Catalytic behavior of YBa2Cu3O7-x in the partial oxidation of methanol to formaldehyde

The partial oxidation of methanol to formaldehyde was studied over YBa₂Cu₃O_7-x catalyst in a flow reactor. The structural change of YBa₂Cu₃O_7-x before and after the reaction was measured by means of XRD and iodometric titration method. The catalytic characteristics of YBa₂Cu₃O_7-x for the partial oxidation of methanol to formaldehyde was due to copper ions. It was found that Cu⁺² was responsible for the higher selectivity for formaldehyde.     

Effects of Na+ and Mg2+ on the structures of supercoiled DNAs: comparison of simulations with experiments

Recent cryo-electron microscopy (cryo-EM) results suggest that sufficient NaCl concentration (> or approximately 0.1 M) and superhelix density (> or approximately-0.05) cause circular DNAs to adopt highly extended, tightly interwound configurations, in which the strands are laterally contiguous along almost their entire length. Millimolar levels of MgCl2 reportedly act synergistically with NaCl to produce similar conformations. However, Monte Carlo simulations with purely repulsive interduplex forces failed to reproduce such structures. In the present work, solution measurements of particular physical properties were performed both to characterize the effects of Na+ and Mg2+ on DNA structure and to provide quantitative tests of Monte Carlo simulations of circular DNAs. Supercoiled p30 delta DNAs in 10 mM Tris plus 0, 0.122, and 0.1 M NaCl, and 0.1 M NaCl plus 4 mM Mg2+ were examined by static and dynamic light scattering (LS and DLS), time-resolved fluorescence polarization anisotropy (FPA) of intercalated ethidium, and circular dichroism (CD) spectroscopy. Upon addition of 0.122 M NaCl, the radius of gyration (Rg) decreased substantially, which indicates that p30 delta adopts a more compact structure. This contradicts the cryo-EM studies, where molecular extension and Rg both increase upon adding 0.1 M NaCl. In 0.1 M NaCl, the torsion constant measured by FPA is practically invariant to superhelix density, and the plateau diffusion coefficient at large scattering vector (Dplat) is likewise nearly the same at both relaxed and native superhelix densities. Such invariance is difficult to reconcile with any transition from relaxed circles to tightly interwound structures with laterally contiguous strands. Metropolis Monte Carlo simulations were performed to generate canonically distributed sets of structures, from which average Do values and scattered intensity ratios, [symbol: see text]I (zero) [symbol: see text]/[symbol: see text] l(k) [symbol: see text], were calculated. Agreement between simulations and experiments in regard to [symbol: see text] I(O) [symbol: see text] /[symbol: see text] I(k) [symbol: see text], D(zero) and the supercoiling free energy, delta Gsc (delta l), is remarkably good for the most extensively studied p30 delta samples. The simulated structures exhibit no sign of very tight interwinding with extensive lateral contacts, but instead exhibit most probable superhelix diameters of 85 to 90 A. When 4 mM Mg2+ was added to native supercoiled p30 delta in 0.1 M NaCl, Rg decreased, D(zero) increased, and the longest internal relaxation rate (1/tau 2(zero)) increased, all of which indicate a further overall contraction of the molecular envelope. The torsion constant exhibited a slight increase that is hardly statistically significant. In this case, agreement between the simulations and experiments was only semi-quantitative for most samples investigated, although the predicted contraction was exhibited by all five samples of p30 delta and one of pBR322 DNA. The simulated structures in 0.1 M NaCl plus 4 mM Mg2+ again showed no sign of extensive lateral contacts. A plausible explanation is proposed for the highly extended, tightly interwound structures seen in cryo-EM, and explicitly tested by Monte Carlo simulations of a 1000 bp circular DNA at +25 and -50 degrees C. Structures identical to those seen in cryo-EM are in fact the equilibrium structures in the simulations at -50 degrees C, and the estimated time for equilibration (2.3 x 10(-6) second) is much smaller than the estimated time for vitrification (1 x 10(-4) second).     

Conservation surgery for breast cancer: selection criteria and technical considerations

Patients with stage I or II breast cancer are candidates for either modified radical mastectomy or breast preservation therapy involving limited resection of the primary tumor, axillary dissection, and breast irradiation. The overall survival rates of both these approaches are comparable according to retrospective reviews and ongoing clinical trials, and long-term follow-up confirms the earlier findings. Thus, patients should be given the choice between these two options by surgeons, radiation therapists, and other physicians involved in their care. However, not all breast cancer patients will choose breast preservation surgery, and because of tumor-related and other factors not all patients are candidates. The patient selection criteria are discussed herein and the optimal surgical techniques are reviewed.     

The rank one mixed μ problem and ‘kharitonov-type’ analysis

The general mixed μ problem has been shown to be NP hard, so that the exact solution of the general problem is computationally intractable, except for small problems. In this paper we consider not the general problem, but a particular special case of this problem, the rank one mixed μ problem. We show that for this case the mixed μ problem is equivalent to its upper bound (which is convex), and it can in fact be computed easily (and exactly). This special case is shown to be equivalent to the so-called ‘affine parameter variation’ problem (for a polynomial with perturbed coefficients) which has been examined in detail in the literature, and for which several celebrated ‘Kharitonov-type’ results have been proven.     

Formation of C4 species in the deactivation of a Pd/SiO2 catalyst during the selective hydrogenation of acetylene

The deactivation characteristics of Pd/SiO₂ in the selective hydrogenation of acetylene were correlated with changes in the amount of the C4 species produced. The amounts of butenes produced changed in parallel with the catalyst activity, indicating that the rate limiting step for butene production was the same as that for acetylene hydrogenation. On the other hand, the amount of 1,3-butadiene produced changed, showing a maximum with catalyst deactivation because 1,3-butadiene is an intermediate in the sequential reaction process which involves both the production and consumption of 1,3-butadiene. This was verified by a simultaneous TG/reaction experiment showing that 1,3-butadiene was a precursor of green oil. The catalyst showed a self-regenerative behavior in its activity and the amounts of C4 species produced during the early stage of deactivation because two opposite factors, which contributed to either the lowering or the promotion of activity, were involved in the process. A specific type of polymer species, produced during the initial period of deactivation, is proposed to be responsible for the promotion of catalyst activity.     

Bias-temperature instabilities of polysilicon gate HfO/sub 2/ MOSFETs

Bias-temperature instabilities (BTI) of HfO/sub 2/ metal oxide semiconductor field effect transistors (MOSFETs) have been systematically studied for the first time. NMOS positive BTI (PBTI) exhibited a more significant V/sub t/ instability than that of PMOS negative BTI (NBTI), and limited the lifetime of HfO/sub 2/ MOSFETs. Although high-temperature forming gas annealing (HT-FGA) improved the interface quality by passivating the interfacial states with hydrogen, BTI behaviors were not strongly affected by the technique. Charge pumping measurements were extensively used to investigate the nature of the BTI degradation, and it was found that V/sub t/ degradation of NMOS PBTI was primarily caused by charge trapping in bulk HfO/sub 2/ rather than interfacial degradation. Deuterium (D/sub 2/) annealing was found to be an excellent technique to improve BTI immunity as well as to enhance the mobility of HfO/sub 2/ MOSFETs.     

Impairment of energy metabolism and excitotoxic cell death in Huntington disease

The gene for Huntington's disease is widely expressed in brain and yet the illness is characterized pathologically by a distinct regional pattern of cell death. Various theories for this selective vulnerability have been offered but the most compelling remains that of abnormal energy metabolism. These issues are reviewed.