Senior Scientist, Chemistry Department

Lyudmila Bronstein received a M.S. degree with honors from Kalinin Polytechnic Institute, Russia, in 1974. She was awarded her Ph.D. from the Nesmeyanov Institute of Organoelement Compounds, Moscow, Russia, in 1979 under the guidance of Professor Alexander Rusanov. Prior to joining Indiana University in 1999 she was a Leading Scientist at the Nesmeyanov Institute of Organoelement Compounds.

Dr. Bronstein’s research program focuses on developing new materials with important applications in the fields of energy, catalysis, and life sciences. Her research group has been working on making solid polymer electrolytes and electrodes for Li ion batteries with enhanced performance, efficient and selective catalytic systems based on nanostructured polymers, and multifunctional magnetic nanoparticles as bioprobes.

Research

We are interested in synthesis and study of nanostructured polymeric and hybrid organic-inorganic materials. Nanostructured materials containing metal, metal oxide or semiconductor nanoparticles present an exciting area of nanoscience and nanotechnology as particle incorporation allows imparting unique properties to polymeric materials: catalytic, optical, magnetic, sensing etc. If the polymeric matrix is already nanostructured before nanoparticle formation, i.e. contains domains of different chemical nature divided by interfaces, this reflects a further degree of nanostructural organization. Normally, the presence of such nanostructures in polymer systems (presence of interfaces) allows carrying out a subtle control over nanoparticle growth, particle size distribution, and particle surface interactions. The above characteristics are most important in determining properties of these nanomaterials and their possible applications. Interfaces are equally important in the hybrid-organic materials proposed as solid polymer electrolytes (SPE) for secondary lithium batteries. The other example of hybrid organic-inorganic materials is core-shell particles containing a magnetic inorganic core and a functional organic shell.

Functionalized Magnetic Nanoparticles

Magnetic metal oxide nanoparticles can be prepared by incorporation of metal ions (Fe, Co) in block copolymer micelles followed by oxidation. As a block copolymer, we used poly(ethylene oxide)-block-poly(methacrylic acid) (PEO-b-PMAA) forming micelles due to interaction of the PMAA block with metal ions. The important advantage of these block copolymer stabilized magnetic nanoparticles is their remarkable solubility in water. The solid samples immediately dissolve in water and retain their solubility for years. Because PEO-containing copolymers are the materials of choice for incorporating in the living cells or stabilization of nanoparticles for biomedical applications, the magnetic nanoparticles stabilized by PEO-b-PMAA can be considered as promising bioprobes for in vitro and in vivo studies.

Another avenue is development of core-shell particles with well-defined magnetic cores of different shapes and sizes and functional shells. The proper functionalization can make these particles hydrophobic or hydrophilic and can determine the interaction forces between the particles. As major means of functionalization we use hydrophobic interactions of the nanoparticle protective layer with functionalized lipids or amphiphilic copolymers or covalent interaction of the particle surface with functional silanes. In turn, the functional shells can be filled with other inorganic guest particles imparting optical or catalytic properties. These core-shell particles are of interest as ferrofluids with designed properties and bioprobes for incorporation into viral-like particles.

Catalytic Nanoparticles Formed in Micro/Macroporous Hypercrosslinked Polystyrene (HPS)

Catalytic nanoparticles of platinum (shown) and iron or cerium oxides can be successfully formed in HPS where micropores (~ 2 nm) control the nanoparticle growth while macropores (50-80 nm) allow transport of reactant molecules to catalytic sites. These catalysts can be used in oxidation of L-sorbose to a vitamin C precursor or phenols from wastewaters to CO2 and water.

 

Hybrid Organic-Inorganic Solid Polymer Electrolytes for Li Batteries

We developed and studied solid polymer electrolytes (SPE) built from two major components: an organic-inorganic component (OIC) prepared by hydrolytic condensation of various precursors, and a conventional salt-in-polymer constituent. The latter consists of poly(ethylene glycol) (PEG) and a Li salt. Since OIC forms in situ in the salt-in-polymer component, it provides fresh interfaces and enhanced SPE properties. Variation of organically modified silanes allows us to modify the SPE structure and properties, varying conductivity, Li transference numbers, and mechanical stability. Use of silanes bearing anionic groups allows synthesis of single ion conductors.

Publications

Bronstein, L.M.; Ivanovskaya, A.; Mates, T.; Holten-Andersen, N.; Stucky, G. D. Bioinspired Gradient Materials via Blending of Polymer Electrolytes and Applying Electric Forces. J. Phys. Chem. B (2009), 113(3), 647-655.

