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21.
Several radical cyclisation reactions involving indoles are described. Most notably, we have shown that radical additions to C3 of an indole are frequently facile. A dichotomy in the course of radical cyclisation reactions to C2 of the indole has also been exposed wherein 6-endo-trig cyclisations are propagated by the loss of a hydrogen atom from C2 while 5-exo-trig cyclisations are propagated by hydrogen atom abstraction at C3 from tributyltin hydride. Cyclisations involving the addition of indolyl radical intermediates to arenes have also been demonstrated. 相似文献
22.
James K. Chen Stuart L. Schreiber 《Angewandte Chemie (International ed. in English)》1995,34(9):953-969
Combinatorial chemistry is a laboratory emulation of natural recombination and selection processes. Strategies in this developing discipline involve the generation of diverse, molecular libraries through combinatorial synthesis and the selection of compounds that possess a desired property. Such approaches can facilitate the identification of ligands that bind to biological receptors, promoting our chemical understanding of cellular processes. This article illustrates that the coupling of combinatorial synthesis, multidimensional NMR spectroscopy, and biochemical methods has enhanced our understanding of a protein receptor used commonly in signal transduction, the Src Homology 3 (SH3) domain. This novel approach to studying molecular recognition has revealed a set of rules that govern SH3–ligand interactions, allowing models of receptor–ligand complexes to be constructed with only a knowledge of the polypeptide sequences. Combining combinatorial synthesis with structural methods provides a powerful new approach to understanding how proteins bind their ligands in general. 相似文献
23.
Stuart D. R.?GallowayEmail author Elizabeth M.?Broad 《Monatshefte für Chemie / Chemical Monthly》2005,136(8):1391-1410
Summary. Oral L-carnitine supplementation is frequently reported to have beneficial effects on exercise capacity in clinical populations and has been considered as a potential ergogenic aid for endurance athletes. However, this latter view is largely unsubstantiated possibly due to many experimental studies being poorly controlled or difficult to compare. The potential for oral L-carnitine supplementation to influence skeletal muscle carnitine content has been questioned and there are several key factors identified that may explain variations between study outcomes. Recent more well controlled research suggests some potential for L-carnitine to act as a key regulator of cellular stress, possibly through an impact on the integration of carbohydrate and lipid metabolism, and this work should be followed up in future by well controlled studies in both athlete and clinical subject groups. 相似文献
24.
25.
Leung KC Aricó F Cantrill SJ Stoddart JF 《Journal of the American Chemical Society》2005,127(16):5808-5810
The versatility and efficiency of dynamic covalent chemistry (DCC) has been exploited in the convergent synthesis of mechanically interlocked dendrimers that are based upon the mutual recognition expressed between secondary dialkylammonium ions and crown ether-like macrocycles. Reversible imine bond formation is employed to clip two acyclic fragments, one of them a diformylpyridine unit bearing a dendritic side chain, and the other a complementary dianiline in the shape of the di(o-aminophenyl)ether of tetraethylene glycol, around each arm of a tritopic trisammonium ion core, thereby affording a branched [4]rotaxane. This template-directed strategy has been demonstrated to work in very high yields (>90%) with successive generations (G0-G2) of a modified Fréchet-type dendritic wedge attached to the 4-position of the diformylpyridine unit. Reduction of these dynamic dendritic systems is achieved upon treatment with borane.THF and results in kinetically stable compounds. The inherent modularity of the overall process should allow for the rapid and straightforward access to many other analogous mechanically interlocked systems in which either the branched core or the dendritic periphery can be modified to suit the needs of any given application of these molecules. Indeed, the dynamic nature of the initial thermodynamically mediated assembly could be utilized in order to amplify particular products from a potential library as a result of a selective recognition process. 相似文献
26.
Wei Q Nieuwenhuyzen M Meunier F Hardacre C James SL 《Dalton transactions (Cambridge, England : 2003)》2004,(12):1807-1811
The metal-organic framework [Co(INA)(2)]x0.5EtOH (INA = isonicotinate, NC(5)H(4)-4-CO(2)(-)), was synthesised under solvothermal conditions. Its X-ray crystal structure shows channels containing ethanol guests which are hydrogen-bonded to carboxylate oxygens of the framework. The pyridyl rings of the framework alternate between 'open' and 'closed' positions along the channels resulting in large variation in the channel cross-sectional area from ca. 1.4 by 2.3 A at the narrowest point to 4.9 by 5.3 A at the widest. Despite the very small windows, the ethanol guests (of van der Waals diameter ca. 4.2-6.1 A) may be reversibly desorbed and sorbed into the structure quantitatively, as shown by in situ variable-temperture IR spectroscopy and XRPD. The single-crystal structure of the desolvated form [Co(INA)(2)] shows that there is no change in the overall connectivity on desolvation, but the rotational positions of the pyridine rings are altered. This suggests that pyridyl rotation may occur to allow guests to pass in and out. When the synthesis was conducted in 1-propanol solvent [Co(INA)(2)]x0.5Pr(n)OHxH(2)O, was obtained, and a single-crystal X-ray structure revealed the same overall connectivity as in but with pyridine rings disordered over closed and open positions. There was no evidence of included guests from X-ray crystallography, suggesting that they are also highly disordered. Variable-temperature XRPD performed on bulk samples showed peaks which were unsymmetrical and exhibited shoulders, suggesting that for each pattern obtained the material actually consisted of several closely-related phases. The movements of the peaks during desolvation showed the presence of intermediate phases before the final desolvated product was formed. The peak positions of the intermediate phases matched more closely with the calculated pattern for than with or, suggesting that they may have disordered structures similar to. The results also suggest that the intermediate phase represents an initial increase in volume before a larger decrease in volume occurs to give the final desolvated material. 相似文献
27.
