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61.
We have investigated the transport properties of nanopore alumina membranes that were rendered hydrophobic by functionalization with octadecyltrimethoxysilane (ODS). The pores in these ODS-modified membranes are so hydrophobic that they are not wetted by water. Nevertheless, nonionic molecules can be transported from an aqueous feed solution on one side of the membrane, through the dry nanopores, and into an aqueous receiver solution on the other side. The transport mechanism involves Langmuir-type adsorption of the permeating molecule onto the ODS layers lining the pore walls, followed by solid-state diffusion along these ODS layers; we have measured the diffusion coefficients associated with this transport process. We have also investigated the transport properties of membranes prepared by filling the ODS-modified pores with the water-immiscible (hydrophobic) liquid mineral oil. In this case the transport mechanism involves solvent extraction of the permeating molecule into the mineral oil subphase confined with the pores, followed by solution-based diffusion through this liquid subphase. Because of this different transport mechanism, the supported-liquid membranes show substantially better transport selectivity than the ODS-modified membranes that contain no liquid subphase. 相似文献
62.
Optically pure enone 9c, available in three steps from known 6-deoxy D-galactal derivative 7b, reacts with cyanophthalide 6 to directly afford the natural product (-)-hongconin (1), a compound from traditional Chinese medicine recently shown to exhibit antianginal activity. The enantiomer of 1 and its (+)-cis-diastereomer were also synthesized in a parallel fashion from the L-sugar counterpart. The use of C-glycoside Michael acceptors, as opposed to their O-glycoside counterparts, represents a potentially useful simplification of phthalide annulation methodology in synthesizing numerous other such optically pure isochromanquinoids, since it obviates the inconvenience of additional steps late in the synthetic scheme associated with reductive manipulation of a remaining acetal moiety into the desired pyran ring substituent. 相似文献
63.
Binding of steroid hormones is inhibited by protease inhibitors and substrates. The protease inhibitors phenylmethyl sulphonylfluoride, tosyl-lysine chloromethyl ketone, and tosylamide-phenylethyl-chloromethyl ketone and the protease substrates tosyl arginine methyl ester and tryptophan methyl ester eliminate specific binding of aldosterone, dexamethasone, dihydrotestosterone, estrogen, and progesterone to their respective receptors. These protease inhibitors and substrates also inhibit binding of progesterone to the 20,000 molecular weight mero-receptor formed from the progesterone receptor in chick oviduct. The binding of estradiol to rat alpha-fetoprotein is inhibited by the protease inhibitors and substrates but not by tryptophan or tryptophan amide, indicating the importance of an ester structure in the inhibition of steroid binding. Our results suggest that all steroid hormone receptors have a site with both common structural features and a role in the regulation of steroid hormone binding. 相似文献
64.
A novel approach to the fabrication of metal ring-disk (RD) microelectrodes is presented that employs flexible chemical vapor deposition (CVD) and electrode modification techniques. Specifically, the development of a copper ring-disk microelectrode is described utilizing a combination of CVD coating, electroetching, and electroplating. Initially, a 25 μm diameter tungsten wire is concentrically coated by CVD with an insulating layer of silica, a layer of tungsten metal, and finally, a second outer layer of silica. The copper surface was prepared by first creating micrometer cavities by electrochemical etching the tungsten in hydroxide solutions followed by electrodeposition of copper from aqueous solutions of Cu(II). Each step of the process was characterized by scanning electron microscopy, optical microscopy, and cyclic voltammetry, demonstrating the preparation of a viable metal-based dual ring-disk microelectrode system. For the purpose of demonstrating the concept of introducing specific selectivity into the device, amperometric detection of galactose in 0.1 M NaOH was performed at +0.60 V in bulk solution and after flow injection analysis in a capillary column. 相似文献
65.
