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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 various functionalized nanoparticles and polymer based nanocomposites. They represent an exciting area of nanoscience and nanotechnology allowing unique properties such optical, magnetic, catalytic, sensing etc and applications of these materials for energy, in biomedical fields and in catalysis. If the polymer 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, such nanostructures (presence of interfaces) allow 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 applications. Interfaces are equally important in the hybrid-organic materials proposed as solid polymer electrolytes 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. In this case the nanoparticle growth occurs either in the presence of capping molecules or due to a ligand exchange reaction.

Functionalized Magnetic Nanoparticles

Magnetic nanoparticles are of increased importance for various biomedical applications such as enhanced contrast agents for magnetic resonance imaging (MRI) and for hyperthermia cancer treatment. Because magnetic properties are size dependent, monodisperse magnetic nanoparticles are preferred.

We synthesize monodisperse magnetic nanoparticles of different shapes, sizes and composition via organometallic routes. 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, covalent interaction of the particle surface with functional silanes, or ligand exchange. The negatively charged water soluble nanoparticles (left, below) can be additionally coated with virus protein forming virus-like particles (right, below).

Another avenue for magnetic nanoparticles is the development of magnetically recoverable catalysts. In this case, magnetic nanoparticles can be synthesized in the presence of functional capping molecules such as polyphenylenepyridyl dendrons (collaboration with Dr. Zinaida Shifrina’s group from A.N. Nesmeyanov Institute of Oranoelement Compounds of Russian Academy of Sciences, Moscow, Russia) or post-synthesis functionalized with long-chain hydrocarbon acids bearing multiple double bonds such as linolenic acid (see left, below). Double bonds easily interact with (CH3CN)2PdCl2 leading to the olefin Pd complexes in the magnetic nanoparticle shells (center, below). These composite nanoparticles are easily separated using rare-earth magnet (right, below).

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

Catalytic nanoparticles of platinum (shown) and iron or cerium oxides can be successfully formed in HPS where mesopores (~ 4 nm) control the nanoparticle growth while large mesopores (20-50 nm) allow transport of reactant molecules to catalytic sites. For example, 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 (SPEs) 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 and thus affording more efficient, safer batteries. Use of silanes bearing anionic groups allows synthesis of single ion conductors eliminating the problem of a short battery life due to battery polarization.

Publications

Shtykova, E.V.; Kuchkina, N.V.; Shifrina, Z.B.; Bronstein, L.M.; Svergun, D. I. Unusual Structural Morphology of Dendrimer/CdS Nanocomposites Revealed by Synchrotron X-ray Scattering. J. Phys. Chem. C (2012), ASAP. DOI: 10.1021/jp210998h. Cover article.

Budgin, A.M.; Kabachii, Y.A.; Shifrina, Z.B.; Valetsky, P.M.; Kochev, S. S.; Stein, B. D.; Malyutin, A.; Bronstein, L.M. Functionalization of Magnetic Nanoparticles with Amphiphilic Block Copolymers: Self-Assembled Thermoresponsive Submicrometer Particles.  Langmuir (2012), 28(9), 4142-4151.

Kuchkina, N.V.; Morgan, D.G.; Stein, B.D.; Puntus, L.N.; Sergeev, A.M.; Peregudov, A.S.; Bronstein, L.M.; Shifrina, Z.B. Polyphenylenepyridyl Dendrimers as Stabilizing and Controlling Agents for CdS Nanoparticle Formation. Nanoscale (2012), 4 (7), 2378 - 2386.

Tsvetkova, I.B.; Matveeva, V.G.; Doluda, V.Y.; Bykov,  A.V.; Sidorov, A.I.; Schennikov, S.V.; Sulman, M.G.; Valetsky, P.M.; Stein, B.D.; Chen, C.-H.; Sulman, E.M.; Bronstein, L.M. Pd(II) nanoparticles in porous polystyrene: factors influencing the nanoparticle size and catalytic properties. J. Mater. Chem. (2012), 22 (13), 6441 - 6448.

Bronstein, L.M.; Shifrina, Z. B. Dendrimers as encapsulating, stabilizing, or directing agents for inorganic nanoparticles. Chem. Rev. (2011) 111(9), 5301-5344.

Bronstein, L.M. Virus-Based Nanoparticles with Inorganic Cargo: What Does the Future Hold? Small (2011), 7(12), 1609-1618.

Huang, X.; Stein, B. D.; Cheng, H.; Malyutin, A.; Tsvetkova, I. B.; Baxter, D. V.; Remmes, N. B.; Verchot, J.; Kao, C.; Bronstein, L. M.; Dragnea, B.   Magnetic Virus-like Nanoparticles in N. benthamiana Plants: A New Paradigm for Environmental and Agronomic Biotechnological Research.    ACS Nano   (2011),  5(5),  4037-4045. Cover article.

Bronstein, L. M.; Atkinson, J. E.; Malyutin, A. G.; Kidwai, F.; Stein, B. D.; Morgan, D. G.; Perry, J. M.; Karty, J. A.   Nanoparticles by Decomposition of Long Chain Iron Carboxylates: From Spheres to Stars and Cubes.    Langmuir  (2011),  27(6),  3044-3050. 

Shtykova, E.V.; Malyutin, A.; Dyke, J.; Stein, B.; Konarev, P.V.; Dragnea, B.; Svergun, D. I.; Bronstein, L. M. Hydrophilization of Magnetic Nanoparticles with Modified Alternating Copolymers. Part 2: Behavior in Solution. J. Phys. Chem. C (2010), 114(50), 21908-21913. Cover article.

Bronstein, L.M.; Shtykova, E.V.; Malyutin, A.; Dyke, J.C.; Gunn, E.; Gao, X.; Stein, B.; Konarev, P. V.; Dragnea, B.; Svergun, D. I. Hydrophilization of Magnetic Nanoparticles with Modified Alternating Copolymers. Part 1: The Influence of the Grafting. J. Phys. Chem. C (2010), 114(50), 21900-21907. Cover article.

Sulman, E.M.; Matveeva, V.G.; Doluda, V.Yu.; Sidorov, A.I.; Lakina, N.V.; Bykov, A.V.; Sulman, M.G.; Valetsky, P.M.; Kustov, L.M.; Tkachenko, O.P.; Stein, B.D.; Bronstein, L.. Efficient polymer-based nanocatalysts with enhanced catalytic performance in wet air oxidation of phenol. Applied Catalysis, B: Environmental (2010), 94(1-2), 200-210.

Huang, X.; Schmucker, A.; Dyke, J.; Hall, S.M.; Retrum, J.; Stein, B.; Remmes, N.; Baxter, D.V.; Dragnea, B.; Bronstein, L.M. Magnetic nanoparticles with functional silanes: Evolution of well-defined shells from anhydride containing silane. J. Mater. Chem. (2009), 19(24), 4231-4239.

Sulman, E.M.; Matveeva, V.G.; Sulman, M.G.; Demidenko, G.N.; Valetsky, P.M.; Stein, B.; Mates, T.; Bronstein, L.M. Influence of heterogenization on catalytic behavior of mono- and bimetallic nanoparticles formed in poly(styrene)-block-poly(4-vinylpyridine) micelles. J. Catal. (2009), 262(1), 150-158.

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.

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, 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.; 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.
• A Distinguished Adjunct Professorship at the King Abdulaziz University, Jeddah, Saudi Arabia, 2012.

Highlights