Paper Based Microfluidic Devices (microPADs) are a new platform for point-of-care diagnostic assays for use in resource-limited settings. These devices rely typically on enzymatic assays to produce their results, which makes them susceptible to degradation when exposed to extreme environmental conditions such as high temperature. In order to overcome this limitation, this research project focused on investigating the use of polymers instead of enzymes to detect analytes on microPADs. Polymer-bound boronic acid, a glucose and pH sensitive polymer, was incorporated into microPADs in order to develop a chronometric, paper-based glucose assay. The polymer was tested with both lateral and vertical flow microPADs made from three different types of paper, and several different methods of incorporating the polymer into the devices were also explored. While some devices appeared to show a trend in signal versus concentration of glucose, none of the results were statistically significant due to the large standard deviations in the signal. Upon further analysis of the results, the overall conclusion was that the devices were not sensitive enough to detect glucose in the range of concentrations that would be practical for clinical diagnostic applications.

This dissertation explores the potential of improving the performance of poly(ethylene terephthalate) fibers by incorporating novel thermotropic liquid crystalline polymers. To determine if a system exhibited desirable characteristics, a screening procedure was developed to assess the various blends. Evaluations focused on blend compositions ranging from 2 to 20 wt.% LCP. Fibers were obtained by melt extrusion and the effect of processing conditions, i.e. spinning temperature, stretch ratio, and post treatment evaluated. The fibers were tested for mechanical performance, dimensional instability (shrinkage), and the development of shrinkage stresses. Test results were used to determine the critical parameters necessary for in-situ reinforcement and to develop strategies for improving LCP architecture and processing techniques. The novel TLCP's incorporated into the PET were mesogenic copolymers containing either alternating or random flexible groups within the polymer backbone. The flexible moieties were used to promote compatibility between the PET matrix phase and the TLCPs. Two systems were found to significantly improve fiber stiffness compared to neat PET fibers. A Random Copolymer based on the reaction of oxyethylene substituted hydroquinone, ethylene glycol, and terephthaloyl chloride was found to effectively enhance the performance of PET fibers. Fibers containing only 5% TLCP exhibited a 50% increase in modulus, while maintaining an ultimate strength equivalent to the PET control. The thermal behavior of the 5% blend, as determined by free shrinkage and force-temperature experiments, was similar to the PET control. A segmented block copolymer consisting of rigid-rod, diad, and flexible coil segments was also found to improve the performance of PET fibers. At a concentration of 20 wt. percent, the alternating block copolymer, Triad2 (2:6:7), increased the tensile modulus of the fibers 40% and decreased free shrinkage by 20% compared to neat PET. The mechanism of reinforcement for these systems is unclear, but morphological, thermal and mechanical evidence suggest that the TLCPs are modifying the PET matrix and not providing true mechanical reinforcement.

This thesis describes the synthesis and characterization of segmented, triblock and star block copolymers with mesogenic hard segments and long flexible spacers. This thesis explores two important aspects of structure-property relationships of phase separated block copolymers: (1) the effect of soft segment structure on the polymer thermal phase behavior; (2) the effects of hard segment structure and soft segment topology on polymer properties. The first part tests the hypothesis that the soft segment substituents that are adjacent to the hard segment lower the polymer thermal transitions temperatures. Copolymers with pentad hard segments and soft segments with varying degrees of substitution were synthesized to test this hypothesis. Pentad copolymers with completely substituted soft segments showed the lowest melting transition and exhibited no liquid crystallinity. When the substituents are separated from the hard segment, the polymer exhibits higher melting transitions and liquid crystalline behavior. In the second part, efforts were concentrated to synthesize block co-oligomers that behave as high polymers at ambient temperatures but have low melt viscosities. As part of this study, block co-oligomers with dyad esteramide and bisamide hard segments and amine terminated poly(propylene glycol)s of linear and star topologies were synthesized. The block co-oligomers showed that variations in the hard segment structure have a dramatic effect on both the melting temperature and the stability of the liquid crystalline phase. Topology of the soft segment does not effect the thermal transitions, but does affect hard segment organization. In general, star block co-oligomers showed better organization than their linear counterparts.

