Piotr Piotrowiak - US grants

This award from the Chemistry Research Instrumentation and Facilities (CRIF) Program and the Major Research Instrumentation (MRI) Program will assist the Department of Chemistry at Rutgers University to acquire an Raman spectrometer and an Ar+ pumped mode-locked Ti:sapphire laser. This equipment will enhance research in a number of areas including the following: (1) monomolecular films at the air/water interface, (2) the ultrafast kinetic investigation of excited states and reactive species, (3) synthetic proteins as models, and (4) enzyme mechanisms. A laser can provide important information about chemical reactivity. Its use may enable breakthroughs in our understanding of the properties of reactivity and non-reactivity of molecules..

Elena Galoppini of Rutgers University at Newark, Gerald Meyer of Johns Hopkins University and Piotr Piotrowiak of Rutgers University at Newark, are supported by a NIRT grant (Nanoscience Interdisciplinary Research Teams) for their interdisciplinary effort to improve our fundamental understanding of electronic interactions at organic molecule-nanoparticle interfaces and to allow us to control them in a predictable manner. The research employs synthetic methodologies that allow control over the distance and orientation of surface bound organic molecules with respect to the nanoparticle surface. The materials that will be prepared will enable these researchers to probe long-standing fundamental questions concerning interfacial electronic interactions in molecular detail that was not previously possible. Experiments will be carried out in which the position of redox and photo-active organic compounds relative to a nanoparticle surface will be fixed to control and tune the interfacial electronic interactions through systematic molecular-level variation of surface-attached dyes and nanoparticle materials.

The preparation of assemblies of molecular components (supramolecular structures) that perform desired functions such as light harvesting antennas or fluorescent sensors is a significant long term research goal. This research will probe interfacial interactions between semiconductor nanoparticles and attached molecular species. The research will contribute to our fundamental understanding of electronic interactions occuring at the interfaces between semiconductor nanoparticles and attached molecular species in order that we might control them in a predictable manner. Graduate students, undergraduate students and postdocs will receive excellent training and research experiences in a forefront nanoscience research program.

With this award from the Chemistry Research Instrumentation and Facilities (CRIF) Program, the Department of Chemistry at Rutgers University in Newark will acquire a dual non-collinear optical parametric amplifier (NOPA) system for ultrafast electron transfer studies. This equipment will enhance research in the following areas: a) ultrafast long-distance electron injection in dye-sensitized solar cells; b) conformationally gated electron transfer in bio-mimetic peptide systems; c) ultrafast fragmentation reactions of carbenes; and d) photoinduced electron transfer in host-guest assemblies and at interfaces.

This instrumentation will be shared by faculty at the Newark and New Brunswick campuses of Rutgers University. Several of the projects have direct implications for the design of new hybrid solar energy conversion materials.

With support from the Chemistry Research Instrumentation and Facilities: Departmental Multi-User Instrumentation (CRIF:MU) Program, the Department of Chemistry at Rutgers University New Brunswick will acquire an X-ray diffractometer with CCD detector. This equipment will enhance research in a number of areas including studies on new multifunctional Lewis acids for applications in catalysis and materials chemistry, new electronically interesting oligomers and polymers, rigid organic linkers for electron injection in dye-sensitized solar cells, and enzymes as catalysts for the synthesis of chiral intermediates for pharmaceuticals. The new diffractometer will allow training a highly diverse student population in crystallographic methods at both the graduate (Ph.D.) and undergraduate levels. Efforts include development of a new module for an advanced undergraduate "Synthesis and Characterization" laboratory course to give students hands-on experience in structure determination. The X-ray diffractometer will also be used in established outreach programs at Rutgers-Newark (ACS SEED program and outreach to local high schools).

The X-ray diffractometer allows accurate and precise measurements of the full three dimensional structure of a molecule, including bond distances and angles, and it provides accurate information about the spatial arrangement of the molecule relative to the neighboring molecules. Such structural studies have a large impact in a number of areas, especially in the synthesis of important organic and inorganic chemicals and in understanding chemical interactions in polymers and biomolecules.

This award is funded under the American Recovery and Reinvestment Act of 2009 (Public Law 111-5).

With this award from the Major Research Instrumentation (MRI) program, Piotr Piotrowiak and his research group from Rutgers University - Newark will develop an ultrafast fluorescence microscope. The proposed microscope will combine ultrafast laser technology with non-linear optical detection to create images with sub-100 femtosecond resolution. The proposed microscope will be used to study nano- and micro-structured materials. The project will be carried out by a diverse group of young scientists, from high school students through the American Chemical Society's Project SEED Program, through post-doctoral scientists.

