Aerobic oxidation reactions catalyzed by vanadium complexes of bis(phenolate) ligands

Vanadium(V) complexes of the tridentate bis(phenolate)pyridine ligand H(2)BPP (H(2)BPP = 2,6-(HOC(6)H(2)-2,4-(t)Bu(2))(2)NC(5)H(3)) and the bis(phenolate)amine ligand H(2)BPA (H(2)BPA = N,N-bis(2-hydroxy-4,5-dimethylbenzyl)propylamine) have been synthesized and characterized. The ability of the complexes to mediate the oxidative C-C bond cleavage of pinacol was tested. Reaction of the complex (BPP)V(V)(O)(O(i)Pr) (4) with pinacol afforded the monomeric vanadium(IV) product (BPP)V(IV)(O)(HO(i)Pr) (6) and acetone. Vanadium(IV) complex 6 was oxidized rapidly by air at room temperature in the presence of NEt(3), yielding the vanadium(V) cis-dioxo complex [(BPP)V(V)(O)(2)]HNEt(3). Complex (BPA)V(V)(O)(O(i)Pr) (5) reacted with pinacol at room temperature, to afford acetone and the vanadium(IV) dimer [(BPA)V(IV)(O)(HO(i)Pr)](2). Complexes 4 and 5 were evaluated as catalysts for the aerobic oxidation of 4-methoxybenzyl alcohol and arylglycerol β-aryl ether lignin model compounds. Although both 4 and 5 catalyzed the aerobic oxidation of 4-methoxybenzyl alcohol, complex 4 was found to be a more active and robust catalyst for oxidation of the lignin model compounds. The catalytic activities and selectivities of the bis(phenolate) complexes are compared to previously reported catalysts.     

Nonideal effects behind reflected shock waves in a high-pressure shock tube

Abstract. Shock tubes often experience temperature and pressure nonuniformities behind the reflected shock wave that cannot be neglected in chemical kinetics experiments. Because of increased viscous effects, smaller tube diameters, and nonideal shock formation, the reflected-shock nonidealities tend to be greater in higher-pressure shock tubes. Since the increase in test temperature () is the most significant parameter for chemical kinetics, experiments were performed to characterize in the Stanford High Pressure Shock Tube using infrared emission from a known amount of CO in argon. From the measured change in vibrationally equilibrated CO emission with time, the corresponding ddt (or for a known time interval) of the mixture was inferred assuming an isentropic relationship between post-shock temperature and pressure changes. For a range of representative conditions in argon (24–530 atm, 1275–1900 K), the test temperature 2 cm from the endwall increased 3–8 K after 100 s and 15–40 K after 500 s, depending on the initial conditions. Separate pressure measurements using a shielded piezoelectric transducer confirmed the isentropic assumption. An analytical model of the reflected-shock gas dynamics was also developed, and the calculated 's agree well with those obtained from experiment. The analytical model was used to estimate the effects of temperature and pressure nonuniformities on typical chemical kinetics measurements. When the kinetics are fast (s), the temperature increase is typically negligible, although some correction is suggested for kinetics experiments lasting longer than 500 s. The temperature increase, however, has a negligible impact on the measured laser absorption profiles of OH (306 nm) and CH (216 nm), validating the use of a constant absorption coefficient. Infrared emission experiments are more sensitive to temperature and density changes, so nonuniformities should be taken into account when interpreting ir-emission data. Received 25 April 2000 / Accepted 8 September 2000     

Restricted Percolation Critical Exponents in High Dimensions

Despite great progress in the study of critical percolation on ℤ^d for d large, properties of critical clusters in high-dimensional fractional spaces and boxes remain poorly understood, unlike the situation in two dimensions. Closely related models such as critical branching random walk give natural conjectures for the value of the relevant high-dimensional critical exponents; see in particular the conjecture by Kozma-Nachmias that the probability that 0 and (n, n, n, …) are connected within [−n, n]^d scales as n^{−2 − 2d} . In this paper, we study the properties of critical clusters in high-dimensional half-spaces and boxes. In half-spaces, we show that the probability of an open connection (“arm”) from 0 to the boundary of a sidelength n box scales as n⁻³ . We also find the scaling of the half-space two-point function (the probability of an open connection between two vertices) and the tail of the cluster size distribution. In boxes, we obtain the scaling of the two-point function between vertices which are any macroscopic distance away from the boundary. Our argument involves a new application of the “mass transport" principle which we expect will be useful to obtain quantitative estimates for a range of other problems. © 2020 Wiley Periodicals LLC     

Ion coupling efficiency for an extraction applied-B ion diode onthe HELIA linear-induction adder in positive polarity

Initial experiments to investigate coupling of the four-stage HELIA linear-induction accelerator to a uniformly insulated applied-B ion diode in planar extraction geometry are reported. Results describing the efficient operation of an applied-B extraction ion diode coupled to the HELIA linear induction accelerator operated in positive polarity are reported. Operation of a close-coupled, undermatched, applied-B diode on HELIA was consistent with magnetically insulated transmission line (MITL) electron flow intermediate between locally emitted flow and generalized flow, rather than with full-gap flow. Peak ion coupling efficiencies of 60-70% and peak ion power levels of 0.3-0.4 TW have been achieved     

An NMR Investigation of the Conformational Effect of Nitroxide Spin Labels on Ala-Rich Helical Peptides

Nitroxide spin labels, in conjunction with electron spin resonance (ESR) experiments, are extensively employed to probe the structure and dynamics of biomolecules. One of the most ubiquitous spin labeling reagents is the methanethiosulfonate spin label which attaches a spin label selectively to Cys residues via a disulfide bond (Cys-SL). However, the actual effect of the nitroxide spin label upon the conformation of the peptide or protein cannot be unambiguously determined by ESR. In this study, a series of 16-residue Ala-rich helical peptides was characterized by nuclear magnetic resonance techniques. The C_αH chemical shift analysis, NOEs, and³J_NHαcoupling constants for peptides with no Cys, free Cys, and Cys-SL (with the N–O group reduced) were compared. These results indicate that while replacement of an Ala with a Cys residue causes a loss of overall helical structure, the Cys-SL residue is helix supporting, as would be expected for a non-β-branched aliphatic amino acid. Thus, the Cys-SL residue does not perturb helical structure and, instead, exhibits helix-stabilizing characteristics similar to that found for Ala, Met, and Leu.     

Polarization dependency of enhanced multipath radar backscattering from an ocean-like surface

Previous analyses of electromagnetic scattering from a two-scale ocean surface assumed the tilts on a large-scale surface to be small. This means that multiple scattering between large-scale roughnesses is insignificant. If the tilts are not small, multipath-enhanced backscattering may occur due to quasi-specular reflections between the opposite slopes of a large-scale surface component. We have considered the simplest situation; this involves one reflection from the large-scale component and one single-scattering from the small-scale component. The coherent addition of this process to the reciprocally reverse one creates multipath-enhanced backscattering. The relative gain in the HH backscattering cross section up to the level of the VV signal was obtained for surface-wave slopes of about 30° and for large incidence angles. This gain occurs because the VV signal experiences an extinction during reflection at incident angles close to the pseudo-Brewster angle. The presented model provides insight into one scattering mechanism that is possibly responsible for the departure of radar sea experimental data from predictions by the conventional two-scale model.