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161.
Jacqueline T. Rajamathi Mohammed F. Ahmed N. Ravishankar C. Nethravathi Michael Rajamathi 《Solid State Sciences》2009,11(7):1270-1274
Nickel zinc hydroxysalt–Pt metal nanoparticle composite was prepared by intercalation of the anionic platinum complex, [PtCl6]2? in nickel zinc hydroxysalt through ion exchange reaction and subsequent reduction of the platinum complex by ethanol. Powder X-ray diffraction and microscopy studies indicate that the process of reduction of the platinum complex in the interlayer region of the anionic clay takes place topotactically without destroying the layers. 相似文献
162.
Time-resolved absorbance difference spectra were collected at delays from 1 to 128 micros after photolysis of membrane and detergent suspensions of rhodopsin at 20 degrees C. Fitting both sets of data with two exponential decays plus a constant showed a similar fast process (lifetime 11 micros in membrane, 12 micros in 5% dodecyl maltoside) with a small but similar spectral change. This demonstrates that the Lumi I - Lumi II process, previously characterized in detergent suspensions, has similar properties in membrane without significant effect of detergent. The slower exponential process detected in the data is quite different in membrane compared to detergent solubilized samples, showing that the pronounced effect of detergent on the later rhodopsin photointermediates begins fairly abruptly near 20 micros. Besides affecting the late processes, the data collected here shows that detergent induces a small blue shift in the 1 micros difference spectrum (the Lumi I minus rhodopsin difference spectrum). The blue shift is similar to one induced by chloride ion in the E181Q rhodopsin mutant and may indicate that the ionization state of Glu181 in rhodopsin is affected by detergent. 相似文献
163.
Vieira HS Takahashi JA Gunatilaka AA Boaventura MA 《Magnetic resonance in chemistry : MRC》2006,44(2):146-150
A highly rearranged novel dilactone was the single product isolated from Baeyer-Villiger oxidation of a norketone prepared from grandiflorenic acid, a natural kaurane diterpene. The complete 1H and 13C NMR assignment is presented for this novel compound that showed discrete in vitro antibacterial activity. 相似文献
164.
Riegert D Collin J Meddour A Schulz E Trifonov A 《The Journal of organic chemistry》2006,71(6):2514-2517
Ytterbium and lutetium ionic complexes derived from enantiopure substituted (R)-binaphthylamine ligands, of the general formula [Li(THF)n][Ln[(R)-C20H12(NR)2]2], have been investigated for the hydroamination/cyclization of several aminopentenes and an aminohexene. Complexes with isopropyl or cyclohexyl substituents on nitrogen atoms were found to be efficient catalysts under mild conditions for the formation of N-containing heterocycles with enantiomeric excesses up to 78%. 相似文献
165.
We here report the rates of water substitution by methanol-d(4) for four new oxo-centered trinuclear rhodium(III) clusters with different carboxylate-bridging ligands, [Rh3(mu3-O)(mu-O2CR)6(OH2)3]+ (R = CH2CH3, CH2CH2Cl, CH2Cl, and CHCl2), and [Rh3(mu3-O)(mu-O2CCH3)6(OH2)3]+. By varying the R group alkyl chain, water substitution rates were found to span almost 3 orders of magnitude (k(298K) = 1.2 x 10(-2)-2.3 x 10(-5) s(-1)) and reflect the following trend R = CH2CH3 > CH3 > CH2CH2Cl > CH(2)Cl > CHCl2. Activation parameters for substitution point toward a dissociative activation pathway (DeltaH = 99-115 kJ mol(-1); DeltaS = 48-52 J mol(-1) K(-1)), indicating that there is little association with the incoming methanol molecule during the formation of the transition-state complex. Because the mechanism for substitution in all five trimers has a considerable dissociative character, substitution rates are likely very similar to water exchange rates. These data suggest that the kinetic reactivity of the ligated waters is heavily influenced by the inductive ability of the aliphatic substituents, but yet the mechanism of substitution remains virtually unchanged. Structural data are also reported for the four new rhodium(III) trimer salts as well as 103Rh NMR spectra. We find that 103Rh NMR chemical shifts span more than 200 ppm and mirror the same reactivity trend found for the rates of water substitution (103Rh delta (9406-9620 ppm): R = CH2CH3 < CH3 < CH2CH2Cl < CH2Cl < CHCl2). Taken together, these data suggest a means for estimating water exchange rates for other oxo-centered rhodium(III) trimers from chemical shift data alone. 相似文献
166.
