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21.
Iqbal M Black RJ Winn J Reeder AT Blake AJ Clarke PA 《Organic & biomolecular chemistry》2011,9(14):5062-5078
A series of diverse natural product-like structures have been synthesised by the use of a number of novel transannulation reactions across a cyclononene ring. Transannular cyclisations through oxygen functionality have generated a number of bicyclo[5.3.1]systems containing bridged cyclic ethers and bicyclo[5.2.2]lactones, as well as a tetrahydrofuran-containing bridged analogue of hexacyclinic acid. An unprecedented Br?nsted acid mediated transannular cyclisation between proximal carbons generated bicyclo[4.3.0]nonanes which form the core of the pinguisane and austrodorane families of sesquiterpenoids. In all cases the key factor that determined the mode of reactivity was the conformation of the nine-membered ring and the distance between the reacting centres. 相似文献
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Stacy Slavin James Burns David M. Haddleton C. Remzi Becer Author vitae 《European Polymer Journal》2011,47(4):435-446
This mini-review describes recent work in the field of glycopolymer synthesis, with a focus on methods that have employed “click chemistry” and controlled polymerization methodology. A variety of carbohydrates with clickable groups such as azide, alkyne, and thiol moieties provide new routes to glycopolymers. Several studies use copper catalyzed azide-alkyne cycloaddition (CuAAC) reactions to synthesize glycomonomers or to incorporate carbohydrates into a clickable polymeric backbone. Alternatively, there are many thiol based click reactions which provide metal-free synthesis, which are discussed in details. 相似文献
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Dennis J. Reeder Margaret C. Kline Kristy L. Richie 《Fresenius' Journal of Analytical Chemistry》1995,352(1-2):246-249
Although DNA typing is an accurate, precise, and robust procedure, quality assurance is enhanced by availability of a suitable reference material. The National Institute of Standards and Technology (NIST) recently released a Standard Reference Material (SRM) that meets the calibration and quality assurance needs of laboratories that perform DNA typing. Each step of the analytical process of DNA typing may be verified by one or more of twenty different components of the SRM. As newer, more sensitive methods for DNA typing have been introduced into the human identification laboratory repertoire, new SRMs will be required for quality assurance. A second SRM for PCR-based tests is under development and soon to be available, is also described. 相似文献
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Timberlake GT Yousef AL Chiles SR Moses RA Givens RS 《Photochemistry and photobiology》2005,81(5):1180-1185
Photoactivated bis-diazopyruvamide-N,N'-bis(3-diazopyruvoyl)-2,2'-(ethylenedioxy)bis-(ethylamine), (DPD)-was previously shown to bond materials containing type I collagen. However, tensile strength of bonded collagenous tissue ( approximately 78% water) was low compared with that of dehydrated collagenous gelatin ( approximately 14% water). Here we investigated the role of water in corneal tissue bond strength and in bonding corneal tissue to glass. Bonding corneal tissue to glass may be of value in surgically anchoring keratoprostheses to corneas to alleviate problems with extrusion. Bovine corneal samples were lyophilized for various times resulting in tissue hydrations of zero (no water content) to approximately 3.7 (normal water content). The lyophilized corneal tissue was bonded to solid gelatin sheets, to other corneal samples and to glass using 0.3M DPD in chloroform. Control runs used chloroform only. Samples were irradiated with 100 or 200 J of 320-500 nm light. Strong bonds formed with all three materials when corneal tissue hydration was =1. No bonds or extremely weak bonds formed when tissue hydration levels were >1. No bonding occurred with chloroform alone. Formation of strong bonds only occurs with hydration levels =1 because corneal collagen fibrils are tightly packed and close enough to cross-link with the 1.78 nm long DPD. 相似文献
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The kinetics of aromatic nucleophilic substitution of the nitric oxide‐generating diazeniumdiolate ion, DEA/NO, by thiols (L ‐glutathione, L ‐cysteine, DL ‐homocysteine, 1‐propanethiol, 2‐mercaptoethanol, and sodium thioglycolate) from the prodrug, DNP‐DEA/NO, has been examined in aqueous solution and in solutions of cationic DOTAP vesicles. Second‐order rate constants in buffered aqueous solutions (kRS‐ = 3.48–30.9 M?1 s?1; 30 °C) gave a linear Brønsted plot (βnuc = 0.414 ± 0.068) consistent with the rate‐limiting SNAr nucleophilic attack by thiolate ions. Cationic DOTAP vesicles catalyze the thiolysis reactions with rate enhancements between 11 and 486‐fold in Tris‐HCl buffered solutions at pH 7.4. The maximum rate increase was obtained with thioglycolate ion. Thiolysis data are compared to data for nucleophilic displacement by phenolate (kPhO‐ = 0.114 M?1 s?1) and hydroxide (kOH‐ = 1.82 × 10?2 M?1 s?1, 37 °C) ions. The base hydrolysis reaction is accelerated by CTAB micelles and DODAC vesicles, with the vesicles being ca 3‐fold more effective as catalysts. Analysis of the data using pseudo‐phase ion‐exchange (PIE) formalism implies that the rate enhancement of the thiolysis and base hydrolysis reactions is primarily due to reactant concentration in the surfactant pseudo‐phase. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
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Steven R. Woodcock Stacy G. Wendell Francisco J. Schopfer Bruce A. Freeman 《Tetrahedron letters》2018,59(39):3524-3527
15-oxo-Lipoxin A4 (15-oxo-LXA4) has been identified as a natural metabolite of the fatty acid signaling mediator Lipoxin A4. Herein, we report a total synthesis of the methyl ester of 15-oxo-LXA4 to be used in investigations of potential electrophilic bioactivity of this metabolite. The methyl ester of 15-oxo-LXA4 was synthesized in a convergent 15 step (9 steps longest linear) sequence starting from 1-octyn-3-ol and 2-deoxy-d-ribose with Sonogashira and Suzuki cross-couplings of a MIDA boronate as key steps. 相似文献