Possible role of Lewis acid catalysis in the oxidation of alkenes and α,β-unsaturated ketones using bleomycin-zn(ii) and bleomycin-fe(iii)-iodosylbenzene in aqueous methanol

C₆H₅IO in CH₃OH-H₂0 is activated towards electrophilic attack upon various alkenes by Fe(ClO₄).9H₂O, FE(III) bleomycin and ZN(II) bleomycin. The results imply that direct transfer of oxygen from an Fe(V)=0 intermediate is not required in the mechanism of oxygenation by iron-containing species, and that much earlier work is questionable as models for biological oxygenation.     

Some polishing experiments on copper in a hyperbolic cell

Some polishing experiments have been carried out on copper anodes in a hyperbolic cell designed by Gilmont and Walton, using orthophosphoric acid as the electrolyte. The results obtained have been compared to those obtained in similar experiments in a Hull cell. It has been found that very similar bands of different reflectivity and polishes are found to form in both the cells. These bands shift with time and a study of such displacements has been made. The results are briefly discussed.     

Raman microscopy of haidingerite Ca(AsO3OH)·H2O and brassite Mg(AsO3OH)·4H2O

Raman spectroscopy has been used to study the arsenate minerals haidingerite Ca(AsO₃OH)·H₂O and brassite Mg(AsO₃OH)·4H₂O. Intense Raman bands in the haidingerite spectrum observed at 745 and 855 cm⁻¹ are assigned to the (AsO₃OH)²⁻ν₃ antisymmetric stretching and ν₁ symmetric stretching vibrational modes. For brassite, two similarly assigned intense bands are found at 809 and 862 cm⁻¹. The observation of multiple Raman bands in the (AsO₃OH)²⁻ stretching and bending regions suggests that the arsenate tetrahedrons in the crystal structures of both minerals studied are strongly distorted. Broad Raman bands observed at 2842 cm⁻¹ for haidingerite and 3035 cm⁻¹ for brassite indicate strong hydrogen bonding of water molecules in the structure of these minerals. OH···O hydrogen‐bond lengths were calculated from the Raman spectra based on empirical relations. Copyright © 2009 John Wiley & Sons, Ltd.     

The tree property at the double successor of a singular cardinal with a larger gap

Starting from a Laver-indestructible supercompact κ and a weakly compact λ above κ, we show there is a forcing extension where κ is a strong limit singular cardinal with cofinality ω, $2^{\kappa }={\kappa }^{+3}={\lambda }^{+}$, and the tree property holds at ${\kappa }^{++}=\lambda$. Next we generalize this result to an arbitrary cardinal μ such that $\kappa <\mathrm{cf}(\mu )$ and ${\lambda }^{+}\le \mu$. This result provides more information about possible relationships between the tree property and the continuum function.     

Improved convergence estimate for a multiply polynomially smoothed two-level method with an aggressive coarsening

A variational two-level method in the class of methods with an aggressive coarsening and a massive polynomial smoothing is proposed. The method is a modification of the method of Section 5 of Tezaur, Vaněk (2018). Compared to that method, a significantly sharper estimate is proved while requiring only slightly more computational work.     

Structure and NMR properties of 6‐substituted‐5,6‐dihydrobenzo[c]phenanthridine alkaloids

We report a preparation of new 6‐substituted‐5,6‐dihydrobenzo[c]phenanthridines by the reaction of azoles with quaternary benzo[c]phenanthridine alkaloids sanguinarine and chelerythrine. The prepared compounds have been characterized by NMR spectroscopy, mass spectrometry, and single‐crystal X‐ray diffraction. Conformational behaviors of carbazole derivatives in solution have been investigated by low‐temperature NMR experiments. Barriers to rotation around newly formed C6–N bonds were determined to be 12–13 kcal/mol. Quantum chemical calculations have been used to reproduce the experimental observations. Large structural effects on several ¹H NMR resonances were observed experimentally, analyzed by Density Functional Theory (DFT) calculations at B3LYP/6‐311+G(d,p)/PCM level, and interpreted by ring‐current effects of the benzo[c]phenanthridine and carbazole units. Copyright © 2013 John Wiley & Sons, Ltd.     

