%0 Journal Article %J Biochimica et Biophysica Acta (BBA)-General Subjects %D 2020 %T Gold nanomaterials as key suppliers in biological and chemical sensing, catalysis, and medicine %A Falahati, M. %A Attar, F. %A Sharifi, M. %A Saboury, A.A. %A Salihi, A. %A Aziz, F.M. %A Kostova, I. %A Burda, C. %A Priecel, P. %A Lopez-Sanchez, J.A. %A Laurent, S. %A Hooshmand, N. %A El-Sayed, M.A. %B Biochimica et Biophysica Acta (BBA)-General Subjects %G eng %0 Journal Article %J ChemPhysChem %D 2018 %T UV Resonance Raman Study of Apoptosis, Platinum‐based Drugs, and Human Cell Lines %A Geng, J %A M. Aioub %A El‐Sayed, M. A. %A B.A. Barry %B ChemPhysChem %G eng %0 Journal Article %J Journal of Physical Chemistry C %D 2016 %T Enhanced Electrocatalytic Activity toward the Oxygen Reduction Reaction through Alloy Formation: Platinum–Silver Alloy Nanocages %A Bordley, JA %A et al. %B Journal of Physical Chemistry C %G eng %0 Journal Article %J The Journal of Physical Chemistry C %D 2016 %T The Sensitivity of the Distance Dependent Plasmonic Coupling between Two Nanocubes to their Orientation: Edge-to-Edge versus Face-to-Face %A Hooshmand, Nasrin %A Bordley, Justin A %A El-Sayed, Mostafa A. %B The Journal of Physical Chemistry C %V 120 %P 4564–4570 %G eng %0 Journal Article %J Nano Letters %D 2015 %T The Coupling between Gold or Silver Nanocubes in Their Homo-Dimers: A New Coupling Mechanism at Short Separation Distances %A Bordley, Justin A %A Hooshmand, Nasrin %A El-Sayed, Mostafa A. %B Nano Letters %V 15 %P 3391-3397 %G eng %U http://dx.doi.org/10.1021/acs.nanolett.5b00734 %R 10.1021/acs.nanolett.5b00734 %0 Journal Article %J The Journal of Physical Chemistry C %D 2015 %T Plasmonic Spectroscopy: The Electromagnetic Field Strength and its Distribution Determine the Sensitivity Factor of Face-to-Face Ag Nanocube Dimers in Solution and on a Substrate %A Hooshmand, Nasrin %A Bordley, Justin A %A El-Sayed, Mostafa A. %B The Journal of Physical Chemistry C %V 119 %P 15579-15587 %G eng %U http://dx.doi.org/10.1021/acs.jpcc.5b05395 %R 10.1021/acs.jpcc.5b05395 %0 Journal Article %J The Journal of Physical Chemistry Letters %D 2014 %T Are hot spots between two plasmonic nanocubes of silver or gold formed between adjacent corners or adjacent facets? A DDA examination %A Hooshmand, Nasrin %A El-Sayed, Mostafa A. %A Bordley, Justin A %B The Journal of Physical Chemistry Letters %@ 1948-7185 %G eng %0 Journal Article %J Energy & Environmental Science %D 2014 %T High-temperature surface enhanced Raman spectroscopy for in situ study of solid oxide fuel cell materials %A Li, Xiaxi %A Lee, Jung-Pil %A Blinn, Kevin S %A Chen, Dongchang %A Yoo, Seungmin %A Kang, Bin %A Bottomley, Lawrence A %A El-Sayed, Mostafa A. %A Park, Soojin %A Liu, Meilin %B Energy & Environmental Science %V 7 %P 306-310 %G eng %0 Journal Article %J Journal of Physical Chemistry C %D 2013 %T Properties of pi-Conjugated Fluorescence Polymer-Plasmonic Nanoparticles Hybrid Materials (vol 116, 13336, 2012) %A Mahmoud, M A %A Poncheri, A. J. %A El-Sayed, M. A. %A Bryant, J. %A Bunz, U. %B Journal of Physical Chemistry C %V 117 %P 4876-4876 %8 Mar %@ 1932-7447 %G eng %M WOS:000315707600060 %! J. Phys. Chem. C %R 10.1021/jp4006197 %0 Journal Article %J Small %D 2013 %T Surface Assembly and Plasmonic Properties in Strongly Coupled Segmented Gold Nanorods %A Gupta, Maneesh K. %A Konig, Tobias %A Near, Rachel %A Nepal, Dhriti %A Drummy, Lawrence F. %A Biswas, Sushmita %A Naik, Swati %A Vaia, Richard A. %A El-Sayed, Mostafa A. %A Tsukruk, Vladimir V. %X An assembly strategy is reported such that segmented nanorods fabricated through template-assisted methods can be robustly transferred and tethered to a pre-functionalized substrate with excellent uniformity over large surface areas. After embedding the rods, sacrificial nickel segments were selectively etched leaving behind strongly coupled segmented gold nanorods with gaps between rods below 40 nm and as small as 2 nm. Hyper-spectral imaging is utilized to measure Rayleigh scattering spectra from individual and coupled nanorod elements in contrast to common bulk measurements. This approach discerns the effects of not only changing segment and gap size but also the presence of characteristic defects on the plasmonic coupling between closely spaced nanorods. Polarized hyper-spectral measurements are conducted to provide direct observation of the anisotropic plasmonic resonance modes in individual and coupled nanorods, which are close to those predicted by computer simulations for nanorods with ideal shapes. Some common deviations from ideal shape such as non-flat facets and asymmetric tails are demonstrated to result in the appearance of characteristic plasmon resonances, which have not been considered before. The large-scale assembly of coupled noble nanostructures with fine control over geometry and high uniformity provides means to strongly tune the scattering, absorption, and near-field plasmonic properties through the geometric arrangement of precisely controlled nanorod segments.