Zur Analyse der ätherischen Öle

Ohne Zusammenfassung     

High-sensitive heat-flow calorimetry

Heat production rates of chemical reactions or of biological cultures are a valuable signal, able to provide crucial information about the system under investigation. Commercially available bench-scale calorimeters reach a sensitivity of ≈100 mW/l. This sensitivity is usually sufficient for investigations in the field of reaction engineering or for safety studies. For the investigation of processes that exhibit only small exothermic or endothermic effects on the observation of the growth of biological material, the sensitivity of the calorimeter needs to be improved. This paper describes the modifications undertaken to reach a sensitivity of a few milliwatts per liter with an RC1 from Mettler-Toledo.     

Relations among neutral current couplings to test the SU(2) ⊗ U(1) gauge group structure

The experimental implications of neutral heavy leptons N in e⁺e^? annihilation are examined. We calculate the production rate of both right-handed and left-handed N's at SPEAR and PEP/PETRA energies and show that observation of the process $\text{e}{}^{\mathrm{+}}\text{e}{}^{\mathrm{?}}\text{→}\text{ν}\text{?}\text{N}\text{,}\text{N}\text{→}\text{e}$ (or μ)π allows the determination of both the mass and handedness of N.     

A Global Wellordering of Norms Defined via Blackwell Games

We define a global order of norms using strongly optimal strategies in Blackwell games and prove that it is a prewellordering under the assumption of the Axiom of Blackwell determinacy.     

Optimization of augmentation functions for correlated calculations of spin-spin coupling constants and related properties

A new hierarchy of augmented basis sets optimized for the calculation of molecular properties such as indirect spin-spin coupling constants is presented. Based on the Dunning hierarchy of cc-pVXZ (X = D, T, Q, and 5) basis sets augmentation functions with tight exponents have been optimized for coupled-cluster calculations of indirect spin-spin coupling constants. The optimal exponents for these tight functions have been obtained by optimizing the sum of the absolute values of all contributions to the coupling constant. On the basis of a series of test cases (CO, HF, N(2), F(2), H(2)O, NH(3), and CH(4)) we propose a set of tight s, p, and d functions to be added to the uncontracted Dunning basis sets, and, subsequently, to recontract. The resulting ccJ-pVXZ (X = D, T, Q, and 5) basis sets demonstrate excellent cost efficiency in benchmark calculations. These new basis sets should generally be applicable for the calculation of spin-spin coupling constants and other properties that have a strong dependence on powers of 1r or even contain a delta distribution for correlated ab initio methods.     

IR-renormalon contributions to the structure functions g 3 and g 5

We calculate the leading 1/N _f perturbative contributions to the polarized nonsinglet structure functions g ₃ and g ₅ to all orders in α_s. The contributions from the first renormalon pole are determined. It is a measure for the ambiguity of the perturbative calculation and is hypothetically assumed to dominate the power corrections. The corrections Δg ₃ and Δg ₅ are given as functions of the Bjorken variable x and turn out to be negligible. The anomalous dimensions of the leading twist operators are obtained in the next-to-leading order. Received: 10 June 1998 / Revised version: 25 September 1998     

Picomolar FKBP inhibitors enabled by a single water-displacing methyl group in bicyclic [4.3.1] aza-amides

Methyl groups can have profound effects in drug discovery but the underlying mechanisms are diverse and incompletely understood. Here we report the stereospecific effect of a single, solvent-exposed methyl group in bicyclic [4.3.1] aza-amides, robustly leading to a 2 to 10-fold increase in binding affinity for FK506-binding proteins (FKBPs). This resulted in the most potent and efficient FKBP ligands known to date. By a combination of co-crystal structures, isothermal titration calorimetry (ITC), density-functional theory (DFT), and 3D reference interaction site model (3D-RISM) calculations we elucidated the origin of the observed affinity boost, which was purely entropically driven and relied on the displacement of a water molecule at the protein–ligand–bulk solvent interface. The best compounds potently occupied FKBPs in cells and enhanced bone morphogenic protein (BMP) signaling. Our results show how subtle manipulation of the solvent network can be used to design atom-efficient ligands for difficult, solvent-exposed binding pockets.

Enhancement by displacement. A single methyl group displaces a water molecule from the binding site of FKBPs, resulting in the most potent binders known, outperforming the natural products FK506 and rapamycin in biochemical and cellular assays.