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491.
Frantz DK Linden A Baldridge KK Siegel JS 《Journal of the American Chemical Society》2012,134(3):1528-1535
Dynamic gearing of molecular spur gears, the most common type of mechanical gear, is elucidated. Molecular design and conformational analysis show that derivatives of 4,4-bis(triptycen-9-ylethynyl)bibenzimidazole represent suitable constructs to investigate gearing behavior of collateral triptycene (Tp) groups. To test this design, DFT calculations (B97-D/Def2-TZVP) were employed and the results suggest that these molecules undergo geared rotation preferentially to gear slippage. Synthesis of derivatives was carried out, providing a series of molecular spur gears, including the first desymmetrized spur gear molecules, which were subsequently subjected to stereochemical analysis. 相似文献
492.
493.
Harscoat-Schiavo C Nioi C Ronat-Heit E Paris C Vanderesse R Fournier F Marc I 《Analytical and bioanalytical chemistry》2012,403(7):1939-1949
A new method to predict elementary amino acid (AA) composition of peptides (molar mass <1,000 g/mol) is described. This procedure is based on a computer-aided method using three combined analyses-reversed phase liquid chromatography (RPLC), hydrophilic interaction chromatography (HILIC) and capillary electrophoresis coupled with mass spectrometry-and using a software calculating all possible amino acid combinations from the mass of any given peptide. The complementarity between HILIC and RPLC was demonstrated. Peptide retention prediction in HILIC was successfully modelled, and the achieved prediction accuracy was as high as r2=0.97. This mathematical model, based on amino acid retention contributions and peptide length, provided the information about peptide hydrophilicity that was not redundant with its hydrophobicity. Correlations between respectively the hydrophobicity coefficients and RPLC retention time, hydrophilicity and HILIC retention time, and electrophoretic mobility and migration time were used for ranking all potential AA combinations corresponding to the given mass. The essential contribution of HILIC in this identification strategy and the need to combine the three models to significantly increase identification capabilities were both shown. Applied to an 18-standard peptide mixture, the identification procedure enabled the actual AA combination determination of the 14 di- to pentapeptides, in addition to an over 98 % reduction of possible combination numbers for the four hexapeptides. This procedure was then applied to the identification of 24 unknown peptides in a rapeseed protein hydrolysate. The effective AA composition was found for ten peptides, whereas for the 14 other peptides, the number of possible combinations was reduced by over 95 % thanks to the association of the three analyses. Finally, as a result of the information provided by the analytical techniques about peptides present in the mixture, the proposed method could become a highly valuable tool to recover bioactive peptides from undefined protein hydrolysates. 相似文献
494.
Sobieski DN Mulvihill G Broz JS Augustine MP 《Solid state nuclear magnetic resonance》2006,29(1-3):191-198
A rapid throughput method for the quantitation of the oxidation level of intact full bottles of wine based on the 1331 water suppression pulse sequence is described. The ideal pulse sequence suppresses water in the (1)H nuclear magnetic resonance spectrum while uniformly and phase coherently exciting the resonances pertaining to ethyl alcohol at 1.1 ppm and oxidation products at 2.1 ppm. The anticipated results of the pulse sequence based on simulations are tested in small sample and full bottle standards and an application to the detection of wine spoilage in more than century old wine is provided. 相似文献
495.
Bergman SD Frantz R Gut D Kol M Lacour J 《Chemical communications (Cambridge, England)》2006,(8):850-852
Effective homochiral recognition occurs between the cationic [Fe(eilatin)3]2+ complex and TRISPHAT anions even in polar media such as 90% acetone-CHCl3 (de > or = 89%). 相似文献
496.
[reaction: see text] Photolysis of 4-nitroanisole with aliphatic amines gives mainly N-substituted 4-nitroanilines. Reactions of this type have been widely attributed to a geminate radical mechanism. We questioned this interpretation and have searched for and found by NMR spectroscopy a new class of stable nitronate adducts generated under the reaction conditions. The adducts imply that photosubstitution by amines para to the nitro group occurs by meta sigma complex formation followed by an unprecedented sigmatropic rearrangement. 相似文献
497.
498.
The upper rim of 1,3,5-triaza-7-phosphaadamantane (PTA) has been modified for the first time. Lithiation of PTA, with n-butyllithium, resulted in deprotonation of an alpha-phosphorus methylene and the formation of 1,3,5-triaza-7-phosphaadamantane-6-yllithium (PTA-Li). The chiral chelating phosphine 6-(diphenylphosphino)-1,3,5-triaza-7-phosphaadamantane (PTA-PPh2) was synthesized, in racemic form, by the reaction of PTA-Li with ClPPh2. PTA-PPh2 has been fully characterized in solution by multinuclear NMR spectroscopy and mass spectrometry and in the solid state by X-ray crystallography. The 31P NMR spectrum contains a pair of doublets at -19.8 and -100.1 ppm (d, (2)J(PP) = 65 Hz). Unlike PTA, the new bidentate phosphine, PTA-PPh2, is insoluble in aqueous solutions. Two group 6 metal carbonyl complexes, [M(CO)4(PTA-PPh2)] (M = W and Mo), were synthesized by the addition of PTA-PPh2 to cis-[M(CO)4(pip)2] and characterized by NMR spectroscopy, IR spectroscopy, and X-ray crystallography. Also reported are the solid-state structures of cis-[W(CO)4PTA2], cis-[W(CO)4(PTA)(PPh3)], and [W(CO)4DPPM] (DPPM = diphenylphosphinomethane). PTA-PPh2 appears to be sterically similar to and slightly more electron-donating than DPPM. 相似文献
499.
OHNUMA Takao 《高等学校化学研究》2009,25(2)
To improve catalytic activity of ribozyme on its substrate,the multi-ribozyme expression system was designed and constructed from 20 cis-acting hammerhead ribozymes undergoing self-cleavage with 10 trans-acting hammerhead ribozymes inserted altematively regularly and the plasmid of pGEM-MDRI/MRPI used to transcribe the M DRI/MRPI(196/210) substrate containing double target sites was also constructed by DNA recombination.Endonuclease digestion analysis and DNA sequencing indicate all the recombinant plasmids were correct.The cleavage activities were evaluated for the multi-ribozyme expression system on the MDR1/MRP1 substrate in the cell free system.The results demonstrate that the cis-acting hammerhead ribozymes in the multi-ribozyme expression system were able to cleave themselves and the 72 nt of 196Rz and the 71 nt of 210Rz trans-acting hammerhead ribozymes were liberated effectively,and the trans-acting hammerhead ribozymes released were able to act on the MDR1/MRP1 double target RNA substrate and cleave the target RNA at specific sites effectively.The multiribozyme expression system of the [Coat'A196Rz/Coat'B210Rz]5 is more significantly superior to that of the [Coat'A 196Rz/Coat'B210Rz]1 in cleavage of RNA substrate.The fractions cleaved by [Coat'A196Rz/Coat'B210Rz]5 on the MDR1/MRP1 substrate for 8 h at observed temperatures showed no marked difference.The studies of Mg2+ on cleavage efficiency indicate that cleavage reaction is dependent on Mg2+ ions concentration.The plot of Ig(kobs) vs.Igc(Mg2+) displays a linear relationship between 2.5 mmol/L and 20 mmol/L Mg2..It suggests that Mg2+ ions play a crucial role in multi-ribozyme cleavage on the substrate. 相似文献
500.