[on SciFinder (R)] %B Small %8 // %@ 1613-6829 %G eng %0 Journal Article %J Nanoscale %D 2013 %T Well-organized raspberry-like Ag@ Cu bimetal nanoparticles for highly reliable and reproducible surface-enhanced Raman scattering %A Lee, Jung-Pil %A Chen, Dongchang %A Li, Xiaxi %A Yoo, Seungmin %A Bottomley, Lawrence A %A El-Sayed, Mostafa A. %A Park, Soojin %A Liu, Meilin %B Nanoscale %V 5 %P 11620-11624 %G eng %0 Journal Article %J Journal of the American Chemical Society %D 2012 %T Aggregation and Interaction of Cationic Nanoparticles on Bacterial Surfaces %A Hayden, S. C. %A Zhao, G. X. %A Saha, K. %A Phillips, R. L. %A Li, X. N. %A Miranda, O. R. %A Rotello, V. M. %A El-Sayed, M. A. %A Schmidt-Krey, I. %A Bunz, U. H. F. %X Cationic monolayer-protected gold nanoparticles (AuNPs) with sizes of 6 or 2 nm interact with the cell membranes of Escherichia coli (Gram-) and Bacillus subtilis (Gram+), resulting in the formation of strikingly distinct AuNP surface aggregation patterns or lysis depending upon the size of the AuNPs. The aggregation phenomena were investigated by transmission electron microscopy and UV-vis spectroscopy. Upon proteolytic treatment of the bacteria, the distinct aggregation patterns disappeared. %B Journal of the American Chemical Society %V 134 %P 6920-6923 %8 Apr %@ 0002-7863 %G eng %M WOS:000303139800009 %R 10.1021/ja301167y %0 Journal Article %J Physical Chemistry Chemical Physics %D 2012 %T Application of surface enhanced Raman spectroscopy to the study of SOFC electrode surfaces %A Li, X. X. %A Blinn, K. %A Fang, Y. C. %A Liu, M. F. %A Mahmoud, M A %A Cheng, S. %A Bottomley, L. A. %A El-Sayed, M. %A Liu, M. L. %X SERS provided by sputtered silver was employed to detect trace amounts of chemical species on SOFC electrodes. Considerable enhancement of Raman signal and lowered detection threshold were shown for coked nickel surfaces, CeO2 coatings, and cathode materials (LSM and LSCF), suggesting a viable approach to probing electrode degradation and surface catalytic mechanism. %B Physical Chemistry Chemical Physics %V 14 %P 5919-5923 %@ 1463-9076 %G eng %M WOS:000302363700004 %R 10.1039/c2cp40091j %0 Journal Article %J Acs Nano %D 2011 %T Remote Triggered Release of Doxorubicin in Tumors by Synergistic Application of Thermosensitive Liposomes and Gold Nanorods %A Agarwal, A. %A Mackey, M. A. %A El-Sayed, Mostafa A %A Bellamkonda, R. V. %X Delivery cif chemotherapeutic agents after encapsulation in nanocarriers such as liposomes diminishes side-effects, as PEGylated nanocarrier pharmacokinetics decrease dosing to healthy tissues and accumulate in tumors due to the enhanced permeability and retention effect. Once in the tumor, however, dosing of the chemotherapeutic to tumor cells is limited potentially by the rate of release from the carriers and the size-constrained, poor diffusivity of nanocarriers in tumor interstitium. Here, we report the design and fabrication of a thermosensitive liposomal nanocarder that maintains its encapsulation stability with a high concentration of doxorubicin payload, thereby minimizing "leak" and attendant toxicity. When used synergistically with PEGylated gold nanorods and near-infrared stimulation, remote triggered release of doxorubicin from thermosensitive liposomes was achieved in a mouse tumor model of human glioblastoma (U87), resulting in a. significant increase in efficacy when compared to nontriggered or nonthermosensitive PEGylated liposomes. This enhancement in efficacy is attributed to increase in tumor-site apoptosis, as was evident from noninvasive apoptosis imaging using Annexin-Vivo 750 probe. This strategy afford; remotely triggered control of tumor dosing of nanocarrier-encapsulated doxorubicin without sacrificing the ability to differentially dose drugs to tumors via the enhanced permeation and retention effect. %B Acs Nano %V 5 %P 4919-4926 %8 Jun %@ 1936-0851 %G eng %M WOS:000292055200077 %R 10.1021/nn201010q %0 Journal Article %J Journal of the American Chemical Society %D 2009 %T Gold Nanoparticles Surface Plasmon Field Effects on the Proton Pump Process of the Bacteriorhodopsin Photosynthesis %A Biesso, A. %A Qian, Wei %A Huang, Xiaohua %A El-Sayed, Mostafa A %X The rate of the proton pump of bacteriorhodopsin photosynthetic system is examined in the presence of a gold nanorod plasmon field. It is found that while the rate of the proton dissociation from the protonated Schiff base is not affected, the rate of its reprotonation increases. These results are qualitatively discussed in terms of several possible mechanisms. %B Journal of the American Chemical Society %V 131 %P 2442-+ %8 Feb %@ 0002-7863 %G eng %M WOS:000263576100012 %R 10.1021/ja8088873 %0 Journal Article %J Journal of the American Chemical Society %D 2008 %T Gold nanoparticle plasmonic field effect on the primary step of the other photosynthetic system in nature, bacteriorhodopsin %A Biesso, A. %A Qian, Wei %A El-Sayed, Mostafa A %X In regards to the effect of the surface plasmon