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101.
Muranaka A Shibahara M Watanabe M Matsumoto T Shinmyozu T Kobayashi N 《The Journal of organic chemistry》2008,73(22):9125-9128
A racemic mixture of three-layered [3.3]paracyclophane ([3.3]PCP), 1, has been resolved into two enantiomers, and their absolute configuration was determined from a comparison of experimental chiroptical properties and density functional theory (DFT) calculations. A simple model comprising two p-xylenes and 1,2,4,5-tetramethylbenzene (durene) was used to explain the origin of the chiroptical properties of the three-layered cyclophane system. 相似文献
102.
Mack J Bunya M Shimizu Y Uoyama H Komobuchi N Okujima T Uno H Ito S Stillman MJ Ono N Kobayashi N 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(16):5001-5020
The optical spectra of a series of core-modified tetrabenzoporphyrins were analyzed to determine the effects of core modification, ligand folding, and partial benzo substitution at the ligand periphery on the electronic structure by using magnetic circular dichroism (MCD) and NMR spectroscopy, X-ray crystallography, cyclic and differential pulse voltammetry, and TD-DFT calculations. Planar 21-carba-, 21-thia-, 21,23-dithia-, and 21-oxa-23-thiatetrabenzo[b,g,l,q]porphyrins reported previously were studied together with the previously unreported 21-oxa- and 21-carba-23-thiatetrabenzo[b,g,l,q]porphyrins. The optical properties of these compounds are compared to those of tetrabenzo[b,g,l,q]-, 5,10,15,20-tetraphenyl-, 5,10,15,20-tetraphenyltetrabenzo[b,g,l,q]-21-thia-, 5,10,15,20-tetraphenyltetrabenzodithia-, 5,10,15,20-tetraphenyldibenzo[g,q]-21,23-dithia-, 5,10,15,20-tetraphenyldibenzo[b,l]-21,23-dithia-, 5,10,15,20-tetraphenyltribenzo[g,q,l]-21-thia-, and 5,10,15,20-tetraphenylbenzo[b]-21-thiaporphyrins. Michl's perimeter model and Gouterman's four-orbital model are used to conceptualize the results and to account for red shifts commonly observed in the spectral bands of nonplanar porphyrinoids. 相似文献
103.
Philip Prathipati Chioko Nagao Shandar Ahmad Kenji Mizuguchi 《Journal of computer-aided molecular design》2016,30(9):817-828
The D3R 2015 grand drug design challenge provided a set of blinded challenges for evaluating the applicability of our protocols for pose and affinity prediction. In the present study, we report the application of two different strategies for the two D3R protein targets HSP90 and MAP4K4. HSP90 is a well-studied target system with numerous co-crystal structures and SAR data. Furthermore the D3R HSP90 test compounds showed high structural similarity to existing HSP90 inhibitors in BindingDB. Thus, we adopted an integrated docking and scoring approach involving a combination of both pharmacophoric and heavy atom similarity alignments, local minimization and quantitative structure activity relationships modeling, resulting in the reasonable prediction of pose [with the root mean square deviation (RMSD) values of 1.75 Å for mean pose 1, 1.417 Å for the mean best pose and 1.85 Å for the mean all poses] and affinity (ROC AUC = 0.702 at 7.5 pIC50 cut-off and R = 0.45 for 180 compounds). The second protein, MAP4K4, represents a novel system with limited SAR and co-crystal structure data and little structural similarity of the D3R MAP4K4 test compounds to known MAP4K4 ligands. For this system, we implemented an exhaustive pose and affinity prediction protocol involving docking and scoring using the PLANTS software which considers side chain flexibility together with protein–ligand fingerprints analysis assisting in pose prioritization. This protocol through fares poorly in pose prediction (with the RMSD values of 4.346 Å for mean pose 1, 4.69 Å for mean best pose and 4.75 Å for mean all poses) and produced reasonable affinity prediction (AUC = 0.728 at 7.5 pIC50 cut-off and R = 0.67 for 18 compounds, ranked 1st among 80 submissions). 相似文献
104.
