@article {1111, title = {Effect of Orientation on Plasmonic Coupling between Gold Nanorods}, journal = {Acs Nano}, volume = {3}, number = {11}, year = {2009}, note = {Tabor, Christopher Van Haute, Desiree El-Sayed, Mostafa A.}, month = {Nov}, pages = {3670-3678}, abstract = {Radiative coupling of induced plasmonic fields in metal nanoparticles has drawn increasing attention in the recent literature due to a combination of improved experimental methods to study such phenomena and numerous potential applications, such as plasmonic nanoparticle rulers and plasmonic circuitry. Many groups, including ours, have used a near-exponential fit to express the size scaling of plasmonic coupling. First, we show experimental agreement between previously simulated nanorod coupling and plasmonic coupling in electron beam lithography (EBL) fabricated nanorods using the near-exponential expression. Next, we study the effect of nanoparticle orientation on plasmonic coupling using EBL and DDA simulations. We develop a mathematical relationship that is consistent with our findings and quantitatively describes plasmonic coupling between nanorods as a function of orientation, separation, induced dipole strength, and the dielectric constant of the medium. For applications utilizing plasmonic coupling to become viable with particle shapes that do not have spherical symmetry, such as nanoprisms and nanorods, comparison of the experimental and theoretical results of how particle orientation affects plasmonic coupling is essential.}, isbn = {1936-0851}, doi = {10.1021/nn900779f}, author = {Tabor, C. E. and Van Haute, D. and El-Sayed, Mostafa A} } @article {1115, title = {Surface-Enhanced Raman Scattering Enhancement by Aggregated Silver Nanocube Monolayers Assembled by the Langmuir-Blodgett Technique at Different Surface Pressures}, journal = {Journal of Physical Chemistry C}, volume = {113}, number = {14}, year = {2009}, note = {Mahmoud, M. A. Tabor, C. E. El-Sayed, M. A.}, month = {Apr}, pages = {5493-5501}, abstract = {The surface-enhanced Raman scattering spectrum of poly(vinyl) pyrrolidone (PVP) molecules capping 50 nm silver nanocubes assembled in a monolayer via the Langmuir-Blodgett (LB) technique is studied at different surface pressures (at different nanoparticle densities). The observed correlation between the intensity of different SERS bands of the PVP with the nanoparticle density and those of the extinction intensity of the localized surface plasmon resonance bands (as a measure of the surface plasmon field) suggests the following: (1) the observed SERS enhancement results mostly from surface fields of the aggregated nanoparticles; and (2) the relative intensities of the different Raman bands are in reasonable agreement with those expected from the electromagnetic mechanism of enhancement. Besides the large surface plasmon field used in the Raman scattering enhancement, the broad SPR band of the aggregated nanocubes provides an additional advantage in the analytical applications of Raman spectroscopy.}, isbn = {1932-7447}, doi = {10.1021/jp900648r}, author = {Mahmoud, M A and Tabor, C. E. and El-Sayed, Mostafa A} } @article {1112, title = {On the Use of Plasmonic Nanoparticle Pairs As a Plasmon Ruler: The Dependence of the Near-Field Dipole Plasmon Coupling on Nanoparticle Size and Shape}, journal = {Journal of Physical Chemistry A}, volume = {113}, number = {10}, year = {2009}, note = {Tabor, Christopher Murali, Raghunath Mahmoud, Mahmoud El-Sayed, Mostafa A.}, month = {Mar}, pages = {1946-1953}, abstract = {The localized surface plasmon resonance (LSPR) spectral band of a gold or silver nanoparticle is observed to shift as a result of the near-field plasmonic field of another nanoparticle. The dependence of the observed shift on the interparticle distance is used as a ruler in biological systems and gave rise to a plasmonic ruler equation in which the fractional shift in the dipole resonance is found to decrease near exponentially with the interparticle separation in units of the particle size. The exponential decay length constant was observed to be consistent among a small range of nanoparticle sizes, shapes, and types of metal. The equation was derived from the observed results on disks and spherical nanoparticles and confirmed using results on a DNA conjugated nanosphere system. The aim of the present paper is to use electron beam lithography and DDA calculations to examine the constancy of the exponential decay length value in the plasmonic ruler equation on particle size and shape of a number of particles including nanoparticles of different symmetry and orientations. The results suggest that the exponent is almost independent of the size of the nanoparticle but very sensitive to the shape. A discussion of the nanoparticles most suitable for different applications in biological systems and a comparison of the plasmonic ruler with Forster resonance energy transfer (FRET) is mentioned.