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991.
Sessler JL Cho WS Gross DE Shriver JA Lynch VM Marquez M 《The Journal of organic chemistry》2005,70(15):5982-5986
The anion binding properties of fluorinated calix[n]pyrroles (n = 4-6) in aprotic solvents (acetonitrile and DMSO) and modified reaction conditions allowing for the synthesis and isolation of the hitherto missing dodecafluorocalix[6]pyrrole from the condensation of 3,4-difluoro-1H-pyrrole and acetone are described. In acetonitrile solution containing 2% water, the association constants for the 1:1 binding interaction between octafluorocalix[4]pyrrole and chloride anion obtained with isothermal titration calorimetry (ITC) and (1)H NMR titration methods were found to match reasonably well. As compared to its nonfluorinated congener, octafluorocalix[4]pyrrole was found to display enhanced binding affinities for several representative anions in pure acetonitrile as judged from ITC analyses. Similar analyses of the fluorinated calix[n]pyrroles revealed an increase in the relative affinity for bromide over chloride with increasing macrocycle size, as manifest in a decrease in the binding ratio K(a(Cl))/K(a(Br)). Anion binding studies in the solid state, involving single-crystal X-ray diffraction analyses of the chloride and acetate anion complexes of octafluorocalix[4]pyrrole and decafluorocalix[5]pyrrole, respectively, confirmed the expected hydrogen bond interactions between the pyrrolic NH protons and the bound anions. 相似文献
992.
Quantitation of mutagenic/carcinogenic heterocyclic aromatic amines in food products. 总被引:1,自引:0,他引:1
A method for screening genotoxic heterocyclic aromatic amines in cooked foods using solid-phase extraction and high-performance liquid chromatography with ultraviolet and fluorescence detection is described. Solid-phase extraction includes basic extraction on diatomaceous earth (Extrelut) and subsequent purification on propylsulphonic acid silica gel. This convenient procedure separates the analytes into a polar group and an apolar group. We have identified the following components in the two groups. The polar group contains aminoimidazoazaarenes i.e. 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline, 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline, 2-amino-3-methylimidazo[4,5-f]quinoline, 2-amino-3,4-dimethylimidazo[4,5-f]quinoline, 2-amino-1-methyl-6-phenylimidazo-[4,5-b]pyridine, and glutamic acid pyrolysates, i.e. 2-amino-6-methyldipyrido[1,2-a:3',2'-d]imidazole and 2-aminodipyrido[1,2-a:3',2'-d]-imidazole. The apolar group consists of five carbolines: 3-amino-1,4-dimethyl-5H-pyrido[4,3-b]indole, 3-amino-1-methyl-5H-pyrido[4,3-b]indole, 2-amino-9H-pyrido[2,3-b]indole, 9H-pyrido[3,4-b]indole and 1-methyl-9H-pyrido[3,4-b]indole. The extraction efficiencies range from 45 to 90%, and the detection limits are in the low nanogram per gram range. The method was applied to the analysis of heterocyclic aromatic amines in pan-fried, oven-cooked and barbecued salmon. 相似文献
993.
Pedersen JM Bowman WR Elsegood MR Fletcher AJ Lovell PJ 《The Journal of organic chemistry》2005,70(25):10615-10618
[reaction: see text] Imidoyl selanides, synthesized from amides, have been used as radical precursors of imidoyl radicals in cascade reactions. The novel radical cascade has been developed for the simple synthesis of the medicinally important aryl-annulated[b]carbazoles. The protocol has been exemplified with the high-yielding total synthesis of the anticancer alkaloid ellipticine. 相似文献
994.
The current status for the development of novel open-tubular gas chromatography (GC) stationary phases consisting of thin films of gold-centered monolayer protected nanoparticles (MPNs) is reported. Dodecanethiol MPNs, in which the monolayer is dodecanethiol linked to the gold nanoparticle, have shown great promise as a GC stationary phase with efficient columns having been produced in a variety of capillary i.d.'s with stationary phase film depths ranging from 10 to 60 nm, +/-2 nm at a given film depth. Stationary phase operational parameters are discussed including maximum operating temperature, sample capacity, and stationary phase lifetime and robustness. An overview of the general method employed for column production is also included. The sample capacity was determined for a 2.5 m, 250 microm i.d. column with a stationary phase film thickness of 40 nm, at 50 degrees C using anisole (k' = 1.86) as the probe analyte. The sample capacity was experimentally found to be 2.3 ng under these conditions, similar to values reported for thicker, polymer stationary phases. The efficiency of the dodecanethiol MPN stationary phase was determined with a 100 microm i.d. capillary and found to have a reduced plate height hmin value of 0.95 for octane (k' = 0.68). Areas of application illustrated and discussed utilizing the dodecanethiol MPN stationary phase include complementary separations such as two-dimensional GC (GC x GC), potential utilization within a model system for a micro-fabricated GC (microGC), as well as efficient single dimension high-speed separations. Initial development of polar stationary phases utilizing 4-chlorobenzenethiol MPNs and 4-(trifluoromethyl)benzenethiol MPNs is discussed. Included is a selectivity comparison of the retention behavior of the 4-chlorobenzenethiol MPN stationary phase and the dodecanethiol MPN stationary phase. 相似文献
995.
