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81.
Ronald G. Sutherland Adam Pirko Udai S. Gill Choi Chuck Lee 《Journal of heterocyclic chemistry》1982,19(4):801-803
A method for the synthesis of heterocylic systems related to 9,10-dihydroanthracene with two hetero-atoms at the 9,10-positions is described. It involves the nucleophilic substitution reaction of η6-o-dichlorobenzene-η5-cyclopentadienyliron hexafluorophosphate with two nucleophilic groups (OH, SH and/or NH2) located in the 1,2-positions of a benzene ring to give a cyclopentadienyliron complexed heterocycle. Upon pyrolytic sublimation of the complex, the free heterocyclic compound is then obtained. 相似文献
82.
Cappa CD Smith JD Wilson KR Messer BM Gilles MK Cohen RC Saykally RJ 《The journal of physical chemistry. B》2005,109(15):7046-7052
Measurements of the oxygen K-edge X-ray absorption spectrum (XAS) of aqueous sodium halide solutions demonstrate that ions significantly perturb the electronic structure of adjacent water molecules. The addition of halide salts to water engenders an increase in the preedge intensity and a decrease in the postedge intensity of the XAS, analogous to those observed when increasing the temperature of pure water. The main-edge feature exhibits unique behavior and becomes more intense when salt is added. Density functional theory calculations of the XAS indicate that the observed red shift of the water transitions as a function of salt concentration arises from a strong, direct perturbation of the unoccupied molecular orbitals on water by anions, and does not require significant distortion of the hydrogen bond network beyond the first solvation shell. This contrasts the temperature-dependent spectral variations, which result primarily from intensity changes of specific transitions due to geometric rearrangement of the hydrogen bond network. 相似文献
83.
Stephen D. Pastor Sai P. Shum Ronald K. Rodebaugh Anthony D. Debellis Frank H. Clarke 《Helvetica chimica acta》1993,76(2):900-914
The synthesis and characterization of 2-{1-{3,5-bis(1,1-dimethylethyl)-2-{[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy}phenyl}ethyl}-4,6-bis(1,1-dimethylethyl)phenyl diphenyl phosphite ( 6 ) is described. In the 31P-NMR spectrum (1H-decoupled) of 6 , an unprecedented eight-bond P,P coupling of J = 72.8 Hz is observed. In the X-ray crystal structure of 6 , an intramolecular P–P distance of 3.67 Å is found, which is within the sum of the van-der-Waals radii of the P-atoms. The observed intramolecular P–P distance suggests that a through-space coupling mechanism is operative. The solid-state conformation of 6 is compared to the conformation obtained by semi-empirical MO geometry optimizations (PM3 method). The calculated geometry suggests that the solid-state structure is near a true energy minimum, but that crystal-packing forces decrease the intramolecular P–P distance in the solid state. In the absence of crystal-packing forces, however, the collisional and vibrational energy available in solution may lead to the population of states with a shortened intramolecular P–P distance in 6 . The proximity of the P-atoms in 6 is due to restricted conformational freedom resulting from steric congestion within the molecule. The free energy of activation (ΔG* = 10.2 and 10.8 kcal/mol for unequal populations of exchanging conformers) for ring inversion of the dibenzo[d,f][1,3,2]dioxaphosphepin ring in 6 is determined by variable-temperature 31P-NMR spectroscopy. Semi-empirical MO calculation on model compounds suggest that the structure of the transition state for ring inversion has the two aryl rings and O-atoms in a common plane, with the P-atom lying above this plane. 相似文献
84.
