Elena Galoppini - US grants

Professor Elena Galoppini, Department of Chemistry, Rutgers University at Newark is supported by the Organic and Macromolecular Program of the Chemistry Division under a Research Planning Grant to establish a synthetic methodology leading to novel organic cage molecules. Derivatives prepared from commercially available adamantanes and tetraphenylmethanes are coupled to achieve robust, rigid cages with internal cavities ranging from 18 to 28 angstroms in diameter. Professor Galoppini presents a clever approach to the synthesis of organic cage structures that possess the rigidity needed to serve as moduli for the synthesis of extended, porous, supramolecular organic networks. A Research Planning Grant at this stage in Professor Galoppini's career offers a means to exploit the chemistry, and develop the methodology needed for an NSF research proposal in a very competitive area. Porous organic materials of tailorable architecture are an attractive complement to currently available porous, inorganic materials. The synthesis of such materials, however, rests on building blocks of sufficient rigidity to support an extended three dimensional array of the individual units. A synthetic methodology using commercially available reagents will be developed to afford a series of rigid organic cages that will serve as building blocks. Three dimensional materials will be assembled with tailorable porosities to allow the diffusion and encapsulation of different reagents.

This POWRE award by the Chemistry Division will support Dr. Elena Galoppini in establishing a collaboration with professor Gerald Meyer of Johns Hopkins to synthesize a new class of coordination compounds and use them to study the dynamics of electron injection at the interface of Titantium Dioxide nanoparticles. The results obtained are expected to contribute to better understanding of the photophysics of semiconducting nanoparticles and dye-sensitized regenerative solar cells as well as contribute to knowledge of the materials chemistry of polymeric light emitting diodes, sensors and other information storage devices.

Both graduate and undergraduate students will receive interdisciplinary training in both organic synthesis and photophysical and photoelectrochemical methods for study of semiconductors and Dr. Galoppini will integrate the subject matter into an undergraduate course. This award will permit Dr. Galoppini to access new techniques and facilities such as surface attachment of complexes, preparation of sol-gel Titantium Dioxide films and electrochemical cells, steady state and time-resolved spectroscopic studies, etc. and to implement them at her home institution.

This award from the Major Research Instrumentation (MRI) Program will enable the Chemistry Department at Rutgers University in Newark to acquire a suite of instruments for research in materials chemistry: a gel permeation chromatograph (GPC), simultaneous static and dynamic light scattering (SSDLS) instrumentation and a voltammetric analyzer. The GPC and light-scattering instrument will be used to determine molecular weights of polymers, and the voltammetric analyzer will be used to study the electrochemical properties of novel metal-containing polymers and to make critical electrochemical measurements for organic materials.

Dynamic light scattering experiments allow one to determine the sizes and shapes of inorganic nanoparticles, and of self-assembled polymer superstructures, whereas the voltammetric analyzer is a critical tool when designing nanomolecular devices. These instruments are essential for materials characterization.

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.

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.

Dye-sensitized solar cells (DSSC) are a very promising technology for low-cost conversion of solar energy to electricity. The device has three essential components: a wide-bandgap semiconductor (nanocrystalline TiO2) film deposited on a transparent conducting glass electrode and coated with a dye; a platinized counterelectrode; and an electrolyte solution containing the iodide/triiodide redox couple. However, cell efficiencies have been limited due largely to the high electrochemical overpotential (about 0.5 V) needed to drive the critical dye regeneration reaction, where iodide reduces an oxidized dye molecule bound to a TiO2 nanoparticle, yielding triiodide and the uncharged dye as products. The PIs, Professors Alex Agrios of the University of Connecticut, Storrs, CT, and Elena Galoppini of Rutgers University, Newark, NJ, propose to attach catalytic Pt nanoparticles to the dye molecules anchored to the TiO2 surfaces. They hypothesize that Pt bound to the dye molecule can catalyze dye regeneration, routing the reaction through less energetic intermediates and greatly reducing the overpotential required between oxidized dye and iodide. This work will employ catalysis to remove a longstanding limitation on the energy conversion efficiency of low-cost dye-sensitized solar cells.