field of gold nanospheres on the rate of primary steps leading to retinal photoisomerization in the photosynthesis of bacterirhodopsin (bR), 4 is believed that the light absorption of bR that leads to its retinal isomerization first involves the formation of a highly polar electronic excited state (1460) of the all-trans isomer which strongly polarizes the protein around it. This is followed by its decay to a viibrationally excited 13-cis isomer (J(625)). The effect of plasmonic field of gold nanospheres of different sizes and concentrations is found to slow down the rate of the isomerization of the polar electronic excited-state to the J625 but has no effect on the vibration relaxation of the isomeric state itself. This is consistent with the electrostatic nature of the plasmonic field. %B Journal of the American Chemical Society %V 130 %P 3258-+ %8 Mar %@ 0002-7863 %G eng %M WOS:000253951900013 %R 10.1021/ja7099858 %0 Journal Article %J Journal of Physical Chemistry C %D 2008 %T Time-resolved investigation of the acoustic vibration of a single gold nanoprism pair %A Burgin, J. %A Langot, P. %A Del Fatti, N. %A Vallee, F. %A Huang, Wenyu %A El-Sayed, Mostafa A %X The acoustic vibration of single gold nanoprism pairs on a glass substrate has been investigated in the time-domain combining a spatial modulation spectroscopy microscope with a high-sensitivity femtosecond pump-probe setup. Three modes were observed and ascribed to two in-plane and one out-of-plane vibration of the nanoprisms forming the pair, in agreement with a theoretical analysis. The periods of the two former modes with similar nature show weak (about 10%) and well correlated pair to pair fluctuations that can be unambiguously ascribed to variation of the prism geometry. In contrast, strong fluctuations, by almost a factor of 6, of the mode damping are evidenced with no correlation with their period. This indicates large variations of the prism-substrate coupling, providing a unique way for its local investigation. %B Journal of Physical Chemistry C %V 112 %P 11231-11235 %8 Jul %@ 1932-7447 %G eng %M WOS:000257927100026 %R 10.1021/jp802365s %0 Journal Article %J Chemical Reviews %D 2005 %T Chemistry and properties of nanocrystals of different shapes %A Burda, Clemens %A Chen, X. %A Narayanan, Radha %A El-Sayed, Mostafa A %B Chemical Reviews %I ACS Publications %V 105 %P 1025-1102 %@ 0009-2665 %G eng %U http://dx.doi.org/10.1021/cr030063a %N 4 %R 10.1021/cr030063a %0 Journal Article %J Physical Review BPhys. Rev. B %D 2002 %T Determination of the localization times of electrons and holes in the HgS well in a CdS/HgS/CdS quantum dot–quantum well nanoparticle %A Braun, Markus %A Link, Stephan %A Burda, Clemens %A El-Sayed, Mostafa A %X The femtosecond time-resolved electron-hole dynamics of the CdS/HgS/CdS quantum dot–quantum well system (QDQW) was investigated as a function of excitation energy. In the transient absorption spectra four bleach bands and a stimulated emission signal in the visible spectral range between 450 and 780 nm were resolved. By using an IR probe pulse at 4.7 μm a transient induced absorption due to intraband transitions was found. The decay and rise times of these signals were measured when the CdS core or the HgS well of the nanoparticles was excited by the pump pulse. After excitation within the HgS well the transient signals rise within the resolution of our pump pulse, while after core excitation slower rise times were measured. From the 1.5 ps rise time of the stimulated emission originating from the HgS well and the intraband hole IR absorption (150 fs) after excitation into the CdS core, the electron localization time (transfer time from the core to the well) is found to be 1.5 ps while that of the hole is ∼150 fs. This large difference in the observed dynamics of the electron and hole in crossing the CdS/HgS interface is discussed. %B Physical Review BPhys. Rev. B %I American Physical Society %V 66 %P 205312 - %8 2002/11/11/ %G eng %U http://link.aps.org/doi/10.1103/PhysRevB.66.205312 %N 20 %! PRB %R 10.1103/PhysRevB.66.205312 %0 Journal Article %J Chemical Physics Letters %D 2002 %T The effect of surface adsorption on the hyper-Rayleigh scattering of large and small CdSe nanoparticles %A Landes, Christy F. %A Braun, Markus %A El-Sayed, Mostafa A %X Hyper-Rayleigh scattering is used to compare the effect of the addition of n-butylamine to large (3.2 nm) and small (1.6 nm) Use nanoparticles (NPs). It is found that although the adsorption of n-butylamine on large NPs enhances their nonlinear optical response, it has the opposite effect when adsorbed on the small nanoparticles for which the amine adsorption was found previously to induce structural changes. This observation is consistent with an increase in the symmetry of the nanocrystal structure such as would be observed in a phase change from a 4-coordinate wurtzite crystal structure to that of a 6-coordinate zinc-blend form. (C) 2002 Published by Elsevier Science B.V. %B Chemical Physics