Subramaniam V Alves ID Salgado GF Lau PW Wysocki RJ Salamon Z Tollin G Hruby VJ Brown MF Saavedra SS 《Journal of the American Chemical Society》2005,127(15):5320-5321
Transmembrane proteins (TMPs), particularly ion channels and receptors, play key roles in transport and signal transduction. Many of these proteins are pharmacologically important and therefore targets for drug discovery. TMPs can be reconstituted in planar-supported lipid bilayers (PSLBs), which has led to development of TMP-based biosensors and biochips. However, PSLBs composed of natural lipids lack the high stability desired for many technological applications. One strategy is to use synthetic lipid monomers that can be polymerized to form robust bilayers. A key question is how lipid polymerization affects TMP structure and activity. In this study, we have examined the effects of UV polymerization of bis-Sorbylphosphatidylcholine (bis-SorbPC) on the photoactivation of reconstituted bovine rhodopsin (Rho), a model G-protein-coupled receptor. Plasmon-waveguide resonance spectroscopy (PWR) was used to compare the degree of Rho incorporation and activation in fluid and poly(lipid) PSLBs. The results show that reconstitution of Rho into a supported lipid bilayer composed only of bis-SorbPC, followed by photoinduced lipid cross-linking, does not measurably diminish protein function. 相似文献
85.
Andre Rosowsky Ronald A. Forsch Richard G. Moran 《Journal of heterocyclic chemistry》1996,33(4):1355-1361
Nα-[4-[[(4-Aminopteridin-6-yl)methyl]amino]benzoyl]-L-ornithine (dAPA-Orn) was synthesized, and its ability to inhibit folylpolyglutamate synthetase from mouse liver was compared with that of the corresponding 2,4-diamino analogue APA-Orn. Also compared were the inhibitory activities of the deaza analogues 5-deazaAPA-Orn, 8-deazaAPA-Orn, and 5,8-dideazaAPA-Orn, as well as those of Nα-pteroyl-L-ornithine (PteOrn) and its deaza analogues 5-deazaPteOrn and 5,8-dideazaPteOrn. The inhibition constant Ki of dAPA-Orn was 7-fold greater than that of APA-Orn, indicating that the 2-amino group plays a role in binding to the active site. The binding affinity of the 2,4-diamino compounds increased in the order 5-deazaAPA < APA-Orn <5,8-dideazaAPA-Orn < 8-deazaAPA-Orn, and that of the 2-amino-4(3H)-oxo compounds increased in the order 5-deazaPteOrn < PteOrn < 5,8-dideazaPteOrn. The most potent inhibitor of both groups was 8-deazaAPA-Orn, with a Ki of 0.018 μM, coresponding to an 8-fold and 15-fold increase in affinity relative to APA-Orn and 5-deazaAPA-Orn, respectively. The results suggest (a) that the binding of Orn-containing folylpolyglutamate synthetase inhibitors is affected to a greater degree by replacement of N8 by a carbon atom than it is by the corresponding change at N5, (b) that the effect of carbon for nitrogen replacement is greater in the 2,4-diamino derivatives than in the 2-amino-4(3H)-oxo compounds, and (c) that the 2,4-diamines are the better inhibitors. Comparison of the Ki values of the Orn-containing inhibitors with the Km values of the corresponding glutamate-containing substrates revealed that Km/Ki ratio can vary as much as 100-fold depending on the nature of the heterocyclic moiety, suggesting that caution should be exercised in using Km values of known substrates to predict Ki values of putative inhibitors. 相似文献
86.
The base-catalyzed addition of thiamin to benzaldehyde produces 2-(1-hydroxybenzyl)thiamin (HBnT), but in neutral solution HBnT undergoes base-catalyzed irreversible fragmentation into pyrimidine and thiazole derivatives. The fragmentation (rather than elimination) occurs in proportion to the extent that N1' is protonated or alkylated. Generating the conjugate base of HBnT by decarboxylation surprisingly leads to fragmentation independent of the state of N1'. Therefore, a cationic state at N1' specifically promotes removal of the C2alpha proton rather than the fragmentation process itself. It is suggested that benzoylformate decarboxylase, which generates a similar intermediate, exerts stereoelectronic control of the conformation of the carbanion, blocking fragmentation and facilitating protonation. 相似文献
87.
Understanding molecular orientation on a metal surface is key to designing molecular electronic device junctions. Though platinum device electrodes are of particular interest as a more stable alternative to the often used gold electrodes, the chemisorption of conducting molecules onto platinum surfaces has not been thoroughly studied. We present herein the first detailed study of the ability and manner in which soluble oligothiophene isocyanides, of lengths ranging from 2 to 7 nm, chemisorb onto platinum surfaces and nanoparticles. It was found that these oligothiophene isocyanides stand at a 41 degrees angle from the platinum surface normal, suggesting their applicability in molecule-bridged platinum electrode devices. 相似文献
88.
