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High-pressure solution behavior such as density and phase behavior is a critical fundamental property for the design and optimization of various chemical processes, such as distillation and extraction in the production and purification of oils, polymers, and other natural materials. In this PhD study, solution behavior data are experimentally determined and equation of state (EoS) modeled for n-hexadecane, n-octadecane, n-eicosane, methylcyclohexane, ethylcyclohexane, cis-1,2-dimethylcyclohexane, cis-1,4-dimethylcyclohexane, trans-1,4-dimethylcyclohexane, o-xylene, m-xylene, p-xylene, and 2-methylnaphthalene at temperatures to 525 K and pressures to 275 MPa. A variable-volume view cell coupled with a linear variable differential transformer is used for the high-pressure determination. The reported density data are less than 0.4% of available literature data, which is within the estimated accumulated experimental uncertainty, 0.75%. Special attention is paid to the effect of architectural differences on the resultant high-pressure solution behavior. The reported data of low molecular weight hydrocarbons are modeled with Peng-Robinson (PR) equation of state (EoS), high-temperature high-pressure volume-translated cubic (HTHP VT-cubic) EoS, and perturbed-chain statistical fluid theory (PC-SAFT) EoS. The three pure-component parameters in PC-SAFT EoS can be either obtained from literature or from a group contribution (GC) method. Generally, PR EoS gives the worst predictions and HTHP VT-cubic EoS provides modest improvements over the PR EoS, but both of the equations underpredict the densities at high pressures. On the other hand, PC-SAFT EoS, with parameters from the literature or from a GC method, gives the improved density predictions with respect to PR EoS and HTHP VT-cubic EoS, although an overprediction of densities is found at high pressures. Model calculations also highlight the capability of these equations to account for the different densities observed for the hydrocarbon isomers. However, none of the EoS investigated in this study can fully account for the effect of isomeric structural differences on the high-pressure densities. For a better prediction of densities at high pressures, a new set of PC-SAFT pure-component parameters are obtained from a fit of the experimental density data obtained in this study and the mean absolution percent deviation is within 0.4%. The experimental technique and PC-SAFT EoS modeling method are extended to a star polymer-propane mixture. Star polymers with a fixed number of arms have a globular structure that does not promote chain entanglements. Star polymers can be synthesized with a large number of functional groups that can be readily modified to adjust their physical properties for specific applications in the areas of catalysis, coatings, lubrication, and drug delivery. In this study, a star polymer with a divinylbenzene core and statistically random methacrylate copolymer arms is synthesized with reversible addition-fragmentation-transfer method and fractionated with supercritical carbon dioxide and propane to obtain fractions with low molecular weight polydispersity. The phase behavior and density behavior are experimentally determined in supercritical propane for fractionated star polymers and the corresponding linear copolymer arms at temperatures to 423 K and pressures to 210 MPa. Experimental data are presented on the impact of the molecular weight, the backbone composition of the lauryl and methylmethacrylate repeat units in the copolymer arms, and the DVB core on the polymer-propane solution behavior. The star polymer is significantly more soluble due to its unique structure compared with the solubility of the linear copolymer arms in propane. The resultant phase behavior for the two homopolymers and the copolymers in propane are modeled using the PC-SAFT and copolymer PC-SAFT EoS, which give reasonable predictions for both phase behavior and density behavior. Model calculations are not presented for the phase behavior of the star polymers in propane since the PC-SAFT approach is not applicable for star polymer structures.

Fullerene research has advanced to elevated levels in a short period of time due to the unique chemical and physical properties of the caged molecule that have been utilized in numerous applications. Due to the spherical shape of the fullerene molecule which allows for a hollow cavity, encapsulation of atoms or small molecules can occur within the ball structure. This encapsulation creates an endohedral component that is limited from interacting with other molecules which creates potential of control over electronic information of the isolated molecule. Endohedral fullerenes have the potential as serving as the base unit in a quantum computer if control over global alignment is attained. Thus, by using the inherent self-assembling capabilities of some organic materials, ordered endohedral fullerenes can be achieved. This dissertation investigates the ability to use self-assembling strategies to obtain alignment which include ordering within a morphologically controlled copolymer matrix, forming a supramolecular polymer complex with cyclodextrin, and encapsulation within the helical wrap of polymer chains. The ultimate goal is to understand the dynamics that control association and orientation of varying fullerene-based molecules in each strategy in order to maximize control over the final alignment of endohedral elements.

No description available.