Letters %V 363 %P 465-470 %8 Sep %@ 0009-2614 %G eng %M WOS:000178894900009 %R 10.1016/s0009-2614(02)01169-7 %0 Journal Article %J The Journal of chemical physics %D 2002 %T The pump power dependence of the femtosecond relaxation of CdSe nanoparticles observed in the spectral range from visible to infrared %A Burda, Clemens %A Link, Stephan %A Mohamed, MB %A El-Sayed, Mostafa A %X The pump power dependence of the relaxation dynamics of CdSe nanoparticles (NPs) was studied with femtosecond pump probe spectroscopy at observation wavelengths of the first exciton transition at 560 nm, the near infrared (NIR) absorption at 2 μm, and the transient mid-infrared (IR) absorption at 4.5 μm. Excitation with less than one photon per particle leads to bleaching of the excitonic transitions, and the bleach intensity is initially linear to the pump power. At higher pump power the bleach intensity levels off, when complete saturation of the excitonic transition is reached. At the same time, increasing pump power causes an acceleration of the bleach decay, which is due to additional Auger processes when multiple excitons are formed in the NPs. In addition, the pump power effect was investigated for the NIR and IR regions, at 2 and 4.5 μm wavelength, respectively. Whereas the IR transients are very similar to the ones observed for the bleach, the NIR transients behave completely different. No pump power dependence was found for the transients at 2 μm when pumped in a power range from 0.5 to 5 μJ per pulse. The results show that the fs transients in the visible (bleach) and IR (absorption) regions are due to electron relaxation in the conduction band and the NIR transients are due to the relaxation of the hole. Furthermore, it suggests that in the investigated CdSe NPs, Auger processes act much more efficiently on the electrons than for the holes. %B The Journal of chemical physics %V 116 %P 3828 %G eng %U http://link.aip.org/link/doi/10.1063/1.1446851 %R 10.1063/1.1446851 %0 Journal Article %J Photochemistry and Photobiology %D 2002 %T The quenching of CdSe quantum dots photoluminescence by gold nanoparticles in solution %A Nikoobakht, Babak %A Burda, Clemens %A Braun, Markus %A Hun, M. %A El-Sayed, Mostafa A %X The photoluminescence (PL) of CdSe quantum dots (QD) in aqueous media has been studied in the presence of gold nanoparticles (NP) with different shapes. The steady state PL intensity of CdSe QD (1.5-2 nm in size) is quenched in the presence of gold NP. Picosecond bleach recovery and nanosecond time-resolved luminescence measurements show a faster bleach recovery and decrease in the lifetime of the emitting states of CdSe QD in the presence of quenchers. Surfactant-capped gold nanorods (NR) with aspect ratio of 3 and surfactant-capped and citrate-capped nanospheres (NS) of 12 nm diameter were used as quenchers in order to study the effect of shape and surface charge on the quenching rates. The Stern-Volmer kinetics model is used to examine the observed quenching behavior as a function of the quencher concentration. It was found that the quenching rate of NR is more than 1000 times stronger than that of NS with the same capping material. We also found that the quenching rate decreases as the length of the NR decreases, although the overlap between the CdSe emission and the NR absorption increases. This suggests that the quenching is a result of electron transfer rather than long-range (Forster-type) energy transfer processes. The quenching was attributed to the transfer of electron with energies below the Fermi level of gold to the trap holes of CdSe QD. The observed large difference between NR and NS quenching efficiencies was attributed to the presence of the {110} facets only in the NR, which have higher surface energy. %B Photochemistry and Photobiology %V 75 %P 591-597 %8 Jun %@ 0031-8655 %G eng %M WOS:000176364000007 %R 10.1562/0031-8655(2002)075<0591:tqocqd>2.0.co;2 %0 Journal Article %J Langmuir %D 2002 %T Size effects of PVP-Pd nanoparticles on the catalytic Suzuki reactions in aqueous solution %A Li, Y. %A Boone, E. %A El-Sayed, Mostafa A %X A series of poly(N-vinyl-2-pyrrolidone) (PVP)-stabilized Pd nanoparticles with varying particle size are prepared by using the stepwise growth reaction. The effect of Pd particle size on the Suzuki reaction between phenylboronic acid and iodobenzene is investigated by the use of four Pd catalysts with mean particle sizes of 3.0, 3.9, 5.2, and 6.6 nm, respectively. The catalytic activity of the Pd nanoparticles expressed in terms of the initial turnover frequency (moles of the biphenyl product per mole of total surface Pd atoms per min) is found to be in the order of Pd (3.9 nm) > Pd (3.0 nm) approximate to Pd (5.2 nm) > Pd (6.6 nm), indicating that surface Pd atoms do not all have the same reactivity in this reaction. The general trend of increased catalytic activity with the decrease in the particle size suggests that the low-coordination number vertex and edge atoms on the particle surface are active