}, isbn = {1089-5639}, doi = {10.1021/jp807904s}, author = {Tabor, C. E. and Murali, R. and Mahmoud, M A and El-Sayed, Mostafa A} } @article {1120, title = {Can the observed changes in the size or shape of a colloidal nanocatalyst reveal the nanocatalysis mechanism type: Homogeneous or heterogeneous?}, journal = {Topics in Catalysis}, volume = {48}, number = {1-4}, year = {2008}, note = {Narayanan, Radha Tabor, Christopher El-Sayed, Mostafa A.}, month = {May}, pages = {60-74}, abstract = {The surface energy of metallic nanocrystals is relatively high compared to bulk materials due to the metal-metal bond deficiency of the surface atoms. This results in an insufficient chemical valency. In addition, smaller nanoparticles possess a higher degree of curvature, weakening, the bonding of their surface atoms. This is especially true for non-spherical shapes, which are comprised of a large number of sharp corner and edge sites. These atomic sites possess higher surface energies due to the lower number of shared bonds with the nanoparticle, resulting in instability of the surface atoms and rendering them physically unstable and chemically active. In many instances, the constant "bombardment" of these surface atoms by the solvent molecules as well as by the reactant molecules when these nanocrystals are in colloidal solution could lead to surface atom dissolution, both physically and/or chemically. This phenomenon could alter the functionality of the metallic colloidal nanoparticle from supplying catalytically active sites (in heterogeneous catalysis) to serving as a reservoir of catalytically active species to the solution (in homogeneous catalysis). In the latter type, if the atoms of the nanocatalyst appear in the products, the nanoparticle is no longer a catalyst but a reactant. In this review we attempt to answer the question raised in the title by examining our Previous work on the changes in size, shape, and other physical and chemical properties of colloidal transition metal nanoparticles during the nanocatalysis of two fundamentally different and important reactions: (1) the gentle electron-transfer reaction at room temperature involving the reduction of hexacyanoferrate (III) ions with thiosulfate ions and (2) the more harsh Suzuki cross-coupling reaction between phenylboronic acid and iodobenzene that takes place at 100 degrees C for 12 h. Changes in the nanoparticle dimensions were followed with TEM and HRTEM. Raman and FTIR spectroscopies were used to follow the chemical changes. For each change, we will use the above definition to see if the observed change can help us determine whether the catalysis is homogeneous or heterogeneous.}, isbn = {1022-5528}, doi = {10.1007/s11244-008-9057-4}, author = {Narayanan, Radha and Tabor, C. E. and El-Sayed, Mostafa A} } @article {1122, title = {A new catalytically active colloidal platinum nanocatalyst: The multiarmed nanostar single crystal}, journal = {Journal of the American Chemical Society}, volume = {130}, number = {14}, year = {2008}, note = {Mahmoud, Mahmoud A. Tabor, Christopher E. El-Sayed, Mostafa A. Ding, Yong Wang, Zhong Lin}, month = {Apr}, pages = {4590-+}, abstract = {Nanocatalysts that possess large amounts of atoms on sharp corners and edges and high indexed sites are known to be more catalytically active. We report here on a novel yet simple method to synthesize in large yields a very active platinum nanocatalyst; the multiarmed nanostar single crystal. We utilize a seed mediated method using tetrahedral nanoparticles that are also synthesized by a new and simple technique. High-resolution TEM shows that the nanostar has many arms, varying from a few to over 30, whereby even the largest ones :re found to have single-crystal structures. This strongly suggests that they are formed by a growth mechanism of the seed crystals and not by the aggregation of seed crystals, which should produce twinning planes. Due to the reduction reaction of ferricyanide by thiosulfate, the nanostars are found to have an activation energy, which is nearly 60\% of that of the tetrahedral seeds themselves, both having the same PVP capping agent. This is undoubtedly due to the multiarms with edges, corners, and the presence of high indexed facets in the nanostar catalyst.