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Ilya Zharov ORGANIC, INORGANIC & MATERIALS CHEMISTRY Assistant Professor B.Sc. (Hons), Chelyabink State University, 1990 M.Sc., Technion – Israel Institute of Technology, 1994 Ph.D., University of Colorado at Boulder, 2000 Beckman Postdoctoral Fellow, University of Illinois at Urbana-Champaign, 2000-2003 Phone: (801) 587-9335 Office: 3416 HEB-S Email: i.zharov@utah.edu Research Group Publications

Activities & Awards

• NSF CAREER Award, 2007
• Dreyfus New Faculty Award 2003
• Beckman Foundation Postdoctoral Fellowship, 2000
• Link Foundation Graduate Fellowship, 1999

Research Interests

We are working in four main areas. The focus of the first area is on responsive inorganic nanopores. In particular, we work on the preparation and study of nanoporous colloidal materials. Synthetic colloidal crystals form via self-assembly of nanoscale-sized silica spheres into a close-packed face-centered cubic lattice and contain highly ordered arrays of three-dimensional interconnected pores 5-100 nm in size (Figure 1). We use nanoporous colloidal films, membranes and microfluidic channels for size-selective transport of drug molecules and biomacromolecules. Furthermore, we modify the surface of colloidal nanopores with organic moieties that can non-covalently interact with ions and molecules, and whose charge and shape respond to external stimuli, such as pH or light. As a result of the surface modification, we are able to control molecular transport through the colloidal nanopores, either by tuning the nature and strength of the non-covalent interactions or by changing the environmental conditions. Our research addresses fundamental problems of controlling molecular transport through nanoscale-sized artificial pores by their surface modification. Using colloidal crystals creates a new paradigm within the field of nanoporous materials because they (i) form through self-assembly, (ii) allow straightforward control of nanopore size in a broad range, (iii) possess exceptionally high molecular throughput, and (iv) offer a large variety of surface chemistries. Integrating nanoscale, functional organic molecules into the surface chemistry of colloidal materials will allow creating responsive nanoscale devices with a host of technological applications in drug delivery, separations and sensing.

Our work includes studying the mechanism of the colloidal membranes formation, preparing colloidal films on porous supports, investigating the role of defects in transport and controlling defect formation, improving mechanical strength of colloidal films and membranes, and preparing gold-coated colloidal materials. We develop and study the surface chemistry inside colloidal nanopores by introducing organic moieties onto the colloidal nanopore surface that can: (i) acquire charge by protonation/deprotonation, binding of ions, and oxidation; (ii) bind neutral molecules via non-covalent interactions; (iii) change conformation in response to temperature, pH, light, and binding. We study the transport of small molecules and biomacromolecules through unmodified and surface-modified colloidal membranes. By using films and membranes possessing well defined nanopores, we are able to quantitatively analyze the molecular transport rate as a function of pore size, surface modification and environmental conditions. These studies provide mechanistic insights and allow achieving a fine control of molecular transport through the nanopores.

More recently we became involved in the preparation of novel proton-conducting nanoporous membranes. We are working on designs of proton-conducting materials for fuel cells that are considered very promising for a broad array of applications. A key component of a fuel cell is the proton-conducting membrane that separates fuels while conducting protons from the anode to the cathode. We develop novel designs for proton-conducting membranes based on hybrid colloidal materials.

In the third research area we are working on two designs of modular macromolecular anti-cancer agents that will utilize boron neutron capture (BNC) as a cancer-fighting method. First, we prepare dendritic integrin antagonists. We are designing conjugates of synthetic integrin ligands with neutron capture functionality to allow highly selective targeting of the tumor neovasculature. Our modular approach, outlined in Figure 2, offers a high degree of structural flexibility and potential for rapid modification of each individual module. It simplifies the optimization of binding properties and bioavailability of the designed molecular antagonists without significant additional synthetic effort.