Mechanisms for water exchange from the bioxo-capped M-M-bonded trinuclear clusters, [M3(mu3-O)2(mu-O2CCH3)6(OH2)3]2+ [M = Mo(IV) and W(IV)], were investigated using high-pressure 17O NMR and compared to our previous work on a similar Rh(III) trimer. Reaction rates decrease by more than a factor of 2 when pressure is increased from 6 to 250 MPa for the Mo(IV) trimer, while exchange rates increase by less than a factor of 1.2 (10-229 MPa) for the W(IV) trimer. From the pressure dependence of the reaction rate, activation volumes (DeltaV()) were calculated to be DeltaV() = +8.0 (+/-0.4) cm(3) mol(-1) and DeltaV = -1.9 (+/-0.2) cm(3) mol(-1) for the Mo(IV) cluster and W(IV) cluster, respectively, which is the largest difference ( approximately 10 cm(3) mol(-1)) in activation volumes for any pair of 4d-5d (and 3d-4d) transition metal species located within the same group of the periodic table. If we interpret these activation volumes in terms of Swaddle's semiempirical model, which he established for simple octahedral monomers (Associative (A) = DeltaV approximately -13; Interchange (I) = DeltaV approximately 0; or Dissociative (D) = DeltaV approximately +13), our results suggest that water exchange follows a dissociative-interchange (Id) mechanism for the Mo(IV) cluster and an associative-interchange (Ia) activation mode for the W(IV) trimer. These volumes exhibit a unique changeover in the water-exchange mechanism despite considerable similarities in molecular structure and reactivity. This changeover could provide a standard for computational simulations of ligand-exchange pathways in molecules that are more complicated than monomers. 相似文献
167.
168.
Acortatarins A and B have been synthesized via stereoselective spirocyclizations of glycals. Mercury-mediated spirocyclization of a pyrrole monoalcohol side chain leads to acortatarin A. Glycal epoxidation and reductive spirocyclization of a pyrrole dialdehyde side chain leads to acortatarin B. Acid equilibration and crystallographic analysis indicate that acortatarin B is a contrathermodynamic spiroketal with distinct ring conformations compared to acortatarin A. 相似文献
169.
Vankayala SL Hargis JC Woodcock HL 《Journal of chemical information and modeling》2012,52(5):1288-1297
Hydroxyurea is the only FDA approved treatment of sickle cell disease. It is believed that the primary mechanism of action is associated with the pharmacological elevation of nitric oxide in the blood; however, the exact details of this are still unclear. In the current work, we investigate the atomic level details of this process using a combination of flexible-ligand/flexible-receptor virtual screening coupled with energetic analysis that decomposes interaction energies. Utilizing these methods, we were able to elucidate the previously unknown substrate binding modes of a series of hydroxyurea analogs to hemoglobin and the concomitant structural changes of the enzyme. We identify a backbone carbonyl that forms a hydrogen bond with bound substrates. Our results are consistent with kinetic and electron paramagnetic resonance (EPR) measurements of hydroxyurea-hemoglobin reactions, and a full mechanism is proposed that offers new insights into possibly improving substrate binding and/or reactivity. 相似文献
170.
As potential inhibitors of penicillin‐binding proteins (PBPs), we focused our research on the synthesis of non‐traditional 1,3‐bridged β‐lactams embedded into macrocycles. We synthesized 12‐ to 22‐membered bicyclic β‐lactams by the ring‐closing metathesis (RCM) of bis‐ω‐alkenyl‐3(S)‐aminoazetidinone precursors. The reactivity of 1,3‐bridged β‐lactams was estimated by the determination of the energy barrier of a concerted nucleophilic attack and lactam ring‐opening process by using ab initio calculations. The results predicted that 16‐membered cycles should be more reactive. Biochemical evaluations against R39 DD‐peptidase and two resistant PBPs, namely, PBP2a and PBP5, revealed the inhibition effect of compound 4d , which featured a 16‐membered bridge and the N‐tert‐butyloxycarbonyl chain at the C3 position of the β‐lactam ring. Surprisingly, the corresponding bicycle, 12d , with the PhOCH2CO side chain at C3 was inactive. Reaction models of the R39 active site gave a new insight into the geometric requirements of the conformation of potential ligands and their steric hindrance; this could help in the design of new compounds. 相似文献