Kevin H. Shaughnessy, Ph.D. - US grants

The focus of this research is the development of highly reactive catalysts for synthetically useful reactions such as the Heck, Suzuki and Buchwald-Hartwig couplings. To this end, water-soluble alkylphosphines will be synthesized and used in conjunction with aqueous-phase palladium-catalyzed coupling reactions. These reactions efficiently provide structures of interest in areas ranging from pharmaceuticals and agricultural chemicals to electronic materials and commodity chemicals.

With this new NSF/EPA Technology for a Sustainable Environment (TSE) award, the Organic and Macromolecular Chemistry Program and the Office of Multidisciplinary Activities of the Directorate of Mathematics and Physical Sciences are supporting the research efforts of Dr. Kevin H. Shaughnessy of the Department of Chemistry at the University of Alabama, Tuscaloosa. Professor Shaughnessy will focus his research on developing methodology for the use of a new class of sterically demanding, water-soluble alkylphosphines in palladium-catalyzed C-C and C-heteroatom bond forming reactions using environmentally benign aqueous solvent. Adoption of this methodology by industry could result in the decrease of hazardous waste generation, decrease in energy consumption and decrease in the use of volatile organic solvents. The undergraduate, graduate and post-doctoral students working on this project will gain a fundamental education in organic and organometallic chemistry and approaches to developing environmentally benign chemical reactions.

Chemistry (12) Nuclear Magnetic Resonance (NMR) is a powerful technique for structural determination and quantification that is widely used across all areas of science. In the traditional undergraduate curriculum, hands-on experience with NMR is typically limited outside of sophomore organic classes. This project uses NMR as a cornerstone technique in nine undergraduate laboratory classes. In additional to traditional uses of NMR to identify and characterize structures in organic and inorganic chemistry, NMR is being used to demonstrate principles in analytical, physical chemistry, and biochemistry labs. The specific goal of this project is to improve student understanding of chemical principles, by using NMR as a cornerstone technique, with which students become proficient over their career. To achieve our goals of expanding NMR beyond the sophomore organic lab, we are using a modern, high-field NMR spectrometer. The new instrument is used in a hands-on fashion by both chemistry majors and non-majors taking sophomore through senior level chemistry lab classes. Published experiments, primarily from the Journal of Chemical Education, are being adapted and integrated within the nine courses in order to achieve our curricular goals. A tutorial page is used to walk students through the transfer and processing of a standard NMR data file, with the processing system modeled on one used at Florida State University. Finally, a workshop is being offered annually to regional four-year institutions that are interested in having student samples run on our NMR. The results are e-mailed back to the students who then use software capable of all standard NMR processing functions to analyze their data.
Intellectual Merit: The use of technology in the classroom is of increasing importance to teach modern scientific concepts and engage computer literate students. NMR is a central technique since it can be used to study a variety of problems. This project is leading to the development of a number of new laboratory experiments, and these experiments will be made available to other instructors interested in increasing the use of NMR in their laboratory classes.
Broader Impact: The proposed project is involving approximately 300 undergraduate students per year. These students receive hands-on experience as a means to learn fundamental chemical concepts. We also expect that students will be excited about chemistry, and science in general, as a result of this project. In particular, by reaching out to non-majors we hope to encourage these students, particularly those from under-represented groups, to consider careers in the sciences.

The Chemistry Department at the University of Alabama Tuscaloosa will acquire a liquid chromatograph mass spectrometer (LC-MS) with this award from the Chemistry Research Instrumentation and Facilities: Multi User (CRIF:MU) program. The requested LC-MS will facilitate ongoing research projects including: cofactor identification and proteomic analysis of photosynthetic systems; elucidation of the role of chromium in human metabolism and its implications in insulin sensitivity and treatments of diabetes; the development of water-soluble ligands for aqueous-phase catalysis and studies of metal-catalyzed modification of nucleosides; preparation and characterization of pentafluorosulfanyl-benzenes and fluorinated polymers for use in a range of industrial applications; and fundamental and applied studies into the sequencing of metallopeptides and deprotonated peptides.

Mass spectroscopy is a basic tool used by physical and biological scientists to identify and characterize materials and chemical species by accurate measurement of their mass as they are vaporized and fragmented in the instrument. Liquid chromatography is a purification technique that separates a complex mixture into individual components before introduced to the mass spectrometer. These are important tools to be used in the training of young scientists. Over 60 student researchers will use LC-MS in their research projects over the next few years. This includes graduate students, undergraduate academic year and summer students (including students from UA's NSF REU program), and high school teachers participating in summer programs. Through the use of an autosampler and cyber-control, educators and researchers located at 4 or more regional undergraduate institutions including two minority serving institutions, will have access to the instrument for the purposes of laboratory classes and undergraduate research.

