» Maye Research Group		Mathew M. Maye  Assistant Professor Inorganic chemistry, materials science, biomaterials, energy conversion, nanotechnology, catalysis, self-assembly mmmaye@syr.edu phone: 315-443-2146 / fax: 315-443-4070 Office: CST 4-014D Education: • B.S., 2001, SUNY-Binghamton • Ph.D., 2005, SUNY-Binghamton • Goldhaber Fellow, 2005-2008, Brookhaven National Laboratory Honors & Awards: • DoD PECASE, Sponsored by the Air Force Office of Scientific   Research (AFOSR) • ACS-PRF New Investigator Award 2011 • DOE Gordon Battelle Prize 2011 • Goldhaber Distinguished Fellowship, 2005-2008, Brookhaven   National Laboratory • NDSEG Graduate Fellowship, 2002-2005, Sponsored by Army   Research Office (ARO) • MRS Graduate Student Gold Award, 2002 Courses: • CHE 116: General Chemistry • CHE 411/611: Inorganic Chemistry • CHE 600: Engineered Nanomaterials and Biomaterials in Energy    Conversion • CHE 616: Solid State Chemistry

Research Interests Our group's background in inorganic chemistry, catalysis, materials science, and biotechnology allows for a unique perspective on the current limitations in energy conversion/storage and national security capabilities. The underlying technologies of these energy and sensor applications are very similar, and depend on the precision of which interfaces are constructed, accessible surface areas and reaction sites, as well as high fidelity microstructure control of packaging. These technologies can benefit from the integration and optimization of materials based on inorganic nanoparticles for lighter, cleaner, and more efficient energy conversion processes, increased sensitivities of chemical and biological sensors, and self-healing interfaces and processes. These nanomaterials posses a unique set of conditions that enable the tuning of optoelectronic properties and catalytic activity. First, each nanoparticle has a size around 1-10 nanometers, where each nanometer is one billionth of a meter. This allows each particle to posses a set, "quantized", number of atoms, each of which bring with it a set number of electrons, and orbitals. Second, this collection of atoms are confined to a 'box' which is only a few nanomaterials, which further adjusts the energy levels, pushing them to higher energies. This allows for the tuning of optical and electrical characteristics, such as light absorption and emission in quantum dots (see below). Third, each nanoparticle posses a high percentage of it’s atoms at the particle surface, leading to poor coordination, and "dangling" bonds. Moreover, these surface atoms are often packed in high-energy configurations, such as corners and edges (see image). It is at these high energy surfaces in which heterogeneous catalysis takes place, such as that found in a fuel cell. Taken together, the tuning of energy levels by quantization and confinement lead to novel optical and electronic properties of nanomaterials, while their energetic surfaces allow for novel catalysis to take place with higher efficiency and stability. Synthesis & Fabrication: The synthesis of these nanomaterials is an interesting combination of wet-chemical synthesis and materials "solid-state" processing. For example, we employ methods that are similar to organic synthesis, but add in components such as high temperature processing, annealing, nucleation and growth, and quenching. Thus, in our studies, "nanofabrication" takes place not in expensive clean rooms or fabrication facilities, but instead in a beaker, schlenk line, and glove box. There, we utilize air-free inorganic and materials chemistry to carry out the synthesis of a number of nanoparticles, including semiconductive quantum dots. As mentioned above, the energies with nanoparticles are controlled by size. This is perhaps best shown by the light absorption and emission properties of CdSe quantum dots (see image). In addition to the metallic, or semiconductive solid cores, these nanoparticles also posses a ligand "shell" that surrounds and protects the particle. This