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The synthesis of chiral 12-phenyi(2H)dodecanoic acids as metabolic probes for the evaluation of the stereo-chemical course of the biosynthesis of 1-alkerses from fatty acids in plants and insects is described. The diastereoisomeric (2R, 3R)- or (2S, 3S)-12-phenyl(2,3?2H2)dodecanoic acids 11 are obtained in high chemical and optical yield (>97% e.e.) from the readily available (E)-12-phenyl(2,3-2H2)dodec-2-enoic acid ( 10 ) or (E)-12-phenyldodec-2-enoic acid ( 10a ) by microbial reduction with wet packed cells of Clostridium tyrobutyricum in either 2H2O or H2O buffer. (2R)- and (2S)-12-phenyl(2?2H)dodecanoic acids 9 (>97% e.e.) are accessible from the allylic alcohol 6 via Sharpless epoxidation with (+)-L- or (?)-D-diethyl tartrate, Synthetic routes to the (E)- and (Z)-11-phenyl(1?2H) undec-1-enes 16 and 16a as reference compounds are also included. 相似文献
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24.
Exploring the Effect of Ligand Structural Isomerism in Langmuir–Blodgett Films of Chiral Luminescent EuIII Self‐Assemblies
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Agostino Galanti Dr. Oxana Kotova Dr. Salvador Blasco Chloe J. Johnson Dr. Robert D. Peacock Shaun Mills Prof. John J. Boland Prof. Martin Albrecht Prof. Thorfinnur Gunnlaugsson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(28):9709-9723
Here we have investigated the influence of the antenna group position on both the formation of chiral amphiphilic EuIII‐based self‐assemblies in CH3CN solution and, on the ability to form monolayers on the surface of quartz substrates using the Langmuir–Blodgett technique, by changing from the 1‐naphthyl ( 2(R) , 2(S) ) to the 2‐naphthyl ( 1(R) , 1(S) ) position. The evaluation of binding constants of the self‐ assemblies in CH3CN solution was achieved using conventional techniques such as UV/Visible and luminescence spectroscopies along with more specific circular dichroism (CD) spectroscopy. The binding constants obtained for EuL , EuL2 and EuL3 species in the case of 2‐naphthyl derivatives were comparable to those obtained for 1‐naphthyl derivatives. The analysis of the changes in the CD spectra of 1(R) and 1(S) upon addition of EuIII not only allowed us to evaluate the values of the binding constants but the resulting recalculated spectra may also be used as fingerprints for assignment of the chiral self‐assembly species formed in solution. The obtained monolayers were predominantly formed from EuL3 (≈85 %) with the minor species present in ≈15 % EuL2 . 相似文献
25.
W. Boland 《Nachrichten aus der Chemie》1986,34(5):467-468
26.
This review covers the research on brown algal pheromones from the first structural characterisation of an active principle in 1971 to the recent detailed insight into their biosynthesis. Development of analytical methods and bioassays that lead to the identification of a structural variety of different fatty acid-derived pheromones are reported. Special emphasis is focused on the inactivation of initially released pheromones through pericyclic reactions. The impact of pheromone-research on the defensive chemistry of brown algae and diatoms is discussed. 121 references are cited. 相似文献
27.
We experimentally and theoretically studied the photon lifetime spectral distribution in two coherently coupled spherical microcavities of 3-16 microm diameter forming a photonic molecule, which shows a multipeak narrowband modal structure resulting from lifting of the mode degeneracy with respect to the azimuthal quantum number. The results demonstrate the feasibility of photonic molecules as a basis for a multichannel, wavelength-tunable optical delay-line device, which can be used for delay times in the range 10 ps to 1 ns. 相似文献
28.
It is well established that absorbate-absorbate interactions play a key role in determining the distribution of adsorbates on surfaces. In cases where these interactions are repulsive adsorbates frequently arrange so as to minimize these unfavorable interactions. This simple picture, however, neglects the influence of adsorption on the properties on the underlying substrate. Here, using STM, we show that on Si(100) many intrinsically repulsive adsorbates cluster to form surface patches even at low surface coverages. With the aid of density functional theory calculations and Monte Carlo simulations, we show that patch formation is an intrinsic property of the Si(100) surface that is driven by the energy lowering associated with the formation of extended regions of bare dimers. The enhanced attraction between anticorrelated tilted bare dimers is sufficient to offset the repulsions between adsorbates. 相似文献
29.
Background
Growth hormone (GH) plays an incompletely understood role in the development of the central nervous system (CNS). In this study, we use transgenic mice expressing a growth hormone antagonist (GHA) to explore the role of GH in regulating postnatal brain, spinal cord and body growth into adulthood. The GHA transgene encodes a protein that inhibits the binding of GH to its receptor, specifically antagonizing the trophic effects of endogenous GH. 相似文献30.
N-(17-Acyloxy-acyl)-glutamine conjugates such as N-(17-linolenoyloxy-linolenoyl)-glutamine (6), N-(17-linolenoyloxy-linoleoyl)-glutamine (7), N-(17-linoleoyloxy-linolenoyl)-glutamine (8), and N-(17-linoleoyloxy-linoleoyl)-glutamine (9) were identified as novel surfactants in the oral secretion of several lepidopteran larvae (S. exigua, S. littoralis, S. frugiperda, and H. virescens) by LC-MS/MS and chemical degradation. Authentic reference compounds were synthesized via a dissymmetric bis-Wittig approach and confirmed the assigned structures. 相似文献