The Chemical Catalysis Program in the Chemistry Division at the National Science Foundation supports Professor Kevin Shaughnessy of the University of Alabama, for a combined experimental and theoretical investigation of the ligand structural effects on the performance of Pd catalysts for coupling reactions. The goal of this work is to understand the balance of steric and electronic properties of the ligands, typically phosphines, that make one catalyst operate at a faster rate or with higher turnover numbers than another. The Pd catalyst systems to be investigated here are popular reagents due to their high functional group compatibility and ease of use.

The broader impacts of this research are centered in the combination of experimental and theoretical approaches to the problem of catalyst structure/reactivity relationships. The systematic approach applied through this collaboration will expose students to both techniques simultaneously, making it an excellent training ground for young scientists. The potential for rational design of new catalyst systems with improved performance is important for conservation of natural resources and the construction of "atom economical" manufacturing processes.

ABSTRACT

PI: Hartman, Ryan L.
Institutions: University of Alabama Tuscaloosa
Proposal Number: 1264630
Title: Microreaction Engineering of Aqueous Phase Metal Catalyzed Reactions

Intellectual Merit

The use of water as a reaction solvent has the potential to impact the sustainable, continuous flow manufacturing of specialty chemicals. Successfully engineering such processes require the ability to overcome some challenges, including 1) management of the formation of solids as non-covalently bonded materials on reactor surfaces (e.g., scale deposition), 2) design of efficient catalysts using understanding of the fundamental mechanisms that govern synthetic transformations, 3) innovation of novel reactors that efficiently couple the aromatics that make-up intermediates in fine chemical production, and 4) integration of analytics with laboratory synthesis tools for online reaction discovery and optimization. This research will address each of these four challenges. The PIs plan the engineering and integration of microreactors with confocal Raman microscopy, where the intrinsic kinetic and mechanistic knowledge of palladium-catalyzed C-H functionalization reactions with hydrophilic ligands will be made available in the absence of transport limitations. The use of hydrophilic ligands, and hence water as a reaction solvent, in fine chemical manufacturing presents the opportunity for greener pathways to useful compounds. The PIs will combine reactor design principles, analytical chemistry, and synthetic methodologies aimed at developing a platform, which can be used to continuously synthesize fine chemical intermediates with water as a reaction solvent. The enabling technology will combine concepts of (i) microreactor technology, (ii) the design of hydrophilic ligands for synthetic organic reactions, (iii) non-invasive analytical techniques for reaction monitoring, and (iv) multi-step microchemical synthesis involving reactions and separations. If successful, the knowledge generated will foster a new paradigm of sustainable chemical process design: the use of water as a solvent to manufacture fine chemicals.

Broader Impacts

This research seeks to establish fundamental understanding of reactor and process design of synthetic pathways that utilize water as a solvent. This understanding will advance chemical processes that synthesize specialty chemicals, in a sustainable way. Undergraduate and graduate students will benefit from this work through the evolution of the reaction engineering curricula and undergraduate research opportunities for underrepresented groups. Furthermore, students K-12+ will be engaged by the creation of online YouTube videos through an undergraduate competition between the University of Southern California and the University of Alabama aimed at the interfacing of advanced chemistry and reactor design concepts, real world engineering problems, and pop culture. The work will also expose graduate students to international research experiences through collaboration with the Institute of Condensed Matter Chemistry Bordeaux (ICMCB). These educational components will strengthen the undergraduate engineering education at the University of Alabama, foster early interest in engineering careers from K-12 students, and provide unique opportunities for graduate students to gain international exposure.

The University of Alabama (UA) Noyce Scholars program is designed to increase the number and diversity of teachers graduating from UA in chemistry, mathematics, and physics. The targeted disciplines are in great demand in Alabama and the nation. The project has 3 major goals with objectives that include 1) recruitment through early teaching experiences, 2) collaborative strategies supporting and sustaining juniors and seniors, and 3) extensive and evolving induction for graduates aimed at retaining quality teachers in high-need school districts. Noyce scholars are actively recruited from high schools and community colleges throughout the state, universities, in addition to STEM professionals, with a focus on underrepresented, diverse candidates. The project is enhancing the UA teacher preparation program in the targeted disciplines with activities leading to the production of 21 new science and mathematics teachers including: 1) freshman orientation experiences at UA and 8 collaborating community colleges followed by 75 summer UA internships to work with a researcher and visit exemplary classrooms, 2) sophomore extended orientation followed by 45 summer internships as learning assistants in UA classrooms, 3) junior and senior year training and inquiry oriented teaching experiences using lab technology supported by 14 scholarships, 4) MA STEM professional certification program supported by 7 stipends, and 5) a multistage induction process beginning with expert teacher mentoring in high needs schools through graduate coursework leading to mentoring of new teachers by the Noyce scholar. For each year of funding received, Noyce Scholars commit to teaching two years in a high needs school district. UA Noyce accomplishes these goals first through strong collaboration with Alabama community colleges in regions with many high-need schools. Each community college has a designated liaison faculty mentor who assists with student recruitment into UA Noyce and placement of summer interns following the freshman and sophomore years. Second is collaboration with the statewide Alabama Math Science and Technology Initiative recognized as an exemplary model program by the Center for Excellence in Education. Third is partnership with rural and urban school districts providing students with teaching experiences throughout their program. The districts have a high percentage of underrepresented low income students with few STEM role models. The schools provide mentor teachers, assist in recruiting, offer exemplary classrooms for field experiences, and collaborate with UA in developing, implementing, and sustaining an extensive 4-year induction program.

