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961.
962.
Lépine F Milot S Déziel E He J Rahme LG 《Journal of the American Society for Mass Spectrometry》2004,15(6):862-869
The opportunistic pathogen Pseudomonas aeruginosa produces a large array of 4-hydroxy-2-alkylquinolines (HAQs). These compounds were analyzed by LC/MS, using positive electrospray ionization, in the culture supernatant of strain PA14. Fifty-six HAQs and related compounds were detected and their [M + H](+) ions were further analyzed by collision induced dissociation (CID). These HAQs were grouped into five different series based on the presence of an hydrogen or hydroxyl group at the 3 position, an N-oxide group in place of the quinoline nitrogen, and an unsaturation on their alkyl side chain. Two new analogs of 3,4-dihydroxy-2 heptylquinoline, the Pseudomonas quinolone signal (PQS), were found with an alkyl chain longer by one and two methylene groups. Moreover, two additional series of compounds were identified in which a saturated or unsaturated alkyl side chain is located at the 3 position along with an hydroxyl group at the 3 position and a ketone at the 2 position. No HAQ N-oxides, nor any compounds from the latter two series, were detected in a pqsL mutant derivative of PA14, indicating that this gene is involved in the biosynthesis of these compounds. This work demonstrates the large repertoire of HAQ and HAQ-related compounds produced by P. aeruginosa, and provides insight into N-oxides biosynthesis and confirm the hypothesis that N-oxides are the precursors of compounds from Series 6 and 7. 相似文献
963.
Addition of terpyridine to (TMEDA)Ni(CH3)2 results in the high-yield formation of (terpyridyl)NiMe (3). This NiI organometallic complex was found to be capable of transferring its methyl group to iodocyclohexane to produce methylcyclohexane in high yield. Compound 3 can also serve as an initiator for the catalytic cross-coupling of alkyl electrophiles performed under Negishi-like conditions. 相似文献
964.
Resistant starches and health 总被引:3,自引:0,他引:3
It was initially hypothesized that resistant starches, i.e., starch that enters the colon, would have protective effects on chronic colonic diseases, including reduction of colon cancer risk and in the treatment of ulcerative colitis. Recent studies have confirmed the ability of resistant starch to increase fecal bulk, increase the molar ratio of butyrate in relation to other short-chain fatty acids, and dilute fecal bile acids. However the ability of resistant starch to reduce luminal concentrations of compounds that are damaging to the colonic mucosa, including fecal ammonia, phenols, and N-nitroso compounds, still requires clear demonstration. As such, the effectiveness of resistant starch in preventing or treating colonic diseases remains to be assessed. Nevertheless, there is a fraction of what has been termed resistant (RS1) starch, which enters the colon and acts as slowly digested or lente carbohydrate in the small intestine. Foods in this class are low glycemic index and have been shown to reduce the risk of chronic disease. They have been associated with systemic physiological effects such as reduced postprandial insulin levels and higher HDL cholesterol levels. Consumption of low glycemic index foods has been shown to be related to reductions in risk of coronary heart disease and Type 2 diabetes. Type 2 diabetes has in turn been related to a higher risk of colon cancer. If carbohydrates have a protective role in colon cancer prevention this may lie partly in the systemic effects of low glycemic index foods. The colonic advantages of different carbohydrates, varying in their glycemic index and resistant starch content, therefore, remain to be determined. However, as recent positive research findings continue to mount, there is reason for optimism over the possible health advantages of those resistant starches, which are slowly digested in the small intestine. 相似文献
965.
[reaction: see text] A novel cycloaldol approach to the isobenzofuran core common to many of the eunicellin diterpenes is described. The cycloaldol precursor was prepared by aldol addition of (S)-(+)-carvone and methacrolein followed by etherification to a glycolate ester. Chemoselective enolization of the glycolate ester led to the cycloaldol adduct in high yield and diastereoselectivity. An oxidative rearrangement-allylic diazene rearrangement sequence established the requisite cis ring fusion. 相似文献
966.
HuiGUO WuXinZOU QiJI JiBenMENG 《中国化学快报》2005,16(6):751-754
A series of photo active azido analogues have been synthesized and their photochromic properties have also been investigated by UV-Vis spectrum. It will be used for the rapid and reliable preparation of large amounts of stable, non-radioactive labeled DNA and RNA hybridization probes. And it is supposed to be easily detected for its photochromic properties. 相似文献
967.
Frank D. Popp Miland Rajopadhye David S. Brown David Waddington Barrie C. Uff 《Journal of heterocyclic chemistry》1987,24(1):261-265
The title compounds have been prepared by the cyclocondensation of mercaptosuccinic acid with isatin-3-imines. The 1-benzyl derivatives have been synthesized by simultaneously reacting 1-benzylisatin, substituted anilines and mercaptosuccinic acid. The structure of the products has been confirmed by X-ray diffraction measurements. 相似文献
968.