This thesis presents our recent study of few interesting problems involving activated processes. This chapter gives an overview of the thesis. It is now possible to do single molecule experiments involving enzyme molecules. The kinetics of such reactions exhibits dynamic disorder associated with conformational changes of the enzyme-substrate complex. The static disorder and dynamic disorder of reaction rates, which are essentially indistinguishable in ensemble-averaged experiments, can be determined separately by the real-time single-molecule approach. In our present work we have given a theoretical description of how rate of reactions involving dynamic disorder is studied using path integral approach. It is possible to write the survival probability and the rate of the process as path integrals and then use variational approaches to get bounds for both. Though the method is of general validity, we illustrate it in the case of electronic relaxation in stochastic environment modeled by a particle experiencing diffusive motion in harmonic potential in presence of delta function sink. The exact solution of corresponding Smoluchowski equation was found earlier[1] analytically in Laplace domain with sink having arbitrary strength and position. Exact evaluation of path integral calculation to survival probability is not possible analytically. Wolynes et al.[2] have done an approximate calculation to get bounds to the survival probability in the Laplace domain. A bound in the Laplace domain is not as useful as a bound in the time domain and hence we use the direct approximate variational path integral technique to calculate both lower and upper bound of survival probability in time domain. We mimic the delta function sink by quadratic sink for which the path integral can be solved exactly. The strength of the quadratic sink is treated as variational parameter and using the optimized value for it, one can estimate the optimized lower as well as upper bound of survival probability. We have also calculated a lower bound to the rate. The variational results are compared with the exact ones, and it is found that the results for the two parameter case are better than those of one parameter case. To understand how good our approximation is, we calculate the bounds in survival time and found them to be in good agreement with exact results. Our approach is valid for any arbitrary initial distribution that one may start with. We consider the Kramers problem for a long chain polymer trapped in a biased double well potential. Initially the polymer is in the less stable well and it can escape from this well to the other well by the motion of its N beads across the barrier to attain the configuration having lower free energy. In one dimension we simulate the crossing and show that the results are in agreement with the kink mechanism suggested earlier. In three dimensions, it has not been possible to get analytical “kink solution”for an arbitrary po-tential; however, one can assume the form of the solution of the non-linear equation as a kink solution and then find a double well potential in three dimensions. To verify the kink mechanism, simulations of the dynamics of a discrete Rouse polymer model in a double well in three dimensions were done. We find that the time of crossing is proportional to the chain length which is in agreement with the results of kink mechanism. The shape of the kink solution is also in agreement with the analytical solution in both one and three dimensions. We then consider the dynamics of a short chain polymer crossing over a free energy barrier in space. Adopting the continuum version of the Rouse model, we find exact expressions for the activation energy and the rate of crossing. For this model, the analysis of barrier crossing is analogous to semiclassical treatment of quantum tunneling. Finding the saddle point for the process requires solving a Newton-like equation of motion for a fictitious particle. The analysis shows that short chains would cross the barrier as a globule. The activation free energy for this would increase linearly with the number of units N in the polymer. The saddle point for longer chains is an extended conformation, in which the chain is stretched out. The stretching out lowers the energy and hence the activation free energy is no longer linear in N . The rates in both the cases are calculated using a multidimensional approach and analytical expressions are derived using a new formula for evaluating the infinite products. However, due to the harmonic approximation made in the derivation, the rates are found to diverge at the point where the saddle point changes over from the globule to the stretched out conformation. The reason for this is identified to be the bifurcation of the saddle to give two new saddles. A correction formula is derived for the rate in the vicinity of this point. Numerical results using the formulae are presented. It is possible for the rate to have a minimum as a function of N . This is due to the confinement effects in the initial state. We analyze the dynamics of a star polymer of F arms confined to a double well potential. Initially the molecule is confined to one of the minima and can cross over the barrier to the other side. We use the continuum version of Rouse-Ham model. The rate of crossing is calculated using the multidimensional approach due to Langer[3].Finding the transition state for the process is shown to be equivalent to the solution of Newton’s equations for F independent particles, moving in an inverted potential. For each star polymer, there is a critical total length N Tc below which the polymer crosses over as a globule. The value of NTc depends on the curvature at the top of the barrier as well as the individual arm lengths. So we keep the lengths of (F -1) arms fixed and increase the length of the F th arm to get the minimum total length NTc. Below NTc the activation energy is proportional to the total arm length of the star. Above N Tc the star crosses the barrier in a stretched state. Thus, there is a multifurcation of the transition state at NTc. Above NTc, the activation energy at first increases and then decreases with increasing arm length. This particular variation of activation energy results from the fact that in the stretched state, only one arm of the polymer is stretched across the top of the barrier, while others need not to be. We calculate the rate by expanding the energy around the saddle upto second order in the fluctuations. As we use the continuum model, there are infinite modes for the polymer and consequently, the prefactor has infinite products. We show that these infinite products can be reduced to a simple expression, and evaluated easily. However, the rate diverges near N Tc due to the multifurcation, which results in more than one unstable mode. The cure for this divergence is to keep terms upto fourth order in the expansion of energy for these modes. Performing this, we have calculated the rate as a function of the length of the star. It is found that the rate has a nonmonotonic dependence on the length, suggesting that longer stars may actually cross over faster.