ligand shell can be functionalized, and undergo classical chemical reactions. In addition, these ligands and their functionality can be used as anchor sites to attach additional nanoparticles, or biomaterials for self-assembly studies, as described next. Biomimetic Assembly: Nature has given us a tremendous example of the potential to self-assemble an organized hierarchy of autonomous nano- and micro-components. These components posses functional; structure, reaction centers, and molecular recognition sites that signal and transduce all biochemical processes. This includes highly efficient energy transfer, ion transport, information storage, replication, and self-healing. Each of these natural biological and biochemical processes can be considered the ultimate state of the art, and a model for non-biological systems. One of our research pursuits is to impart our nanoparticles with these types of properties. Thus, we attempt to "mimic" these systems using inorganic nanomaterials that have their interfaces modified with both native and synthetic biomaterials. One interesting question to ask is: If coated with a particular biomaterial, can a nanoparticle take the properties of the biomaterial? That is to say, can we start to self-assemble our synthesized nanomaterials into structures that mimic cells, membranes, or DNA? And if so, will our abiotic materials have similar functionality as their biotic analogues? In order to do this however, requires multiple surface chemistry steps, as well as purification processes. However, when successful a number of "biomimetic" processes emerge, such as those discussed next. Energy Transfer: These nanomaterials also have the propensity for energy transfer. To explore this phenomenon, we are currently interested in a number of fundamental studies. The first, is to employ quantum dots in novel Fluorescence (Forster) Resonance Energy Transfer (FRET). In FRET, an excited electron in a donor (D*) will transfer non-radiatively to an acceptor (A) due to virbrational overlap accompanying their coupled dipole-dipole interaction (through-space), which is enhanced during excitation. The transferred 'energy' (D*+A→A*+D) is then radiatively released from the excited A (A*), revealing emission (F) at lower energy. In our systems, the quantum dots are employed as both Donors & Acceptors, as well as in conjunction with molecular fluorophores. An interesting case emerges when D-to-A distances are tuned. The ability to tune these distances (r) however is often limited by synthetic chemistry. If however, the r is defined by the structural tunability of a biomaterial, then the systems become very interesting. The second use of these quantum dots is to employ their light harvesting (absorbing) properties for future, third-generation, photovoltaic applications. These photovoltaics have the potential for decreased manufacture cost, higher conversion efficiencies, flexibility, and incorporate molecules and nanomaterials for current generation. One such "solar cell" is that of dye sensitized solar cells (DSSCs), which utilize molecular dye to absorb light, generating an excited electron, which is then transported to a semiconductive surface. In our systems, the quantum dot serves as the dye, and a metal oxide, such as titanium dioxide, is used to rectify electron transport. The advantage here is that the quantum dot above can be synthesized to absorb different wavelengths of light, as described above, allowing for more solar radiation to be converted to electricity. This project is in its infancy, however we are currently progressing in the preparation of all the necessary nanomaterials, with construction of a cell to begin soon.

