Isoxazolidines and oxazines: preliminary studies for the synthesis of N,O-heterocyclic systems via an organocatalyzed 1,3-Dipolar Cycloaddiction and a tandem reaction mediated by TEMPO salts

This thesis is the result of the study of two reactions leading to the formation of important heterocyclic compounds of potential pharmaceutical interest. The first study concerns the reaction of (1,3)-dipolar cycloaddition between nitrones and activated olefins by hydrogen bond catalysis of thioureas derivatives leading to the formation of a five-membered cyclic adducts, an interesting and strategic synthetic intermediate, for the synthesis of benzoazepine. The second project wants to explore the direct oxidative C(sp3)-H α-alkylation of simple amides with subsequent addition of an olefin and cyclization in order to obtain the corresponding oxazine. Both reactions are still under development.

Reaction Control in Quiescent Systems of Free-Radical Retrograde-Precipitation Polymerization

Free-radical retrograde-precipitation polymerization, FRRPP in short, is a novel polymerization process discovered by Dr. Gerard Caneba in the late 1980s. The current study is aimed at gaining a better understanding of the reaction mechanism of the FRRPP and its thermodynamically-driven features that are predominant in controlling the chain reaction. A previously developed mathematical model to represent free radical polymerization kinetics was used to simulate a classic bulk polymerization system from the literature. Unlike other existing models, such a sparse-matrix-based representation allows one to explicitly accommodate the chain length dependent kinetic parameters. Extrapolating from the past results, mixing was experimentally shown to be exerting a significant influence on reaction control in FRRPP systems. Mixing alone drives the otherwise severely diffusion-controlled reaction propagation in phase-separated polymer domains. Therefore, in a quiescent system, in the absence of mixing, it is possible to retard the growth of phase-separated domains, thus producing isolated polymer nanoparticles (globules). Such a diffusion-controlled, self-limiting phenomenon of chain growth was also observed using time-resolved small angle x-ray scattering studies of reaction kinetics in quiescent systems of FRRPP. Combining the concept of self-limiting chain growth in quiescent FRRPP systems with spatioselective reaction initiation of lithography, microgel structures were synthesized in a single step, without the use of molds or additives. Hard x-rays from the bending magnet radiation of a synchrotron were used as an initiation source, instead of the more statistally-oriented chemical initiators. Such a spatially-defined reaction was shown to be self-limiting to the irradiated regions following a polymerization-induced self-assembly phenomenon. The pattern transfer aspects of this technique were, therefore, studied in the FRRP polymerization of N-isopropylacrylamide (NIPAm) and methacrylic acid (MAA), a thermoreversible and ionic hydrogel, respectively. Reaction temperature increases the contrast between the exposed and unexposed zones of the formed microgels, while the irradiation dose is directly proportional to the extent of phase separation. The response of Poly (NIPAm) microgels prepared from the technique described in this study was also characterized by small angle neutron scattering.

Second Annual Kansas State–Nebraska Biochemical Engineering Symposium (April 29, 1972)

This booklet contains abstracts of papers presented at a biochemical engineering symposium conducted at the University of Nebraska-Lincoln on April 29, 1972. This was the second annual symposium on this subject, the first having been held at Kansas State University on June 4, 1971. It is expected that future symposia will alternate between the two campuses. ContentsS.H. Lin, Kansas State University, "Enzyme Reaction in a Tubular Reactor with Laminar Flow" Gregory C. Martin, University of Nebraska, "Estimation of Parameters in Population Models for Schizosaccharomyces pombe from Chemostat Data" Jaiprakash S. Shastry and Prakash N. Mishra, Kansas State University, "Immobilized Enzymes: Analysis of Ultrafiltration Reactors" Mark D. Young, University of Nebraska, "Modelling Unsteady-State Two-Species Data Using Ramkrishna's Staling Model" G.C.Y. Chu, Kansas State University, "Optimization of Step Aeration Waste Treatment Systems Using EVOP" Shinji Goto, University of Nebraska, "Growth of the Blue-Green Alga Microcytis aeruginosa under Defined Conditions" Prakash N. Mishra and Thomas M.C. Kuo, Kansas State University, "Digital Computer Simulation of the Activated Sludge System: Effect of Primary Clarifier on System Performance" Mark D. Young, University of Nebraska, "Aerobic Fermentation of Paunch Liquor"

Modeling of ore-forming and geoenvironmental systems: Roles of fluid flow and chemical reaction processes

