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Molecular dynamics simulations with a combined quantum mechanical and molecular mechanical (QM/MM) potential have been carried out to investigate the squalene-to-hopene carbocation cyclization mechanism in squalene-hopene cyclase (SHC). The present study is based on free energy simulations by constructing the free energy surface for the cyclization steps along the reaction pathway. The picture that emerges for the carbocation cyclization cascade is a delicate balance of thermodynamic and kinetic control that ultimately favors the formation of the final hopanoids carbon skeleton. A key finding is that the five- to six-membered ring expansion process is not a viable reaction pathway for either C- or D-ring formation in the cyclization reaction. The only significant intermediate is the A/B-bicyclic cyclohexyl cation (III), from which two asynchronous concerted reaction pathways lead to, respectively, the 6,6,6,5-tetracyclic carbon skeleton and the 6,6,6,6,5-pentacyclic hopanoids. Experimentally, these two products are observed to have 1% and 99% yields, respectively, in the wild-type enzyme. We conclude that the product distribution in the wild-type enzyme is dictated by kinetic control of these two reaction pathways. 相似文献
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Jayshree Ramkumar 《Talanta》2007,71(3):1054-1060
The single ion transport of transition metal ions like Cu2+, Co2+, Ni2+ and Zn2+ were carried out through the H+ and alkali metal ion forms of Nafion membrane. These studies showed that the ion exchange selectivity coefficient of the permeating ion had an effect on its transport process. It was found that the diffusion coefficient values (D) were directly proportional to the selectivity coefficient (K). This shows that the initial stage of permeation is governed by ion exchange process (effect of K on D). 相似文献
4.
How Does Solvation Affect the Binding of Hydrophilic Amino Saccharides to Cucurbit[7]uril with Exceptional Anomeric Selectivity?
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Jianping Wang Yoonjung Jang Jayshree K. Khedkar Jin Young Koo Yonghwi Kim Chang Jun Lee Young Min Rhee Kimoon Kim 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(44):15791-15799
Cucurbit[7]uril (CB[7]) is known to bind strongly to hydrophilic amino saccharide guests with exceptional α‐anomer selectivities under aqueous conditions. Single‐crystal X‐ray crystallography and computational methods were used to elucidate the reason behind this interesting phenomenon. The crystal structures of protonated galactosamine (GalN) and glucosamine (GluN) complexes confirm the inclusion of α anomers inside CB[7] and disclose the details of the host–guest binding. Whereas computed gas‐phase structures agree with these crystal structures, gas‐phase binding free energies show preferences for the β‐anomer complexes over their α counterparts, in striking contrast to the experimental results under aqueous conditions. However, when the solvation effect is considered, the binding structures drastically change and the preference for the α anomers is recovered. The α anomers also tend to bind more tightly and leave less space in the CB[7] cavity toward inclusion of only one water molecule, whereas loosely bound β anomers leave more space toward accommodating two water molecules, with markedly different hydrogen‐bonding natures. Surprisingly, entropy seems to contribute significantly to both anomeric discrimination and binding. This suggests that of all the driving factors for the strong complexation of the hydrophilic amino saccharide guests, water mediation plays a crucial role in the anomer discrimination. 相似文献
5.
Kalkote Uttam Ramrao Choudhary Anil Ramkumar Natu Arvind Anant Ayyangar Nagaraja Ramanuja 《合成通讯》2013,43(10-11):1129-1135
1-Alkylaminoanthraquinones ( 2 a-f) and 1,4-bisalkylaminoanthraquinones ( 4 a-c) were prepared from aminoanthraquinones ( 1,3 ) by alkylation with alkyl sulphate/alkyl halide in presence of powdered sodium hydroxide, potassium carbonate and phase transfer catalyst. 相似文献
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Synthesis of conformationally restricted dispiro- and bis-dispiro-1,3-dioxolanes via three-component reaction of diazoamides, ketoamides/diketones, and aromatic/heteroaromatic aldehydes in the presence of rhodium(II) acetate dimer catalyst at room temperature involving carbonyl ylides is demonstrated with diastereoselectivity. Synthesis of macrocyclic dispiro-1,3-dioxolanes via intramolecular carbonyl ylide is also delineated in high yield. The conformationally restricted symmetrical as well as unsymmetrical dispiro-1,3-dioxolanes were obtained under mild conditions in a highly diastereo- and regioselective manner. 相似文献
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Mosquitoes have developed resistance to various synthetic insecticides, making their control increasingly difficult. Insecticides of botanical origin may serve as suitable natural control. This study evaluates the toxic potential of Ocimum canum (Sims) leaf extract and powder against Anopheles stephensi (Liston), Aedes aegypti (Lin) and Culex quinquefasciatus (Say) larval and adult mosquitoes. Larval mortality was observed after 24 h recovery period and adult smoke toxicity observed for 40 min duration at 10 min interval. Methanol extract of O. canum showed highest larval mortality against the larvae of C. quinquefasciatus LC50 = 28.3225, LC90 = 44.1150; Ae. aegypti LC50 = 43.327, LC90 = 61.249; and An. stephensi LC50 = 30.2001, LC90 = 48.2866 ppm. The smoke toxicities were 93% mortality in C. quinquefasciatus, 74% in Ae. aegypti and 79% in An. stephensi adults, respectively, whereas 100% mortality was recorded in the commercial mosquito control. Our results suggest that O. canum leaf extract and powder are natural insecticide, and ideal eco friendly approach for mosquito control. 相似文献
10.
We describe the implementation of an adaptive umbrella sampling method, making use of the weighted histogram analysis method, for computing multidimensional potential of mean force for chemical reaction in solution. The approach is illustrated by investigating the effect of aqueous solution on the free energy surface for the proton transfer reaction of [H(3)N-H-NH(3)](+) using a combined quantum mechanical and molecular mechanical AM1/TIP3P potential. 相似文献