This collaborative EAGER proposal covers experiments to carry out the initial syntheses and experiments to test the main hypothesis to demonstrate the possibility of nanocatalysts to improve DSSC solar energy conversion efficiency. About half of the electrochemical energy of each electron hole pair is lost due to energy losses in the electrochemical processes driving the cell. It is generally acknowledged that the next breakthrough in DSSC research will be the recovery of this lost energy. The significance of this work will be both practical and fundamental, with the concept of molecularly anchored nanocatalysts having potential implications in diverse fields.

The Chemical Structure, Dynamics and Mechanisms Program supports collaborative research between Professor Robert Bartynski of Rutgers University at New Brunswick and Professor Elena Galoppini at Rutgers University at Newark on the synthesis and characterization of tunable linker dipoles for improved solar energy conversion devices. This research, which brings together a synthetic chemist and a surface physicist, aims to achieve precise control of the electronic properties of the interface between an organic molecule and a semiconductor by tailoring the properties of the organic overlayer at the molecular level. Ultimately, this work will enhance the fundamental understanding and performance of organic-inorganic and organic-organic hybrid materials that are used in a wide variety of application areas including molecular electronics and photovoltaics. By molecular design of a variety of functional organic compounds, the research team will modify molecular energy levels (HOMO-LUMO) alignment, tune the donation and withdrawal of charge, and influence molecule bonding geometries at organic molecule/semiconductor interfaces. This will be accomplished using compounds with a Head-Linker-Anchor (HLA) configuration bound to metal oxide (TiO2 and ZnO) or organic (rubrene) semiconductor surfaces. The head groups (H) will be either organic chromophores or electron donor or acceptor groups, and the linker units (L) will contain an internal molecular dipole. The rigid linkers will be designed to bind at a well-defined orientation and distance from the semiconducting organic or inorganic surfaces. The electronic structure, dye-oxide energy level alignment, binding geometry, and effects of intermolecular interactions of HLA compounds on semiconductor substrates will be studied using a wide array, state-of-the-art ultrahigh vacuum-based surface characterization techniques. Spectroscopic and electrochemical measurements will complement the surface studies.

The broader impact of this research, derived mainly from molecular level control of the organic/semiconductor interface, will touch many areas of science and technology including photocatalytic materials, photovoltaics, light-emitting diodes, and other devices. The educational component of the program will generate two innovative research modules where students gain hands-on experience that will solidify the connection between basic scientific research and technological advances that benefit society. Students will build simple solar cells based on molecules similar to those used in this research, but found in everyday items. The modules are easily adaptable for undergraduate laboratories at the two Rutgers campuses, and for demonstrations that will involve K-12 students. These activities will target underrepresented groups including high-school students from the Newark urban area. Student exchanges and co-advising of Ph.D. theses are integral to the program and the interdisciplinary collaboration between a synthetic chemist and a physicist will broaden the scientific education and training of the students from both laboratories.

With this award from the Major Research Instrumentation (MRI) and support from the Chemistry Research Instrumentation and Facilities (CRIF) Programs Professor John Sheridan from Rutgers Universvity Newark and colleagues Frank Jordan, Elena Galoppini, Frieder Jaekle and Darren Hansen will aquire a 500 MHz NMR spectrometer. The proposal is aimed at enhancing research training and education at all levels, especially in areas such as (a) development of functional conjugated macrocycles and polymers for optoelectronic applications and synthesis of chiral Lewis pairs for small molecule activation; (b) investigation of stimuli-responsive metal-containing polymers; (c) synthesis of functional molecules for dye-sensitized solar cells (DSSCs), host-guest complexes, and biosensors; (d) development of sustainable polymers from renewable resources; (e) investigation of thiamin diphosphate (ThDP)-dependent enzymes as well as synthesis of labeled coenzymes, substrate analogues and inhibitors; and (f) mechanistic studies on quinolone quorum sensing.


Nuclear Magnetic Resonance (NMR) spectroscopy is one of the most powerful tools available to chemists for the elucidation of the structure of molecules. It is used to identify unknown substances, to characterize specific arrangements of atoms within molecules, and to study the dynamics of interactions between molecules in solution. Access to state-of-the-art NMR spectrometers is essential to chemists who are carrying out frontier research. The results from these NMR studies will have an impact in synthetic organic/inorganic chemistry, materials chemistry and biochemistry. Many research projects associated with this application will have a direct impact on society, as they aim to develop polymers fo optoelectronics, metal containing polymers, materials for solar cells, and investigations of enzyme inhibitors and bio-sensing. This instrument will be an integral part of teaching as well as research at Rutgers University Newark.

