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71.
Erich Widmer Milan Soukup Reinhard Zell Emil Broger Hans Peter Wagner Marquard Imfeld 《Helvetica chimica acta》1990,73(4):861-867
Starting from the readily available, optically active (4R)-4-hydroxy-2,2,6-trimethylcyclohexanone ( 1 ), a new technical synthesis of (3R,3′R)-zeaxanthin is described. According to a 2(C9 + C6) + C10 = C40 construction scheme, the ketone 1 was first transformed with (E)-3-methylpent-2-en-4-yn-1-ol ( 5 ) into a C15-intermediate which, by a three-step sequence, could be converted into the known olefinic C15-Wittig salt 4 . Optimized conditions for the final Wittig reaction of 4 with the C10-dialdehyde 3 are discussed. Based on 1 , the overall yield of the entire technical process is ca. 40%. 相似文献
72.
The thermodynamic and extra-thermodynamic dependencies of five types of cytochrome c in water-acetonitrile mixtures of different composition in the presence of immobilised n-octyl ligands as a function of temperature from 278 K to 338 K have been investigated. The corresponding enthalpic, entropic and heat capacity parameters, deltaHdegrees assoc, deltaS degrees assoc and delta C degrees p, have been evaluated from the observed non-linear Van't Hoff plots of these globular proteins in these heterogeneous systems. The relationships between the free energy dependencies, various molecular parameters and extra-thermodynamic dependencies (empirical correlations) of these protein-non-polar ligand interactions have also been examined. Thus, the involvement of enthalpy-entropy compensation effects has been documented for the binding of these cytochrome cs to solvated n-octyl ligands. Moreover, the results confirm that this experimental approach permits changes in molecular surface area due to the unfolding of these proteins on association with non-polar ligands as a function of temperature to be correlated with other biophysical properties. This study thus provides a general procedure whereby the corresponding free energy dependencies of globular proteins on association with solvated non-polar ligands in heterogeneous two-phase systems can be quantitatively evaluated in terms of fundamental molecular parameters. 相似文献
73.
Thomas Höche Wolfgang NeumannSaeid Esmaeilzadeh Reinhard UeckerMarkus Lentzen Christian Rüssel 《Journal of solid state chemistry》2002,166(1):15-23
Sr2TiSi2O8 single crystals were grown by Czochralski pulling and from a high-temperature solution. X-ray diffractometry revealed the modulated crystal structure of Sr2TiSi2O8 to belong to the 5D superspace group P4bm (−α, α, 1/2; α, α, 1/2) with α=0.3. Atomic positions, anisotropic displacement factors and positional modulation parameters for Sr2TiSi2O8 are determined and discussed. The positional modulation is further investigated by electron diffraction and high-resolution transmission electron microscopy. In the latter experiments, the 2D modulation appears to be superimposed by some 1D modulation waves. This effect is discussed in terms of growth conditions. 相似文献
74.
Engel CK Pirard B Schimanski S Kirsch R Habermann J Klingler O Schlotte V Weithmann KU Wendt KU 《Chemistry & biology》2005,12(2):181-189
Inhibitors for matrix metalloproteinases (MMPs) are under investigation for the treatment of cancer, arthritis, and cardiovascular disease. Here, we report a class of highly selective MMP-13 inhibitors (pyrimidine dicarboxamides) that exhibit no detectable activity against other MMPs. The high-resolution X-ray structures of three molecules of this series bound to MMP-13 reveal a novel binding mode characterized by the absence of interactions between the inhibitors and the catalytic zinc. The inhibitors bind in the S1' pocket and extend into an additional S1' side pocket, which is unique to MMP-13. We analyze the determinants for selectivity and describe the rational design of improved compounds with low nanomolar affinity. 相似文献
75.