Zhang X Liu Z Kobayashi N Jiang J 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2007,67(3-4):1135-1138
Chemical shifts of some reduced symmetry peripheral fused-ring-substituted phthalocyanines, namely Zn3B1N, Zncis2B2N, Zntrans2B2N, Zn1B3N and Zn3B0N, have been calculated at density functional B3LYP level using the gauge-independent atomic orbital (GIAO) method. The geometries were optimized using the 6-31G(d) basis set and the following NMR calculations were performed using 6-31G(d) and 6-311G(d,p) basis sets, respectively. The calculated NMR shielding tensors and chemical shifts are compared with previous experimental results. The chemical shifts are assigned according to the calculated data and satisfying results are obtained. The NMR shielding tensor simulation of Zn3B0N has been raised as a significant theoretical topic. 相似文献
105.
106.
107.
Hayashi K Kujime E Katayama H Sano S Nagao Y 《Chemical & pharmaceutical bulletin》2007,55(12):1773-1775
In the imine aldol reactions of 1 with aromatic aldehydes using magnesium salts in the presence of amines, the threo/erythro ratios of products increased in the order Mg(ClO4)2>MgI2>MgBr2>MgCl2>Mg(OTf)2 and N,N,N',N'-tetramethylethylenediamine (TMEDA)>Et3N. This increase in the threo/erythro ratios of products was estimated to be caused by a retro-imine aldol reaction under thermodynamic control. 相似文献
108.
Enders D Nagao T Nakayama T Aono M 《Langmuir : the ACS journal of surfaces and colloids》2007,23(11):6119-6125
The adsorption and desorption of Au nanoparticles (AuNP) in colloidal D2O suspension on the (3-aminopropyl)triethoxysilane treated SiO2/Si surface was investigated by in situ attenuated total reflection surface enhanced infrared absorption (ATR-SEIRA) spectroscopy with a liquid flow cell. With increasing surface density of AuNP, the absorption of the vibrational modes of D2O and of the citrate molecules covering the AuNP increases due to SEIRA. Repulsive electrostatic Coulomb forces between the AuNP lead to the saturation of the AuNP surface density at submonolayer coverage. We show that the adsorption kinetics can be investigated by monitoring in situ the molecular vibrational modes of D2O and the citrate molecules. Furthermore, we clarify that the adsorption process can be described very well by a diffusion-limited first-order Langmuir kinetics model. When exposing a saturated AuNP submonolayer to 2-aminoethanethiol (AET)/D2O solution, the AuNP are removed from the surface and the IR absorption of the D2O vibrational modes become weaker again. Taking into account the time dependencies of the OD and the CH peaks, we propose a microscopic model where the AET molecules quickly adsorb on the AuNP by replacing most of the precovering citrate molecules exposed to the AET solution. As this takes place, the AuNP agglomerate-as we could detect with scanning electron microscopy-and are finally removed from the surface. 相似文献
109.
Kataoka T Nagao Y Kidowaki M Araki J Ito K 《Colloids and surfaces. B, Biointerfaces》2007,56(1-2):270-Optics
Liquid–liquid equillibria (LLE) of the tertiary system of hydroxypropylated polyrotaxane (HPPR)–poly(vinyl alcohol) (PVA)–solvent have been investigated by focusing on the internal structures of HPPR–PVA blend gels. The phase diagrams of the HPPR–PVA aqueous systems displayed two liquid phases at a high concentration and molecular weight of PVA. This result was consistent with the prediction of the Flory–Huggins lattice model. On the contrary, the HPPR–PVA–DMSO system exhibited only a single phase. The HPPR–PVA blend gels crosslinked in dimethylsulfoxide (DMSO) were highly transparent over a wide concentration range, while the gels prepared in water were opaque at high polymer concentrations. Spherical domains were observed in the opaque gels by laser scanning confocal microscopy, and the sizes of the domains were significantly dependent on the amount of cross-linking reagent utilized. These results indicated that the transparency of the HPPR–PVA blend gels was strongly affected by the competition between the liquid–liquid two-phase separation and the crosslinking HPPR and PVA polymers during the preparation of the blend gels. 相似文献
110.