Synthesis and Structure of Linear and Cyclic Oligomers of 3-Hydroxybutanoic Acid with Specific Sequences of (R)- and (S)-Configurations

To study the stereoselectivity of enzymatic cleavage of poly(3-hydroxybutyrates) (PHB) in a well-defined system (purified depolymerase and monodisperse substrate of specific relative configuration), linear and cyclic oligomers of HB (OHBs) containing (R)- and (S)-3-hydroxybutanoate residues were synthesized. The starting material (R)-HB was prepared from natural sPHB, and (S)-HB by enantioselective reduction of 3-oxobutanoate with yeast or with H₂/Noyori-Taber catalyst (Scheme 2). The HB building blocks were then protected (O-benzyl/tert-butyl ester; Scheme 3) and coupled to give dimers 3 , 4 , tetramers 5 – 9 , and octamers 10 – 18 ; for analytical comparison, a 3mer, 5mer, 6mer, and 7mer ( 19 – 22 ) were also prepared. Two of the tetramers were subjected to macrolactonization conditions (Yamaguchi) to give the cyclic tetramers 23 and 25 and octamers 24 and 26 . All new compounds were fully characterized (m.p., [α]_D, CD, IR, ¹H- and ¹³C-NMR, MS, elemental analysis). Single-crystal X-ray structure analyses were performed with oligolides 24 and 25 (Figs. 2 and 4), and the structures, as well as the crystal packing, were compared with those of analogs containing only (R)-HB units or consisting of 3-amino- instead of 3-hydroxybutanoic-acid moieties.     

Eine neue Methode zur stereochemischen Analyse offenkettiger terpenoider Carbonyl-Verbindungen,

A New Method for the Stereochemical Analysis of Acyclic Terpenoid Carbonyl Compounds A new method for the determination of the enantiomeric and diastereoisomeric composition of terpenoid carbonyl compounds is presented. Separation of the diastereoisomeric (+)-L -diisopropyl-tartrate acetals derived from dihydrocitronellal ( 6 ), hexahydropseudoionone ( 3 ), hexahydrofarnesal ( 7 ), and hexahydro far nesy lace tone ( 4 ), the C₁₀, C₁₃, C₁₅, and C₁₈ intermediates in various syntheses of naturally occurring tocopherols and vitamin K₁, can be achieved by capillary GC on a cyanopropylsilicon-coated glass column under standardized conditions. This technique, presenting a significant improvement over existing methodologies, is considered to be particularly useful for the analysis of highly enriched samples, typically obtained by present-day asymmetric synthesis. With reproducibilities of ± 0.3%, and, therefore, safe for routine analysis, the complete Stereochemical characterization of terpenoids with 15 and 18 C-atoms bearing two stereogenic centres is performed in a single operation for the first time.     

Is the definition of mathematics as used in the PISA assessment Framework applicable to the HarmoS Project?

The project known as the “Harmonisation of the Obligatory School”, or in its shortened form as “HarmoS”, has a high priority for Switzerland's educational policy in the coming years. Its purpose is to determine levels of competency, valid throughout Switzerland, for specific areas of study and including the subject of mathematics. The general theoretical basis of the overall HarmoS Project is constituted by the expertise written under the direction of Eckhard Klieme and entitled “Zur Entwicklung nationaler Bildungsstandards” (Klieme 2003) [i.e. “On the Development of National Education Standards”]. The proposal announcing the HarmoS partial project devoted to Mathematics includes references to the results and subsequent analysis of PISA 2003. It thus seems appropriate for us to begin our work on HarmoS with a critical consideration of the definition of mathematics and mathematical literacy as they are used in the PISA Study. In a first part, we want to describe the core ideas of HarmoS. In a second part, we will address the meaning of general educational goals for the development of competency models and education standards to the extent that it is necessary to properly locate our problem. In a third part we will analyse the concept of mathematics which is at the basis of the PISA Study (OECD 2004) and more precisely defined in the publication “Assessment Framework” (OECD 2003) In the fourth and last part, we will try to provide a differentiated answer to the question posed in the title of this paper.     

Side-chain H and C resonance assignment in protonated/partially deuterated proteins using an improved 3D(13)C-detected HCC-TOCSY

We propose the use of (13)C-detected 3D HCC-TOCSY experiments for assignment of (1)H and (13)C resonances in protonated and partially deuterated proteins. The experiments extend 2D C-13-start and C-13-observe TOCSY type experiments proposed earlier. Introduction of the third (1)H dimension to 2D TOCSY: (i) reduces the peak overlap and (ii) increases the sensitivity per unit time, even for highly deuterated (>85%) protein samples, which makes this improved method an attractive tool for the side-chain H and C assignment of average sized proteins with natural isotope abundance as well as large partially deuterated proteins. The experiments are demonstrated with a 16 kDa (15)N, (13)C-labeled non-deuterated apo-CcmE and a 48 kDa uniformly (15)N, (13)C-labeled and fractionally ( approximately 90%) deuterated dimeric sFkpA. It is predicted that this method should be suitable for the assignment of methyl (13)C and (1)H chemical shifts of methyl protonated, highly deuterated and (13)C-labeled proteins with even higher molecular weight.     

Methyl-triisopropoxy-titanium,a highly selective nucleophilic methylating reagent. Preliminary Communication

Replacement of lithium or magnesium by titanium can furnish nucleophilic organometallic reagents of high selectivity as exemplified by the title compound 1 (see Tables 1–3).     

Photochemische Reaktionen. 74. Mitteilung. Notiz zur Photoreaktivität ausgewählter ungesättigter Ketoalkohole der Jononreihe

UV.-irradiation (λ = 254 nm) of the hydroxy-enones 3 and 6 in acetonitrile results in the cyclization to the unstable isomeric allylic alcohols 4 and 7 , which dehydrate easily to the isolated unsaturated ether 5 and 8 . The racemic γ,δ-dihydroxy-enone 9 upon irradiation under the same conditions gives rise to the exclusive formation of the furane-compound 11 .     

Common Principal Components for Dependent Random Vectors

Let the kp-variate random vector X be partitioned into k subvectors X_i of dimension p each, and let the covariance matrix Ψ of X be partitioned analogously into submatrices Ψ_ij. The common principal component (CPC) model for dependent random vectors assumes the existence of an orthogonal p by p matrix β such that β^tΨ_ijβ is diagonal for all (i, j). After a formal definition of the model, normal theory maximum likelihood estimators are obtained. The asymptotic theory for the estimated orthogonal matrix is derived by a new technique of choosing proper subsets of functionally independent parameters.