Siwy Z Trofin L Kohli P Baker LA Trautmann C Martin CR 《Journal of the American Chemical Society》2005,127(14):5000-5001
There is increasing interest in the concept of using nanopores as the sensing elements in biosensors. The nanopore most often used is the alpha-hemolysin protein channel, and the sensor consists of a single channel embedded within a lipid bilayer membrane. An ionic current is passed through the channel, and analyte species are detected as transient blocks in this current associated with translocation of the analyte through the channel-stochastic sensing. While this is an extremely promising sensing paradigm, it would be advantageous to eliminate the very fragile lipid bilayer membrane and perhaps to replace the biological nanopore with an abiotic equivalent. We describe here a new family of protein biosensors that are based on conically shaped gold nanotubes embedded within a mechanical and chemically robust polymeric membrane. While these sensors also function by passing an ion current through the nanotube, the sensing paradigm is different from the previous devices in that a transient change in the current is not observed. Instead, the protein analyte binds to a biochemical molecular-recognition agent at the mouth of the conical nanotube, resulting in complete blockage of the ion current. Three different molecular-recognition agents, and correspondingly three different protein analytes, were investigated: (i) biotin/streptavidin, (ii) protein-G/immunoglobulin, and (iii) an antibody to the protein ricin with ricin as the analyte. 相似文献
66.
The adverse effects of injection solvent strength on microbore packed column SFC band broadening are demonstrated and a solventless injection system that eliminates these effects is introduced. The injection system removes solvent in a GC-like manner using a retention gap and an on-column capillary GC syringe. The analyte is delivered to the analytical column in a solvent-free plug of supercritical fluid mobile phase. 相似文献
67.
The first stable crystalline geminal diol of an aldehyde lacking electron-withdrawing groups on the-carbon was synthesized fromd-sorbitol and characterized by1H and13C nuclear magnetic resonance (NMR) and single-crystal x-ray studies. Each hydroxyl is a donor for a single, unique intermolecular hydrogen bond. Only one hydroxyl acts as an acceptor. No intramolecular hydrogen bonding is observed in the crystal. 相似文献
68.
Potter CV Thomas S Dean JL Kybett AP Kidd R James M Saxton H 《Chemical communications (Cambridge, England)》2004,(24):2781-2786
In January 2004, the Royal Society of Chemistry launched Organic & Biomolecular Chemistry (OBC) - a journal promising to provide high quality research from all aspects of synthetic, physical and biomolecular organic chemistry. The journal was set to build upon the foundations laid down by its predecessor publications (J. Chem. Soc., Perkin Trans. 1 and J. Chem. Soc., Perkin Trans. 2) as well as complement the subject coverage already published in prestigious general chemistry journals such as Chemical Communications and Chemical Society Reviews. Nearly two years on, just how is the programme developing and what can the community expect to see from the Royal Society of Chemistry (RSC)? 相似文献
69.
Bao J Baker RK Doss GA Kayser F Kotliar A Miao S Parsons WH Rupprecht KM 《Organic letters》2002,4(11):1871-1873
[reaction: see text] Pentacyclic triterpenoid natural product correolide (1) was converted to ketone 2 via ozonolysis. An unusual fragmentation reaction of ketone 2 with LiCl was discovered. This reaction is general among several similar substrates examined and appears to be specific for the correolide-type E-ring structure (ketone). A mechanism involving a retroaldol reaction, a nucleophilic opening of the epoxide, and a subsequent acetoxy elimination reaction was proposed. 相似文献
70.
Friedman LA You F Sabat M Harman WD 《Journal of the American Chemical Society》2003,125(49):14980-14981
The rhenium furan complexes TpRe(CO)(MeIm)(eta2-2-methylfuran) (1) and TpRe(CO)(MeIm)(eta2-2,5-dmethylfuran) (2) undergo Lewis acid-promoted cyclopentannulation reactions with enones and enals to generate 3-acetylcyclopentene complexes. During the reaction, a rearrangement occurs such that the alpha and beta carbons of the enone are incorporated into the new carbocycle. Treatment of these complexes with an oxidant (H2O2 or silver triflate) liberates the acetylcyclopentene. When a resolved form of the rhenium complex is used, the acetylcyclopentenes can be obtained enantioselectively. 相似文献