Campus Access Only
All rights reserved. This publication is intended for use solely by faculty, students, and staff of University of the Pacific. No part of this publication may be reproduced, distributed, or transmitted in any form or by any means, now known or later developed, including but not limited to photocopying, recording, or other electronic or mechanical methods, without the prior written permission of the author or the publisher.
Date of Award
Thesis - Pacific Access Restricted
Master of Science (M.S.)
Pharmaceutical and Chemical Sciences
First Committee Member
Second Committee Member
Poly-N-isopropylacrylamide (PNIPAM) gels grafted to redox-active metal monomers undergo sudden expansion-contraction activity in response to change in environmental conditions, such as temperature, pH, ion concentration, and oxidation states of the metal. The relevance of these conditions to biological systems has garnered attention for PNIPAM-based polymer as potential biomedical materials. Candidate transition metal monomers containing ruthenium and nickel cores were designed and synthesized for copolymerization with NIPAM and cross-linker methylene-bis-acrylamide in order to attain metallopolymer microspheres with a high percentage of metal incorporation. Synthesis of 4-vinyl-4'-methyl-2,2'-bipyridine (vmbpy) was optimized from literature procedures for usage in the metal-containing monomers. Metal-containing monomers were then synthesized, purified, and characterized using electrospray ionization mass spectrometry (ESI-MS), proton nuclear magnetic resonance ( 1 H-NMR), X-ray diffraction, Ultraviolet-Visible light (UV-Vis) spectroscopy, and spectrofluorometry. While the Ru complex was pure and exhibited interesting photochemical properties, lability of the ligands on the Ni monomers resulted in complication of their synthesis. Polymer microspheres of poly(NIPAM-co-vmbpy), the cross-linked copolymer constructed from NIPAM and vmbpy monomers, were synthesized from modified emulsion polymerization procedures. Experimental setup parameters and conditions—such as the methods of injection of initiator and stirring, the time duration for incubating the emulsion, and the initiation temperature—were varied to assess their influences on the material properties of the final product. The polymers were tested for size and morphological uniformity by dynamic light scattering (DLS) and scanning electron microscopy (SEM). While varying the method of initiator injection had no measurable effect on the product, strong mechanical stirring and incubation of the polymer emulsion for 15-25 minutes at 71 °C procured similar polymer products. Consistent properties ensured the polymers' suitability for further material development. Preliminary morphological and spectroscopic characterization was conducted of metallopolymers made from Ru and Ni grafted to PNIPAM. Metallopolymers containing polypyridyl Ru cores exhibited desirable spectroscopic properties and spherical morphology.
Tran-Math, Carolyn. (2014). Synthesis of poly(NIPAM-co-vmbpy) microspheres and transition metal monomers for metallopolymeric material construction. University of the Pacific, Thesis - Pacific Access Restricted. https://scholarlycommons.pacific.edu/uop_etds/271
Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-No Derivative Works 4.0 International License.
To access this thesis/dissertation you must have a valid pacific.edu email address and log-in to Scholarly Commons.Find in ProQuest
If you are the author and would like to grant permission to make your work openly accessible, please email
In Copyright. URI: http://rightsstatements.org/vocab/InC/1.0/
This Item is protected by copyright and/or related rights. You are free to use this Item in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you need to obtain permission from the rights-holder(s).