The project addresses the development of the teacher from the freshman year into the early years as an inservice teacher. It provides research-based practices including development of a recruiting network, early teaching experiences to motivate and sustain student interest, mentoring relationships with inservice teachers, extensive quality field experiences in STEM content and pedagogy, and induction courses as new teachers. The project has strong evaluation and research components examining factors that affect the recruitment, retention, diversity, preparation, and induction of Noyce teachers. Some important questions for which data are collected include characteristics of successful recruits, impact of early learning experiences, the success of the Noyce program in keeping teachers in the profession, and the effectiveness of inservice Noyce teachers compared with non-Noyce teachers.

The project is disseminating a synergistic model for the use of collaboratives to create, build upon, and increase the STEM pathway. The UA model establishes an extensive recruitment network for teachers in chemistry, mathematics, and physics using community colleges located in rural and urban regions often lacking in role models for students in the targeted fields. The model demonstrates the use and upgrading of existing infrastructure to enhance research-based STEM teacher education program development.

The University of Alabama Tuscaloosa Noyce Teaching Fellowship Track 2 project, Developing Leaders in Science Teaching (LIST), will be a teacher education model focusing on creating 15 new science teacher leaders through teacher certification and induction support. An overall goal of the project will be to increase the quality and quantity of biology, chemistry, and physics STEM professionals entering and remaining in science teaching careers, while developing them as science teacher leaders. By increasing the number of highly qualified middle and high school science teachers, the program will help ease acute shortages in science teaching in Alabama and throughout the nation. LIST will increase the diversity of the teacher workforce by encouraging the participation of Fellows from underrepresented minority groups. Teaching Fellows will benefit from working relationships already established with high-need local educational agencies. A 4-year intensive induction program will sustain the project's Teaching Fellows as they develop science teaching expertise and ability to engage diverse students.

This Noyce Teaching Fellowship Track 2 project will be a partnership between University of Alabama Tuscaloosa, two high-need Alabama local educational agencies (LEAs), the nonprofit Texas STEM Coalition (T-STEM), and the Alabama Math, Science, and Technology Initiative (AMSTI/ASIM). The project will develop and implement a model to increase the number and diversity of STEM professionals in biology, chemistry, or physics as certified secondary science teachers in high-need school districts. Teaching Fellows will participate in a strong clinically-based program developing skills in engaging diverse students. The program will have a long-term focus on moving teachers from mentored novices to teacher leaders. The project's timeline will begin in Year 1 with preservice coursework, ending with graduation and teacher certification in an Master of Arts (MA) program. A 4-year induction program will follow in LEAs. LIST has four major goals with objectives addressing high-need LEAs including: 1) increasing the number and diversity of certified science teachers, 2) developing preservice teacher expertise through intensive clinical field experiences, 3) mentoring through collaborative strategies supporting and sustaining Fellows through an evolving induction program, and 4) fostering Fellows' leadership skills. LIST will actively recruit STEM professionals from university science graduates, local communities surrounding a coalition of 12 community colleges, campus student professional organizations, and social/local media outreach. The LIST model will provide a multistage transformative approach incrementally moving STEM professionals to teacher leaders. The model will be disseminated for use by other teacher preparation programs to increase the quality of science teachers and their students' depth of learning. The LIST model will demonstrate the use and upgrading of existing infrastructure to enhance research-based science teacher education.

This award is supported by the Major Research Instrumentation and the Chemistry Research Instrumentation programs. Professor Elizabeth Papish from University of Alabama Tuscaloosa and colleagues Kevin Shaughnessy, Paul Rupar, Jack Dunkle and Jared Allred have acquired a dual source single crystal diffractometer equipped with a high resolution detector. In general, an X-ray diffractometer allows accurate and precise measurements of the full three-dimensional structure of a molecule, including bond distances and angles, and provides accurate information about the spatial arrangement of a molecule relative to neighboring molecules. The studies described here impact many areas, including organic and inorganic chemistry, materials chemistry and biochemistry. This instrument is an integral part of teaching as well as research and research training of graduate and undergraduate students in chemistry and biochemistry at this institution. Students are involved in chemical and protein research. The resource is also utilized by several neighboring primarily undergraduate institutions and historically black colleges and universities (HBCUs).

The award of the diffractometer is aimed at enhancing research and education at all levels. It especially impacts the characterization of solid materials and new polymers to harness solar energy and studies of diffuse X-ray scattering to determine how local changes in structure lead to macroscopic properties. The instrumentation is also used for studies following the syntheses of monodisperse small nanomolecules and the design of catalysts for carbon dioxide reduction and cross-coupling. The diffractometer benefits studies of biological macromolecules to understand gene expression and antibiotic resistance.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.