}, isbn = {0002-7863}, doi = {10.1021/ja710646t}, author = {Mahmoud, M A and Tabor, C. E. and El-Sayed, Mostafa A and Ding, Y. and Wang, Z.L.} } @article {1134, title = {Dependence of the threshold energy of femtosecond laser ejection of gold nanoprisms from quartz substrates on the nanoparticle environment}, journal = {Journal of Physical Chemistry C}, volume = {111}, number = {25}, year = {2007}, note = {Tabor, Christopher Qian, Wei El-Sayed, Mostafa A.}, month = {Jun}, pages = {8934-8941}, abstract = {Recently, it was reported that gold nanoprisms in a monolayer array on a quartz substrate were ejected in air when irradiated with femtosecond laser pulses near their surface plasmon absorption maximum. It was deduced from the measured reduction in particle thickness upon irradiation that the ejection mechanism involved ablation of surface atoms from the gold particle, which generates an intense pressure at the particle-substrate interface. The present study reports on this phenomenon when the substrate-bound nanoparticle is immersed in a liquid environment. In this system, it is found that the nanoparticle ejection requires less than one tenth the energy required if the system was irradiated in air. The ejected nanoparticle is also found to increase in thickness instead of the decrease observed in air. These results suggest another photoinitiated ejection mechanism, different from surface ablation, when the particles are surrounded by a liquid environment. From this and other spectroscopic and microscopic results on the ejected nanoprisms, we suggest a mechanism that involves energy transfer from the photoexcited nanoprism to the solvent within cavities and defects at the particle-substrate interface. The hot-solvent molecules result in an intense pressure at the particle-substrate interface, resulting in particle ejection. Ejection is proposed to consist of two processes, namely nanoparticle-substrate dissociation and nanoparticle solvation and diffusion away from the substrate. These two processes have independently been studied as a function of solvent property.}, isbn = {1932-7447}, doi = {10.1021/jp070282q}, author = {Tabor, C. E. and Qian, Wei and El-Sayed, Mostafa A} } @article {1155, title = {Using silica films and powders modified with benzophenone to photoreduce silver nanoparticles}, journal = {Journal of Photochemistry and Photobiology a-Chemistry}, volume = {181}, number = {2-3}, year = {2006}, note = {Eustis, Susie Krylova, Galina Smirnova, Natalie Eremenko, Anna Tabor, Christopher Huang, Wenyu El-Sayed, Mostafa A.}, month = {Jul}, pages = {385-393}, abstract = {Porous silica (SiO2 films and powders), modified with benzophenone (BP), facilitates the formation of stable sliver nanoparticles by taking advantage of the solid supported photosensitizer. The silica serves as a carrier for the BP into an aqueous solution and its subsequent removal. Benzophenone, bound to a silica film, was able to reduce silver ions to generate nanoparticles in solution, while silica powder with bound BP generates silver nanoparticles that are attracted to the silica. Silver nanoparticles are also fabricated in porous silica films by incorporating silver ions into the films before casting and then irradiating the film in a solution containing BP. From pH studies, it is concluded that the ketyl-radicals and anion-radicals of BP and IPA both take part in the reduction of silver ions. These synthetic studies provide a new photochemical reduction method by immobilizing the reactant on a silica surface allowing generation of silver nanoparticles in solution attached to powders or inside a film for catalytic applications or increased conductivity of silica films. (c) 2006 Elsevier B.V. All rights reserved.}, isbn = {1010-6030}, doi = {10.1016/j.jphotochem.2005.12.024}, author = {Eustis, Susie and Krylova, G. and Smirnova, N. and Eremenko, A. and Tabor, C. E. and Huang, Wenyu and El-Sayed, Mostafa A} }