂₂[b ₂₁ t+e ^−b ₂₁ ^t−1]}^1/(1−γ). From this model, it was found that the rate of reaction for the chlorination of Ga₂O₃ is of the order 0.68 with respect to Cl₂ and the activation energy is 113.23 kJ/mol. On the other hand, the order of the activation rate of the interface surface is 0.111 with respect to Cl₂ and its activation energy is 23.81 kJ/mol.     

Ferroelectric/ferroelastic interactions and a polarization switching model

Ferroelectric and ferroelastic switching cause ferroelectric ceramics to depolarize and deform when subjected to excessive electric field or stress. Switching is the source of the classic butterfly shaped strain vs electric field curves and the corresponding electric displacement vs electric field loops [1]. It is also the source of a stress—strain curve with linear elastic behavior at low stress, non-linear switching strain at intermediate stress, and linear elastic behavior at high stress [2, 3]. In this work, ceramic lead lanthanum zirconate titanate (PLZT) is polarized by loading with a strong electric field. The resulting strain and polarization hysteresis loops are recorded. The polarized sample is then loaded with compressive stress parallel to the polarization and the stress vs strain curve is recorded. The experimental results are modeled with a computer simulation of the ceramic microstructure. The polarization and strain for an individual grain are predicted from the imposed electric field and stress through a Preisach hysteresis model. The response of the bulk ceramic to applied loads is predicted by averaging the response of individual grains that are considered to be statistically random in orientation. The observed strain and electric displacement hysteresis loops and the nonlinear stress—strain curve for the polycrystalline ceramic are reproduced by the simulation.     

Nature of the adhesion of gallium solders to oxide materials

Powder Metallurgy and Metal Ceramics -     

Myosin conformational states determined by single fluorophore polarization

Muscle contraction is powered by the interaction of the molecular motor myosin with actin. With new techniques for single molecule manipulation and fluorescence detection, it is now possible to correlate, within the same molecule and in real time, conformational states and mechanical function of myosin. A spot-confocal microscope, capable of detecting single fluorophore polarization, was developed to measure orientational states in the smooth muscle myosin light chain domain during the process of motion generation. Fluorescently labeled turkey gizzard smooth muscle myosin was prepared by removal of endogenous regulatory light chain and re-addition of the light chain labeled at cysteine-108 with the 6-isomer of iodoacetamidotetramethylrhodamine (6-IATR). Single myosin molecule fluorescence polarization data, obtained in a motility assay, provide direct evidence that the myosin light chain domain adopts at least two orientational states during the cyclic interaction of myosin with actin, a randomly disordered state, most likely associated with myosin whereas weakly bound to actin, and an ordered state in which the light chain domain adopts a finite angular orientation whereas strongly bound after the powerstroke.     

Oxygen imaging in perfused hearts by dynamic nuclear polarization

The feasibility of localized oximetry by dynamic nuclear polarization (DNP) imaging is demonstrated on perfused sheep hearts. DNPI is a magnetic, double resonance technique, in which the electron paramagnetic resonance (EPR) of a free radical dissolved in a perfusion medium is saturated, while the nuclear magnetic resonance (NMR) of water protons is used to perform conventional NMR imaging. The presence of oxygen reduces the enhancement of the NMR signal induced by DNP. The oxygen content of sheep heart tissues was detected by the subtraction of the DNP image of the heart, perfused with a nitrogen-equilibrated solution, from an image obtained when the heart was perfused with an oxygen-equilibrated solution. This result was obtained with extreme oxygen partial pressure, and the discussion presents physical and chemical means for improving the DNP imaging method. Physical means include field cycling, electron paramagnetic rotary saturation, and the use of a 180 degrees NMR pulse before EPR irradiation. The chemical means discussed are deuterium substitution in nitroxides and the potential use of solid, free radical probes. It is suggested to use the perfused heart model for comparing the numerous methods available to measure the oxygen content of tissues.     

Dynamic nuclear polarization at very low magnetic fields

Non-mosaic Klinefelter patients are generally azoospermic due to primary testicular failure. Nevertheless, in some cases, testicular spermatozoa may be recovered and utilized to fertilize oocytes via intracytoplasmic sperm injection (ICSI). As the risk for an increased number of gonosomes in these spermatozoa is unclear, preimplantation genetic diagnosis (PGD) may be attempted in the resulting embryos. In the present study, we report our experience with the combined approach of sperm retrieval by testicular fine needle aspiration (FNA), ICSI and PGD in seven consecutive non-mosaic Klinefelter individuals. In four patients, between one and five spermatozoa were retrieved in five out of nine consecutive attempts. In a fifth patient, only 10 round spermatids could be isolated. Mature spermatozoa were injected into a total of 16 metaphase-II oocytes, of which 11 (69%) remained intact. Two distinct pronuclei (2PN) were observed in four oocytes (36%) while a single pronucleus (1PN) was documented in two oocytes. Five cleavage stage embryos developed from the oocytes of two couples. Upon the request of one couple, their three embryos (two derived from 1PN oocytes) were transferred without PGD but pregnancy was not achieved. PGD by fluorescence in-situ hybridization (FISH) was performed in the two embryos of the other couple which were derived from normal fertilization. PGD results of one embryo were 18,18,X,X,Y, the embryo was not transferred and FISH analysis of the remaining blastomeres identified variable chromosome numbers in the nuclei. The second embryo was diagnosed as normal and was transferred, resulting in a successful pregnancy and birth. In conclusion, the results of this report indicate that a pregnancy and birth may be attained in azoospermic non-mosaic Klinefelter individuals by testicular FNA combined with ICSI. Due to the unknown risk of gonosomes aneuploidy in embryos from Klinefelter patients, PGD or prenatal diagnosis should be recommended.