Selected Publications R. Alam, M.M. Maye* "Asymmetric Quantum Dot Growth via Temperature Cycling" Inorganica Chimica Acta 2011 (Accepted) H. Han, J. Zylstra, M.M. Maye* "Direct Attachment of Oligonucleotides to Quantum Dot Interfaces" Chem. Mater. 2011 (In-Press) (» full article) P.N. Njoki, L. Solomon, W. Wu, R. Alam, M.M. Maye* "Attenuating Surface Plasmon Resonance using Core/Alloy Architectures" Chem. Commun. 2011 (In-Press, 10.1039/c1cc12596f.) (» full article) W. Wu, P.N. Njoki, H. Han, H. Zhao, E. A. Schiff, P. S. Lutz, L. Solomon, S. Matthews, M. M. Maye* "Processing Core/Alloy/Shell Nanoparticles: Tunable Optical Properties and Evidence for Self-Limiting Alloy Growth" J. Phys. Chem. C, 2011, 115, 9933–9942. (» full article) P.N. Njoki, W. Wu, H. Zhao, L. Hutter, E. A. Schiff, M.M. Maye* "Layer-by-Layer Processing and Optical Properties of Core/Alloy Nanostructures" J. Am. Chem. Soc., 2011, 133, 5224–5227(Communication). (» full article) J. Zylstra, J. Amey, N. J. Miska, L. Pang, C. R. Hine, J. Langer, R. P. Doyle, M. M. Maye* "A Modular Phase Transfer and Ligand Exchange Protocol for Quantum Dots" Langmuir, 2011, 27, 4371–4379. (» full article) C. M. Alexander, M. M. Maye*, J. C. Dabrowiak* "DNA-capped nanoparticles designed for doxorubicin drug delivery" Chem. Commun., 2011, 47, 3418-3420. (» full article) A. L. Stadler, D. Sun, M. M. Maye, D. van der Lelie, O. Gang "Site-Selective Binding of Nanoparticles to Double-Stranded DNA via Peptide Nucleic Acid 'Invasion'" ACS Nano, 2011, 5, 2467–2474. (» full article) H. Han, G. Di Francesco, M. M. Maye* "Size Control and Photophysical Properties of Quantum Dots Prepared via a Novel Tunable Hydrothermal Route" J. Phys. Chem. C, 2010, 114, 19270–19277. (» full article) M.M. Maye, M. Cotlet, O. Gang "Photoluminescence enhancement in CdSe/ZnS-DNA linked-Au nanoparticle heterodimers probed by single molecule spectroscopy" Chem. Commun. 2010, 33, 6111-6113. (» full article) H. Han; G.N. Di Francesco, A. Sexton; A. Tretiak, M.M. Maye* Mater. Res. Soc. Symp. Proc. Vol. 1220, 2010, 12220-BB03-02. M.M. Maye, M.T. Kumara, D. Nykypanchuk, W.B. Sherman, O. Gang "Switching Binary States of Nanoparticle Superlattices and Dimer Clusters by DNA Strands" Nature Nanotechnology, 2010, 5, 116-120. (» full article) M. M. Maye, D. Nykypanchuk, D. van der Lelie, O. Gang "Stepwise Surface Encoding for High-Throughput Assembly of Nanoclusters" Nature Materials, 2009, 8, 388-391. (» News & Views) (» full article) D. Nykypanchuck*, M. M. Maye*, D. van der Lelie, O. Gang, "DNA Guided Crystalline Organization of Nanoparticles" Nature, 2008, 451, 549-552. (» co-COVER ARTICLE) (» News & Views) (» Editors Favorite-2008) (» full article) M. M. Maye, M. T. Kumara, D. Nykypanchuk, W. B. Sherman, O. Gang 2009, (submitted) M. M. Maye, P. Freimuth, O. Gang, "Adenovirus Knob Trimers as Tailorable Scaffolds for Nanoparticle Assembly" Small, 2008, 4, 1941-1944. (» full article) M. M. Maye*, D. Nykypanchuck*, D. van der Lelie, O. Gang, "DNA-regulated micro- and nano-particle assembly" Small, 2007, 3, 1678 – 1682. (» full article) M. M. Maye, D. Nykypanchuck, D. van der Lelie, O. Gang, "A Simple Method for Kinetic Control of DNA-Induced Nanoparticle Assembly" J. Am. Chem. Soc., 2006, 128, 14020-14021. (» full article) M. M. Maye, I-I. S. Lim, J. Luo, Z. Rab, D. Rabinovich, T. Liu, C.J. Zhong, "Mediator-Template Assembly of Nanoparticles" J. Am. Chem. Soc., 2005, 127, 1519-1529. (» full article) I.I. S. Lim, M. M. Maye, J. Luo, C. J. Zhong, "An Assessment of the Thermodynamic Driving Force for the Mediator-Template Assembly of Nanoparticles" J. Phys. Chem. B., 2005, 109, 2578-2583. (» full article) M. M. Maye, J. Luo, I-I. S. Lim, L. Han, N. N. Kariuki, D. Rabinovich, T. Liu, C.J. Zhong, "Size-Controlled Assembly of Gold Nanoparticles Induced by a Tridentate Thioether Ligand" J. Am. Chem. Soc., 2003, 125, 9906-9907. (» full article) M. M. Maye, J. Luo, Y. Lin, M. H. Engelhard, M. Hepel, C. J. Zhong, "X-Ray Photoelectron Spectroscopic Study of the Activation of Molecularly-Linked Gold Nanoparticle Catalysts" Langmuir, 2003, 19, 125-131. (» full article) M. M. Maye, S.C. Chun, L. Han, D, Rabinovich, C.J. Zhong, "Novel Spherical Assembly of Gold Nanoparticles Mediated by a Tetradentate Thioether" J. Amer. Chem. Soc., 2002, 124, 4958-4959. (» full article)