Gary J. Blanchard - US grants

This research project, supported by the Analytical and Surface Chemistry Program, studies the dynamical behavior of tethered chromophores in self-assembled organic overlayers. Using steady state and ultrafast laser spectroscopic probes and the evolution of fluorescence from the chromophore, the reorientation dynamics of the tethered probe molecule will be examined as a function of its micro-environment. This information will be useful for the design of interfaces with highly specific properties. This study will provide the first dynamical information about these interesting and important material systems. %%% The molecular level organization and time-dependent behavior of molecules imbedded in organic overlayers is the subject of this research project. Using short time scale spectroscopic methods, the behavior of probe molecules in self-assembled monolayers will be examined. Information about the dynamics of these organic overlayers is essential to the eventual application of these materials in useful electronic devices.

9412354 Scranton The Departments of Chemical Engineering and Chemistry at Michigan State University will purchase FTIR equipment that will be dedicated to research in engineering. The equipment will be used for several research projects, including in particular, high-speed FTIR studies of cationic photopolymerizations, controlling polymer structure and morphology for photonic switching applications and structural characterization of a high performance organic interfacial system. ***

This research focuses on behavior of the solvent to understand nucleation, cluster formation, and solute-solvent structure in aqueous supersaturated sugar solutions and the relationship of these to crystal nucleation and growth. Fluorescent probes at very low concentrations will be utilized for this purpose. The "tailor-made" probes are to contain sugar moieties to ensure their participation in solute aggregation phenomena. Bulk nucleation experiments will be conducted with the fluorophores as probes of glucose and sucrose crystallization.

The dynamical behavior of interfacial systems is the subject of this research project at Michigan State University supported by the Analytical and Surface Chemistry Program. Ultrafast spectroscopic methods using interfacially bound fluorescent probe molecules are applied to the study of defect structure, motional freedom of molecules, permeability of solvent into the interface, and energy migration and dissipation in two classes of well characterized interfacial layers in this work. Self-assembled monolayers of alkanethiols on gold surfaces, and zirconium phosphonate multilayers synthesized on metal and dielectric substrates serve as the model systems for developing a molecular understanding of the dynamical properties of interfacial materials. This information is crucial to the use of these materials in a variety of important technologies, including molecular electronic devices and chromatographic separations. Molecular interfaces play important roles in a range of critical technologies, from catalysis to molecular electronic device fabrication. The work of this research project is devoted to developing a molecular level understanding of the dynamics of molecular interfaces using state-of-the-art fast spectroscopic methods. Information obtained from these studies is essential to the rational design and application of interfacial molecular layers.

Many of the breakthroughs in modern interdisciplinary science occur at interfaces between two phases of matter. Unfortunately, the undergraduate chemistry laboratory curriculum at many institutions offers little in the way of enhancing the student's understanding of interfaces. The MSU undergraduate curriculum offers a solid foundation in the traditional areas such as wet chemical quantitative analysis, instrumental analysis, a variety of spectroscopic measurements, chromatography and separations science and electrochemistry. At present, there is little opportunity for undergraduate students to gain experience in state of the art surface and interface science within the laboratory or course sequence at MSU. An archetypal interfacial system is used for these undergraduate experiments; alkanethiols on gold. These compounds easily form highly reproducible interfaces. The initial adsorption process for the monolayers is rapid and is dominated by Au-S interactions while longer term monolayer structural formation is mediated by aliphatic chain annealing. Students perform a suite of experiments to access these separate monolayer formation steps as well as the steady state properties of the monolayers. The first experiment monitors the growth of the monolayer in real time using a quartz crystal microbalance. This technique also allows for the direct measurement of the Gibbs energy of initial adsorption of alkanethiols onto gold and demonstrates graphically the reversible nature of this adsorption. The second experiment measures the layer thickness and extent of organization using FTIR and optical ellipsometry. To relate these experiments to physical properties of interfaces, students characterize the monolayers using the traditional interface methods of cyclic voltammetry and contact angle measurements. These experiments offer students an experience ranging from traditional characterization to state of the art monolayer spectroscopy on a single well-characterized chemical system.

The objective of this research project, carried out by Professor Gary Blanchard and his coworkers at Michigan State University, is to develop ways to control the density and distribution of reactive functional groups at interfaces. A synthetic approach using polymeric molecular layers is used to control the density and distribution of interface functionalities. Optical probes, including picosecond lifetime measurements, molecular reorientation and isomerization measurements, and surface second harmonic generation intensity and imaging measurements are used to characterize the synthesized interfaces. With the support of the Analytical and Surface Chemistry Program, the results of this research provide an enabling foundation for future understanding of the chemistry of structurally complex surfaces.

Synthesis and characterization of complex interfaces is the focus of this research project carried out with Analytical and Surface Chemistry Program support. Polymeric synthetic approaches coupled with state of the art optical characterization provides detailed fundamental information about the distribution, type, and density of chemical functionalities at these complex interfaces.