David A. Place Gerald P. Ferrara Joseph J. Harland James C. Dabrowiak 《Journal of heterocyclic chemistry》1980,17(3):439-443
Using a metal template reaction, a series of [14]azaannulenes formed from a β-diketone and an aromatic diamine in the presence of nickel(II) have been synthesized. Attempted cyclizations with bulky β-diketones and certain substituted diamines showed that the cyclization is sensitive to steric effects. At least one of the nickel complexes readily reacts with a series of nucleophilic reagents to give methine-substituted products. 相似文献
969.
The conformational properties of the furanose ring of purine- and pyrimidine--nucleosides and-nucleotides are studied quantum-mechanically with the help of the PCILO method, using the pseudorotational concept. The computations point to the existence of two stable conformational zones centered around the C(3)-endo and C(2)-endo conformations which in the isolated furanose ring are separated by barriers of the order of 4 kcal/mole. In nucleosides one of the barriers (the one running through the O(1)-exo-C(2)-exo path) becomes very high. A detailed study is made of the relation between the phase angle of pseudorotation, P, and the torsion angle about the glycosyl bond,
CN. A very satisfactory agreement with the available experimental data is observed.
This research was supported by the R.C.P. 173 and the A.T.P. A 655-2303 of the C.N.R.S. 相似文献
Zusammenfassung Die Konformationseigenschaften des Furanoserings in -Nucleosiden und Nucleotiden von Purin und Pyrimidin werden nach der PCILO-Methode unter Berücksichtigung der pseudorotatorischen Betrachtungsweise studiert. Die Rechnung läßt auf die Existenz zweier stabiler Konformationszonen schließen, die in der Umgebung der C(2)-endo und der C(3)-endo Konformationen liegen, und die im isolierten Furanosering durch Energiebarrieren der Größenordnung von 4 kcal/mol voneinander getrennt sind. In Nucleosiden wird eine der Barrieren (die durch den Weg O(1)-exo-C(2)-exo gekennzeichnete) sehr hoch. Die Relation zwischen dem Phasenwinkel der Pseudorotation, P, und dem Drehwinkel um die Glycosylbindung, CN, wird einer eingehenden Untersuchung unterworfen. Man beobachtet eine sehr zufriedenstellende Übereinstimmung mit den verfügbaren experimentellen Daten.
Résumé Les propriétés conformationnelles du noyau furanose des -nucleosides et nucleotides des purines et pyrimidines sont étudiées par la méthode PCILO en faisant appel au concept de la pseudorotation. Les calculs indiquent l'existence de deux zones de conformations stables, centrées autour des conformations C(2)-endo et C(3)-endo, qui sont dans le sucre isolé séparées par des barrières de l'ordre de 4 kcal/mole. Dans les nucleosides, l'une de ces barrières (celle qui passe par le chemin O(1)-exo-C(2)-exo) devient très élevée. Une étude détaillée est effectuée sur la relation entre l'angle de phase de la pseudorotation P et l'angle de torsion autour de la liaison glycosylique, CN. Un excellent accord avec les données expérimentales disponibles est observé.
This research was supported by the R.C.P. 173 and the A.T.P. A 655-2303 of the C.N.R.S. 相似文献
970.
Katsuhiko?Kamio Yoshifumi?Kusumoto Masashi?Sakai Katumitu?HayakawaEmail author 《Colloid and polymer science》2003,281(7):608-613
The conformation of the sodium salt of poly(l-glutamic acid) (P(Glu)) in solutions of the cationic bipolar amphiphile 1, 20-isosanediylbis(alkylammonium chloride) (C 20(RA) 2) with different alkyl head groups as a function of amphiphile concentration was investigated using circular dichroism (CD). RA included methylammonium (MA), ethylammonium (EA), propylammonium (PA), butylammonium (BA), and pentylammonium (PeA) cationic groups. The CD spectrum of each C 20(RA) 2 had a double minima corresponding to the a-helix of P(Glu), which was replaced by CD spectra with a single minimum at wavelengths larger than 222 nm as concentration increased. These changes in the CD spectrum were ascribed to the conformational change from random coil to a-helix and to aggregates of helices. In C 20(EA) 2 solutions, a step-like change in the CD intensity was observed at 222 nm as a function of the ratio of C 20(RA) 2 to P(Glu). At the step, the CD spectrum of the complete a-helix was observed. At 10–35 °C, an a-helix was induced in P(Glu) in the order: C 20(EA) 2>C 20(MA) 2>C 20(PA) 2>C 20(BA) 2>C 20(PeA) 2. This order was ascribed to the best fit of ethylammonium to the P(Glu) side chain. 相似文献