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991.
The synthesis sugar-transport properties of a family of five cavitand rim-appended boronic acids are reported. These conformationally rigid compounds are not observed to leach out of lipophilic membranes, and they exhibit unprecedented fructose to glucose transport selectivities and give higher fluxes than other neutral boronic acids. These properties make the cavitand boronic acids the best artificial fructose transporters described thus far. [structure: see text] 相似文献
992.
Dolman SJ Sattely ES Hoveyda AH Schrock RR 《Journal of the American Chemical Society》2002,124(24):6991-6997
The first catalytic asymmetric ring-closing metathesis method for the synthesis of N-containing heterocycles is reported; this is accomplished through Mo-catalyzed kinetic resolution or desymmetrization of unsaturated amines. Importantly, this catalytic asymmetric method delivers medium-ring unsaturated amines (including eight-membered rings) in high yield, with exceptional enantioselectivity and without the need for solvents. These enantioselective reactions can be effected by catalysts prepared in situ from commercially available reagents. 相似文献
993.
Nolan EM Jaworski J Okamoto K Hayashi Y Sheng M Lippard SJ 《Journal of the American Chemical Society》2005,127(48):16812-16823
QZ1, 2-[2-chloro-6-hydroxy-3-oxo-5-(quinolin-8-ylaminomethyl)-3H-xanthen-9-yl]benzoic acid, and QZ2, 2-[6-hydroxy-3-oxo-4,5-bis-(quinolin-8-ylaminomethyl)-3H-xanthen-9-yl]benzoic acid, two fluorescein-based dyes derivatized with 8-aminoquinoline, have been prepared and their photophysical, thermodynamic, and zinc-binding kinetic properties determined. Because of their low background fluorescence and highly emissive Zn(II) complexes, QZ1 and QZ2 have a large dynamic range, with approximately 42- and approximately 150-fold fluorescence enhancements upon Zn(II) coordination, respectively. These dyes have micromolar K(d) values for Zn(II) and are selective for Zn(II) over biologically relevant concentrations of the alkali and alkaline earth metals. The Zn(II) complexes also fluoresce brightly in the presence of excess Mn(II), Fe(II), Co(II), Cd(II), and Hg(II), offering improved specificity for Zn(II) over di(2-picolyl)amine-based Zn(II) sensors. Stopped-flow kinetic investigations indicate that QZ1 and QZ2 bind Zn(II) with k(on) values of (3-4) x 10(6) M(-1) s(-1), compared to (6-8) x 10(5) M(-1) s(-1) for select ZP (Zinpyr) dyes, at 4.3 degrees C. Dissociation of Zn(II) from QZ1 and QZ2 occurs with k(off) values of 150 and 160 s(-1), over 5 orders of magnitude larger than those for ZP probes, achieving reversibility on the biological (millisecond) time scale. Laser scanning confocal and two-photon microscopy studies reveal that QZ2 is cell-permeable and Zn(II)-responsive in vivo. Because of its weaker affinity for Zn(II), QZ2 responds to higher concentrations of intracellular Zn(II) than members of the ZP family, illustrating that binding affinity is an important parameter for Zn(II) detection in vivo. 相似文献
994.
Heins EA Baker LA Siwy ZS Mota MO Martin CR 《The journal of physical chemistry. B》2005,109(39):18400-18407
Ion-current measurements were made on synthetic polymer membranes that contained a single conically shaped nanopore. This entailed placing an electrolyte solution on either side of the membrane, using an electrode placed in each solution to control the transmembrane potential, and measuring the resulting transmembrane ion current. The effect of the crown ether commonly called 18-crown-6 (18C6) on the measured ion current was investigated. Adding 18C6 to the electrolyte solution on one side of a conical nanopore membrane provides a way to rectify the ion current flowing through the nanopore. This chemical rectification is observed only when the cation of the electrolyte is complexed by 18C6 (e.g., K+), and when the mouth diameter of the conical nanopore is of molecular dimensions, in this case approximately 1.5 nm. This chemical rectification can either augment or diminish the inherent electrostatic rectification observed with these small mouth-diameter nanopores. We have interpreted these results using a model based on the formation of a junction potential at the membrane-solution interface. This junction potential arises because the transference number for the K+-18C6 complex in bulk solution is larger than its transference number in the mouth of the conical nanopore. 相似文献
995.
Gliadin is a fraction of wheat gluten, a protein supramolecular complex known for its remarkable and biotechnologically relevant viscoelastic properties. Very high molecular mass characterise these systems, thus hindering high-resolution structural investigations. It is known, however, that these proteins comprise rather extended, extensively interassociated structures, which respond for their peculiar mechanical behaviour. Besides these properties, some of gluten's fractions, such as gliadin, are also known to be involved in a nutritionally relevant pathology of auto-immune character, the celiac disease, supposedly related to some unusual structural features of the protein. Despite its medical relevance, however, the role played by gliadin in the etiology of the celiac disease is not sufficiently understood to date. In this work, we investigated the role of gliadin on mechanical properties of a membrane model of dioleoylphosphatidylcholine (DOPC) giant unilamellar vesicles. The technique of micropipette aspiration, coupled to videomicroscopy, was applied. The microvesicles, produced by electric field pulsing over metal-covered plates, were suctioned into the micropipettes under varying applied pressures. A significant increase in the values of the bilayer curvature constant, k(c), was observed, with a saturation effect being verified at around 0.02-0.03 gliadin/DOPC mass ratio, indicating that the membrane becomes less elastic in the presence of the protein. Possible correlations between the observed membrane fluctuation properties and the celiac disease etiology are suggested and discussed. 相似文献
996.
