One monomer molecularly imprinted polymers (referred to as 'OMNiMIPs'), synthesized from novel crosslinking monomers developed in the PI's group, exhibit fundamental differences that give rise to new and enhanced properties versus traditionally formed molecularly imprinted polymers (MIPs). First, the use of one monomer ultimately affords a higher loading capacity per gram of polymer, which can improve applications such as solid phase extraction and analytical separations. The increased rebinding capacity of OMNiMIPs could lead to applications beyond current limits of MIPs, such as high capacity removal of target compounds in solid phase extraction, environmental clean-up, or protein-purification strategies. We are currently investigating the underlying principles that are responsible for the high capacity and selectivity of OMNiMIPs. The higher capacity also affords higher performance for imprinting several different target compounds simultaneously, facilitating assays and separations of multiple analytes. This could be important for assays on mixtures of different compounds, such as the analysis of pharmaceutical formulations or solid phase extraction of an array of different molecules. In addition, novel chiral OMNiMIPs appear capable of imprinting racemic mixtures, providing an easier route to chiral stationary phases. This would eliminate the need for enantiopure templates, normally required for traditional MIPs. Last, OMNiMIPs will be hybridized with conjugated polymers to provide a material that can generate a fluorescence signal upon binding the target molecule, which is useful for sensors and other detection strategies. An important theme for the research described in this proposal is to utilize molecular control of the monomer starting materials toward optimizing macroscopic properties (e.g. loading capacity and selectivity) of OMNiMIPs. The heart of this proposal is the design, synthesis and evaluation of new crosslinkers for the OMNiMIP process that will maximize the performance of these materials for the applications described above. Using the molecular structure of successful crosslinkers as lead compounds, analogs with rational changes will be evaluated for improvements in structure-property relationships. This proposal describes the fundamental development of new MIP materials that both improve performance and are capable of unique applications that have not been available from this technology in the past. It is important to determine the optimal crosslinker structures as quickly as possible in order to provide researchers worldwide with the best materials for their applications.
For society, the promise of molecular imprinting is the detection of medical and environmental toxins, detection and neutralization of national security target compounds, tailored catalysts, and separation media that will serve the health and advancement of mankind in numerous ways. These broader impacts of molecular imprinting will be enhanced in several ways by the development of OMNiMIPs for novel applications such as those described above. While the development of these materials should be seen as a major practical outcome of this research, these studies will also contribute to the fundamental understanding of the underlying principles of the OMNiMIP effect and how these differ from traditional molecular imprinting approaches. Furthermore, the development of OMNiMIPs has stimulated numerous collaborations with researchers, both nationally and internationally, resulting in many interesting studies toward the increased performance of these materials for current and new applications. OMNiMIP research has also provided opportunities for undergraduates and a high school student to participate in cutting edge research and present their results at conferences. The real credit for the success and fun of OMNiMIP research belongs to the diverse group of graduate students and post-doctoral fellows who have engaged themselves in the day-to-day problem solving that has made this research flourish. Our group is talented and draws evenly from underrepresented groups that are mentored well here at LSU. Their training in molecular imprinting and OMNiMIPs continues to present opportunities that interface important chemical disciplines naturally, providing an interdisciplinary education that will enhance their competitiveness in the current and future marketplace. The people and the research in this overall program will reach the broader community in Louisiana, especially younger generations, through public lectures and presentations with the goal to improve their awareness and interest of basic science and technology.
The intellectual merit of this NSF award by the Chemical and Biological Separations program supports work by Professor David Spivak and Evgueni Nesterov at Louisiana State University concluded with the advanced development of sensors and purification materials using one monomer molecularly imprinted polymers (referred to as "OMNiMIPs"). To make an OMNiMIP to a target such as an environmental toxin, pharmaceutical or explosive like TNT; polymers are molded around the target molecule. When the target molecule is removed, a specific binding cavity is left in the polymer. When the polymer is exposed to a toxic waste stream in air or water, it can soak-up the toxic molecule. Or, if a sensor at the airport has an OMNiMIP made to recognize TNT, it can detect this dangerous compound in the air. The heart of this proposal is the design, synthesis and evaluation of new polymers for the OMNiMIP process that maximize the performance of these materials. The fundamental differences of the new materials verus those traditionally used are three-fold. First, one type of polymer was found ultimately to give a higher loading capacity per gram of polymer, which can improve applications such as solid phase extraction and analytical separations. The increased rebinding capacity of OMNiMIPs could lead to applications beyond current limits of MIPs, such as high capacity removal of target compounds in solid phase extraction, environmental clean-up, or protein-purification strategies. The higher capacity also affords higher performance for imprinting several different target compounds simultaneously, facilitating assays and separations of multiple analytes. Second, chiral OMNiMIPs were found to be capable of imprinting racemic mixtures, providing an easier route to chiral stationary phases, often used in the pharmaceutical industry. Third, novel conjugated OMNiMIPs were developed that provide fluorescent signaling materials for sensor applications. The broader impacts of molecular imprinting using OMNiMIPs includes the detection of medical and environmental toxins, detection and neutralization of national security target compounds, tailored catalysts, and separation media that will serve the health and advancement of mankind in numerous ways. The real credit for the success and fun of OMNiMIP research belongs to the diverse group of graduate students and post-doctoral fellows who have engaged themselves in the day-to-day problem solving that has made this research flourish. Their training in molecular imprinting and OMNiMIPs continues to present opportunities that interface important chemical disciplines naturally, providing an interdisciplinary education that will enhance their competitiveness in the current and future marketplace. Even with a rigorous research schedule, the students and their Mentor still find time to visit schools to give chemistry demonstrations, serve as judges for state, local, and national chemistry competitions, and give public chemistry demonstrations at local events such as Earth Day, Superscience Saturday, and the Louisiana State University Fall Fest.
