排序方式: 共有63条查询结果,搜索用时 0 毫秒
1.
Carl Mayer Clinton Ludlow Green Werner Trueb Peter Christian Wlchli Conrad Hans Eugster 《Helvetica chimica acta》1978,61(2):905-921
Degradation of palustrin to (?)-dihydropalustramic acid ((2R,6S,1′S)-[6-(1′-hydroxypropyl)-2-piperidyl]acetic acid), and the structure of palustrin and palustridin The structure of the macrocyclic alkaloid palustrin is shown to be 1a . Its piperidine unit can be obtained as (?)-dihydropalustramic acid ( 6a ) by the following sequence of degradation reactions (Scheme 1): catalytic hydrogenation of 1a followed by methylation and Hofmann degradation provides the allyl base 4 . the regioselectivity of the Hofmann elimination is explained by intramolecular proton abstraction at C(3) by C(18)-O?. Catalytic reduction of 4 and subsequent acidic hydrolysis yielded 6a and N, N-dimethylputrescine (?N,N-dimethyl-1,4-butanediamine; 7 ). Loss of the N-alkyl group in the formation of 6a occurs during the catalytic hydrogenation step. This interpretation is supported by the results of model experiments. The position of the double bond in 1a is deduced from the IR. spectrum of the bromo-δ-lactone 19 prepared by treatment of 1a with N-bromosuccinimide at pH 4 (Scheme 3). Some of our previously published results on the degradation of dihydropalustrin ( 2a ) are obviously at variance with the newly proposed structure for palustrin ( 1a ). They can easily be explained by assuming a partial hydrogenolysis of the C(17)-N(1) bond during the preparation of dihydropalustrin from palustrin. Periodate cleavage of dihydropalustramic acid methyl ester ( 6b ) liberates propionaldehyde, which can be trapped by working at pH 7.5 (Scheme 2); at lower pH values it condenses rapidly with the simultaneously generated 3,4,5,6-tetrahydropyridine derivative 15 . The structure of the condensation product is proposed to be 16 on the basis of the isolation of its hydrogenation product, an isomeric dihydropalustramic acid ( 17 ). 相似文献
2.
Overtone spectrum of o, m and p-nitrobenzaldehydes and p-chlorobenzaldehyde has been studied in 2000–12000 cm−1 region. Vibrational frequencies and anharmonicity constants for aryl as well as alkyl CH stretch vibrations have been determined.
We have also determined the internuclear distances for the aryl CH bond in the different molecules. The small variation observed
in these distances is an indication of the substitution effect.
It is observed that in the case of p-disubstituted benzens, the shift in aryl CH bond is proportional to sum of the Hammet σ of the substituents. However in the
case of o-disubstituted benzenes it is only 80% of the para-substituted shift. 相似文献
3.
4.
This study examined whether vocal fold kinematics prior to phonation differed between hard (glottal), normal, or breathy onsets in men and women. Glottal landmarks were identified and digitized from videotape recorded with a rigid laryngoscope during different voice onset types. Significant linear relationships (p 0.0055) were found among onset types on measures of (a) gesture duration when moving from 80% to 20% of maximum distance during adduction, (b) maximum velocity, (c) duration between the completion of adduction and phonation onset, and (d) ratios of maximum velocity to maximum distance between the vocal processes, an estimate of stiffness. The gesture duration was greatest for breathy onsets and least for hard onsets, while the maximum velocity, latency between adduction and phonation onset, and estimated stiffness were greatest for hard onsets and least for breathy onsets. The results suggest that one trajectory seems to be used with increases in gesture duration being accompanied by decreases in articulator stiffness when moving from hard to normal to breathy voice onset types. 相似文献
5.
M. Sc. Yasemin Akbulut Hannah J. Gaunt Prof. Katsuhiko Muraki Dr. Melanie J. Ludlow Dr. Mohamed S. Amer Dr. Alexander Bruns Dr. Naveen S. Vasudev Dr. Lea Radtke Dr. Matthieu Willot M. Sc. Sven Hahn M. Sc. Tobias Seitz Dr. Slava Ziegler Prof. Dr. Mathias Christmann Prof. Dr. David J. Beech Prof. Dr. Herbert Waldmann 《Angewandte Chemie (International ed. in English)》2015,54(12):3787-3791
Current therapies for common types of cancer such as renal cell cancer are often ineffective and unspecific, and novel pharmacological targets and approaches are in high demand. Here we show the unexpected possibility for the rapid and selective killing of renal cancer cells through activation of calcium‐permeable nonselective transient receptor potential canonical (TRPC) calcium channels by the sesquiterpene (?)‐englerin A. This compound was found to be a highly efficient, fast‐acting, potent, selective, and direct stimulator of TRPC4 and TRPC5 channels. TRPC4/5 activation through a high‐affinity extracellular (?)‐englerin A binding site may open up novel opportunities for drug discovery aimed at renal cancer. 相似文献
6.
Quinlan F Fortier TM Kirchner MS Taylor JA Thorpe MJ Lemke N Ludlow AD Jiang Y Diddams SA 《Optics letters》2011,36(16):3260-3262
We present an optical frequency divider based on a 200 MHz repetition rate Er:fiber mode-locked laser that, when locked to a stable optical frequency reference, generates microwave signals with absolute phase noise that is equal to or better than cryogenic microwave oscillators. At 1 Hz offset from a 10 GHz carrier, the phase noise is below -100 dBc/Hz, limited by the optical reference. For offset frequencies >10 kHz, the phase noise is shot noise limited at -145 dBc/Hz. An analysis of the contribution of the residual noise from the Er:fiber optical frequency divider is also presented. 相似文献
7.
We obtain a solution of the DGLAP equation for the gluon at low x first by expanding the gluon in a Taylor series and then using the method of characteristics. We test its validity by comparing
it with that of Glück, Reya and Vogt. The convergence criteria of the approximation used are also discussed. We also calculate
εF
2(x,Q)2/ε In Q
2 using its approximate relations with the gluon distribution at low x. The predictions are then compared with the HERA data. 相似文献
8.
9.
10.
Tanya Zelevinsky Dr. Sebastian Blatt Martin M. Boyd Dr. Gretchen K. Campbell Dr. Andrew D. Ludlow Jun Ye Prof. 《Chemphyschem》2008,9(3):375-382
Cooling and trapping of neutral atoms using laser techniques has enabled extensive progress in precise, coherent spectroscopy. In particular, trapping ultracold atoms in optical lattices in a tight confinement regime allows us to perform high‐resolution spectroscopy unaffected by atomic motion. We report on the recent developments of optical lattice atomic clocks that have led to optical spectroscopy coherent at the one second timescale. The lattice clock techniques also open a promising pathway toward trapped ultracold molecules and the possible precision measurement opportunities such molecules offer. 相似文献