1264508(Lu) The goal of the proposed research is to perform in-depth scientific understanding of surface and interface chemistry of nanostructured ZnO and MgZnO and biomolecules in order to design and develop the innovative surface functionalization at the molecular level to enable a new generation of biosensors with ultra-high sensitivity and selectivity, and multi-modal operation. This multidisciplinary research will include MOCVD growth of ZnO and MgZnO nanostructures with controlled dimension and morphology, design and experiments of chemical binding of molecular linker layers, comprehensive characterization of the ZnO/organic molecule interfaces, and implementation of the functionalization technology for sensing applications. The main approach includes (i) synthesis of highly ordered ZnO and MgZnO nanostructures with controlled dimension, morphologies, and surface wettability; (ii) Study of the photophysical and chemical properties between these nanostructures and the molecular linker layers designed by using the probe chromophores to achieve unprecedented understanding of the interfacial chemistry, and (iii) Implementation of the interfacial chemistry to design and develop the surface functionalization technology for application in the ZnO nanostructure-based biosensors.

General public statement:
This project will study how molecules important in sensor development, for example antibodies or enzymes, may be immobilized on nanomaterials. Ensuring that biomolecules function well after immobilization is critical to the successful development of biosensors and this proposal will develop new immobilization strategies.

Collaborative Research: Dye Molecule-Anchored Platinum Nanocatalysts

One of the most intensely studied systems for low-cost solar energy conversion is the dye-sensitized solar cell (DSSC), in which a dye molecule attached to a nanoparticulate semiconductor absorbs sunlight and injects an electron into the semiconductor. The electron can be extracted and used for electrical power, but before the dye can repeat the cycle, its electron must be replaced by reaction with a dissolved redox couple. One option for this redox couple combines iodide and triiodide ions, both of which are extremely cheap and abundant. The iodide/triiodide couple is nearly ideal for this purpose but for one problem: electrons lose a significant amount of energy while transferring from these ions to the dye. This project aims to reduce that energy loss by positioning a nano-sized catalyst precisely at the site where the dye reacts with the iodide/triiodide. The award is for a collaboration between Prof. Alexander G. Agrios at the University of Connecticut, providing expertise in nanoparticle synthesis and DSSC device fabrication and measurement, and Prof. Elena Galoppini at Rutgers University?Newark, for the synthesis expertise, and is derived from a previous EAGER award to the investigators. The work has the potential to increase the solar power conversion efficiency of the DSSC by as much as 50% while retaining the cheap redox couple. In addition, the concept of tethering catalytic metal nanoparticles directly to the site of an electrochemical reaction using molecular design can be applied to other kinds of renewable energy projects, such as photocatalytic systems. The research will be coupled to outreach efforts in which solar cells will be used as a teaching tool in K?12 education to explain concepts of chemistry, engineering and energy and to excite and inspire the next generation of STEM students and researchers. These activities will target underrepresented groups including high-school students from the Newark urban area, also through the ACS project SEED program.

This project makes use of specially made dye molecules with two different attachment groups on opposite sides of the molecule. One group (a carboxylic acid) attaches to the surface of metal oxides such as titanium dioxide (TiO2). The other group (a thiolane) attaches to certain metals, and will be used here to anchor platinum nanoparticles (Pt NPs). The project has three main intellectual components. First, fabricating the TiO2-dye-catalyst assembly will require (a) preparing the desired Pt NPs, (b) synthesizing the specialized dye molecule, and (c) assembling the components to give the desired structure. Second, groups capable of ?molecular rectification? will be incorporated into the dye at its point of connection to the Pt NP to ensure that electrons transfer from the Pt NP to the dye, as desired, and not in the reverse direction, which would short-circuit the device and reduce its solar power conversion efficiency. Third, electron energy levels in the dye molecule will be tuned by structural modification to the values that will give rapid electron transfer in the desired direction with minimal energy loss.

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.