Siwy Z Heins E Harrell CC Kohli P Martin CR 《Journal of the American Chemical Society》2004,126(35):10850-10851
Ion channels are protein pores that span cell membranes and open and close in response to stimuli like changes in the transmembrane potential, binding of a ligand, or mechanical stress. When open, ions pass through the pore, and hence across the cell membrane, and when closed, ion-transport is precluded. Hence, these channels are nanodevices that have a current-rectification function. There is intense research effort aimed at understanding the molecular-level mechanism for this function. One approach for elucidating the mechanism is to construct a simple abiotic system that mimics this function and to use the mechanistic details of this mimic as a guide to understand the more complex biological channel. We describe here such an abiotic mimic: a synthetic membrane that contains a single conical gold nanotube. The advantage of this mimic is that the surface charge and chemistry of the nanotube wall can be varied, at will, by judicious choice of electrolyte or by thiol chemisorption. This has allowed us to make conical Au nanotubes that rectify the ion current and, just as importantly, to definitively elucidate the mechanism of this function. 相似文献
997.
A study has been made of the polarographic (DC and DPP) behaviour of the food dyes Sunset Yellow and Tartrazine in acid and alkaline media and in the absence and presence of polyvinylpyrrolidone. Methods are proposed for the determination of both dyes by DPP over a concentration range of 0.1-10 ppm. The methods have been applied to their determination in soft drinks. 相似文献
998.
The effects of different concentrations of several volatile organic compounds (VOC) such as ethanol, acetate, propionate,
and butyrate ranging from 0 to 2000 mg/L as well as a mixture of volatile fatty acids (MVFA) at a 4:1:1 (acetate:propionate:butyrate)
ratio on the nitrification rate in batch cultures were studied. The results showed that ethanol and acetate were consumed
in a mixotrophic way by the nitrifying sludge. At a concentration of 500 mg/L, the nitrification rate of inhibition was different
for each compound in which propionate and butyrate were the most inhibitory. At 2000 mg/L the inhibition was 80% with ethanol
and 100% with acetate, propionate, and butyrate. With similar concentrations of MVFA, the inhibition was also similar to that
in acetate. The effect of the addition of pulses of MVFA at a ratio of 4:1:1 during 14 h on the performance of the continuous
nitrifying process with a hydraulic retention time of 3 d was also studied. No inhibition of the nitrification process was
observed with pulses of 750–3000 mg of MVFA/L in the input of the reactor. The results in batch cultures suggest that the
different degrees of inhibition of the nitrification process were related to the type of organic matter added. The noninhibitory
effect of the organic matter in the continuous cultures on the nitrification efficiency of the nitrifying sludge might be
related to the feeding pattern. 相似文献
999.
John C. Bevington Stephen W. Breuer Elizabeth N. J. Heseltine Thomas N. Huckerby Sushil C. Varma 《Journal of polymer science. Part A, Polymer chemistry》1987,25(4):1085-1092
Polymers have been prepared at 60 and 100°C using initiators giving the 2-cyano-2-propyl radical enriched with carbon-13 in the nitrile group. Examination by NMR of the (CH3)2C(CN)? end groups in the resulting polymers of vinyl acetate (VAC) and of appropriate model compounds has indicated that up to 20% of these end groups correspond to the product of head-addition of the primary radical to VAC at 60°C. Similar end groups have been found in poly(vinyl formate) but not in poly(methyl methacrylate) and polystyrene. In polyVAC prepared at 100°C, the proportion of end groups attached to the head of a monomeric unit is higher than for polymers made at 60°C. 相似文献
1000.
Nettles SM Matos K Burkhardt ER Rouda DR Corella JA 《The Journal of organic chemistry》2002,67(9):2970-2976
When stabilized BH(3-)THF (BTHF) was added to a mixture of ketone and tetrahydro-1-methyl-3,3-diphenyl-1H,3H-pyrrolo[1,2-c][1,3,2]oxazaborole (MeCBS-ozaxaborolidine, MeCBS) catalyst 1, low enantioselectivities resulted. Several relative rate experiments showed that a borohydride species in BTHF catalyzed the nonselective borane reduction of ketones, effectively competing with enantioselective MeCBS reduction of ketones, lowering the overall selectivity of the reaction. Improved enantioselectivities in the reaction are obtained by reversing the mode of addition (ketone to BTHF and catalyst), lowering the concentration of NaBH(4) stabilizer in the BTHF solution (87-95% ee) and increasing the concentration or addition rate of BTHF. Decreased reaction temperature and increased catalyst loading only slightly improved the selectivity of the reaction. Upon reaction parameter optimization, simultaneous addition of substrate and BTHF to MeCBS catalyst stabilizer resulted in the highest overall enantioselectivities (96% ee) and diminished the effect of the borohydride. Alternatively, the addition of Lewis acids such as BF(3-)THF to the reaction mixture effectively destroyed the NaBH(4) stabilizer in BTHF solutions, restoring the enantioselectivity to acceptable levels. 相似文献