Gordon K. Anderson Ronald J. Cross Ljubica Manojlovic-Muir Kenneth W. Muir Tihomir Solomun 《Journal of organometallic chemistry》1979,170(3):385-397
The known complex, -(η-C5H5)2Rh2(CO)2(CF3C2CF3) is formed in high yield from (η-C5H5)Rh(CO)2 and CF3FCCF3 at 100°. The less stable -isomer of the complex is obtained in low yield from the same reaction. The infrared, 1H, 19F and 13C NMR spectra of the two isomers are compared. The -isomer undergoes CO scrambling in solution at room temperature, and the variable temperature 13C NMR spectra are consistent with a pairwise bridge opening and closing mechanism. The mechanism is extended to account for the isomerization of to isomer, whihc has a half-life of 12 h at room temperature. The 13C spectrum indicates that the -isomer is static in solution at room temperature. The -isomer is reversibly protonated by protonic acids, and BF4? and PF6? salts of the protonated species can be isolated. The spectroscopic properties of these salts are consistent with protonation at one of the alkynyl-carbons, but it is not possible to distinguish between two alternative structures for the complex cation.Treatment of (η-C5H5)2Rh2(CO)2(CF3C2CF3) with (η-C5H5)Rh(CO)2 gives the trinuclear complex (η-C5H5)3Rh3(CO)(CF3C2CF3) in 80% yield. The analogoug but-2-yne complex is formed from (η-C5H5)3Rh3(CO)3 and MeCCMe. The infrared, 1H, 19F and 13C NMR spectra indicate that the hexafluorobut-2-yne complex exists in two different structural arrangements in solution. One has an edge bridging, and the other a face bridging carbonyl. The proportion of the isomers is affected by the solvent polarity. The spectra of the but-2-yne complex indicate it is fluxional at room temperature, and has a face bridging structure in solution regardless of the polarity of the solvent. Reversible protonation of the hexafluorobut-2-yne complex occurs in protonic acids, and the salt [(η-C5H5)3Rh3(CO)(CF3C2CF3)H]+[BF4]?,H2O can be isolated. The spectroscopic properties of this complex are consistent with a structure incorporating an edge-bridging carbonyl, and probably, an edge-bridging hydride ligand. 相似文献
89.
Electrochemistry and Raman spectroscopy have shown that aquocob(III)alamin (Cbl(III)) can be reduced by nitric oxide (NO) to form Cbl(II) on an electrode surface. The Cbl(II) formed in this way can bind NO to form nitrosyl-cobalamin, Cbl(II)-NO, which is reduced to form Cbl(I) at about -1.0 V vs a KCl saturated Ag/AgCl reference electrode. In addition, nitrite was found to bind both Cbl(III) and Cbl(II) and a binding constant of 3.5 x 10(2) M(-1) was measured for (NO(2)-Cbl(II))(1-). UV-vis spectrophotometry and mass spectroscopy were used to show that Cbl(I) reduces NO to form Cbl(II)-NO and N(2)O and N(2), and this reaction is involved in the cyclic voltammetry of cobalamin in the presence of excess NO where a catalytic reduction of NO occurs involving the cycling of Cbl(II)-NO/Cbl(I). This redox couple is also involved in the electrochemical catalytic reduction of nitrite. These results can be used to explain a number of physiological effects involving NO interaction in biological systems with added cobalamin or with cobalamin in the methionine synthase enzyme. 相似文献
90.
A model of a gamma sterilizer was built using the ITS/ACCEPT Monte Carlo code and verified through dosimetry. Individual dosimetry measurements in homogeneous material were pooled to represent larger bodies that could be simulated in a reasonable time. With the assumptions and simplifications described, dose predictions were within 2–5% of dosimetry. The model was used to simulate product movement through the sterilizer and to predict information useful for process optimization and facility design. 相似文献