sites for the Suzuki reaction. The lower catalytic activity for the smallest Pd nanoparticles might be due to stronger adsorption of the reaction intermediates on the particle surface, in which the strongly adsorbed species act as a poison to the reaction thereby decreasing the rate of the reaction. %B Langmuir %V 18 %P 4921-4925 %8 Jun %@ 0743-7463 %G eng %M WOS:000176091900056 %R 10.1021/la011469q %0 Journal Article %J Chemical physics letters %D 2002 %T Transfer times of electrons and holes across the interface in CdS/HgS/CdS quantum dot quantum well nanoparticles %A Braun, Markus %A Link, Stephan %A Burda, Clemens %A El-Sayed, Mostafa A %X The electron and hole trapping times in the HgS well of a 6 nm CdS/HgS/CdS quantum dot quantum well nanoparticle were determined from the rise time of the ultrafast transient absorption in the visible and IR regions as well as the trap fluorescence when the CdS core is excited. From the 1.5 ps observed rise time of the well fluorescence (which is determined by the trapping time of the slowest carrier) and the intraband hole IR absorption (150 fs), the electron localization time is found to be 1.5 ps while that of the hole is ∼150 fs. This large difference in the observed dynamics of the electron and hole in crossing the CdS/HgS interface is discussed. %B Chemical physics letters %I Elsevier %V 361 %P 446-452 %@ 0009-2614 %G eng %U http://dx.doi.org/10.1016/S0009-2614(02)01001-1 %N 5-6 %R 10.1016/S0009-2614(02)01001-1 %0 Journal Article %J Journal of Physical Chemistry B %D 2002 %T Visible to infrared luminescence from a 28-atom gold cluster %A Link, Stephan %A Beeby, A. %A FitzGerald, S. %A El-Sayed, Mostafa A %A Schaaff, T. G. %A Whetten, R. L. %X The luminescence properties of chemically prepared gold nanoclusters, each composed of a 28-atom core and a glutathione (GSH) adsorbate layer consisting of 16 molecules, were investigated. These clusters show a distinct absorption onset at 1.3 eV corresponding to the opening of an electronic gap within the conduction band (HOMO-LUMO gap). Here we report on the radiative properties of these molecular-like Bald clusters. By using a combination of different detectors with sensitivities in the visible to the infrared (2.0-0.8 eV), a broad luminescence extending over this entire spectral range was observed. Our results further suggest that the luminescence can be separated into two bands with maxima around 1.5 and 1.15 eV indicating that radiative recombination between the ground state and two distinctively different excited states takes place. The: origin of the observed luminescence bands is discussed using a solid state as well as a molecular model for the electronic structure and relaxation of the clusters. The total quantum yield of the luminescence: as measured at ambient temperature was approximated to be about (3.5 +/- 1.0) x 10(-3). %B Journal of Physical Chemistry B %V 106 %P 3410-3415 %8 Apr %@ 1520-6106 %G eng %M WOS:000174792600011 %R 10.1021/jp014259v %0 Journal Article %J Journal of Chemical Physics %D 2001 %T Formation of quantum-dot quantum-well heteronanostructures with large lattice mismatch: ZnS/CdS/ZnS %A Little, Reginald %A El-Sayed, Mostafa A %A Bryant, G. W. %A Burke, S. %X Two-dimensional heterostructures have been exploited extensively in the synthesis of optoelectronic devices. Structures with small lattice mismatch can be synthesized readily. Large lattice mismatch in II-VI film heterostructures makes synthesis of devices with these materials more difficult. However, these large mismatch heterostructures usually have useful optical properties. One such heterostructure is the ZnS/CdS system with a large exciton binding energy and a large band gap useful for blue-green emitting devices. In this work, small II-VI nanoparticles are studied. We show that II-VI heterostructures can be made in quantum dots, despite the large bulk lattice mismatch. Two well-known techniques are combined to synthesize first very small ZnS and CdS seed nanoparticles and then do nanoepitaxy on them to produce ZnS/CdS core/shell quantum-dot quantum-well heteronanostructures. These structures are characterized by UV visible absorbance. Measured spectra are compared with electronic level structures calculated for the fabricated heteronanostructures with a tight-binding model. The consistency of the observed spectra with the predicted transitions indicates that the desired core/shell and core/shell/clad structures were grown. The metastability of the ZnS/CdS/ZnS heteronanostructures is attributed to low-temperature construction and small crystal size (<3 nm). The small particle size should produce large surface forces and ZnS core contraction. Also, the small particle size should accommodate strain, as a result of the ZnS/CdS interfacial curvature, which is not possible for planar systems. Furthermore, this new structure is kinetically stabilized against alloying by the large size difference between the Cd2+ ion and Zn2+ ions. We suggest that all of these factors