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991.
G. J. Goetz-Grandmont J. P. Brunette A. De Cian N. Kyritsakas 《Structural chemistry》2002,13(5-6):459-470
From IR, UV, 31P, 1H, and 13C NMR spectroscopic data, it is shown that the three 3-phenyl-4-acyl-isoxazol-5-ones, HPXI (HPBI, HPTI, and HPtbBI with acyl-, benzoyl-, toluoyl-, and para-(tert-butyl)benzoyl-, respectively), promising extractants of actinides, appear under the same major tautomeric forms, both in the solid and in solutions in various solvents: the diketo-enamine form in methanol, a -ketoenolic form in the solid, and in chloroform, benzene, and toluene. The radiocrystallographic structures of HPTI and HPtbBI have been determined. They appear as 3-phenyl-4-(-hydroxybenzylidene)isoxazol-5-ones, forming intramolecular chelates through H-bonds. -Aryl interactions might influence the relative positions of the -ketoenolic oxygen atoms and, hence, the bite angle and the cone angle of these ligands. Spectroscopic data give evidence of strong TOPO–HPXI interactions (TOPO: tri-n-octylphosphine oxide) in toluene, of the same order of magnitude for the three acylisoxazolones, in the order: HPBI > HPTI > HPtbBI. 相似文献
992.
Syvitski RT Li Y Auclair K Ortiz De Montellano PR La Mar GN 《Journal of the American Chemical Society》2002,124(48):14296-14297
Solution 1H NMR is used to probe the environments of the donor protons of eight strong hydrogen bonds on the distal side of the heme substrate in the cyanide-inhibited, substrate-bound complex of human heme oxygenase, hHO. It is demonstrated that significant magnetization transfer from the bulk water signal to the eight labile protons does not result from chemical exchange, but from direct nuclear Overhauser effect due to the dipolar interaction of these labile protons with "ordered" water molecules. The enzyme labile proton to water proton distances are estimated at approximately 3 A. It is proposed that the role of the strong hydrogen-bonding network is to immobilize numerous water molecules which both stabilize the activated hydroperoxy species and funnel protons to the active site. 相似文献
993.
Tinnefeld P Weston KD Vosch T Cotlet M Weil T Hofkens J Müllen K De Schryver FC Sauer M 《Journal of the American Chemical Society》2002,124(48):14310-14311
The photophysics of a dendrimer containing four chromophores are investigated at the single-molecule level. First, the multichromophoric character of single dendrimers' absorption is probed by modulating the linear polarization of the excitation beam. Subsequently, using circular polarization, the same dendrimers are excited, and their fluorescence transients are recorded. Using pulsed excitation in combination with the classical Hanbury-Brown and Twiss coincidence setup the presented data demonstrate that efficient singlet-singlet annihilation ensures that always only one photon is emitted even when several excitations are generated in an individual multichromophoric molecule. 相似文献
994.
TREN (Tris(2-aminoethyl)amine): an effective scaffold for the assembly of triple helical collagen mimetic structures 总被引:1,自引:0,他引:1
Kwak J De Capua A Locardi E Goodman M 《Journal of the American Chemical Society》2002,124(47):14085-14091
A new scaffold, TREN-(suc-OH)(3) where TREN is tris(2-aminoethyl)amine and suc is the succinic acid spacers, was incorporated to assemble triple helices composed of Gly-Nleu-Pro sequences (Nleu denotes N-isobutylglycine). Extensive biophysical studies which include denaturation studies, CD and NMR spectroscopy, and molecular modeling demonstrated that TREN-[suc-(Gly-Nleu-Pro)(n)-NH(2)](3) (n = 5 and 6) form stable triple helical structures in solution. A comparative analysis of TREN-assembled and KTA-assembled collagen mimetics (KTA denotes Kemp triacid, 1,3,5-trimethylcyclohexane-1,3,5-tricarboxylic acid) indicates that the flexibility of the TREN scaffold is superior to the KTA scaffold in inducing triple helicity. This effect most likely arises from the flexibility of the TREN scaffold which allows the three peptide chains to adjust their register for a tighter triple helical packing. 相似文献
995.
