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21.
The polymerization of isoprene initiated by dimethylallyl alcohols (DMAOH) in the presence of Lewis acids (LAs) as coinitiators has been selected as a potential model of the proposed cationic mechanisms involved in natural rubber (NR) biosynthesis. In view to investigate the activation/ionization mechanism of the allyl alcohol chain terminus (PIAllOH), which was shown to exist in NR, different isomers of DMAOH were used as simple models of polyisoprene chain‐end structures in the presence of tris(pentafluorophenyl)borane (BLA) as a LA. It is shown that cationation of 3,3‐DMAOH by BLA proceeds by direct OH abstraction. However, this process is strongly retarded in the presence of 2,6‐di‐tert‐butylpyridine (dtBP), due to the formation of different BLA complexes, one with 3,3‐DMAOH, active for cationation, and a dormant one involving its ionized form 3,3‐DMAO?. The monomer generated in situ by ionization/proton elimination steps subsequently adds on the primary allylic carbocation form, then resulting in the formation of oligoisoprenes, whereas the tertiary carbocation form of the allylic carbocation yields exclusively to proton elimination and isoprene formation, a possible mechanism of chain‐end termination. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.  相似文献   
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Molecular Diversity - Thiophene-based analogs have been fascinated by a growing number of scientists as a potential class of biologically active compounds. Furthermore, they play a vital role for...  相似文献   
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A novel, simple and sensitive adsorptive stripping voltammetry method was developed for simultaneous determination of Cd and Zn using N‐Nitrozo‐N‐phenylhydroxylamine (Cupferron) as a selective complexing agent. Cadmium and zinc metals gave peaks that were distinctly separated by 450–1200 mV, allowing their determination over a wide range of concentrations. The influence of pH and the nature of supporting electrolytes, concentration of ligand, preconcentration time and applied potential were investigated. The detection limits were 0.058 ng/mL for Zn and 0.092 ng/mL for Cd, and the RSD at a concentration level of 50 ppb, were 1.8–2.1 % for both zinc and cadmium, respectively. The method was applied to the determination of cadmium and zinc in blood, drug, food and water samples with the satisfactory results.  相似文献   
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In this paper the concept of lower and upper solutions combined with the fixed point theorem of Bohnnenblust–Karlin is used to investigate the existence of solutions for a class of the initial value problem for impulsive differential inclusions involving the Caputo fractional derivative.  相似文献   
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This study compared phenolic contents and antioxidant activity in different organs of Acacia albida (leaves and bark) and focuses on identification of phenolic compounds of leaves by HPLC-DAD. The analysed organs exhibited differences in total polyphenol contents (100 and 59.5 mg GAE g? 1 DW). Phenolic contents of leaves were two times higher than those in bark. Ethanolic extracts exhibited good antioxidant activities with IC50 = 26 μg mL? 1 for DPPH and EC50 = 50 μg mL? 1 for FRAP. Identification by HPLC-DAD revealed the presence of nine phenolic compounds known for their high antioxidant activity. The results suggested that this species can be used as source of natural antioxidants.  相似文献   
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In this work, a highly dispersed graphene oxide (GO) was successfully functionalized with 3‐mercaptopropyltrimethoxysilane (MPTS) molecule by silanization method. The chemically generated GO and MPTS functionalized GO (MPTS‐GO) were structurally characterized by thermogravimetric analysis (TGA), X‐ray diffraction analysis (XRD), scanning electron microscope (SEM), energy dispersive X‐ray (EDAX), fourier transform infrared spectroscopy (FT‐IR) and ultraviolet visible spectroscopy (UV‐Vis) techniques. The MPTS‐GO is highly suspensable in water. The thermal and conductivity results for MPTS‐GO are significantly increased compared to GO. Moreover, glassy carbon electrode modified with MPTS‐GO hybrid (MPTS‐GO/GCE) was prepared by casting of the MPTS‐GO solution on GCE. The MPTS‐GO/GCE showed an excellent electrocatalytic activity towards methionine (Met). This was understood from the observed less positive oxidation potential and higher oxidation current when compared to bare GC electrode. The MPTS‐GO has excellent electrocatalytic activity, making it an ideal candidate for sensor applications.  相似文献   
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In this paper, an efficient method for solving nonlinear Stratonovich Volterra integral equations is proposed. By using Bernoulli polynomials and their stochastic operational matrix of integration, these equations can be reduced to the system of nonlinear algebraic equations with unknown Bernoulli coefficient which can be solved by numerical methods such as Newton’s method. Also, an error analysis is valid under fairly restrictive conditions. Furthermore, in order to show the accuracy and reliability of the proposed method, the new approach is compared with the block pulse functions method by some examples. The obtained results reveal that the proposed method is more accurate and efficient than the block pulse functions method.  相似文献   
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