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371.
Conformational changes in both diacyltetrahydropyridazines and piperidazines have been studied by the NMR method. Processes involving both ring inversion and hindered rotation about the N---COR bonds have been recognized. The energy barriers to ring inversion are unusually high for six membered ring systems and appear to be associated with interaction between the adjacent N-acyl substituents. 相似文献
372.
Denis FA Hanarp P Sutherland DS Dufrêne YF 《Langmuir : the ACS journal of surfaces and colloids》2004,20(21):9335-9339
A method for preparing surfaces with well-defined nanoscale chemical patterns is described. The fabrication strategy involves creating nanoscale Au pits surrounded by a TiO2 matrix, or vice versa, using colloidal lithography, followed by selective functionalization of the Au areas by CH3-terminated alkanethiols. Using AFM force spectroscopy with chemically modified tips (OH, CH3), we show that the nanopatterned surfaces display strong chemical contrast, in the form of hydrophobic CH3 nanopatches surrounded by a hydrophilic TiO2 surface, or vice versa. The nanofabrication approach presented here offers several advantages over existing patterning technologies, among which are easiness (no sophisticated instrumentation is required), versatility (patterns with a range of surface functionalities can be prepared), and the possibility to produce patterns over large areas at low cost. 相似文献
373.
The seeds of Millettia dura (Dunn) have yielded durlettone, durmillone, mildurone, (−)-millettone, (−)-millettosin, (−)-rotenone, (−)-tephrosin, (−)-tephrosin, and 6ω12ω-dehydrodeguelin. The constitutions of the new isoflavones durlettone (I), durmillone (IV), and milldurone (VIII) have been established.
Millettone is shown to be the new rotenoid (XIX). The natural co-occurrence of the rotenoids, (−)-millettone (XIX) and (−)-rotenone (XX), with the 12a-hydroxyrotenoids, (−)-millettosin (XXI) and (−)-tephrosin (XXII), and the 6a,121-dehydrorotenoid, 6a,12a-dehydrodeguelin (XII), is established. The relation of these observations to the question of the natural occurrence of 12a-hydroxyrotenoids and 6a,12a-dehydrorotenoids is discussed. 相似文献
374.
375.
T. A. Maryutina S. N. Ignatova B. Ya. Spivakov I. A. Sutherland 《Journal of Analytical Chemistry》2003,58(8):762-767
The effect of hydrodynamic parameters and the specific features of instrument design on the efficiency of substance separation in countercurrent liquid chromatography (CCC) was studied using a constant retention factor of the stationary phase in the column. The study was conducted with the separation of benzyl alcohol and p-cresol in a two-phase liquid system heptane–ethyl acetate–methanol–water (1.4 : 0.6 : 1 : 1) in as an example. It was shown that the peak resolution is improved with an increase in the rotational speed of the column and a decrease in the flow rate of the mobile phase. The best peak separation was attained using columns for which the ratio of the column rotation radius to the radius of column revolution was 0.615. It was shown that countercurrent chromatography allows the separation of substances with low partition constants (K < 1) in dilute solutions. The volume of the test sample may be up to 15% of the total volume of the chromatography column. 相似文献
376.
Three-dimensional quantitative structure-activity relationship (3D-QSAR) modelling using comparative molecular similarity indices analysis (CoMSIA) was applied to a series of 406 structurally diverse dihydrofolate reductase (DHFR) inhibitors from Pneumocystis carinii (pc) and rat liver (rl). X-ray crystal structures of three inhibitors bound to pcDHFR were used for defining the alignment rule. For pcDHFR, a QSAR model containing 6 components was selected using leave-10%-out cross-validation (n= 240, q2 = 0.65), while a 4-component model was selected for rlDHFR (n= 237, q2 = 0.63); both include steric, electrostatic and hydrophobic contributions. The models were validated using a large test set, designed to maximise its diversity and to verify the predictive accuracy of models for extrapolation. The pcDHFR model has r2 = 0.60 and mean absolute error (MAE) = 0.57 for the test set after removing 4 outliers, and the rlDHFR model has r2 = 0.60 and MAE = 0.69 after removing 4 test set outliers. In addition, classification models predicting selectivity for pcDHFR over rlDHFR were developed using soft independent modelling by class analogy (SIMCA), with a selectivity ratio of 2 (IC50,rlDHFR/ IC50,pcDHFR) used for delimiting classes. A 5-component model including steric and electrostatic contributions has cross-validated and test set classification rates of 0.67 and 0.68 for selective inhibitors, and 0.85 and 0.72 for unselective inhibitors. The predictive accuracy of models, together with the identification of important contributions in QSAR and classification models, offer the possibility of designing potent selective inhibitors and estimating their activity prior to synthesis. 相似文献
377.
Claudia Bonfio David A. Russell Nicholas J. Green Angelica Mariani John D. Sutherland 《Chemical science》2020,11(39):10688
The complexity of the simplest conceivable cell suggests that the chemistry of prebiotic mixtures needs to be explored to understand the intricate network of prebiotic reactions that led to the emergence of life. Early cells probably relied upon compatible and interconnected chemistries to link RNA, peptides and membranes. Here we show that several types of vesicles, composed of prebiotically plausible mixtures of amphiphiles, spontaneously form and sustain the methyl isocyanide-mediated activation of amino acids, peptides and nucleotides. Activation chemistry also drives the advantageous conversion of reactive monoacylglycerol phosphates into inert cyclophospholipids, thus supporting their potential role as major constituents of protocells. Moreover, activation of prebiotic building blocks within fatty acid-based vesicles yields lipidated species capable of localising to and functionalising primitive membranes. Our findings describe a potentially prebiotic scenario in which the components of primitive cells undergo activation and provide new species that might have enabled an increase in the functionality of protocells.The complexity of the simplest conceivable cell suggests that the chemistry of prebiotic mixtures needs to be explored to understand the intricate network of prebiotic reactions that led to the emergence of life. 相似文献
378.
R.G. Sutherland B.R. Steele K.J. Demchuk C.C. Lee 《Journal of organometallic chemistry》1979,181(2):411-424
A variety of η6-arene-η5-cyclopentadienyliron cations in which the arene ligand has an α-carbon substituent containing one or more hydrogens can be deprotonated with base to give the corresponding neutral zwitterionic species. These zwitterions can react in situ as nucleaphiles with different substrates such as CH3I, other organic halides. CO2 and CS2 to give a wide range of synthetic applications. 相似文献
379.
380.