Energy and momentum in chiral theories

We calculate the energy momentum tensor to orderE ⁴ in chiral perturbation theory. New terms not present in previous work enter the effective Lagrangian. We describe these and estimate the values of the new coupling constants, using the results of a disperisve analysis of the π andK energy momentum tensors and relying on tensor meson dominance for the spin two component. In addition, we compare our findings with the predictions of known scalar meson dominance models of the conformal anomaly.     

Strong interactions at low energies

The lectures review some of the basic concepts relevant for an understanding of the low energy properties of the strong interactions: chiral symmetry, spontaneous symmetry breakdown, Goldstone bosons, quark condensate. The effective field theory used to analyze the low energy structure is briefly sketched. As an illustration, I discuss the implications of the recent data on the decay K→ππeν for the magnitude of the quark condensate.     

Solid-State CP/MAS 13C-NMR Spectra of Oligolides derived from 3-hydroxybutanoic acid

The solid-state CP/MAS ¹³C-NMR spectra (cross-polarization/magic-angle spinning ¹³C-NMR) of eight lower cyclic and one linear oligomers and several polymers of (R)-3-hydroxybutanoic acid (3-HB) are reported. The polymeric samples of different origin and molecular weight give remarkably similar and well resolved spectra, indicating considerable similarity in the conformations of the molecules and homegeneity in the solid-state environment. The crystalline cyclic oligomers 1 – 8 containing 3–9 units of 3-HB give very well resolved spectra. The number of nonequivalent positions in the solid state can be identified and is in accord with structures from X-ray diffraction where these were determined. The spectra of the oligolides become increasingly similar to those of the polymer as the ring size increases. This spectral evidence supports the view of a homogeneous and well defined conformation for the polymeric material (as proposed previously, based on other experiments).     

Total Synthesis and Bioactivity Mapping of Geodiamolide H

The first total synthesis of the actin-stabilizing marine natural product geodiamolide H was achieved. Solid-phase based peptide assembly paired with scalable stereoselective syntheses of polyketide building blocks and an optimized esterification set the stage for investigating the key ring-closing metathesis. Geodiamolide H and synthetic analogues were characterized for their toxicity and for antiproliferative effects in cellulo, by characterising actin polymerization induction in vitro, and by docking on the F-actin target and property computation in silico, for a better understanding of structure-activity relationships (SAR). A non-natural analogue of geodiamolide H was discovered to be most potent in the series, suggesting significant potential for tool compound design.     

Microscopic solvent shifts in the electronic spectra of large van der waals molecules

The experimental red-shifts of the electronic origins of a number of large non-polar van der Waals molecules are reported. A comparison with the theoretical red-shifts calculated by a formalism given by Longuet-Higgins and Pople yields a good correlation, reflecting the dominant role of dispersion interactions in these complexes.     

Cyclische Oligomere von (R)-3-Hydroxybuttersäure: Herstellung und strukturelle Aspekte

Cyclic Oligomers of (R)-3-Hydroxybutanoic Acid: Preparation and Structural Aspects The oligolides containing three to ten (R)-3-hydroxybutanoate (3-HB) units (12-through 40-membered rings 1–8 ) are prepared from the hydroxy acid itself, its methyl ester, its lactone (‘monolide’), or its polymer (poly(3-HB), mol. wt. ca. 10⁶ Dalton) under three sets of conditions: (i) treatment of 3-HB ( 10 ) with 2,6-dichlorobenzoyl chloride/pyridine and macrolactonization under high dilution in toluene with 4-(dimethylamino)pyridine (Fig. 3); (ii) heating a solution (benzene, xylene) of the β-lactone 12 or of the methyl ester 13 from 3-HB with the tetraoxadistanna compound 11 as trans-esterification catalyst (Fig. 4); (iii) heating a mixture of poly(3-HB) and toluene-sulfonic acid in toluene/1,2-dichloroethane for prolonged periods of time at ca. 100° (Fig. 6). In all three cases, mixtures of oligolides are formed with the triolide 1 being the prevailing component (up to 50% yield) at higher temperatures and with longer reaction times (thermodynamic control, Figs. 3–6). Starting from rac-β-lactone rac- 12 , a separable 3:1 to 3:2 mixture of the l,u- and the l,l-triolide diasteroisomers rac- 14 and rac- 1 , respectively, is obtained. An alternative method for the synthesis of the octolide 6 is also described: starting from the appropriate esters 15 and 17 and the benzyl ether 16 of 3-HB, linear dimer, tetramer, and octamer derivatives 18–23 are prepared, and the octamer 23 with free OH and CO₂H group is cyclized (→ 6 ) under typical macrolactonization conditions (see Scheme). This ‘exponential fragment coupling protocol’ can be used to make higher linear oligomers as well. The oligolides 1–8 are isolated in pure form by vacuum distillation, chromatography, and crystallization, an important analytical tool for determining the composition of mixtures being ¹³C-NMR spectroscopy (each oligolide has a unique and characteristic chemical shift of the carbonyl C-atom, with the triolide 1 at lowest, the decolide 8 at highest field). The previously published X-ray crystal structures of triolide 1 , pentolide 3 , and hexolide 4 (two forms), as well as those of the l,u-triolide rac- 14 , of tetrolide ent- 2 , of heptolide 5 , and of two modifications of octolide 6 described herein for the first time are compared with each other (Figs. 7–10 and 12–15, Tables 2 and 5–7) and with recently modelled structures (Tables 3 and 4, Fig. 11). The preferred dihedral angles τ₁ to τ₄ found along the backbone of the nine oligolide structures (the hexamer and the larger ones all have folded rings!) are mapped and statistically evaluated (Fig. 16, Tables 5–7). Due to the occurrence of two conformational minima of the dihedral angle O? CO? CH₂? CH (τ₃ = + 151 or ?43°), it is possible to locate two types of building blocks for helices in the structures at hand: a right-handed 3₁ and a left-handed 2₁ helix; both have a ca. 6 Å pitch, but very different shapes and dispositions of the carbonyl groups (Fig. 17). The 2₁ helix thus constructed from the oligolide single-crystal data is essentially superimposable with the helix derived for the crystalline domains of poly(3-HB) from stretched-fiber X-ray diffraction studies. The absence of the unfavorable (E)-type arrangements around the OC? OR bond (‘cis-ester’) from all the structures of (3-HB) oligomers known so far suggests that the model proposed for a poly(3-HB)-containing ion channel (Fig. 2) must be modified.