Ehrenfest's theorem reinterpreted and extended with Wigner's function

For a wave packet evolving quantum mechanically, the rates of change of the expectations and uncertainties of the position and momentum are exactly the same as if Wigner's function instantaneously obeyed a classical Liouville equation (whatever the Hamiltonian). This extension of Ehrenfest's theorem should be useful for dealing with the evolution and manipulation of quantum states.     

Conformations in the tetrahydropyran-2-one ring

Force-field calculations in combination with ¹H NMR spectroscopy, IR data and X-rays diffraction unambiguously delineate the conformational properties of tetrahydropyran-2-one derivatives which exhibit psychostimulant and antidepressive activity.     

Etude de la reactivite des coumarines—I : Regioselectivete des reactifs de grignard engages avec la coumarine

The various products obtained by the action of organomagnesium, compounds on coumarin result from 1.2-1.2 di-addition (phenolic alcohols) or 1.2–1.4 di-addition (ketophenols) or 1.4 mono-addition (dihydrobenzopyrones). The results show the importance of the nature of the halogen component of the Grignard reagent. A theoretical model allows regioselectivity of coumarine in relation to the group R and the halogene X to be evaluated.     

Stable attachment of redox groups for modified electrodes via cyanuric chloride

Methylaminopropylviologen (MAV) was covalently attached to glassy carbon electrodes via cyuranic chloride. X-ray photoelectron spectroscopy (XPS) analysis confirmed the presence of bound MAV on the electrode surfaces. Electrochemical experiments of these electrodes indicated that the bound MAV was stable and electrochemically active for extended periods of time in aqueous media. The surface coverage of MAV was in the range, of 2.0–3.0×10^?10 mol cm^?2.     

Relaxation spectroscopy on amorphous high polymers

Summary Measurements of the dynamic Youngs modulus and shear modulus of Polymethylmethacrylate (PMMA) in the frequency range from 10^–3 cps to 10^–1 cps and in the temperature range from –20°C to 100°C up to stress amplitudes of 4 kN/cm² are presented. The measured nonlinear viscoelastic behavior is discussed with regard to nonlinear elasticity and nonlinear effects caused by the shift of relaxation times due to the reaction rate theory.

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Zusammenfassung Es wird über Messungen des dynamischen Elastizitätsmoduls und Schubmodells von Polymethacrylsäuremethylester (PMMA) im Frequenzbereich von 10^–3 Hz bis 10^–1 Hz und im Temperaturbereich von –20°C bis +100°C bei Spannungsamplituden bis zu 4 kN/cm² berichtet. Das gemessene nichtlineare viskoelastische Verhalten wird hinsichtlich einer nichtlinearen Elastizität und hinsichtlich nichtlinearer Effekte, die durch eine Verschiebung der Relaxationszeiten nach der Platzwechseltheorie verursacht sind, diskutiert.

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With 21 figures     

Asymmetric Synthesis of alpha-Amino Phosphonic Acids by Diastereoselective Addition of Trimethyl Phosphite onto Chiral Oxazolidines(1)

A simple and general asymmetric synthesis of alpha-amino phosphonic acids is described. The method involves the highly selective addition of trialkyl phosphite onto various chiral oxazolidines. Oxazaphosphorinanes thus obtained with an excellent diastereoselectivity furnish the corresponding (S)-alpha-substituted amino phosphonic acids in good overall yields and high ee (77-->97%) after simple deprotection.     

Orientation of Na(3p) states excited in Na-He collisions

The orientation of Na(3p) states created in 3–13 keV Na(3s)-He collisions has been studied by the polarised photon-scattered particle coincidence technique at scattering angles corresponding to the impact-parameter range 1–2 a.u. In the standard geometry, at large impact parameters the excitation process exhibits a very high degree of orientation with about 90% of the Na(3p) states havingm ₁=?1. Strong reduction in this propensity is observed at impact parameters smaller than about 1.3 a.u., where a molecular curve crossing causes simultaneous He(n=2) excitation. In this region, also ionisation becomes important.     

Rigid Support Materials for the Immobilization of Enzymes

The purpose of the work presented here was to prepare a support material for enzymes and “affinity ligands” with the following characteristics: low cost, durability, rigidity, and high capacity. Our study encompassed conjugates of porous and nonporous silicas with organic polymers and macroporous ion-exchange resins. Poly-ethyleneimine (PEI), polyacrylic acid (PAA), poly (methyl vinyl ether/maleic anhydride) were attached to porous glass and silica in various combinations. The composite of silica beads with PEI and PAA is a good support for the enzyme trypsin as judged by the activity against N-α-benzoyl-L-arginine ethyl ester.

Amberlyst (macroporous, sulfonated polystyrene) was activated by treatment with thionyl chloride; the resulting resin was either used directly or reacted with a diamine. The diamine derivative was used for enzyme coupling or transformed further to the succinyl or p-aminobenzoyl derivative. None of these derivatives were particularly good as supports for the enzyme trypsin. Duolite converted to a PAA, succinyl, or succinimide derivative was a good support. The enzyme-resin adduct has good activity and stability.

The resin is quite durable and of low cost. The Duolite-trypsin has good activity against protein. In addition, this derivative was active in 7 M urea. The proteolytic activity was nearly doubled by urea, presumably as a result of substrate (casein) denaturation. The michaelis constants and pH dependences are compared for trypsin conjugates with Duolite A-7, Silica-PEI-PAA, agarose, and porous glass. A cost comparison reveals that the Duolite and silica derivatives are much less expensive than agarose and glass.     

Syntheses of 2‐Keto‐3‐deoxy‐D‐xylonate and 2‐Keto‐3‐deoxy‐L‐arabinonate as Stereochemical Probes for Demonstrating the Metabolic Promiscuity of Sulfolobus solfataricus Towards D‐Xylose and L‐Arabinose

Practical syntheses of 2‐keto‐3‐deoxy‐D ‐xylonate (D ‐KDX) and 2‐keto‐3‐deoxy‐L ‐arabinonate (L ‐KDA) that rely on reaction of the anion of ethyl 2‐[(tert‐butyldimethylsilyl)oxy]‐2‐(dimethoxy phosphoryl) acetate with enantiopure glyceraldehyde acetonide, followed by global deprotection of the resultant O‐silyl‐enol esters, have been developed. This has enabled us to confirm that a 2‐keto‐3‐deoxy‐D ‐gluconate aldolase from the archaeon Sulfolobus solfataricus demonstrates good activity for catalysis of the retro‐aldol cleavage of both these enantiomers to afford pyruvate and glycolaldehyde. The stereochemical promiscuity of this aldolase towards these enantiomeric aldol substrates confirms that this organism employs a metabolically promiscuous pathway to catabolise the C5‐sugars D ‐xylose and L ‐arabinose.