Elizabeth L. Gross David R. Youngman Sandra L. Winemiller 《Photochemistry and photobiology》1978,28(2):249-256
Abstract— We have made a photovoltaic cell using Photosystem I subchloroplast particles isolated according to the method of Shiozawa et al. (1974). The particles were placed on a filter between two compartments one of which contained the electron donor, K4 Fe(CN)6 and the other the electron acceptor, FMN. Upon illumination with white light ( I = 80 W/m2 ) a potential of 300 mV was observed across a 3000 Ω load resistance. Both Photosystem I photochemistry and direct photoreactions of FMN contribute to the process. A power output of 20 μW was observed for a 2 cm2 filter containing 60 μg chlorophyll. This corresponds to 0.1 W/m2 . The power efficiency was 0.13%. The short circuit current was 108 μA. 相似文献
996.
Heterologous expression of a myxobacterial natural products assembly line in pseudomonads via red/ET recombineering 总被引:10,自引:0,他引:10
Natural products of microbial origin are widely used as pharmaceuticals and in agrochemistry. These compounds are often biosynthesized by multifunctional megasynthetases whose genetic engineering and heterologous expression offer considerable promise, especially if the natural hosts are genetically difficult to handle, slow growing, unculturable, or even unknown. We describe a straightforward strategy that combines the power of advanced DNA engineering (recombiogenic cloning) in Escherichia coli with the utility of pseudomonads as the heterologous host for the analysis and mutagenesis of known and unknown secondary metabolite pathways. The myxochromide S biosynthetic gene cluster from Stigmatella aurantiaca was rebuilt and engineered in E. coli to contain the elements required for expression in pseudomonads. The successful production in Pseudomonas putida, at unprecedented levels, demonstrates the feasibility of the new approach to the analysis and mutagenesis of these important pathways. 相似文献
997.
Saltsman I Mahammed A Goldberg I Tkachenko E Botoshansky M Gross Z 《Journal of the American Chemical Society》2002,124(25):7411-7420
This work demonstrates the feasibility and power of electrophilic substitution on the peripheral carbon atoms of triarylcorroles as a synthetic tool to new derivatives. The large difference in the reactivity of the various carbon atoms on the macrocycle was shown to be of electronic rather than steric origin. A careful choice of reagents and a delicate control of reaction conditions allowed the selective syntheses of novel derivatives, in all of which substitution took place selectively in only the directly joined pyrrole rings of the macrocycle. This was proven by a combination of X-ray crystallography of the various products and detailed analysis of their NMR spectra. 相似文献
998.
999.
Two-point measurement of tissue T1 from NMR intensity ratios consists of forming an a priori ratio function describing a T1 dependence of the ratio R(T1) and computing T1 from an observed ratio Q by numerically solving R(T1)-Q = 0 or an equivalent equation. Impact of R(T1) designs on the numerical computation and dependence of relative speeds of three numerical methods on desired computational precisions q and on other factors are examined. All three methods begin with computing a table of R(T1) entries in uniform T1 steps (delta T1). In two iterative methods, a step containing the T1 root is looked up, and the precise T1 location within the step is pinpointed to within a q value by either linear-interpolative (LI) or Newton-Raphson (NR) iteration. The third method simply consists of computing a large table of delta T1 = q for a mere "look-up" with no iterative search. All three methods require a monotonous R(T1) for uniformly effective computation over wide T1 ranges. Speeds of either iterative method for computing T1 images are expected to vary with delta T1 and q with unsharp speed maxima at delta T1 near 20, 6, and 2 ms for q = 10(-1), 10(-2), and 10(-3) ms, respectively. Either iterative method is suitable for both low- and high-precision computations, the LI method being generally faster. The simple look-up is the fastest of the three for T1 image computation to low precisions of q greater than or equal to 1 ms, is likely the slowest for that to q = 0.1 ms, and is impractical for that to q less than or equal to 0.01 ms. 相似文献
1000.