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1.
Ragnar Sigurdsson 《Arkiv f?r Matematik》1991,29(1):285-305
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Retrobiosynthetic analysis of the allergenic sesquiterpene lactone, anthecotuloide, suggested that this natural product could be formed either by head to head condensation of geranyl diphosphate with dimethylallyl diphosphate, or from farnesyl diphosphate (FPP), the accepted regular sesquiterpene precursor via the rearrangement of a germacranolide precursor. Isotopic labelling of anthecotuloide has now been achieved by feeding [1-(13)C]-glucose, [U-13C6]-glucose and [6,6-(2)H2]-glucose to aseptically grown plantlets of Anthemis cotula(family Asteraceae). Analysis of labelling patterns and absolute 13C abundances using quantitative 13C NMR spectroscopy showed that the isoprene building blocks of this sesquiterpene are formed exclusively via the MEP terpene biosynthetic pathway. This was supported by results from an experiment using [U-13C6]-glucose. A deuterium labelling experiment using [6,6-(2)H2]-glucose supported the original proposal and showed that anthecotuloide is formed from a non FPP precursor. Isotope ratio mass spectrometry suggested that there were two pathways for sesquiterpene biosynthesis in A. cotula. 相似文献
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[reaction: see text] 2'-Deoxy-3'-deutero pyrimidines have been synthesized in high yields and incorporated into deoxyoligonucleotides using standard phosphoramidite chemistry. A key synthetic step is a stereospecific reduction of 3'-keto nucleosides using sodium triacetoxyborodeuteride to give 3'-deuterated thymidine and 2'-deoxy uridine nucleosides. Conversion of the corresponding phorphoramidites 7a and 7b to 4-triazolo derivatives has, for the first time, enabled incorporation of 2'-deoxy-3'-deutero cytidine and 2'-deoxy-3'-deutero-5-methyl cytidine into oligonucleotides. 相似文献
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A nucleoside carrying a perfluorinated tert-butyl group ( 4) was prepared by a Sonogashira coupling of 5-iodo-2'-deoxyuridine with 4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butyne in nearly quantitative yield and subsequently incorporated into DNA oligomers. Thermal denaturation studies showed that 4 had a negligible effect on duplex stability when compared to thymidine. Transition from single strand to duplex was monitored by (19)F NMR spectroscopy at micromolar concentrations of oligomers, demonstrating the sensitivity of 4 as an NMR reporter nucleoside. 相似文献
7.
Thorsteinn Loftsson Hákon H. Sigurdsson Dagný Hreinsdóttir Fífa Konrádsdóttir Einar Stefánsson 《Journal of inclusion phenomena and macrocyclic chemistry》2007,57(1-4):585-589
Due to anatomic barriers and lacrimal drainage it is difficult to obtain therapeutic drug concentrations in the posterior part of the eye after topical drug administrations. Lipophilic cyclodextrins, such as randomly methylated β-cyclodextrin (RMβCD), are known to act both as solubilizers of water-insoluble drugs in aqueous solutions and as penetration enhancers that reduce the barrier function of lipophilic membranes. The purpose of this study was to investigate the effects of RMβCD on dexamethasone delivery from aqueous eye drop solution into rabbit eyes. Dexamethasone (0.5 and 1.5% w/v) drops (50 μl) were administered to the left eye of rabbits (n = 6) and the drug levels measured in different eye tissues 2 h after administration. In aqueous humor dexamethasone levels were 1,190 ± 110 and 1,670 ± 630 ng/g (mean ± SD) after administration of the 0.5 and 1.5% dexamethasone eye drops, respectively. In the retina the levels were 33 ± 7 and 66 ± 49 ng/g, and in optic nerve 41 ± 12 and 130 ± 50 ng/g, respectively. In a previous study the dexamethasone concentration in aqueous humor after topical administration of 1.3% (w/v) dexamethasone eye drops in aqueous 2-hydroxypropyl-β-cyclodextrin (HPβCD) solution was determined to be 320 ± 230 ng/g and 66 ± 20 ng/g after administration of Maxidex® eye drops. Both the hydrophilic HPβCD and the lipophilic RMβCD enhance topical dexamethasone delivery into the eye, but of the two, the lipophilic RMβCD results in higher dexamethasone concentrations. 相似文献
8.
Matheus Dorneles de Mello Gaurav Kumar Tarnuma Tabassum Sheetal K. Jain Tso‐Hsuan Chen Stavros Caratzoulas Xinyu Li Dionisios G. Vlachos Songi‐I Han Susannah L. Scott Paul Dauenhauer Michael Tsapatsis 《Angewandte Chemie (International ed. in English)》2020,59(32):13260-13266
Phosphorus‐modified all‐silica zeolites exhibit activity and selectivity in certain Brønsted acid catalyzed reactions for biomass conversion. In an effort to achieve similar performance with catalysts having well‐defined sites, we report the incorporation of Brønsted acidity to metal–organic frameworks with the UiO‐66 topology, achieved by attaching phosphonic acid to the 1,4‐benzenedicarboxylate ligand and using it to form UiO‐66‐PO3H2 by post‐synthesis modification. Characterization reveals that UiO‐66‐PO3H2 retains stability similar to UiO‐66, and exhibits weak Brønsted acidity, as demonstrated by titrations, alcohol dehydration, and dehydra‐decyclization of 2‐methyltetrahydrofuran (2‐MTHF). For the later reaction, the reported catalyst exhibits site‐time yields and selectivity approaching that of phosphoric acid on all‐silica zeolites. Using solid‐state NMR and deprotonation energy calculations, the chemical environments of P and the corresponding acidities are determined. 相似文献
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Skidmore MA Patey SJ Thanh NT Fernig DG Turnbull JE Yates EA 《Chemical communications (Cambridge, England)》2004,(23):2700-2701
Glycosaminoglycan oligosaccharides have been attached to thiol-derivatised gold surfaces, via the formation of mercury-sugar adducts at the non-reducing end, representing a new method of generating versatile glycoconjugates incorporating this class of biologically and medically important carbohydrate. 相似文献