We have studied the mechanism of solvolysis of arenesulfonyl chlorides by propan‐1‐ol and propan‐2‐ol at 303‐323 K. Kinetic profiles were appropriately fit by first‐order kinetics. Reactivity increases with electron‐donating substituents. Ortho‐alkyl substituted derivatives of arenesulfonyl chlorides show increased reactivity, but the origin of this “positive” ortho‐effect remains unclear. Likely, ortho‐methyl groups restrict rotation around the C‐S bond, facilitating the attack of the nucleophile. No relevant reactivity changes have been found with propan‐1‐ol and propan‐2‐ol in terms of nucleophile steric effect. The existence of isokinetic relationships for all substrates suggests a single mechanism for the series. Solvolysis reactions of all substrates in both alcohols show isokinetic temperatures (Tiso) close to the working temperature range, which is an evidence of the process being influenced by secondary reactivity factors, likely of steric nature in the TS. Solvation plays a relevant role in this reaction, modulating the reactivity. In some cases, the presence of t‐Bu instead of Me in para‐ position leads to changes in the first solvation shell, increasing the energy of the reaction (ca. 1 kJ·mol?1). The obtained results suggest the same kinetic mechanism of solvolysis of arenesulfonyl chlorides for propan‐1‐ol and propan‐2‐ol, as in MeOH and EtOH, where bimolecular nucleophilic substitution (SN2) takes place with nucleophilic solvent assistance of one alcohol molecule and the participation of the solvent network involving solvent molecules of the first solvation shell. 相似文献
The reduction of vehicle fuel consumption is one of the most important targets for the automotive industry. Plug-in electric vehicles (PHEVs) are considered a viable alternative to improve the vehicle performance and efficiency. This study presents a prototype of a hybridization kit to convert a conventional vehicle into a PHEV that results in an expressive reduction of fuel consumption. Due to this, an interactive adaptive-weight genetic algorithm optimization was applied to find out optimum configurations for the hybridization kit in order to minimize the overall cost to perform FTP-75 and US06 driving cycles and to improve performance. 相似文献
Chagas disease (CD) affects more than 6 million people worldwide. The available treatment is far from ideal, creating a demand for new alternative therapies. Botanical diversity provides a wide range of novel potential therapeutic scaffolds. Presently, our aim was to evaluate the mammalian host toxicity and anti-Trypanosoma cruzi activity of botanic natural products including extracts, fractions and purified compounds obtained from Brazilian flora. In this study, 36 samples of extracts and fractions and eight pure compounds obtained from seven plant species were evaluated. The fraction dichloromethane from Aureliana fasciculata var. fasciculata (AFfPD) and the crude extract of Piper tectoniifolium (PTFrE) showed promising trypanosomicidal activity. AFfPD and PTFrE presented EC50 values 10.7 ± 2.8 μg/mL and 12.85 ± 1.52 μg/mL against intracellular forms (Tulahuen strain), respectively. Additionally, both were active upon bloodstream trypomastigotes (Y strain), exhibiting EC50 2.2 ± 1.0 μg/mL and 38.8 ± 2.1 μg/mL for AFfPD and PTFrE, respectively. Importantly, AFfPD is about five-fold more potent than Benznidazole (Bz), the reference drug for CD, also reaching lower EC90 value (7.92 ± 2.2 μg/mL) as compared to Bz (23.3 ± 0.6 μg/mL). Besides, anti-parasitic effect of eight purified botanic substances was also investigated. Aurelianolide A and B (compounds 1 and 2) from A. fasciculata and compound 8 from P. tuberculatum displayed the best trypanosomicidal effect. Compounds 1, 2 and 8 showed EC50 of 4.6 ± 1.3 μM, 1.6 ± 0.4 μM and 8.1 ± 0.9 μM, respectively against intracellular forms. In addition, in silico analysis of these three biomolecules was performed to predict parameters of absorption, distribution, metabolism and excretion. The studied compounds presented similar ADMET profile as Bz, without presenting mutagenicity and hepatotoxicity aspects as predicted for Bz. Our findings indicate that these natural products have promising anti-T. cruzi effect and may represent new scaffolds for future lead optimization. 相似文献
Summary: Free radical emulsion polymerization of styrene (S) or butyl acrylate (BA) in the presence of latices of linear polyethylene (PE) prepared by catalytic emulsion polymerization affords colloidally stable multiphase latices. Coagulation of a PE/PS latex affords nanocomposites composed of small PE phases dispersed in a PS matrix, as evidenced by the large supercoolings of PE crystallization (by DSC). TEM of PE/PBA latices indicates a PBA phase around the PE particles under the emulsion polymerization conditions investigated. Films formed from these dispersions exhibit homogeneously dispersed PE particles.
Multiphase latices are obtained by free radical emulsion polymerization of butyl acrylate in the presence of latices of linear polyethylene (PE) prepared by catalytic emulsion polymerization. 相似文献
A cooperative hydration effect being favorable for the binding of organic vapors by cross-linked poly(N-6-aminohexylacrylamide) and beta-cyclodextrin was observed in ternary systems in the absence of liquid phase. For these systems the vapor sorption isotherms were determined by the static method of headspace gas chromatographic analysis at 298 K. The obtained isotherms show an increase of binding affinity for vapor of hydrophobic sorbates above a threshold value of receptor hydration. Further hydration gives a saturation of this affinity for the studied hydrophilic polyacrylamide derivative, while the affinity of beta-cyclodextrin for the hydrophilic sorbate ethanol even decreases. A similar behavior of this polymer and beta-cyclodextrin at the change of their hydration helps to explain the observed cooperative hydration effect in terms of clathrate formation. 相似文献
The formation of mixed micelles of amphiphilic calix[4]resorcinarenes with aminomethyl (AMC, PAMC), tris(hydroxymethyl)amide (THAC) fragments and the cationic surfactant cetyl trimethylammonium bromide (CTAB) in water and aqueous DMF solutions (10-50% DMF) leads to the decrease of the critical micelle concentration of the systems and the increase of the size of the mixed micelles in comparison with CTAB micelles. The catalytic activity of the mixed systems in the hydrolysis of phosphorus acid esters is higher than those of CTAB micelle and AMC, PAMC or THAC aggregates. 相似文献