Synthesis,spectroscopic and structural characterisation of vanadium(IV) and oxovanadium(IV) complexes with arsenic donor ligands

The reaction of o-C₆H₄(AsMe₂)₂ with VCl₄ in anhydrous CCl₄ produces orange eight-coordinate [VCl₄{o-C₆H₄(AsMe₂)₂}₂], whilst in CH₂Cl₂ the product is the brown, six-coordinate [VCl₄{o-C₆H₄(AsMe₂)₂}]. In dilute CH₂Cl₂ solution slow decomposition occurs to form the V^III complex [V₂Cl₆{o-C₆H₄(AsMe₂)₂}₂]. Six-coordination is also found in [VCl₄{MeC(CH₂AsMe₂)₃}] and [VCl₄{Et₃As)₂]. Hydrolysis of these complexes occurs readily to form vanadyl (VO²⁺) species, pure samples of which are obtained by reaction of [VOCl₂(thf)₂(H₂O)] with the arsines to form green [VOCl₂{o-C₆H₄(AsMe₂)₂}], [VOCl₂{MeC(CH₂AsMe₂)₃}(H₂O)] and [VOCl₂(Et₃As)₂]. Green [VOCl₂(o-C₆H₄(PMe₂)₂}] is formed from [VOCl₂(thf)₂(H₂O)] and the ligand. The [VOCl₂{o-C₆H₄(PMe₂)₂}] decomposes in thf solution open to air to form the diphosphine dioxide complex [VO{o-C₆H₄(P(O)Me₂)₂}₂(H₂O)]Cl₂, but in contrast, the products formed from similar treatment of [VCl₄{o-C₆H₄(AsMe₂)₂}_x] or [VOCl₂{o-C₆H₄(AsMe₂)₂}] contain the novel arsenic(V) cation [o-C₆H₄(AsMe₂Cl)(μ-O)(AsMe₂)]⁺. X-ray crystal structures are reported for [V₂Cl₆{o-C₆H₄(AsMe₂)₂}₂], [VO(H₂O){o-C₆H₄(P(O)Me₂)₂}₂]Cl₂, [o-C₆H₄(AsMe₂Cl)(μ-O)(AsMe₂)]Cl·[VO(H₂O)₃Cl₂] and powder neutron diffraction data for [VCl₄{o-C₆H₄(AsMe₂)₂}₂].     

Novel approaches to the analysis of the Maillard reaction of proteins

The Maillard reaction comprises a complex network of reactions which has proven to be of great importance in both food science and medicine. The majority of methods developed for studying the Maillard reaction in food have focused on model systems containing amino acids and monosaccharides. In this study, a number of electrophoretic techniques, including two-dimensional gel electrophoresis and capillary electrophoresis, are presented. These have been developed specifically for the analysis of the Maillard reaction of food proteins, and are giving important insights into this complex process.     

General calculation of 4f-5d transition rates for rare-earth ions using many-body perturbation theory

The 4f-5d transition rates for rare-earth ions in crystals can be calculated with an effective transition operator acting between model 4f(N) and 4f(N-1)5d states calculated with effective Hamiltonian, such as semiempirical crystal Hamiltonian. The difference of the effective transition operator from the original transition operator is the corrections due to mixing in transition initial and final states of excited configurations from both the center ion and the ligand ions. These corrections are calculated using many-body perturbation theory. For free ions, there are important one-body and two-body corrections. The one-body correction is proportional to the original electric dipole operator with magnitude of approximately 40% of the uncorrected electric dipole moment. Its effect is equivalent to scaling down the radial integral (5d/r/4f) to about 60% of the uncorrected HF value. The two-body correction has magnitude of approximately 25% relative to the uncorrected electric dipole moment. For ions in crystals, there is an additional one-body correction due to ligand polarization, whose magnitude is shown to be about 10% of the uncorrected electric dipole moment.     

The Role of Torsional Dynamics on Hole and Exciton Stabilization in π‐Stacked Assemblies: Design of Rigid Torsionomers of a Cofacial Bifluorene

Exciton and charge delocalization across π‐stacked assemblies is of importance in biological systems and functional polymeric materials. To examine the requirements for exciton and hole stabilization, cofacial bifluorene ( F 2) torsionomers were designed, synthesized, and characterized: unhindered (model) ^Me F 2, sterically hindered ^tBu F 2, and cyclophane‐like ^C F 2, where fluorenes are locked in a perfect sandwich orientation via two methylene linkers. This set of bichromophores with varied torsional rigidity and orbital overlap shows that exciton stabilization requires a perfect sandwich‐like arrangement, as seen by strong excimeric‐like emission only in ^C F 2 and ^Me F 2. In contrast, hole delocalization is less geometrically restrictive and occurs even in sterically hindered ^tBu F 2, as judged by 160 mV hole stabilization and a near‐IR band in the spectrum of its cation radical. These findings underscore the diverse requirements for charge and energy delocalization across π‐stacked assemblies.     

Bestimmung von Kohlenstoff, Wasserstoff und Schwefel in organischen Substanzen

Ohne Zusammenfassung     

The μSR facilities at PSI

TheSR Facility Instruments presently available at PSI and the envisaged medium- and long-term developments are presented. The plans focus on further upgrades of the existing instruments and the development of new techniques using the very high fluxes becoming available at PSI, in particular the setup of a beamline with a fast kicker for muons on request (MORE) and the development of very low energy muon beams.     

Effect of shear on human insulin in zinc suspension

Human insulin in zinc suspension was used as a model protein to test the effect of shear on the settling rate of proteins, a possible inference for protein denaturation. The rate of settling was determined directly in a spectropho-tometer. Shear effects are important in retaining the activity of proteins and are present in bubble, foam, and droplet protein fractionation processes. A sim pletest, such as that conducted here, mayeven be useful for monitoring changes in protein structure caused by commercial shipping of the protein. The settling ratefor insulin was continously monitored in theoriginal bottle by spectrophotometric absorbance changes as a function of time. A settling curve was determined following each shear experiment, which included shaking the “worked” insulin solution in a vortex mixer for different lengths of time. It was determined, when comparing long shaking times with short ones, that the initial settling rate was less for the long-term shaking of the insulin samples and greater for the short-term shaking. The secondary effects of light and heat, along with shaking, a pparently did not produce differences from shaking alone.