Reaction of N-benzoyl-1,2,3,4-tetrahydroquinoline-2-carboxylic acid with acetic anhydride resulted in 1H,3H,5H-oxazolo[3,4-a]quinolin-3-one derivative 13. Different cyclopropanation processes were applied to 13, but only diazomethane in the presence of water furnished the hitherto unknown methyl 1,2,7,7a-tetrahydro-1aH-cyclopropa[b]quinoline-1a-carboxylate 14, which can be considered as a doubly constrained 1-aminocyclopropane-1-carboxylic acid system. The mechanism of the cyclopropanation was studied in detail. The new ACC ester 14 was transformed into fused tetracyclic hydantoin derivatives, which comprised a new type of heterocyclic system. 相似文献
996.
Dong Q Yan X Wilhoit RC Hong X Chirico RD Diky VV Frenkel M 《Journal of chemical information and computer sciences》2002,42(3):473-480
To a significant degree processes of database development are based upon human activities, which are susceptible to various errors. Propagation of errors in the processing leads to a decrease in the value of original data as well as that of any database products. Data quality is a critical issue that every database producer must handle as an inseparable part of the database management. Within the Thermodynamics Research Center (TRC), a systematic approach to implement database integrity rules was established through the use of modern database technology, statistical methods, and thermodynamic principles. The four major functions of the system--error prevention, database integrity enforcement, scientific data integrity protection, and database traceability--are detailed in this paper. 相似文献
997.
[reaction: see text] A new method for the synthesis of 2',3'-dideoxynucleoside analogues has been developed. An electrochemical activation of 2-substituted furans is followed by the coupling with a pyrimidine or purine base. This gives planar furyl nucleosides as key intermediates, which are hydrogenated cis-selectively to give the corresponding beta-2',3'-dideoxynucleosides as racemic mixtures. An enzymatic kinetic resolution gives rise to beta-D- and beta-L-configured derivatives in high optical purity. This is exemplified by the synthesis of beta-D- and beta-L-3'-deoxythymidine. 相似文献
998.
Lawlor A Reagan D McCullagh GD Gregorio PD Tartaglia P Dawson KA 《Physical review letters》2002,89(24):245503
We introduce an order parameter for dynamical arrest. Dynamically available volume (unoccupied space that is available to the motion of particles) is expressed as holes for the simple lattice models we study. Near the arrest transition the system is dilute in holes, so we expand dynamical quantities in a series of hole density. Unlike the situation when presented in particle density, all cases of simple models that we examine have a quadratic dependence of the diffusion constant on hole density. This observation implies that in certain regimes ideal dynamical arrest transitions may possess a hitherto unnoticed degree of universality. 相似文献
999.
Using diffusion Monte Carlo simulations we have investigated the ground state of a symmetric electron-hole bilayer and determined its phase diagram at T = 0. We find clear evidence of an excitonic condensate, whose stability however is affected by an in-layer electronic correlation. This stabilizes the electron-hole plasma at large values of the density or interlayer distance, and the Wigner crystal at low density and large distance. We have also estimated pair correlation functions and low-order density matrices to give a microscopic characterization of correlations as well as to try and estimate the condensate fraction. 相似文献
1000.
De Vita R Anghinolfi M Burkert VD Dodge GE Minehart R Taiuti M Weller H Adams G Amaryan MJ Anciant E Armstrong DS Asavapibhop B Asryan G Audit G Auger T Avakian H Bagdasaryan H Ball JP Barrow S Battaglieri M Beard K Bektasoglu M Bianchi N Biselli AS Boiarinov S Bonner BE Bosted P Bouchigny S Branford D Brooks WK Bueltmann S Calarco JR Capitani GP Carman DS Carnahan B Cazes A Ciciani L Cole PL Coleman A Connelly J Cords D Corvisiero P Crabb D Crannell H Cummings JP De Sanctis E Degtyarenko PV 《Physical review letters》2002,88(8):082001
The double spin asymmetry in the (-->)e(-->)p --> e(prime)pi(+)n reaction has been measured for the first time in the resonance region for four-momentum transfer Q2 = 0.35-1.5 GeV(2). Data were taken at Jefferson Lab with the CLAS detector using a 2.6 GeV polarized electron beam incident on a polarized solid NH3 target. Comparison with predictions of phenomenological models shows strong sensitivity to resonance contributions. Helicity-1/2 transitions are found to be dominant in the second and third resonance regions. The measured asymmetry is consistent with a faster rise with Q(2) of the helicity asymmetry A1 for the F(15)(1680) resonance than expected from the analysis of the unpolarized data. 相似文献