New kinds of microscopy techniques open up new avenues of research. The instrument developed with this award will allow scientists to study very fast physical processes in nano- and micro-structured materials. In this way, a deeper understanding of important processes in new materials will be developed more quickly. Too often, bulk measurements do not provide the answers that scientists need to understand the behavior of nano- and micro-structured materials, which can only be answered through microscopic measurements of isolated particles, defects, or structures. The research that is enabled by this technology is important in the fields of chemical sensing, catalysis, photovoltaic development and optoelectronics -- all cutting-edge technologies important to society. In addition, the researchers working with Prof. Piotrowiak will receive invaluable training in technology development, an important skill in today's workforce.

With this award from the Major Research Instrumentation (MRI) program, Piotr Piotrowiak and colleagues Elena Galoppini, Frieder Jaekle, Huixin He and Evert Elzinga from Rutgers University Newark will acquire a field emission scanning electron microscope (SEM) with energy dispersed X-ray spectrometer (EDS). The proposal is aimed at enhancing research, research training and education at all levels. The instrument will support research in a number of areas including studies of exciton and charge dynamics in semiconductor nanostructures and hybrid molecular/nanoparticle systems, investigation of geochemical processes at mineral-water interfaces that control the speciation of heavy metals, studies directed at a molecular-level understanding of interfacial electron transfer through the synthesis of 'sensitizer' dyes, the development of new synthetic chemistry of organoboron compounds and functional polymers with sub-micron structure, and the development of hybrid sensors based on nanotube-polymer interactions.

A scanning electron microscope (SEM) is one of the basic tools available for the characterization of materials. A beam of electrons scans the surface of a sample resulting in a microimage of the sample composition. The electron microscope can provide higher resolution and magnification than a microscope using light to probe the material. Characteristic X-rays are produced from interaction with atoms in the sample that when dispersed provide information on the elemental composition (EDS). This instrumentation will provide microscopy training and research opportunities to graduate and undergraduate students across many fields including chemistry, earth sciences and environmental science fields preparing them for the demands of the 21st century workforce in science and technology.

In this award, funded by the Chemical Structure, Dynamics and Mechanisms A (CSDM-A) Program of the Division of Chemistry, Professors Piotr Piotrowiak, Laura Fabris and Deirdre O'Connell of Rutgers University - Newark, their Japanese collaborators (funded by the Japan Society for the Promotion of Science) and Rutgers University graduate and undergraduate student researchers are conducting experiments to study the ways in which electronic and vibrational energy is transferred from small molecules and polymers to metallic nanoparticles. The results from these experiments are of fundamental interest to the physical chemistry and condensed matter physics communities. In addition, the development of a better understanding of these processes could lead to improved photonic devices. Graduate and undergraduate students working on this project will receive training in laser science, microscopy, materials synthesis and theory, while working with scientists from Japan.

Profs. Piotrowiak, Fabris and O'Connell will collaborate with Profs. Iyoda, Vacha and Fujii from Tokyo Institute of Technology. The US and Japanese research groups are conducting a multi-pronged research effort investigating the electronic and vibrational dynamics of molecules and semiconducting polymers in close proximity to nanostructured materials. The two groups will: (1) conduct experimental and theoretical studies aimed at developing a better understanding of molecular excited state dynamics at the plasmonic interface; (2) engineer these materials to maximize the desired radiative enhancement effects through the control of order, periodicity and alignment of the nanostructures and by optimizing the chemical interface between molecule and nanostructure. The US students involved in this project will work alongside Japanese researchers. Rutgers University - Newark is an urban university with a diverse student body. The US investigators will incorporate students from underrepresented groups in this international collaborative project.

This award is supported by the Major Research Instrumentation (MRI) and the Chemistry Research Instrumentation Programs. Professor Piotr Piotrowiak from Rutgers University Newark and colleagues Edward Castner, Elena Galoppini, Jenny Lockhard and Kevin Belfield (New Jersey Institute of Technology) are acquiring a pump-probe transient absorption and fluorescence upconversion spectrometer system. This is a laser based system which enables the study of a wide range of laser phenomena that address significant challenges of social, environmental and economic importance. Research topics focus on solar energy research, renewable energy and green chemistry, photovoltaic materials, and biomarkers linked to human health. The instrumentation strengthens research and training at three institutions: Rutgers-Newark, Rutgers-New Brunswick and the New Jersey Institute of Technology.

This pump-probe transient absorption and fluorescence upconversion spectrometer system enhances research and education at all levels. It serves researcher who are testing the interplay between electron transfer and vibrational cooling in extended donor-acceptor arrays as well as those seeking understanding of ionic liquids. Research probing the fundamental relationship between molecular structure and nonlinear optical properties of chromophores also utilize this instrument. The spectrometer system is used to look for surface modification strategies and synthetic tools to understand interfacial charge separation and electron transfer dynamics. Researchers carry out mechanistic studies on photocatalytic properties of hybrid materials to unify nanoscience, coordination chemistry and catalysis. The spectrometer is important in seeking to unravel terrestrial surface photogeochemistry in the Archaen period.