contribute to the formation of quantum-dot quantum-well ZnS/CdS/ZnS heteronanostructures. (C) 2001 American Institute of Physics. %B Journal of Chemical Physics %V 114 %P 1813-1822 %8 Jan %@ 0021-9606 %G eng %M WOS:000166647300044 %R 10.1063/1.1333758 %0 Journal Article %J Chemical Physics Letters %D 2001 %T Hot electron and phonon dynamics of gold nanoparticles embedded in a gel matrix %A Mohamed, MB %A Ahmadi, Temer S. %A Link, Stephan %A Braun, Markus %A El-Sayed, Mostafa A %X Using pump-probe technique, the dynamics of the hot carriers in metallic nanodots induced by femtosecond laser pulses are investigated in gold nanoparticles embedded in hydrogel and in organic gel and compared to that in aqueous solution. We found that changing the surrounding matrix from aqueous solution to hydrogel and then to organic gel leads to a large increase in the relaxation time of both the electron-phonon (e-ph) and the phonon-phonon (ph-ph) coupling. Furthermore, the ph-ph relaxation time becomes sensitive to the type of the organic solvent trapped in the gel network. This indicates that the relaxation dynamics depend on the thermal conductivity, chemical structure and the molecular dynamics of the surrounding medium. (C) 2001 Elsevier Science BN. All rights reserved. %B Chemical Physics Letters %V 343 %P 55-63 %8 Jul %@ 0009-2614 %G eng %M WOS:000170144200010 %R 10.1016/s0009-2614(01)00653-4 %0 Journal Article %J The Journal of Physical Chemistry B %D 2001 %T On the Nanoparticle to Molecular Size Transition:  Fluorescence Quenching Studies %A Landes, Christy F. %A Braun, Markus %A El-Sayed, Mostafa A %X Semiconductor nanoparticles, NPs, exhibit fluorescence properties that are closely related to the nature of their surface. CdSe NPs that range in size from 2 to 15 nm in diameter fluoresce with both near-band-edge emission and deep-trap emission, depending on the quality of the surface. When butylamine is added to colloidal solutions of NPs in this size range, the amine is thought to bind to the NP surface and eliminate radiant recombination pathways that lead to luminescence. Since the amine binds to the NP surface, the decrease in fluorescence intensity does not follow standard molecular models of collisional fluorescence quenching. NPs that are smaller than ?2 nm are composed entirely of a discontinuous arrangement of atoms that are all in constant chemical contact with capping material, solvent, and contaminants. When butylamine is added to solutions of these smaller NPs, the fluorescence quenching follows more standard collisional quenching models. Thus, by monitoring the interaction between NPs and a hole acceptor such as butylamine, one can observe the transition from NP, with atoms both in the core and on the surface, to molecular cluster, with no core atoms to dominate the electron density, but with only surface atoms that can participate in molecular processes such as electron transfer.Semiconductor nanoparticles, NPs, exhibit fluorescence properties that are closely related to the nature of their surface. CdSe NPs that range in size from 2 to 15 nm in diameter fluoresce with both near-band-edge emission and deep-trap emission, depending on the quality of the surface. When butylamine is added to colloidal solutions of NPs in this size range, the amine is thought to bind to the NP surface and eliminate radiant recombination pathways that lead to luminescence. Since the amine binds to the NP surface, the decrease in fluorescence intensity does not follow standard molecular models of collisional fluorescence quenching. NPs that are smaller than ?2 nm are composed entirely of a discontinuous arrangement of atoms that are all in constant chemical contact with capping material, solvent, and contaminants. When butylamine is added to solutions of these smaller NPs, the fluorescence quenching follows more standard collisional quenching models. Thus, by monitoring the interaction between NPs and a hole acceptor such as butylamine, one can observe the transition from NP, with atoms both in the core and on the surface, to molecular cluster, with no core atoms to dominate the electron density, but with only surface atoms that can participate in molecular processes such as electron transfer. %B The Journal of Physical Chemistry B %I American Chemical Society %V 105 %P 10554 - 10558 %8 2001 %@ 1520-6106 %G eng %U http://dx.doi.org/10.1021/jp0118726 %N 43 %! J. Phys. Chem. B %0 Journal Article %J Nano Letters %D 2001 %T Observation of large changes in the band gap absorption energy of small CdSe nanoparticles induced by the adsorption of a strong hole acceptor %A Landes, Christy F. %A Braun, Markus %A Burda, Clemens %A El-Sayed, Mostafa A %X When butylamine In relatively high concentrations (0.1-0.25 M) is added to a colloidal solution of CdSe nanoparticles (NPs) that are approximately 1.6 nm in diameter, the band gap absorption changes from a broad, relatively weak absorption centered at 445 nm to a narrow, relatively strong absorption centered at 414 nm. The