Reinhard Dallinger 《Applied biochemistry and biotechnology》1994,48(1):27-31
Some species of invertebrate animals are known to be efficient accumulators of trace elements. Generally, metal accumulation by such organisms is based on efficient detoxification mechanisms, such as intracellular compartmentalization, or metal inactivation by binding to metallothioneins. Metal accumulators have often been used as accumulation indicators of environmental metal pollution. This means that, ideally, metal concentrations in the animal’s body reflect quantitatively or semiquantitatively environmental pollution levels. In reality, however, many factors, such as the animal’s weight and age, can disturb such quantitative relationships. These factors have, therefore, to be considered carefully before an invertebrate is utilized as accumulation indicator for metal pollution. Apart from accumulation, many invertebrates exposed to elevated metal concentrations respond to this stress by metal-induced synthesis of metallothioneins. Additionally, metallothionein in metal-loaded organisms can be present in different isoforms that are specifically synthesized in response to different metals. These facts make metallothionein a potential biomarker for metal stress in invertebrates. One possibility may be to assess parameters of metallothionein synthesis at the molecular or biochemical level. Moreover, metallothionein isoform patterns could provide information on different isoforms synthesized in response to different metals or chemicals. In any case, however, care must be taken to consider intrinsic physiological parameters, such as nutritional or developmental factors, which could also interfere with metallothionein synthesis. 相似文献
76.
Xiaoming Ren Jingli Xie Youcun Chen Reinhard Karl Kremer 《Journal of Molecular Structure》2003,660(1-3):139-146
The two ion-pair complexes, [pyH]2[Zn(mnt)2] (1) and [4,4′-bipyH2]-[Zn(mnt)2] (2), were synthesized, where mnt2− denotes maleonitriledithiolate, and [pyH]+, [4,4′-bipyH2]2+ represent pyridinium and diprotonated 4,4′-bipyridinium, respectively. Their single crystal structures show that there are strong bifurcated H-bonding interactions between the cations of the pyridinium derivative and the [Zn(mnt)2]2− anions in both 1 and 2. The bifurcated H-bonding interactions between the N–H of the pyridiniums and the CN groups of the mnt2− ligands give rise to a 2D layered H-bonding network, the adjacent layers come together in such way as mutual embrace to give a tight pack, thus 2D hydrogen-bonding sheets further develop into 3D H-bonding networks through weak C–HS and ππ stacking interactions in 1. As for 2, the cations and anions connect into several types of H-bonding macrorings ([2+2], [3+3] and [4+4]), these H-bonding macrorings fuse to extend into 2D layered structure, the interpenetration between [3+3] and [4+4] type H-bonding macrorings in the adjacent layers give further rise to novel 3D extended H-bonding networks, in which there are clearly parallel stacks of cations and the chelate rings of anions. 相似文献
77.
We have exactly enumerated all sequences and conformations of hydrophobic-polar (HP) proteins with chains of up to 19 monomers on the simple cubic lattice. For two variants of the HP model, where only two types of monomers are distinguished, we determined and statistically analyzed designing sequences, i.e., sequences that have a nondegenerate ground state. Furthermore we were interested in characteristic thermodynamic properties of HP proteins with designing sequences. In order to be able to perform these exact studies, we applied an efficient enumeration method based on contact sets. 相似文献
78.
Elfriede Simon M. G. Weller Reinhard Niessner 《Analytical and bioanalytical chemistry》1998,360(7-8):824-826
The aim of the described method was the characterization of a “atrazine-mercaptopropionic acid” humic acid conjugate, which
was required for the calibration of immunoassays to determine bound residues. In order to estimate the amount of bound triazine,
an oxidative nucleophilic substitution reaction of the covalently linked “atrazine-mercaptopropionic acid” to a new triazine
derivative “atrazine-methoxyethanol” was performed. This cleavage product was quantified by gas chromatography. The conditions
for this cleavage procedure were optimized and applied to the “atrazine-mercaptopropionic acid” humic acid conjugate and to
a humic acid blank. The amount of bound “atrazine-mercaptopropionic acid” was calculated to 16.6 ± 2.5 μmol triazine per gram
humic acid, which is equivalent to 0.39 ± 0.07% atrazine.
Received: 7 August 1997 / Accepted: 12 September 1997 相似文献
79.
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