We are using monomeric avb3-selective integrin ligands as the targeting module and fluorescent dyes as the imaging module. At the moment we are focusing on the preparation of ester-baseddendrons carrying neutral, anionic and metal-coordinated carboranyl clusters. We plan to develop efficient convergent coupling strategies that will allow rapid conjugation of the designed dendritic modules into macromolecular agents. Synthesis of a macromolecular agent from the individual modules will require orthogonal protection of the functional groups to maximize yields of the desired product. In the future we will evaluate the affinity and specificity of the agents toward surface-immobilized integrins. Endothelial cell migration and proliferation assays will be used to evaluate the efficacy of the designed agents. Cellular localization/distribution will be evaluated by laser-scanning confocal microscopy. Functional testing of the pro-apoptotic activity of the macromolecular agents after neutron capture will be conducted at the Lujan Neutron Science Center at Los Alamos National Laboratory.

Secondly, we work on the preparation of nanoparticle BNC materials. In this design we use dye-impregnated silica nanoparticles carrying boron-containing polymer brushes on their surface, or silica nanoparticles containing boron atoms as a part of the nanoparticle oxide structure. Both types of nanoparticles are capped with integrin ligands. This design combines the advantages of the modular approach with the ability to introduce a larger number of boron atoms and additional ease of materials preparation.

Finally, we initiated a project dealing with the synthesis and investigation of molecular wires terminated with metal nanoparticles.

