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41.
Heidi L. Shimp 《Tetrahedron》2008,64(16):3437-3445
Titanium-mediated cross-coupling of allenic alcohols with alkynes has been investigated. Divergent reaction pathways were discovered that provide either stereodefined 1,4-dienes or substituted cross-conjugated trienes. In short, allene substitution plays a critical role in the determination of reaction pathway. 相似文献
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A notion of stability of dynamics under distant perturbations is introduced. It is demonstrated, for quasi-local systems, that the stability of an equilibrium state under the same perturbations implies the state is factorial, i.e. strongly clustering in space. We also characterize the set of perturbations necessary to ensure the equivalence of stability and factorialness. 相似文献
44.
Synthesis of Diterpenes as Possible Biogenetic Precursors of the C20-Carotenoid Crocetin With regard to the investigation of the biosynthesis of the C20-carotenoids in saffron the four diterpenes 6–9 were synthesized, who differ only in their degree of saturation. A detailed analysis of their 1H- and 13C-NMR spectra has been achieved by their mutual comparison. 相似文献
45.
Delong CM Au WW Lemonds DW Harley HE Roitblat HL 《The Journal of the Acoustical Society of America》2006,119(3):1867-1879
The focus of this study was to investigate how dolphins use acoustic features in returning echolocation signals to discriminate among objects. An echolocating dolphin performed a match-to-sample task with objects that varied in size, shape, material, and texture. After the task was completed, the features of the object echoes were measured (e.g., target strength, peak frequency). The dolphin's error patterns were examined in conjunction with the between-object variation in acoustic features to identify the acoustic features that the dolphin used to discriminate among the objects. The present study explored two hypotheses regarding the way dolphins use acoustic information in echoes: (1) use of a single feature, or (2) use of a linear combination of multiple features. The results suggested that dolphins do not use a single feature across all object sets or a linear combination of six echo features. Five features appeared to be important to the dolphin on four or more sets: the echo spectrum shape, the pattern of changes in target strength and number of highlights as a function of object orientation, and peak and center frequency. These data suggest that dolphins use multiple features and integrate information across echoes from a range of object orientations. 相似文献
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Alex G. M. Litherland Lee M. Spurway Sergey N. Gordeev Barak D. B. Aaronson Andrew J. Wain Michael A. O’Connell Heidi Piili Mikko Hovilehto Ville-Pekka Matilainen Anne Vuorema Frank Marken 《Journal of Solid State Electrochemistry》2018,22(6):1755-1762
Galvanic exchange involving dissolution of iron and the simultaneous growth of platinum onto 316 L stainless steel was investigated for specimens manufactured by 3D-printing, and the behavior was compared to conventional stainless steel. Novel phenomena associated with the 3D-printed steel, but not conventional steel, reacting in three distinct phases were observed: first, with low platinum loading, a bright etching pattern linked to the laser-manufacturing process is revealed at the steel surface; second, a nanostructured pore pattern with platinum nano-deposits forms; and third, a darker platinum film coating of typically 500-nm thickness forms and then peels off the steel surface with further platinum growth underneath. Unlike the conventional steel (and mainly due to residual porosity), 3D-printed steel supports well-adhered platinum films for potential application in electrocatalysis, as demonstrated for alkaline methanol oxidation. 相似文献
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Shellhamer DF Davenport KJ Forberg HK Herrick MP Jones RN Rodriguez SJ Sanabria S Trager NN Weiss RJ Heasley VL Boatz JA 《The Journal of organic chemistry》2008,73(12):4532-4538
Reactions of chlorine (Cl(2)) with 4-halo-1,1,2-trifluorobut-1-enes (1, 2, or 3) give open-ion intermediates A and E that are in equilibrium. The open-chloronium ions (E) rearrange to a five-membered-ring halonium ion during ionic chlorination of 3 when the number-4 halo-substituent is iodine. Three-membered-ring bromonium and iodonium ions from alkenes 1, 2, or 3 are rather symmetrical and similar in structure. Quantum chemical calculations show that five-membered-ring halonium ion intermediates are 11 to 27 kcal/mol more stable than the three-membered-ring halonium ions or the open-ions A and E. The five-membered-ring intermediates lead to rearranged products. Rearranged products increase as the number-4 halogen (Z) becomes more nucleophilic (Z: Cl < Br < I). Open chloronium ions from ionic chlorination of terminal fluorovinyl alkenes are compared to the open ions generated by protons to similar alkenes. 相似文献
50.
Cyclodextrins and antibodies have been used as affinity agents to improve relative recovery during microdialysis sampling. Two neuropeptides, methionine-enkephalin (ME) and leucine-enkephalin (LE), were chosen to compare the use of cyclodextrins and antibodies as possible affinity agents for improving their relative recovery across polycarbonate and polyethersulfone membranes during in vitro sampling. Cyclodextrins (CD) including β-CD, 2-hydroxypropyl-β-cyclodextrin (2HPβ-CD), and γ-CD gave improvements of relative recovery for both peptides of less than 2-fold as compared to controls. Comparisons of relative recovery between tyrosine–glycine–glycine, tyrosine, and phenylalanine using different cyclodextrins in the perfusion fluid were also obtained. Inclusion of an antibody against met-enkephalin in the microdialysis perfusion fluid resulted in relative recovery increases of up to 2.5-fold. These results show that using antibodies as affinity agents during microdialysis sampling may be more effective agents to improve the relative recovery of these opioid neuropeptides. 相似文献