Les polymères en étoile connaissent un intérêt accru en raison de leurs propriétés thermiques et mécaniques inimitables. Partant du constat qu’en parallèle la chimie durable se développe à un rythme sans précédent, nous proposons dans cette thèse de développer une stratégie plus « verte » pour la synthèse de polymères en étoile de type D-sorbitol-poly(ε-caprolactone) (star PCL-OHx). Ces derniers seront synthétisés sans solvant (en masse) ou dans des solvants « propres » (CO2 supercritique) et en présence du catalyseur métallique Sn(Oct)2 (qui a été approuvé par la FDA) ou d’un catalyseur enzymatique (Novozym® 435). L’influence de ces paramètres sur l’architecture des étoiles (nombre de bras, masse molaire des bras…) a été rigoureusement analysée et confirmée par différentes techniques d’analyse (RMN 1H, SEC-MALS, SEC-UC, analyse RMN 31P quantitative via la méthode de phosphitylation). Des polymères linéaires monohydroxy (PCL-OH) et téléchéliques dihydroxy (OH-PCL-OH) ont également été synthétisés en parallèle. Ces différentes PCL ont été utilisées comme macroamorceurs hydrophobes pour la polymérisation du monomère cyclique hydrophile éthyl phosphonate d’éthylène. Une large gamme de copolymères amphiphiles a ainsi pu être développée (i.e. des copolymères diblocs en étoile ou des copolymères diblocs et triblocs linéaires). Le comportement d’auto-assemblage en solution de ces copolymères a été étudié par DLS ainsi que par TEM et cryo-TEM. Nous avons également montré que les copolymères amphiphiles triblocs et en étoile sont capables de diminuer la tension de surface (γ) de l’eau en dessous de 45 mN m-1. Enfin, les étoiles PCL-OHx synthétisées en présence d’enzyme ont été fonctionnalisées par réaction avec l’anhydride maléique. Des polymères en étoile, ioniques, tensio-actifs et directement dispersables dans l’eau ont ainsi pu être obtenus. Dans un second temps, ces mêmes polymères ont été photopolymérisés en présence d’une faible quantité de tri(éthylène glycol) divinyl éther (~ 9% par rapport à la masse totale). Les films afférents à ces copolymères en étoile réticulés sous UV ont été analysés par IRTF, DSC et ATG. / Star polymers have attracted considerable attention because of their unique thermal and mechanical properties. At the same time, as sustainable chemistry field is growing in impact at an unprecedented rate, we propose in this work to implement a greener pathway for the synthesis of star D-sorbitol-poly(ε-caprolactone) (star PCL-OHx) using clean solvents (polymerisation in the bulk or in supercritical CO2) and either FDA-approved Sn(Oct)2 catalyst or enzyme catalyst (Novozym® 435). The influence of these parameters on the star architecture (number of arms, MW of arms etc.) was rigorously analysed and corroborated with various analytical techniques (1H NMR, SEC-MALS, SEC-UC, phosphitylation quantitative 31P NMR approach). Linear monohydroxy PCL-OH and dihydroxy telechelic OH-PCL-OH samples were also prepared. The PCL materials obtained were used as hydrophobic macroinitiators for the polymerisation of cyclic hydrophilic ethylene ethyl phosphonate monomer for the synthesis of a range of different amphiphilic materials (i.e. star diblock, linear diblock and triblock copolymers). Self-assembly behaviour in aqueous solution of these copolymers was investigated by DLS, TEM and cryo-TEM. Triblock and star amphiphilic copolymers were revealed to be able to reduce the surface tension (γ) of water down to 45 mN m-1. Finally, enzyme catalysed star PCL-OHx polymers were functionalised with carboxylic end-groups using maleic anhydride. Water-dispersible surface-active ionic star polymers were then obtained. These maleate-functionalised star polymers were then photopolymerised with a small amount of tri(ethylene glycol) divinyl ether (~9wt% of total composition). The UV-cured crosslinked star PCL films produced were then analysed by FTIR, DSC and TGA.