Ore-forming and geoenviromental systems commonly involve coupled fluid flowand chemical reaction processes. The advanced numerical methods and computational modeling have become indispensable tools for simulating such processes in recent years. This enables many hitherto unsolvable geoscience problems to be addressed using numerical methods and computational modeling approaches. For example, computational modeling has been successfully used to solve ore-forming and mine site contamination/remediation problems, in which fluid flow and geochemical processes play important roles in the controlling dynamic mechanisms. The main purpose of this paper is to present a generalized overview of: (1) the various classes and models associated with fluid flow/chemically reacting systems in order to highlight possible opportunities and developments for the future; (2) some more general issues that need attention in the development of computational models and codes for simulating ore-forming and geoenviromental systems; (3) the related progresses achieved on the geochemical modeling over the past 50 years or so; (4) the general methodology for modeling of oreforming and geoenvironmental systems; and (5) the future development directions associated with modeling of ore-forming and geoenviromental systems.

On a comparison method to reaction-diffusion systems and its applications to chemotaxis

In this paper we consider a general system of reaction-diffusion equations and introduce a comparison method to obtain qualitative properties of its solutions. The comparison method is applied to study the stability of homogeneous steady states and the asymptotic behavior of the solutions of different systems with a chemotactic term. The theoretical results obtained are slightly modified to be applied to the problems where the systems are coupled in the differentiated terms and / or contain nonlocal terms. We obtain results concerning the global stability of the steady states by comparison with solutions of Ordinary Differential Equations.

Optimized CUDA-Based PDE Solver for Reaction Diffusion Systems on Arbitrary Surfaces

Partial differential equation (PDE) solvers are commonly employed to study and characterize the parameter space for reaction-diffusion (RD) systems while investigating biological pattern formation. Increasingly, biologists wish to perform such studies with arbitrary surfaces representing ‘real’ 3D geometries for better insights. In this paper, we present a highly optimized CUDA-based solver for RD equations on triangulated meshes in 3D. We demonstrate our solver using a chemotactic model that can be used to study snakeskin pigmentation, for example. We employ a finite element based approach to perform explicit Euler time integrations. We compare our approach to a naive GPU implementation and provide an in-depth performance analysis, demonstrating the significant speedup afforded by our optimizations. The optimization strategies that we exploit could be generalized to other mesh based processing applications with PDE simulations.

Bifurcation Analysis of Reaction Diffusion Systems on Arbitrary Surfaces

In this article we present a computational framework for isolating spatial patterns arising in the steady states of reaction-diffusion systems. Such systems have been used to model many different phenomena in areas such as developmental and cancer biology, cell motility and material science. Often one is interested in identifying parameters which will lead to a particular pattern. To attempt to answer this, we compute eigenpairs of the Laplacian on a variety of domains and use linear stability analysis to determine parameter values for the system that will lead to spatially inhomogeneous steady states whose patterns correspond to particular eigenfunctions. This method has previously been used on domains and surfaces where the eigenvalues and eigenfunctions are found analytically in closed form. Our contribution to this methodology is that we numerically compute eigenpairs on arbitrary domains and surfaces. Here we present various examples and demonstrate that mode isolation is straightforward especially for low eigenvalues. Additionally we see that if two or more eigenvalues are in a permissible range then the inhomogeneous steady state can be a linear combination of the respective eigenfunctions. Finally we show an example which suggests that pattern formation is robust on similar surfaces in cases that the surface either has or does not have a boundary.

An annotated bibliography of compiled thermodynamic data sources for biochemical and aqueous systems (1930 to 1975) : equilibrium, enthalpy, heat capacity, and entropy data /

101 selected references to books and journal articles. Also includes some foreign-language titles. Alphabetical arrangement by primary authors. Each entry gives bibliographical information and annotation. Author, subject indexes.

Reaction-diffusion stochastic lattice model for a predator-prey system

We have the purpose of analyzing the effect of explicit diffusion processes in a predator-prey stochastic lattice model. More precisely we wish to investigate the possible effects due to diffusion upon the thresholds of coexistence of species, i. e., the possible changes in the transition between the active state and the absorbing state devoid of predators. To accomplish this task we have performed time dependent simulations and dynamic mean-field approximations. Our results indicate that the diffusive process can enhance the species coexistence.

The effect of using mixed initiator systems on the efficiency of photopolymerization of dental resins

A study was performed in order to determine the efficiency of the simultaneous use of the photoinitiators phenylpropanedione (PPD) and camphorquinone (CQ) in the polymerization of acrylic polymers and evaluate possible mechanisms leading to synergism or antagonism. It was found that efficiencies of both initiators taken individually are higher than that of their mixture, indicating that when both dyes are used simultaneously there will be an energy transfer from the more efficient initiator (CQ) to the less efficient one (PPD). Also, there was no proof of any reaction between the amine present in the CQ formulation and the PPD excited state.