Aberg, C.M.; Seyam, M.A.; Lassell, S.A.; Bronstein, L.M.; Spontak, R.J. In situ Growth of Pd Nanoparticles in Crosslinked Polymer Matrices. Macromol. Rapid. Comm. (2008), 29(24), 1926-1931.

Bronstein, L.M.; Kostylev, M.; Shtykova, E. V.; Vlahu, T.; Huang, X.; Stein, B. D.; Bykov, A.; Remmes, N.B.; Baxter, D.V.; Svergun, D. I. Mixed Co/Fe Oxide Nanoparticles in Block Copolymer Micelles. Langmuir (2008), 24(21), 12618-12626.

Shtykova, E. V.; Huang, X.; Gao, X.; Dyke, J. C.; Schmucker, A. L.; Dragnea, B.; Remmes, N.; Baxter, D. V.; Stein, B.; Konarev, P. V.; Svergun, D. I.; Bronstein, L. M. Hydrophilic Monodisperse Magnetic Nanoparticles Protected by an Amphiphilic Alternating Copolymer. J. Phys. Chem. C (2008), 112(43), 16809-16817

Bronstein, L.M.; Matveeva, V. G.; Sulman, E. M. Nanoparticulate catalysts based on nanostructured polymers. Nanoparticles and Catalysis. Ed. D. Astruc, Wiley-VCH, Weinheim (2008), 93-127.

Azzam, T.; Bronstein, L.; Eisenberg, A. Water-Soluble Surface-Anchored Gold and Palladium Nanoparticles Stabilized by Exchange of Low Molecular Weight Ligands with Biamphiphilic Triblock Copolymers. Langmuir (2008), 24(13), 6521-6529.

Bronstein, L.M.; Karlinsey, R.L.; Yi, Z.; Carini, J.; Werner-Zwanziger, U.; Konarev, P. V.; Svergun, D.I.; Sanchez, A.; Khan, S. Composite Solid Polymer Electrolytes Based on Pluronics: Does Ordering Matter? Chem. Mater. (2007) 19(25), 6258-6265

Shtykova, E.V.; Huang, X.; Remmes, N.; Baxter, D.; Stein, B.; Dragnea, B.; Svergun, D. I.; Bronstein, L.M. Structure and Properties of Iron Oxide Nanoparticles Encapsulated by Phospholipids with Poly(ethylene glycol) Tails. J. Phys. Chem. (2007) 111(49), 18078-18086.

Tsvetkova, I.B.; Bronstein, L.M.; Sidorov, S.N.; Lependina, O.L.; Sulman, M.G.; Valetsky, P.M.; Stein, B.; Nikoshvili, L.Zh.; Matveeva, V.G.; Sidorov, A.I.; Tikhonov, B.B.; Demidenko, G.N.; Kiwi-Minsker, L.; Sulman, E.M. Structure and behavior of nanoparticulate catalysts based on ultrathin chitosan layers. J. Molec. Catal. A: Chem. (2007), 276(1-2), 116-129.

Huang, X.; Bronstein, L.M.; Retrum, J.; Dufort, C.; Tsvetkova, I.; Aniagyei, S.; Stein, B.; Stucky, G.; McKenna, B.; Remmes, N.; Baxter, D.; Kao, C.C.; Dragnea, B. Self-Assembled Virus-like Particles with Magnetic Cores. Nano Letters (2007), 7 (8) 2407 – 2416.

Bronstein, L.M.; Huang, X.; Retrum, J.; Schmucker, A.; Pink, M.; Stein, B.D.; Dragnea, B. Influence of Iron Oleate Complex Structure on Iron Oxide Nanoparticle Formation. Chem. Mater. (2007), 19 (15) 3624-3632.

Bronstein, Lyudmila M.; Dixit, Suraj; Tomaszewski, John; Stein, Barry; Svergun, Dmitri I.; Konarev, Peter V.; Shtykova, Eleonora; Werner-Zwanziger, Ulrike; Dragnea, Bogdan. Hybrid Polymer Particles with a Protective Shell: Synthesis, Structure, and Templating. Chem. Mater. (2006), 18(9), 2418-2430.

Bronstein, Lyudmila M.; Karlinsey, Robert L.; Stein, Barry; Yi, Zheng; Carini, John; Zwanziger, Josef W. Solid Polymer Single-Ion Conductors: Synthesis and Properties. Chem. Mater. (2006), 18(3), 708-715.

Bronstein, Lyudmila M.; Vamvakaki, Maria; Kostylev, Maxim; Katsamanis, Vasilios; Stein, Barry; Anastasiadis, Spiros H. Transformations of Poly(methoxy hexa(ethylene glycol) methacrylate)-b-(2-(diethylamino)ethyl methacrylate) Block Copolymer Micelles upon Metalation. Langmuir (2005) 21(21), 9747-9755.