De La Rosa Luis B. Reshamwala Sultan Latimer Vivian M. Shawky Bahaa T. Dale Bruce E. Stuart Earnest D. 《Applied biochemistry and biotechnology》1994,(1):483-497
The herbaceous crops that may provide fermentable carbohydrates for production of fuels and chemicals also contain 10–20%
protein. Protein coproduction with biomass-derived fuels and chemicals has important advantages: (1) food and fuel production
can be integrated, and (2) protein is a high-value product that may significantly improve overall process economics. We report
the results of an integrated approach to producing protein and fermentable sugars from one herbaceous species, Coastal Bermudagrass
(CBG). The ammonia fiber explosion (AFEX) process makes possible over 90% conversion of cellulose and hemicellulose to simple
sugars (about 650 mg reducing sugars/g dry CBG) at 5 IU cellulase/g vs < 20% conversion for untreated CBG. The AFEX treatment
also improves protein extraction from CBG; over 80% protein recovery is possible from AFEX-treated CBG vs about 30% recovery
from untreated CBG. 相似文献
28.
Photodynamic therapy (PDT) relies on three main ingredients, oxygen, light and photoactivating compounds, although the PDT response is definitively contingent on the site and level of reactive oxygen species (ROS) generation. This study describes the development of a novel, fluorescent-based actinometer microsphere system as a means of discerning spatially resolved dosimetry of total fluence and ROS production. Providing a high resolution, localized, in situ measurement of fluence and ROS generation is critical for developing in vivo PDT protocols. Alginate-poly-L-lysine-alginate microspheres were produced using ionotropic gelation of sodium alginate droplets, ranging from 80 to 200 microm in diameter, incorporating two dyes, ADS680WS (ADS) and Rhodophyta-phycoerythrin (RPE), attached to the spheres' inside and outside layers, respectively. To test the responsivity and dynamic range of RPE for ROS detection, the production of ROS was initiated either chemically using increasing concentrations of potassium perchromate or photochemically using aluminum tetrasulphonated phthalocyanine. The generation of singlet oxygen was confirmed by phosphorescence at 1270 nm. The resulting photodegradation and decrease in fluorescence of RPE was found to correlate with increased perchromate or PDT treatment fluence, respectively. This effect was independent of pH (6.5-8) and could be inhibited using sodium azide. RPE was not susceptible to photobleaching with light alone (670 nm; 150 Jcm(-2)). ADS, which absorbs light between 600 and 750 nm, showed a direct correlation between radiant exposure (670 nm; 0-100 Jcm(-2)) and diminished fluorescence. Photobleaching was independent of irradiance (10-40 mW cm(-2)). We propose that actinometer microspheres may provide a means for obtaining high spatial resolution information regarding delivered PDT dose within model systems during investigational PDT development and dosimetric information for clinical extracorporeal PDT as in the case of ex vivo bone marrow purging. 相似文献
29.
Transfection mediated by gemini surfactants: engineered escape from the endosomal compartment 总被引:8,自引:0,他引:8
Bell PC Bergsma M Dolbnya IP Bras W Stuart MC Rowan AE Feiters MC Engberts JB 《Journal of the American Chemical Society》2003,125(6):1551-1558
The structure of the lipoplex formed from DNA and the sugar-based cationic gemini surfactant 1, which exhibits excellent transfection efficiency, has been investigated in the pH range 8.8-3.0 utilizing small-angle X-ray scattering (SAXS) and cryo-electron microscopy (cryo-TEM). Uniquely, three well-defined morphologies of the lipoplex were observed upon gradual acidification: a lamellar phase, a condensed lamellar phase, and an inverted hexagonal (H(II)) columnar phase. Using molecular modeling, we link the observed lipoplex morphologies and physical behavior to specific structural features in the individual surfactant, illuminating key factors in future surfactant design, viz., a spacer of six methylene groups, the presence of two nitrogens that can be protonated in the physiological pH range, two unsaturated alkyl tails, and hydrophilic sugar headgroups. Assuming that the mechanism of transfection by synthetic cationic surfactants involves endocytosis, we contend that the efficacy of gemini surfactant 1 as a gene delivery vehicle can be explained by the unprecedented observation of a pH-induced formation of the inverted hexagonal phase of the lipoplex in the endosomal pH range. This change in morphology leads to destabilization of the endosome through fusion of the lipoplex with the endosomal wall, resulting in release of DNA into the cytoplasm. 相似文献
30.
Drawing on the results of an analysis of the nature of the pulse that generates complete transfer of population from one to another level in a system with a discrete spectrum, a generalization of the method of stimulated emission pumping is proposed. It is shown that a small subset of the Fourier components of the optimal pulse will, if their relative amplitudes are the same as in the optimal pulse, generate almost as efficient a population transfer, thereby generating the opportunity to prepare a system in a selected state with a selected population. 相似文献