Ligand and base additive effects on the reversibility of nucleophilic addition in palladium-catalyzed allylic aminations monitored by nucleophile crossover

A nucleophile crossover experiment was used to monitor the reversibility of nucleophilic addition of benzylamine to π-allylpalladium complexes. Dppe, dppp, dppb, and PHOX showed more crossover than PPh₃ and dppm in both DMF and dichloromethane. Crossover was inhibited by the addition of DBU or Cs₂CO₃, but much less elimination to diene side products was observed with Cs₂CO₃. Analysis of percent crossover vs. percent reaction completion using the PHOX ligand revealed that with added DBU or Cs₂CO₃ crossover only began occurring after 100% completion had been reached.     

Modelling hydrogen in silicate materials

The expectation that the hydroxyl analogue state of positive muons implanted in quartz should be stabilized by a suitable charge compensation centre is supported by preliminary data. The diamagnetic fraction correlates with aluminium content over the narrow range investigated. This revised version was published online in August 2006 with corrections to the Cover Date.     

Halide and nitrite recognizing hexanuclear metallacycle copper(II) pyrazolates

Halide-centered hexanuclear, anionic copper(II) pyrazolate complexes [trans-Cu(6)((3,5-CF(3))(2)pz)(6)(OH)(6)X](-), X = Cl, Br, I are isolated in a good yield from the redox reaction of the trinuclear copper(I) pyrazolate complex [μ-Cu(3)((3,5-CF(3))(2)pz)(3)] with a halide source such as PPh(3)AuCl or [Bu(4)N]X, X = Cl, Br, or I, in air. X-ray structures of the anion-centered hexanuclear complexes show that the six copper atoms are bridged by bis(3,5-trifluoromethyl)pyrazolate and hydroxyl ligands above and below the six copper atom plane. The anions are located at the center of the cavity and weakly bound to the six copper atoms in a μ(6)-arrangement, Cu-X = ~3.1 ?. A nitrite-centered hexanuclear copper(II) pyrazolate complex [trans-Cu(6)((3,5-CF(3))(2)pz)(6)(OH)(6)(NO(2))](-) was obtained when a solution of [PPN]NO(2) in CH(3)CN was added dropwise to the trinuclear copper(I) pyrazolate complex [μ-Cu(3)((3,5-CF(3))(2)pz)(3)] dissolved in CH(3)CN, in air. Blue crystals are produced by slow evaporation of the acetonitrile solvent. The X-ray structure of [PPN][trans-Cu(6)((3,5-CF(3))(2)pz)(6)(OH)(6)(NO(2))] complex shows the nitrite anion sits in the hexanuclear cavity and is perpendicular to the copper plane with a O-N-O angle of 118.3(7)°. The (19)F and (1)H NMR of the pyrazolate ring atoms are sensitive to the anion present in the ring. Anion exchange of the NO(2)(-) by Cl(-) can be observed easily by (1)H NMR.     

Oxidative coupling of porphyrins using copper(II) salts

A method for radical coupling of porphyrins using copper(II) salts as one-electron oxidants was developed. A Zn(II)-porphyrin bearing an aminophenyl group yielded porphyrin oligomers, and two tri-arylporphyrins were oxidized to form doubly and triply linked dimers. Bromination of doubly linked dimers gave macrocycles with twisted skeletons.     

Multiplexed inkjet functionalization of silicon photonic biosensors

The transformative potential of silicon photonics for chip-scale biosensing is limited primarily by the inability to selectively functionalize and exploit the extraordinary density of integrated optical devices on this platform. Silicon biosensors, such as the microring resonator, can be routinely fabricated to occupy a footprint of less than 50 × 50 μm; however, chemically addressing individual devices has proven to be a significant challenge due to their small size and alignment requirements. Herein, we describe a non-contact piezoelectric (inkjet) method for the rapid and efficient printing of bioactive proteins, glycoproteins and neoglycoconjugates onto a high-density silicon microring resonator biosensor array. This approach demonstrates the scalable fabrication of multiplexed silicon photonic biosensors for lab-on-a-chip applications, and is further applicable to the functionalization of any semiconductor-based biosensor chip.     

Non-Archimedean Nevanlinna theory in several variables and the non-Archimedean Nevanlinna inverse problem

Cartan's method is used to prove a several variable, non-Archimedean, Nevanlinna Second Main Theorem for hyperplanes in projective space. The corresponding defect relation is derived, but unlike in the complex case, we show that there can only be finitely many non-zero non-Archimedean defects. We then address the non-Archimedean Nevanlinna inverse problem, by showing that given a set of defects satisfying our conditions and a corresponding set of hyperplanes in projective space, there exists a non-Archimedean analytic function with the given defects at the specified hyperplanes, and with no other defects.

     

Gravitationally stabilized nucleons in the theory of the generalized gravitational potential

From the field equation in of the author's general-relativistic scalar field theory in the complex Weyl space an infinite set of Yukawa type equations, representing potential fields, arising from zero rest mass particles is obtained. The simplest of these equations is solved and is used in a nucleon model as the origin of a gravitationally stabilized nucleon. This procedure leads directly to an expression that predicts the representative nucleon radius of 1.21 fm.