Cyclic Ketones in Spiroannulation

Conversion of a cyclic carbonyl carbon into a quaternary carbon has been effected by a Wittig–Horner reaction with diethyl (N-benzyliden)aminomethylphosphonate and a subsequent alkylation with a protected vinyl ketone. The product was a substrate for spiroannulation after initial hydrolysis. The reaction sequence was carried out as a one-pot reaction.     

A theoretical determination of the electronic spectrum of formaldehyde

Summary The electronically excited states of formaldehyde are examined by means of multiconfigurational second-order perturbation (CASPT2) theory with extended ANO-type basis sets. The calculations comprised five valence excited states plus all singlet 3s, 3p, and 3d members of the Rydberg series converging on the first ionization. The computed vertical excitation energies were found to be within 0.2 eV of the available experimental energies. Full geometry optimization has been performed for five valence excited states. Assuming a planar geometry, the 0-0 transition for the valence¹A₁( *) state is calculated to appear near 7.9 eV, close to the (n _y 3p) region. This state is, however, not planar and the true adiabatic energy is 7.4 eV, which is 2.3 eV below the corresponding vertical transition.     

Monitoring the aggregation of single casein micelles using fluorescence microscopy

The aggregation of casein micelles (CMs) induced by milk-clotting enzymes is a process of fundamental importance in the dairy industry for cheese production; however, it is not well characterized on the nanoscale. Here we enabled the monitoring of the kinetics of aggregation between single CMs (30-600 nm in diameter) by immobilizing them on a glass substrate at low densities and subsequently imaging them with fluorescence microscopy. We validated the new method by a quantitative comparison to ensemble measurements of aggregation. Single-particle statistics allowed us to observe for the first time several heterogeneities in CM aggregation. We observed two types of CM growth: a slow increase in the size of CMs and a stepwise increase attributed to interactions between aggregates preformed in solution. Both types of growth exhibit a lag phase that was very heterogeneous between different CMs, suggesting significant differences in their composition or structure. Detailed size histograms of CMs during aggregation also revealed the presence of two distinct subpopulations with different growth amplitudes and kinetics. The dependence of these distinct nanoscale processes/parameters on aggregation conditions is not accessible to bulk measurements that report only ensemble-average values and may prove important to an in-depth understanding of CM aggregation.     

Synthesis of Glycosylated Amino Acids for Use in Solid Phase Glycopeptide Synthesis,Part 2: N-(9-Fluorenylmethyloxycarbonyl)-3-0-[2,4,6-TRI-0-Acetyl-3-0-(2,3,4-TRI-0-Acetyl-α-D-Xylopyranosyl)-β-D-Glucopyranosyl]-L-Serine

Abstract

FMOC-serine phenacylester was glycosylated with a derivative of the disaccharide α-D-Xylp-(1→3)-β-D-Glcp, and the product was treated with zinc to remove the phenacyl group. The title derivative is useful for synthesis of blood clotting factor IX glycopeptide fragments by the solid-phase approach.     

Inclusion of dynamic σ-π polarization in π-electronab initio calculations

Summary A method is presented, whereby dynamic - polarization, i.e. the correlation effect expressed by simultaneous (-*, -*) excitations, can be approximately included in a multi-reference configuration interaction (MRCI) or multi-configurational self-consistent field (MC-SCF) calculation, without need to explicitly correlate the sigma orbitals. The method, which we call the capacitance matrix method, is based on the use of conventional one-electron integrals, from which a polarization potential (SPP) contribution is computed and added to the one- and two-electron Hamiltonian. In the present form, the method requires one parameter for each type of atom, and one for each type of bond. These parameters were adjusted to reproduce the dynamic - polarization energy, computed by restricted multi-reference CI calculations, of a number of states of different hydrocarbons, and the agreement was within a few percent. Using the same parameters in CAS (Complete Active Space) SCF calculations of various states of benzene gives excitation energies, when SPP is included, which is comparable to those obtained by much more elaborate MRCI calculations.     

Determination of90Sr in environmental and biological materials with combined HDEHP solvent extraction-low liquid scintillation counting technique

Low level⁹⁰Sr in environmental and biological samples is determined using a combined HDEHP solvent extraction-liquid scintillation procedure. Yttrium-90 is selectively extracted from nitric acid solution into 5% di(2-ethylhexyl) phosphoric acid (HDEHP) in toluene, and⁹⁰Y in the organic phase is measured directly using an ultra low level liquid scintillation spectrometer.The working program of the Quantulus counter has been optimized. As the counting efficiency using liquid scintillation counting is high and the stripping and precipitation of Yttrium-90 oxalate is omitted, this procedure is simpler and more timesaving than traditional methods. The chemical recoveries of⁹⁰Y were 85.1% for soil, 75.7% for milk and 65.3% for bone. The detection limit is 8 mBq.