Grafting polymeric chains on the surface of nanoparticles is an effective way to enhance particle-matrix interaction and their homogeneous dispersion within the matrix, leading to improved physical and mechanical properties. However, current methods for grafting polymeric chains onto nanoparticles have not produced well-defined polymers with high grafting density. Here, we employed anionic polymerization high vacuum techniques to synthesize in-situ grafted silica nanoparticles with either polystyrene (PS), polystyrene-b-polyisoprene (PS-b-PI) or 3- miktoarm star polymers (3-µ stars polymer) ((PS)2PS, (PS)2PI, and (PS)2PI-b-PS) by hydrolysis/condensation of ω-tetraethyl orthosilicate (TEOS) of PS, PS-b-PI and 3-µ star polymers. The molecular characteristics of the precursors PS-TEOS, PS-b-PI-TEOS, and 3-µ star polymer-TEOS were determined by 1H NMR, SEC, and MALDI-ToF. The synthesis of PS (PS@SiO2 NPs), PS-b-PI (PS-b-PI@SiO2 NPs), and 3-µ star polymer ((PS)2PS)@SiO2, (PS)2PI)@SiO2, and (PS)2PI-b-PS@SiO2 NPs) nanoparticles was verified by FT-IR, 29Si solid-state NMR, TEM, TGA, and DLS. Blends of PS@SiO2 with commercially available PS and PS-b-PI@SiO2 and 3-µ star polymer@SiO2 with anionically synthesized thermoplastic elastomer (PS-b-PI-b-PS), were obtained either in melt by extrusion or in solution by evaporation. The role of polymer@SiO2 on the mechanical and morphological properties was examined by tensile testing and SEM. In the fifth chapter, a high grafting density of polymer on the surface of SiO2 NPs approach that may also be employed in industry was presented. TEOS will be present in every repeating unit in the second block rather than simply the end group as it was in the first three chapters. First, anionic polymerization of PS functionalized with bromide group to utilize as a macroinitioter. Then, the macroinitioter (PS-Br) will initiate the polymerization of VTES (vinyltriethoxysilyl), ATMS (alyltrimethoxysilyl), and SETMS (styrene ethyltrimethoxysilyl) via atom transfer radical polymerization (ATRP) to form PS-b-PVTES, PS-b-PATMS, and PS-b-SETMS. SEC, 1H NMR, FT-IR, 29Si solid-state NMR, TEM, and DLS were used to confirmed copolymer grafting on SiO2 NPs. Lastly, a tensile test was used to study the mechanical properties of the nanocomposite. The proposed method controls the molecular weight, chemical composition, particle size and grafting density of nanoparticles and effectively improves the mechanical characteristics of the two families of PS-based nanocomposites.

In the frame of this thesis different calix[4]resorcin- and calix[4]pyrogallolarene derivatives were used as platform for the synthesis of novel star polymers and dendritic structures. The objectives of this work can be portrayed under the following points: First: Synthesis and modification of calix[4]resorcin- and calix[4]pyrogallolarenes with a varying number and varying type of functional sites and their precise characterization by modern NMR techniques and single crystal X-ray diffraction. Second: Synthesis of well-defined star polymers and dendrimers with different number of arms and accordingly dendrons, based on calix[4]resorcin- and calix[4]pyrogallolarenes, via convenient polymerization and generation growth reactions and analysis of the obtained products by different methods (MALDI-TOF-MS, SEC-RI and SEC-MALLS, NMR).

Two designs of inorganic/organic hybrid micro-structures are discussed: (1) silver nanowire reinforced layer-by-layer (LbL) polyelectrolyte composite film and (2) bimetallic silver-gold core-shell nanoparticles. In this work, zero-dimensional spherical gold nanoparticles (AuNPs), one-dimensional silver nanowires (AgNWs), and two-dimensional silver nanoplates (AgNPls) represent the inorganic component. Three-arm star polymer and polyelectrolytes represent the organic component. In the first design, the one-dimensional AgNWs serves as a mechanical reinforcement for the fabrication of mechanically isotropic and anisotropic polyelectrolyte composite films. The composite film is mechanically isotropic when the AgNWs are randomly oriented, and it is anisotropic when the AgNWs are unidirectionally oriented within the LbL polyelectrolyte matrix. Furthermore, above the AgNWs percolation threshold, the AgNWs reinforced LbL composite film is electrically conductive. Therefore, it can find application in ultrathin LbL film-based sensor. In the second design, the zero-dmensional AuNPs were assembled onto one-dimensional AgNWs and two-dimensional AgNPls by means of star polymer linker, or alternatively using polyelectrolytes via electrostatics interaction. The unique feature of these bimetallic silver-gold core-shell nanoparticles is their ability to greatly enhance electric field, due to the silver-gold intra-particle interaction. This allows it to serve as a single-nanoparticle surface enhanced Raman scattering (SERS) substrate for chemical sensing.

No description available.