With support from the Major Research Instrumentation (MRI) Program, Marcos Dantus and colleagues in the Department of Chemistry at Michigan State University will develop phase-modulated ultrashort laser pulse technology for probing molecular dynamics, optical switches and materials, and coherent control of multiphoton microscopy. The investigators will develop the necessary technology for two unique systems based on ultrashort femtosecond (fs) pulses with pulse characterization methods with unparalleled sensitivity that is directly linked to active phase and amplitude compensation. System A will be an ultrabroad-bandwidth sub-9 fs laser that will require a specially modified amplitude and phase modulator setup that minimizes dispersion and compensates third and fourth order phase distortions. This source will be used to achieve unprecedented selective excitation of molecular probes, as required for functional imaging, for example, using coherent laser control methods developed at Michigan State University and elsewhere. System B will be an amplified sub-20 fs laser source using a two-dimensional pulse shaper to achieve single-shot nonlinear optical excitation spectra of novel materials and nonlinear chromophores over a broad bandwidth. This will use binary pulse shaping technology combined with a novel two-dimensional optical phase modulator. This development will enhance the speed and accuracy of nonlinear optical spectroscopy by orders of magnitude.

A number of interdisciplinary scientific projects linked to biophysics, telecommunications, and advanced materials, will benefit from the development of these systems.

Professor Gary Blanchard of Michigan State University is supported by the Analytical and Surface Chemistry program to construct and then optically characterize a set of monolayer and bilayer fluid interfaces. Hybrid lipid bilayer structures have been created and characterized for over a decade, however, there is still a great deal unknown regarding relationships between membrane composition and physical properties. The PI seeks to establish a linked set of time-resolved fluorescence spectroscopic and imaging measurements in order to extract information about the local environment and its dynamics via fluorescent probes. The optical approaches include epifluorescence microscopy, photobleaching experiments and two-photon fluorescence experiments. The work is being done in collaboration with Prof. Pawel Kryskinski of the Polish Academy of Sciences.

Control over rationally constructed mono- and bi-layer fluid interfaces will benefit biotechnology, biosensor development and efforts to make artificial cell mimicks. These experiments provide fundamental underpinnings for applications such as drug delivery and medical implants.

In this research supported by the NSF Chemistry Division, Analytical and Surface Chemistry Program and Office of International Science and Engineering, Blanchard (Michigan State University) and Marken (University of Bath, UK) research groups focus on studying photo-electrochemical processes at microphase liquid:liquid interfaces and at triple phase boundaries. Such structures offer a unique environment where excited molecules and reaction intermediates are in close proximity to both electrode surfaces and liquid:liquid interfaces. The goal in studying such systems lies in the critical role that these types of structure play in processes such as photosynthetic light harvesting. The project is divided into four main, interconnected parts: (A) the study of electrochemically or photo-electrochemically driven ion transfer processes using fluorescent probe anions, (B) the study and screening of simultaneous electron and ion transfer at liquid:liquid interfaces and triple phase boundaries, (C) the investigation of two-phase processes involving electron and ion transfer at selected interfaces, and (D) characterizing the local environment at liquid:liquid interfaces using fluorescent probe molecules for the purpose of understanding how the potential of the interface and flux of ions across the interface affects the local environment.

The larger purpose of this research program, beyond understanding photo-electrochemical dynamics at complex interphase systems, is to educate students at the cutting edge of multidisciplinary science. It is imperative that the United States train a diverse population of students to be globally competitive for careers in science. This research serves as an important vehicle in that effort. By fostering a synergistic relationship between the Blanchard (Michigan State University) and Marken (University of Bath UK) research groups, a multinational cohort of globally competitive scientists will be educated, directly benefiting both the United States and the United Kingdom. This project will facilitate the creation of a bilateral think tank and will foster the free exchange of ideas in a field of research and development that has direct impact on science at the interface between biosystems and energy conversion. The ideas and experiments developed in this collaborative study can help screen and identify new light harvesting processes, possibly mimicking natural processes, and therefore contribute to new energy harvesting/storage/management systems.

In this research supported by the Analytical and Surface Chemistry Program, the organization and dynamics of supported lipid bilayer films are investigated. Lipid bilayers are essential to life and supported bilayer structures are of critical importance in biosensing applications. These molecular layers have been studied widely but the connection between molecular interactions within these films and their macroscopic behavior remains to be established. Prof. Blanchard and his group at Michigan State University focus in this research on understanding the structure, dynamics and phase separation behavior in unilamellar vesicles and supported lipid bilayers as a function of layer composition and substrate chemical structure. The group evaluates, including with fluorescent probe molecules, the molecular interactions within model bilayers and between the bilayer and substrate that are responsible for bilayer organization and dynamics. A common thread to all of these efforts is the hypothesis that bilayer dynamics and organization are mediated by structural defect sites within the bilayers.

