2026-09-21T21:45:23Z https://www.ideals.illinois.edu/oai-pmh

oai:www.ideals.illinois.edu:2142/18495 2023-07-10 col_2142_5131 col_2142_14789 com_2142_5130 com_2142_14788 com_2142_8903

Murphy, Catherine J. Murphy, Catherine J. Zimmerman, Steven C. Bailey, Ryan C. Wyatt, Michael D. Alkilany, Alaaldin M. 2011-01-21T22:42:50Z 2011-01-21T22:42:50Z 2013-01-22T11:00:24Z 2011-01-21T22:42:50Z 2010-12 "Gold nanorods have unique optical properties and various promising applications. Wet chemical synthesis of gold nanorods requires the use of cetyl trimethylammonium bromide (CTAB) as shape-directing surfactant, which form a bilayer on the surfaces of gold nanorods. CTAB bilayer stabilizes the nanorods against aggregation and has the ability to sequester organic molecules from aqueous bulk. CTAB molecules in the bilayer are held via weak hydrophobic forces and thus tend to desorb resulting in nanorods aggregation and toxicity to cultured cells. Herein, three surface-engineering approaches to enhance the colloidal physical stability and biocompatibility of gold nanorods have been examined: 1) electrostatic approach via overcoating with polyelectrolytes; 2) covalent approach via surfactant polymerization; 3) and hydrophobic approach via cholesterol insertion into the bilayer. Layer-by-layer coating has been used to overcoat CTAB-capped nanorods with both negatively and positively charged polyelectrolytes. Compared to CTAB-capped nanorods, polyelectrolyte-coated gold nanorods showed improved stability against aggregation in culture medium and enhanced biocompatibility to cultured cells. The toxicity of CTAB-capped gold nanorod solutions was assigned quantitatively to free CTAB molecules, where gold nanorods themselves were found not toxic. Similar biocompatibility profiles for both cationic and anionic coated-gold nanorods were observed due to spontaneous protein adsorption. In growth media, all examined nanorods were covered with protein corona and thus bear similar negative effective surface charge explaining their similar toxicity profiles. ! """"""! ! Our covalent approach to stabilize the surfactant bilayer on the surface of gold nanorods relies on synthesizing a polymerizable version of the CTAB, which we have used to prepare gold nanoparticles (both spheres and rods). Surfactant polymerization on the surface of gold nanoparticles was found to retard surfactant desorption and thus enhance both stability against aggregation and biocombatibility of these nanomaterials. The hydrophobic approach to stabilize the CTAB bilayer on gold nanorods relies on using a bilayer-condensing agent such as cholesterol to increase the total hydrophobic interactions. Cholesterol is known to consist of up to 50% of mammalian cell membrane’s total lipids, and thus have important effect on their stability and physical properties. Using cholesterol-rich growth medium, we have prepared gold nanorods with excellent size and shape distribution. The prepared gold nanorods in the presence of cholesterol have a significantly higher surface charge and exhibit superior stability against aggregation compared to the nanorods prepared without cholesterol. In addition to the enhanced aqueous stability and biocompatibility, stabilization the CTAB bilayer on the surface of gold nanorods have allowed for suspension gold nanorods in organic solvents without aggregation. Polyelectrolyte-coated gold nanorods showed remarkable stability in polar organic solvents against aggregation as compared to CTAB-capped nanorods. The suspendability of coated-gold nanorods in polar organic solvents facilitates the incorporation of these nanomaterials into hydrophobic polymers and thus fabrication of thin films that contain uniform gold nanorod dispersions (nanocomposites)." Item withdrawn by Mark Zulauf (zulauf@illinois.edu) on 2010-09-07T21:28:12Z Item was in collections: University of Illinois Theses & Dissertations (ID: 1) No. of bitstreams: 2 Alkilany_Alaaldin.doc: 119519744 bytes, checksum: 5bcd6ed3da1e9237cfaeb53d142496db (MD5) Alkilany_Alaaldin.pdf: 53166334 bytes, checksum: 556c87a54b5b1844f6961a50627527a4 (MD5) Made available in DSpace on 2011-01-21T22:42:50Z (GMT). No. of bitstreams: 3 Alkilany_Alaaldin.pdf: 53166334 bytes, checksum: 556c87a54b5b1844f6961a50627527a4 (MD5) license.txt: 4067 bytes, checksum: 1f01bed0d8634674e83f3e58abd80ed8 (MD5) Alkilany_Alaaldin.doc: 119519744 bytes, checksum: 5bcd6ed3da1e9237cfaeb53d142496db (MD5) Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by William Ingram (wingram2@illinois.edu) on 2011-01-21T22:47:48Z Item is restricted until 2013-01-21T22:47:37Z Item reinstated by Sarah Shreeves (sshreeve@illinois.edu) on 2013-01-22T11:00:24Z Item was in collections: University of Illinois Dissertations and Theses (ID: 204) Dissertations and Theses - Chemistry (ID: 676) No. of bitstreams: 4 Alkilany_Alaaldin.pdf: 53166334 bytes, checksum: 556c87a54b5b1844f6961a50627527a4 (MD5) license.txt: 4067 bytes, checksum: 1f01bed0d8634674e83f3e58abd80ed8 (MD5) Alkilany_Alaaldin.doc: 119519744 bytes, checksum: 5bcd6ed3da1e9237cfaeb53d142496db (MD5) Alkilany_Alaaldin.pdf.txt: 185626 bytes, checksum: 11e58a89264f224ee65913f2a5aa962e (MD5) Item released from any restrictions by Sarah Shreeves (sshreeve@illinois.edu) on 2013-01-22T11:00:24Z http://hdl.handle.net/2142/18495 en Copyright 2010 Alaaldin Mohammad Alkilany Gold nanorods Partitioning admicelles nanotoxicity nanocomposites Polymerization Layer by layer coating cholesterol protein adsorption Molecular engineering of gold nanorod surfaces: towards improved physical properties and understanding nanoparticle-cell interactions Chemistry 1413 Chemistry 0335 University of Illinois at Urbana-Champaign Dissertation Ph.D. PHD:Chemistry -UIUC 10KS0335PHD