Degradation Studies of Polycaprolactone in Banana Fibers Reinforced Thermoplastics Composites

In this paper we report the fabrication, properties and degradation studies of banana fibers–reinforced thermoplastic polymers. In order to impart hydrophobicity to the fibers and also to concomitantly increase interfacial bond strength, which is a critical factor for obtaining better mechanical properties of composites, banana fibers were treated with sodium hydroxide (5% and 10% for 4 h), sebacoyl chloride (SC) (0.5 g, 4 h), or toluene diisocyanate (TDl) (1.5 mL, 4 h). Mechanical properties of banana fibers treated with TDl were not affected to any significant extent, but there was an increase in tensile strength of fibers treated with sodium hydroxide (NaOH). Deterioration in mechanical properties was observed upon SC treatment. In thermograssimetre analogue (TGA) studies fibers showed initial mass loss (6.5%–9.5%) in the 50–150°C temperature region. Major weight loss occurred above 200°C. Scanning electron microscope (SEM) studies revealed an increase in surface roughness after alkali treatment. High density polyethylene (HDPE) modified by blending with poly (ε‐caprolactone) (80:20 w/w) was used as a thermoplastic matrix. Composites were fabricated by using 1 cm long banana fibers; the weight fraction of fibers was varied from 0.05–0.13. An increase in weight fraction of fibers resulted in an increase in tensile strength and modulus and decrease in elongation at break. Thin sheets and dumbbells were used for enzymatic and chemical hydrolysis degradation tests. The degradation of the material was monitored by weight change and loss of mechanical properties. The enzymatic degradation in (PCL) presence of Pseudomonas cepacia lipase (PCL) gave appreciable weight loss in PCL and blended materials.     

Fusion and large cardinal preservation

In this paper we introduce some fusion properties of forcing notions which guarantee that an iteration with supports of size ?κ   not only does not collapse κ⁺${\kappa }^{+}$ but also preserves the strength of κ (after a suitable preparatory forcing). This provides a general theory covering the known cases of tree iterations which preserve large cardinals (cf. Dobrinen and Friedman (2010) [3], Friedman and Halilovi? (2011) [5], Friedman and Honzik (2008) [6], Friedman and Magidor (2009) [8], Friedman and Zdomskyy (2010) [10], Honzik (2010) [12]).     

Structures and energetics of darunavir and active site amino acids of native and mutant HIV–1 protease: a computational study

Structural Chemistry - Quantum chemical calculations have been performed at the M06–2X/6–31G(d,p) level of theory to investigate the strength and nature of interactions between the...     

Colloidal Surface Active Maghemite Nanoparticles for Biologically Safe CrVI Remediation: from Core‐Shell Nanostructures to Pilot Plant Development

The present study is aimed at the exploration of achievable improvements for Cr^VI ex situ and in situ water remediation by using novel naked colloidal maghemite (γ‐Fe₂O₃) nanoparticles (surface active maghemite nanoparticles, SAMNs). The reliability of SAMNs for Cr^VI binding and removal was demonstrated, and SAMN@Cr^VI complex was characterized, as well as the covalent nature of the absorption was unequivocally proved. SAMNs were structurally and magnetically well conserved after Cr^VI binding. Thus, in consideration of their affinity for Cr^VI, SAMNs were exploited in a biological model system, mimicking a real in situ application. The assay evidenced a progressive reduction of revertant colonies of Salmonella typhimurium TA100 strain, as maghemite nanoparticles concentration increased, till the complete suppression of Cr^VI mutagen effect. Finally, an automatic modular pilot system for continuous magnetic removal and recovery of Cr^VI from water is proposed. SAMNs, thanks to their colloidal, binding, and catalytic properties, represent a promising tool as a reliable nanomaterial for water remediation by Cr^VI.