Selected Publications

• Smith, J. J.; Zharov, I. Preparation and Proton Conductivity of Self-Assembled Sulfonated Polymer-Modified Silica Colloidal Crystals. Chem. Mater. 2008, submitted.
• Brozek, E., Zharov, I. Internal Functionalization and Surface Modification of Vinylsilsesquioxane Nanoparticles. Chem. Mater. 2008, submitted.
• Bohaty, A.; Zharov, I. Nano-Frits: Free-Standing Nanoporous Colloidal Membranes. Langmuir 2008, being revised.
• Bohaty, A.; Zharov, I. Light-Gated Transport in Spiropyran-Modified Nanoporous Colloidal Films. J. Porous Mater. 2008, submitted.
• Schepelina, O.; Zharov, I. pH- and Ion-Responsive Colloidal Nanoporous Films Modified with Poly(2-(dimethylamino)ethyl methacrylate) Brushes. Polym. Prepr. 2008, submitted.
• Bohaty, A.; Zharov, I. Transport in Amine-Modified Suspended Colloidal Membranes. J. Mater. Chem. 2008, being revised.
• Schepelina, O.; Zharov, I. Poly(2-(dimethylamino)ethyl methacrylate)-Modified Nanoporous Colloidal Films with pH and Ion Response. Langmuir 2008, submitted.
• Smith, J. J.; Abbaraju, R, R.; Zharov, I. Proton Transport in Assemblies of Silica Colloidal Spheres. J. Mater. Chem. 2008, accepted for publication.
• Abelow, A. Zharov, I. Poly(L-alanine)-Modified Nanoporous Colloidal Films. Soft Matter 2008, accepted for publication.
• 12. Stoikov, I. I.; Ibragimova, D. S.; Shestakova, N. V.; Krivolapov, D. B.; Litvinov, I. A.; Antipin, I. S.; Konovalov, A. I.; Zharov, I. Regioselective Alkylation of the Lower Rim of the p-tert-butylthiacalix[4]arene by N-(p-nitrophenyl)-alpha-bromacetamide. Supramol. Chem. 2008, accepted for publication.
• Smith, J. J.; Zharov, I. Ion Transport in Sulfonated Nanoporous Colloidal Films. Langmuir 2008, 24, 2650-2654.
• 11. Stoikov, I. I.; Yushkova, E. A.; Zhukov, A. Y.; Zharov, I.; Antipin, I. S.; Konovalov, A. I. Solvent Extraction and Self-Assembly of Nanosized Aggregates of p-tert-Butyl Thiacalix[4]arenes Tetrasubstituted at the Lower Rim by Tertiary Amide Groups and Monocharged Metal Cations in the Organic Phase. Tetrahedron 2008, 64, 7489-7497.
• Stoikov, I. I.; Yushkova, E. A.; Zhukov, A. Y.; Zharov, I.; Antipin, I. S.; Konovalov, A. I. The Synthesis of p-tert-Butyl thiacalix[4]arenes Functionalized with Secondary Amide Groups at the Lower Rim and Their Extraction Properties and Self-Assembly into Nanoscale Aggregates. Tetrahedron 2008, 64, 7112-7121.
• Smith, J. J.; Zharov, I. Ion and Molecular Transport through Surface-Modified Silica Colloidal Crystals. In ACS Symposium Series 996: Nanoparticles: Synthesis, Stabilization, Passivation and Functionalization, Nagarajan, R, Hatton, T. A., Eds. American Chemical Society, Washington DC, 2008, Chapter 18, in press.
• Bohaty, A. K.; Cichelli, J.; Schepellina, O.; Zharov, I. Controlling Molecular Transport in Nanoporous Colloidal Systems. In Proceedings of the 5th International Symposium, Sayari, A.; Jaroniec, M., G. Eds. World Scientific, Singapore, 2008, p. 395-406.
• Schepelina, O.; Zharov, I. Poly(N-isopropyl acrylamide) Brushes Inside Opal Nanopores with Dual Temperature Response. Langmuir 2007, 23, 12704-12709.
• Cichelli, J.; Zharov, I. Chiral Permselectivity in Nanoporous Opal Films Surface-Modified with Chiral Selector Moieties. J. Mater. Chem., 2007, 17, 1870-1875 (journal cover).
• Schepelina, O.; Zharov, I. Poly(N-isopropylacrylamide)-modified Nanoporous Opals. Polym. Prepr. 2007, 48, 455-456.
• Mollard, A.; Zharov, I. Tricarboranyl Pentaerythritol-Based Building Block. Inorg. Chem. 2006, 45, 10172-10179.
• Wang, G.; Bohaty, A. K.; Zharov, I.; White, H. S. Photon-Gated Transport through a Single Artificial Nanopore. J. Am. Chem. Soc. 2006, 128, 13553-13558.
• Galie, K. M, Mollard, A.; Zharov, I. Polyester-Based Carborane-Containing Dendrons. Inorg. Chem. 2006, 45, 7815-7820.
• Schepelina, O.; Zharov, I. Polymer-Modified Opal Nanopores. Langmuir 2006, 22, 10523-10527.
• Cichelli, J.; Zharov, I. Chiral Selectivity in Surface-Modified Nanoporous Opal Films. J. Am. Chem. Soc. 2006, 128, 8130-8131.
• Zharov, I. Polymerization Inside Opal Nanopores. Polym. Prepr. 2006, 47, 918-919.
• Bohaty, A. K.; Zharov, I. Suspended Self-Assembled Opal Membranes. Langmuir 2006, 22, 5533-5536.
• Newton, M. R.; Bohaty, A. K.; Zhang, Y.; White, H. S.; Zharov, I. pH and Ionic Strength Controlled Permselectivity in Amine Modified Nanoporous Opal Films. Langmuir 2006, 22, 4429-4432 (journal cover).
• Newton, M. R.; Bohaty, A. K.; White, H. S.; Zharov, I. Chemically Modified Opals as Thin Permselective Nanoporous Membranes. J. Am. Chem. Soc. 2005, 127, 7268.
• Zimmerman S. C.; Wendland, M. S.; Rakow, N. A.; Zharov, I.; Suslik, K. S. Synthetic Hosts by Monomolecular Imprinting Inside Dendrimers. Nature 2002, 418, 399.
• Rotkin, S. V; Zharov, I. Nanotube Light-Controlled Electronic Switch. Int. J. Nanosci. 2002, 1, 347.
• Zharov, I.; Havlas, Z.; Orendt, A. M.; Barich, D. H.; Grant, D. M.; Michl, J. CB₁₁Me₁₁ Boronium Ylides: Carba-closo-dodecaboranes with a Naked Boron Vertex. J. Am. Chem. Soc. 2006, 128, 6089.
• Zharov, I.; King, B. T.; Havlas, Z.; Pardi, A.; Michl, J. Crystal Structure of n-Bu₃Sn⁺CB₁₁Me₁₂^-. J. Am. Chem. Soc. 2000, 122, 10253.
• Apeloig, Y.; Bravo-Zhivotovskii, D.; Zharov, I.; Panov, V.; Leigh, W. J.; Slugget, G. W. Thermal and Photochemical [2+2] Cycloreversion of a 1,2-Disilacyclobutane and a 1,2-Digermacyclobutane. J. Am. Chem. Soc. 1998, 120, 1398.