The synthesis and physical characterization of various poly(1,4-phenylene vinylene) (PPVs) derivatives with electron withdrawing substituents on the phenyl rings and some additional PPV analogues are described. The synthetic routes used were a variation on the Wessling route to PPV which involves a processible precursor polymer. All polymers were characterized by IR, UV and elemental analysis. The effect of substitution on the phenyl ring and solvent effects on polymerization were also discussed. Para-xylylenes were generated by treatment of various 1,4-bis(dialkylsulfoniomethyl) arene dihalides in different solvents and detected by UV-VIS spectroscopy. The utility of studying the UV-VIS spectral behavior of para-xylylenes and analogues in the Wessling polyelectrolyte precursor process for synthesis of poly(arylene vinylene)s is demonstrated by several examples. Electronic spectral properties such as UV-VIS absorption and photoluminescence spectroscopy of PPV derivatives and analogues were investigated.

Yes / Long chain branches (LCB) are successfully grafted to linear poly(lactic acid) (PLA) using functional group reactions with pentaerythritol triacrylate (PETA) and tetraethylthiuram disulfide (TETDS). Results show a high branching degree of PLA (∼49.5%) can be effectively obtained with adding only 1 wt % PETA, contributing remarkably to enhancing strain hardening. The density of the nuclei formed during nonisothermal crystallization for LCB-PLA samples is markedly increased contrasted with PLA, resulting in significantly enhancing crystallinity from 13.3% to 41%, the onset crystallization temperature (∼20 °C), and the crystallization rate. Interestingly, compared with mini-injection molding, the elevated wall shear rates (and corresponding shear stresses) prove to be beneficial to the creation of special crystalline morphologies (β-crystal form) and oriented structures under microinjection molding conditions, resulting in the improvement of tensile strength by ∼45 MPa. / Chinese Scholarship Council

In this work we study three systems of biological interest: the translocation of a heterogeneously charged polymer through an infinitely thin pore, the wrapped of a rigid particle by a soft vesicle and the modification of the dynamical properties of a gel due to the presence of rigid inclusions. We study the kinetics of translocation for a heterogeneously charged polyelectrolyte through an infinitely narrow pore using the Fokker-Planck formalism to compute mean first passage times, the probability of successful translocation, and the mean successful translocation time for a diblock copolymer. We find, in contrast to the homopolymer result, that details of the boundary conditions lead to qualitatively different behavior. Under experimentally relevant conditions for a diblock copolymer we find that there is a threshold length of the charged block, beyond which the probability of successful translocation is independent of charge fraction. Additionally, we find that mean successful translocation time exhibits non-monotonic behavior with increasing length of the charged fraction; there is an optimum length of the charged block where the mean successful translocation time is slowest and there can be a substantial range of charge fraction where it is slower than a minimally charged chain. For a fixed total charge on the chain, we find that finer distributions of the charge along the chain leads to a significant reduction in mean translocation time compared to the diblock distribution. Endocytosis is modeled using a simple geometrical model from the literature. We map the process of wrapping a rigid spherical bead onto a one-dimensional stochastic process described by the Fokker-Planck equation to compute uptake rates as a function of membrane properties and system geometry. We find that simple geometrical considerations pick an optimal particle size for uptake and a corresponding maximal uptake rate, which can be controlled by altering the material properties of the membrane. Finally, we use a mean field approximation, neglecting correlations among the embedded particles, to examine the effect of inclusions in a viscoelastic medium on the effective macroscopic properties of the gel. We find an essentially linear dependence of both components of the complex shear modulus up to arbitrary volume fractions of the inclusions, in contradiction to experimental observations. We conclude that the incorporation of correlations among the particles is needed in order to explain experiments, in analogy with the elastic case.

Organic photovoltaic cells (OPV’s), renewable energy devices that can convert sunlight into electricity, have a bright future. Most OPV’s are made of conjugated polymers since they can absorb light and have semiconducting properties. However, the low power conversion efficiency (PCE) of OPV’s is a challenge in their development. The main structure of OPV’s includes three main parts: an electron donor, an electron acceptor, and electrodes. To improve the PCE of an OPV, many factors need to be considered, such as light absorption, the fundamental gap, the optical gap, and the OPV’s film thickness. The addition of heteroatoms to conjugated polymers is a way to change the electronic properties of the donors and may improve the PCE. This thesis describes the use of computational methods to determine how oxygen and sulfur atoms affect the electronic properties of a conjugated polymer. The data suggest that the fundamental gaps and binding energies decrease after replacing oxygen with sulfur. Additionally, the results also suggest that incorporating a sulfur atom into the conjugated polymer can increase the dipole moment change, which may lead to accelerated charge dissociation and may reduce charge recombination.