Professors Robert Bartynski and Sylvie Rangan of Rutgers University New Brunswick and Professor Elena Galoppini of Rutgers University Newark are supported by the Macromolecular, Supramolecular and Nanochemistry (MSN) Program in the Division of Chemistry of the National Science Foundation to develop new methods for the creation of carbon-based two-dimensional materials on metal surfaces. Ordered arrays of custom designed molecular building blocks are assembled on single crystal surfaces then subjected to an external stimulus, such as heat, light, or energetic electrons, to link together neighboring molecules creating an extended two-dimensional sheet material. The topology and functionality of the sheet are controlled by judicious selection and placement of the chemical building blocks prior to exposure to the external stimulus. The resulting sheets hold the promise of displaying a wide variety of novel properties and phenomena such as new forms of magnetism, conduction of electricity with little or no resistance, and efficient emission or absorption of light. Success of this research project opens the way to new applications of two-dimensional materials in nano-electronics, sensors, solar cells, light-emitting diodes, and other devices that require processability, tunability, high performance, and properties that cannot be obtained with conventional materials. During the course of conducting the project, the students involved are broadly trained in a multidisciplinary science research environment and provided a chance to interact with scientists in national laboratories. Undergraduate students from under-represented minority groups are involved in the project and high school students and teachers are mentored.

The project generates a "toolbox" for on-surface synthesis of two-dimensional (2D) materials. Different bonding mechanisms that are relevant to on-surface synthesis are explored and ways to create a hierarchy of surface reactions to direct the formation of intermolecular C-C bonds between molecular units to create new 2D organic systems are developed. The toolbox involves (a) the development of specially designed molecular precursors with functional groups placed at strategic positions, (b) the use of inter-molecular and/or intra-molecular interactions between functional groups, as well as surface templating effects on textured metals, to control the assembly of the molecular precursors on single crystal surfaces. A particular emphasis is placed on the formation of C-C bonds by dehydrogenation (elimination of H2), dehalogenation (elimination of X2, X = Br, Cl, I) and dehydrofluorination (elimination of HF) reactions. The nature of the resulting 2D structures are studied through an integrated combination of surface science techniques, including scanning tunneling microscopy, and the electronic properties are examined through a combination of synchrotron-based electron spectroscopies, direct and inverse photoemission as well as ab-initio theoretical methods

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.

This award is jointly supported by the Major Research Instrumentation and the Chemistry Research Instrumentation Programs. Rutgers University – Newark is acquiring a high-resolution mass spectrometer (HRMS) equipped with electrospray Ionization (ESI), atmospheric pressure chemical ionization (APCI), and Direct Analysis in Real Time (DART) to support the research of Professor Frieder Jaekle and colleagues Elena Galoppini, Haesun Kim, Michal Szostak, and Colin Kinz-Thompson. This instrument facilitates research in the areas of organic chemistry, catalysis, semiconductors, inorganic chemistry, biochemistry, and biological sciences. In general, mass spectrometry (MS) is one of the key analytical methods used to identify and characterize small quantities of chemical species embedded in complex samples. In a typical experiment, the components are heated and flow into a mass spectrometer where they are ionized. The ions' masses are measured very accurately. The capabilities of the mass spectrometer instrument are augmented by complementary ESI and ambient pressure APCI and DART sources and will serve a wide host of research needs. The acquisition strengthens the research infrastructure at the University and regional area. This instrument enhances the educational, research, and teaching efforts of students at all levels in many departments as well as provides accessibility for use at nearby institutions. The instrument gives students experience using vital instrumentation that they carry with them into their careers. The research groups using the instrument are also actively participate in multiple successful programs to aid recruiting from underrepresented groups. <br/><br/>The award of this mass spectrometer is aimed at enhancing research and education at all levels. The new instrument will serve as an important characterization tool for research that spans areas ranging from synthetic chemistry, catalysis, materials science to biophysical and biological sciences. research will be enabled in amide bond activation, cross-coupling and catalysis, organocatalysis and green synthesis, molecular electrocatalysts for energy conversion, chromophore-semiconductor interfaces, organoboranes in materials science and catalysis, bacterial chemosensing, choline transport in myelin-forming glial cells, lipid metabolism in brain health and disease, lysozyme-mediated bacterial cell-wall-processing, and biological sciences.<br/><br/>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.