DOI

10.17077/etd.3m1xfats

Document Type

Dissertation

Date of Degree

Spring 2016

Access Restrictions

Access restricted until 07/03/2020

Degree Name

PhD (Doctor of Philosophy)

Degree In

Pharmaceutical Sciences and Experimental Therapeutics

First Advisor

Wurster, Dale Eric

First Committee Member

Donovan, Maureen D.

Second Committee Member

Kirsch, Lee E.

Third Committee Member

Stevens, Lewis L.

Fourth Committee Member

Wells, Mickey L.

Abstract

Alkaline degradation of Carbaryl in the presence of CTAB micelles has been reported as the most efficient method; however, the factors accounting for it are not yet clear. The main objective of this work was to study some of the factors affecting the alkaline degradation of Carbaryl in the presence of cetyl trimethylammonium bromide (CTAB). Three specific aims were researched in order to address the main objective.

Solubility studies, UV-vis, fluorescence, and 1D-HNMR and 2D-HNMR spectroscopies were used to research the solubilization of carbaryl in CTAB micelles. Solubility studies showed that carbaryl partitions into CTAB micelles with a binding constant of 553 ± 8 M-1, and each mole of micellized surfactant incorporates about 0.336 moles of carbaryl. Spectroscopy studies showed that carbaryl does not interact electrostatically with micelles but does through van der Waals interactions. 1D-HNMR and 2D-HNMR indicated solubilization in the Stern layer, oriented with its hydrophilic moiety towards the Goüy-Chapman layer and the hydrophobic moiety towards the core of the micelle.

Kinetic studies as a function of the surfactant concentration along with micellar kinetic models were used to calculate micellar rate constants (k’M) for each of four different cationic surfactants: cetyl trimethylammonium hydroxide (CTAOH), cetyl trimethylammonium bromide (CTAB), cetyl trimethylammonium chloride (CTACl), and cetyl pyridinium chloride (CPCl), and compared to the corresponding rate constants (k’W) in water; the results in all cases showed k’M / k’W > 1. This fact led to the conclusion that additional factors beyond solubilization of substrates are playing a role. Solubility studies revealed the following binding constant order and solubilization capacity order: CPCl > CTAOH ≈ CTAB > CTACl, CPCl > CTAOH ≈ CTAC > CTAB, indicating that for CPCl, Coulombic interactions, such as charge-transfer complexes, may be favoring the concentration effects, while for other surfactants, such as CTAOH, the [–OH] as the micelle counterion increases Carbaryl’s concentration in the Stern layer compared to its bulk concentration. In contrast, large, weakly-hydrated polarizable ions such as Br– displace hydrophilic ions, providing less enhancement.

Kinetic experiments as a function of the surfactant head’s charge led to the conclusion that cationic and zwitterionic surfactants have a catalytic effect of the alkaline hydrolysis of carbaryl, while nonionic and anionic surfactants have inhibitory effects: kobs (cationic) > kobs (zwitterionic) > kobs(nonionic) > kobs (anionic). A similar order for solubility parameters (Ks and SC) was observed from equilibrium solubility studies. Experiments as a function of the polarity of the medium in the presence of both polar and nonpolar solvents showed that the hydrolysis rate is inversely proportional to the medium polarity. Ionic strength experiments showed that the hydrolysis rate is inversely proportional to the ion concentration.

Keywords

Carbaryl, Catalysis, Micellar catalysis

Pages

xx, 298 pages

Bibliography

Includes bibliographical references (pages 290-298).

Copyright

Copyright © 2016 Carlos Arturo Peroza Meza

Available for download on Friday, July 03, 2020

Share

COinS