The adsorption of polyelectrolytes, both as monolayers and as multilayers, was investigated as an easy and non-expensive way of producing lignocellulosic fibrous materials with enhanced mechanical properties. In the first part of the work described in this thesis, the adsorption of a polyelectrolyte monolayer onto the surface of unbleached and unbeaten kraft pulp fibres with different kappa numbers was investigated. Adsorption isotherms were obtained in order to determine the amounts of polymer that could be adsorbed by the different pulps. Handsheets were made from the treated fibres and the mechanical properties were studied. The results showed that the use of only 2 mg/g of a polymeric amine such as polyallylamine or polyvinylamine could under certain conditions increase the tensile strength index by up to 50 %. In a second investigation, the Layer-by-Layer deposition technique was used to build up polyelectrolyte multilayers on the surfaces of bleached kraft pulp fibres. Two systems were studied and the presence of added salt in the systems was also investigated. The results showed that the system composed of polyallylamine hydrochloride and hyaluronic acid provided a dramatic increase in both strength (from 20 Nm/g to 70 Nm/g) and strain at break (from 2.0 % to 6.5 %) with only five deposited bilayers. Such a stretchability could make this material very suitable for 3D-forming of packaging materials. The behaviour of this polyallylamine/hyaluronic acid system was then studied from a more fundamental point of view in a third study in order to determine the mechanisms on the nano-scale behind the large improvements observed on the macroscopic paper scale. A quartz crystal microbalance equipment was used to study the adsorption onto model surfaces and show the superlinear trend of the build-up. Atomic force microscopy was also used to study the structural changes occurring upon adsorption of each polymeric layer as well as the adhesive properties of the system. / <p>QC 20121204</p>

A model of non-Markovian random block copolymers is developed and used to study the effects of blockiness and compositional polydispersity on the phase behaviour of random block copolymers. The model approximates a random copolymer as a series of segments with equal lengths, while each segment is composed of sequences of different monomers drawn randomly from a distribution. The phase behaviour of the model random copolymers is first examined using the random phase approximation (RPA) to study the effects of blockiness and polydispersity on the order-disorder transition. It is observed that the critical point is inversely proportional to the blockiness. Compositional polydispersity is found to facilitate phase separation, and could induce macrophase separation. Next, the model is implemented into self-consistent field theory (SCFT) in order to elucidate the full phase behaviour of symmetric (A/B)-A random copolymers. Finally, the model is applied to the particular case of poly(styrenesulfonate-b-methylbutylene) (PSS-PMB) to study the effects of blockiness on the phase behaviour. In particular, the stability and structure of the `swollen gyroid' morphology predicted by previous Monte Carlo simulations is examined. / Thesis / Master of Science (MSc)

A series of para-linked aromatic polyamides synthesized with the aim of making optically uniaxial, transparent films and fibers for optical applications, are found to have anomalous properties. Stretched films of these polyamides are highly birefringent and non-crystalline at the same time. These rod-like polyamides do not form lyotropic solutions and are soluble in common solvents like THF, unlike other rod-like polymers. With the goal of understanding this behavior from a molecular standpoint we have quantitatively characterized the geometric, optical and hydrodynamic properties of one of these polyamides. With angle light scattering measurements on polyamide in THF were used in conjunction with electric birefringence measurements to determine the weight average molecular weight, M$\sb{\rm w}$, the root mean square z-averaged radius of gyration, R$\sb{\rm gz}$, the apparent second virial coefficient, A$\sb{\rm 2app}$ and the monomer molecular anisotropy ratio $\varepsilon$. The polydispersity correction was applied theoretically by assuming the most probable distribution. Hydrodynamic and optical properties were determined with viscometry and differential refractometry respectively. The aromatic polyamide studied can be satisfactorily modeled as a Kratky-Porod wormlike chain with a persistence length of 220 $\pm$ 50 A and a monomer optical anisotropy ratio of 2.3 $\pm$ 0.3. The excluded volume effect is found to be negligible in THF at 25$\sp\circ$C. The small axial ratio of 30 may be partly responsible for the non-lyotropic behavior. The refractive index of 1.67 is in good agreement with that of similar polyamides. The repeat unit has a high optical anisotropy leading to highly birefringent films. It is also conclusively established that there is no aggregation due to H-bonding in the absence of moisture. The light scattering theory of Nagai and the hydrodynamic theory adopted for semiflexible chains is found to hold very well for the polyamide studied. Based on the agreement between experiment and theory we infer that the molecular weight distribution is of the most probable type. Our depolarized light scattering data indicate that the straight line behavior observed in Zimm plots even for $\rm R\sb{g}\sp2q\sp2>1$, upto $\rm R\sb{g}\sp2q\sp2$ of 3.5 is due to the combined effect of polydispersity, large size and optical anisotropy of the molecule.