The larger purpose of this research program, beyond understanding lipid bilayer organization and dynamics, is to educate students at the cutting edge of interfacial science to train a globally competitive cohort of students that reflects the demographic of the Nation for careers in science. This research serves as a vehicle in that effort. Results from this work will form undergraduate research reports, MS theses, PhD dissertations and will be reported in the peer-reviewed literature. This research program is geared for participation by undergraduate and graduate students, and the PI's home institution is strongly supportive of the inclusion of undergraduates in research, ensuring early exposure to multidisciplinary science. The MSU Graduate Program in Chemistry and the Institution as a whole has a long-standing commitment to the inclusion of under-represented groups, and for the past seven years the Blanchard research group has been more than 50% female. The group has an ongoing International collaboration with Professor Pawel Krysiñski (University of Warsaw) that focuses on the use of biological and biomimetic interfaces for chemical sensing. The Krysiñski group expertise dovetails with the Blanchard group, and this collaboration enhances the breadth of both labs. Students from both groups work regularly in the collaborator labs, fostering a global scientific outlook for both US and Polish students and accelerating the movement of fundamental knowledge.

With this award from the Chemistry Research Instrumentation and Facilities: Multi-user (CRIF:MU) program, Professor John McCracken and colleagues Gary Blanchard, Robert Ofoli, Greg Swain and David Weliky from Michigan State University will acquire a series of components to build a rapid acquisition, picosecond fluorescence lifetime and anisotropy imaging system. The award will enhance research training and education at all levels, especially in areas of study such as (a) fluorescence lifetime and anisotropy imaging of lipid structures, (b) optical and electrochemical characterization of biomimetic nanostructured interfaces, (c) chemically modified electrodes for studies of graphene and thin carbon films, and (d) imaging of membrane perturbations induced by viral fusion peptides and proteins.

A rapid acquisition, picosecond fluorescence lifetime and anisotropy imaging system is important to the study of a broad range of structurally heterogeneous and fluid interfaces such as those in biological membranes. These experiments provide novel information on molecular motion and energy transfer, and specifically how these properties vary with the physical condition and chemical composition of the interface. This instrumentation will support not only research activities but also research training to graduate and undergraduate students at Michigan State University and nearby institutions such as Saginaw Valley State University. The instrument will also support international interactions with the University of Warsaw, University of Bath and Shaanxi Normal University as well as activities with local high school students.

Abstract
This proposal is for the construction of an instrument that will provide previously unobtainable information on the organization and dynamics of plasma membranes, biomimetic structures, and light harvesting proteins. The dissipation of energy within lipid bilayers and light harvesting proteins is not well understood but is thought to mediate the function of these two different classes of biomolecular systems. One of the broad biological issues this project addresses is the fundamental, molecular basis for the formation of lipid raft structures, and why such structures vary with the concentrations and identities of the bilayer constituents. Understanding the molecular structural basis for lipid raft organization requires that the viscoelastic properties and intermolecular interactions of the lipid bilayer constituents can be measured. The proposed instrumentation will allow for the measurement of molecular motion and thermal energy flow in biomolecular systems.
This project entails designing, constructing, and characterizing an instrument that will apply stimulated-emission spectroscopy to the study of structure and dynamics of biological membranes and proteins. The instrument will reveal how the lipid and protein components of the mammalian cell membrane interact to yield functional assemblies that are responsible for energy transduction, transmembrane transport, and molecular recognition. The instrument will characterize the lipid-lipid and lipid-protein interactions that control the fluidity of the lipid bilayer assembly and the flow of thermal energy between components that serves as the driving force for chemical reactions and molecular motion.
The instrument will employ tunable picosecond lasers in a two-color pump?probe detection scheme to examine vibrational energy-transfer and fast molecular-scale motions in bilayer membranes and light harvesting proteins. Such measurements have not been possible before. The detection system is phase-sensitive and shot-noise-limited to measure transmission changes of one part in 107. Because the reaction dynamics underlying the formation and decay of short-lived complexes in membranes are controlled by vibrationally activated barrier-crossing processes, the information obtained with the proposed instrument is crucial to reaching an understanding of the dynamics associated with spatially heterogeneous structures, including lipid rafts and proteins.
The creation of broadly accessible instrumentation that advances the state of the art in the measurement of lipid bilayer properties and dynamics will have a major impact on the MSU and regional scientific communities as well as on the global scientific community. The PI and co-PIs collaborate with faculty in a host of other MSU departments (e.g. Biochemistry and Molecular Biology, Food Safety and Toxicology, Cell and Molecular Biology, Microbiology and Molecular Genetics), faculty from nearby institutions (e.g. Saginaw Valley State University, Western Michigan University) and from international institutions (e.g. University of Warsaw (Poland), University of Bath (UK), National University of Singapore, and Shaanxi Normal University (PRC)). They also collaborate with Federal research organizations such as the US Army Engineer Research and Development Center in Champaign, IL.
Broadening inclusion of under-represented groups in science is critically important. Michigan State University has multiple programs in place to connect with under-represented groups at the high school (MSU High School Honors Science/Math/Engineering Program (HSHSP), ACS Project SEED), undergraduate (National Organization of Black Chemists and Chemical Engineers (NOBCChE), DREW/TAC Program), graduate (NOBCChE, MSU African-American, Latino(a)/Chicano(a), Asian/Pacific American, and Native American (ALANA) Program) and post-graduate levels (MSU sponsored minority post-doctoral fellowships). The PI and the co-PIs have collaborated with these programs on several levels and continue to strive to provide students from all groups with hands-on research opportunities and mentoring.