Bronstein, L.M.; Kostylev, M.; Tsvetkova, I.; Tomaszewski, J.; Stein, B.; Makhaeva, E.E.; Okhapkin, I.; Khokhlov, A.R. Core-Shell Nanostructures from Single Poly(N-vinylcaprolactam) Macromolecules: Stabilization and Visualization. Langmuir (2005), 21(7), 2652-2655.

Bronstein, L.M. Polymer Colloids and Their Metallation. In Dekker Encyclopedia of Nanoscience and Nanotechnology, J.A. Schwarz, C.I. Contescu, and K. Putyera, Eds.; Marcel Dekker, Inc.: New York, 2004; pp. 2903-2916.

Bronstein, L. M. Nanoparticles in Nanostructured Polymers. In Encyclopedia of Nanoscience and Nanotechnology, Edited by H. S. Nalwa, American Scientific Publishers, Los Angeles (2004), Vol. 7, pp. 193-206.

Bronstein, L.M.; Karlinsey, R.L.; Ritter, K.; Joo, C.-G.; Stein, B.; Zwanziger, J.W. Design of organic-inorganic solid polymer electrolytes: synthesis, structure, and properties. J. Mater. Chem. (2004), 14(12), 1812-1820.

Bronstein, L.M.; Ashcraft, E.; DeSanto, P., Jr.; Karlinsey, R.L.; Zwanziger, J.W. Structural Study of Inorganic Oxides in a Hybrid Organic-Inorganic Solid Polymer Electrolyte. J. Phys. Chem. B (2004), 108(19), 5851-5858.

Bronstein, L.M.; Linton, C.; Karlinsey, R.; Stein, B.; Timofeeva, G.I.; Svergun, D.I.; Konarev, P.I.; Kozin, M.; Tomaszewski, J.; Werner-Zwanziger, U.; Zwanziger, J.W. Functional Polymer Colloids with Ordered Interior. Langmuir (2004), 20(4), 1100-1110.

Bronstein, L. M.; Linton, C. N.; Karlinsey, R.; Ashcraft, E.; Stein, B. D.; Svergun, D. I.; Kozin, M.; Khotina, I. A.; Spontak, R.J.; Werner-Zwanziger, U.; Zwanziger, J. W. Controlled Synthesis of Novel Metalated Poly(aminohexyl)-(aminopropyl)silsesquioxane Colloids. Langmuir (2003), 19(17), 7071-7083.

Bronstein, L. M.; Nanoparticles Made in Mesoporous Solids. Top. Curr. Chem (2003) 226, 55-89.

Bronstein, L. M.; Chernyshov, D. M.; Karlinsey, R.; Zwanziger, J. W.; Matveeva, V. G.; Sulman, E. M.; Demidenko, G. N.; Hentze, H.-P.; Antonietti, M. Mesoporous Alumina and Aluminosilica with Pd and Pt Nanoparticles: Structure and Catalytic Properties. Chem. Mater. (2003), 15(13); 2623-2631.

Bronstein, L.M.; Linton, C.; Karlinsey, R.; Stein, B.; Svergun, D.I.; Zwanziger, J.W.; Spontak, R.J. Synthesis of Metal-Loaded Poly(aminohexyl)(aminopropyl)silsesquioxane Colloids and Their Self-Organization into Dendrites. Nano Letters (2002), 2(8), 873-876.

Bronstein, L. M.; Joo, C.; Karlinsey, R.; Ryder, A.; Zwanziger, J. W. Nanostructured Inorganic-Organic Composites as a Basis for Solid Polymer Electrolytes with Enhanced Properties. Chem. Mater. (2001), 13(10), 3678-3684.

Bronstein, L.M., Polarz, S.; Smarsly, B.; Antonietti, B. Sub-Nanometer Noble-Metal Particle Host Synthesis in Porous Silica Monoliths. Adv. Mat. (2001), 13 (17), 1333-1336.

Sidorov, S. N.; Volkov, I. V.; Davankov, V. A.; Tsyurupa, M. P.; Valetsky, P. M.; Bronstein, L. M.; Karlinsey, R.; Zwanziger, J. W.; Matveeva, V. G.; Sulman, E. M.; Lakina, N. V.; Wilder, E. A.; Spontak, R. J. Platinum-Containing Hyper-Cross-Linked Polystyrene as a Modifier-Free Selective Catalyst for L-Sorbose Oxidation. J. Am. Chem. Soc. (2001), 123(43), 10502-10510.

Awards

• First prize in Nesmeyanov Institute Competition for the Best Research Work, 1998.
• Second prize in Nesmeyanov Institute Competition for the Best Research Work, 1996.

Highlights