effect of concentration on the observed spectrum shows an isobestic point, suggesting an equilibrium between two species. The possible mechanisms for such a transformation are discussed. %B Nano Letters %V 1 %P 667-670 %8 Nov %@ 1530-6984 %G eng %M WOS:000173721800016 %R 10.1021/nl015619t %0 Journal Article %J Journal of Physical Chemistry B %D 2001 %T Photoluminescence of CdSe nanoparticles in the presence of a hole acceptor: n-butylamine %A Landes, Christy F. %A Burda, Clemens %A Braun, Markus %A El-Sayed, Mostafa A %X Addition of butylamine to a solution of colloidal CdSe nanoparticles (NPs) caused a decrease in fluorescence intensity, with no effect on the picosecond bleach recovery of the exciton formation or on the luminescence dynamics. The relative fluorescence quantum yield was found to decrease with increasing butylamine concentration and to level off at high concentrations, but the fluorescence lifetimes were not influenced. The nonlinear concentration dependence of the fluorescence quantum yield did not follow the Stern-Volmer equation. This is in agreement with the observation that the CdSe luminescence lifetime was not affected by the addition of butylamine. A mechanism is proposed in which the emission observed in CdSe is assumed to result from the combination of surface-trapped electrons and holes. n-Butylamine occupies hole sites, thus blocking the recombination process, which results in decreasing the density of luminescent centers. These results will be discussed in terms of the nature of the binding sites of the amine on the nanoparticle surface. %B Journal of Physical Chemistry B %V 105 %P 2981-2986 %8 Apr %@ 1089-5647 %G eng %M WOS:000168257700017 %R 10.1021/jp0041050 %0 Journal Article %J Proceedings of the National Academy of Sciences of the United States of America %D 2001 %T The relaxation dynamics of the excited electronic states of retinal in bacteriorhodopsin by two-pump-probe femtosecond studies %A Logunov, Stephan L. %A Volkov, V. V. %A Braun, Markus %A El-Sayed, Mostafa A %X We present the results of two-pump and probe femtosecond experiments designed to follow the relaxation dynamics of the lowest excited state (S-1) populated by different modes. In the first mode, a direct (S-0 --> S-1) radiative excitation of the ground state is used. In the second mode, an indirect excitation is used where the S-1 state is populated by the use of two femtosecond laser pulses with different colors and delay times between them. The first pulse excites the S-0 --> S-1 transition whereas the second pulse excites the S-1 --> S-n transition. The nonradiative relaxation from the S-n state populates the lowest excited state. Our results suggest that the S1 state relaxes faster when populated nonradiatively from the S-n state than when pumped directly by the S-0 --> S-1 excitation. Additionally, the S-n --> S-1 nonradiative relaxation time is found to change by varying the delay time between the two pump pulses. The observed dependence of the lowest excited state population as well as its dependence on the delay between the two pump pulses are found to fit a kinetic model in which the S-n state populates a different surface (called Si) than the one being directly excited (S-1). The possible involvement of the A(g) type states, the J intermediate, and the conical intersection leading to the S-0 or to the isomerization product (K intermediate) are discussed in the framework of the proposed model. %B Proceedings of the National Academy of Sciences of the United States of America %V 98 %P 8475-8479 %8 Jul %@ 0027-8424 %G eng %M WOS:000169967000050 %R 10.1073/pnas.141220198 %0 Journal Article %J Journal of Physical Chemistry A %D 2001 %T Variation of the thickness and number of wells in the CdS/HgS/CdS quantum dot quantum well system %A Braun, Markus %A Burda, Clemens %A El-Sayed, Mostafa A %X We report on the first chemically prepared multilayer quantum well structure in a semiconductor quantum dot. By subsequent precipitation of HgS, CdS, HgS, and again CdS from aqueous solution, we obtained nanoparticles which contain two HBS quantum wells separated by a double layer of CdS. The:core:and the capping material is also CdS. The two-well system was characterized by absorption and emission spectroscopy, which clearly reveal the formation of a two-well and not a single double-layered quantum well system. This system allows to study the interaction of quantum wells that are separated by different thicknesses of the CdS barriers. The radiative and relaxation dynamics of the new two-well system are compared with the dynamics of systems having a single-layer well and a double-layer well system. %B Journal of Physical Chemistry A %V 105 %P 5548-5551 %8 Jun %@ 1089-5639 %G eng %M WOS:000169371200006 %R 10.1021/jp010002l %0 Journal Article %J Journal of the American Chemical Society %D 2000 %T Femtosecond dynamics of a simple merocyanine dye: Does deprotonation compete with isomerization? %A Burda, Clemens %A Abdel-Kader, M. H. %A Link, Stephan %A El-Sayed, Mostafa A %X The primary photochemistry of the trans isomer of a simple merocyanine dye of the stilbazolium betaine type 1-methyl-4-(4'-hydroxytyryl)pyridinium betaine (M-trans) and its conjugate acid MHtrans+ in aqueous solution is studied by femtosecond time-resolved pump probe spectroscopy. The measured rate of the primary photodynamics is determined to be k = 1.1 x 10(12) s(-1) for M-trans at pH 10 and 0.8 x 10(12) s(-1) for MHtrans+ at pH 6. This was assigned to either conformational changes or a simple vibrational relaxation before the actual isomerization takes place. Wavelength excitation studies give support for the former assignment. These results an discussed in terms of the recent results found for the primary processes of retinal in bacteriorhodopsin. Time-resolved transient measurements show that no excited-state deprotonation of MHtrans+ occurs in aqueous solutions at pH 6 or pH 0, suggesting that the deprotonation occurs on a longer time scale than the picosecond time domain. This is in agreement with present theories of intermolecular proton-transfer reactions, which require solvent reorganization as well as the time of deprotonation estimated from the pK(a) value of this molecule in the excited state. The results of our MO calculations on the electronic structure of these two compounds could account for the fact that, while MHtrans+ photoisomerizes, its deprotonated form does not. %B Journal of the American Chemical Society %V 122 %P 6720-6726 %8 Jul %@ 0002-7863 %G eng %M WOS:000088320700023 %R 10.1021/ja993940w %0 Journal Article %J Physical Review B %D 2000 %T Femtosecond transient-absorption dynamics of colloidal gold nanorods: Shape independence of the electron-phonon relaxation time %A Link, Stephan %A Burda, Clemens %A Mohamed, MB %A Nikoobakht, Babak %A El-Sayed, Mostafa A %X We studied the femtosecond dynamics of colloidal gold nanorods encapsulated in micelles after excitation with 400 nm pulses of 100 fs duration. It is found that the laser heating of the electron gas of gold nanorods with an average aspect ratio of 3.8 leads to the bleaching of both the transverse and longitudinal mode of the surface plasmon oscillation at 520 and 750 nm. The bleach recovers with the same time constant for both the transverse and longitudinal oscillation, for gold nanodots prepared by photothermal reshaping of the rods as well as for nanodots synthesized chemically by citrate reduction (and known to have twin boundaries and surface defects). Since the bleach recovery on the 3 ps time scale is assigned to electron-phonon relaxation processes, these results suggest that phonon dependent relaxation processes in gold nanoparticles are independent of the shape, size, type of the surfaces, or the mode of the surface plasmon, oscillation excited. The fact that the mean free path of the electron in metallic gold is in the nanometer length scale (similar to 50 nm) raised the question of the importance of surface scattering to the electron-phonon relaxation process in gold nanoparticles. Our previous studies showed little dependence of the relaxation rate of the size of gold nanodots (from 9 to 48 nm). In the present study, the electron-phonon relaxation is measured in gold nanorods, which have different facets from those of gold nanodots. %B Physical Review B %V 61 %P 6086-6090 %8 Mar %@ 1098-0121 %G eng %M WOS:000085707100051 %R 10.1103/PhysRevB.61.6086 %0 Journal Article %J Pure and Applied Chemistry %D 2000 %T High-density femtosecond transient absorption spectroscopy of semiconductor nanoparticles. A tool to investigate surface quality %A Burda, Clemens %A El-Sayed, Mostafa A %X At the high laser excitation intensities used in our experiments, more than 50 electron-hole pairs are formed in colloidal semiconductor nanoparticles used in our studies. At this density of charge carriers, new transient absorptions are observed in the femtosecond transient spectra in the 450 to 700 nm region with unresolved fast rise (<100 fs) and two decay components of 660 fs and >150 ps. The absorption at 510 nm could be quenched with the adsorption of electron accepters (e.g., benzoquinone, 1,2-naphthoquinone), whereas the low-energy transient absorption was not affected. For CdS NPs, we found that passivation eliminated most of the transient absorption. The transient absorptions are thus proposed to result from either trap-state absorption, trapped dimers (or complexes) and/or Stark-shifted exciton absorption resulting from surface electric field of the uncompensated trapped electron-hole pairs. All these possibilities require effective surface trapping at these high levels of excitation. %B Pure and Applied Chemistry %V 72 %P 165-177 %8 Jan-Feb %@ 0033-4545 %G eng %M WOS:000087833100019 %R 10.1351/pac200072010165 %0 Journal Article %J Journal of Physical Chemistry B %D 2000 %T Laser-induced shape changes of colloidal gold nanorods using femtosecond and nanosecond laser pulses %A Link, Stephan %A Burda, Clemens %A Nikoobakht, Babak %A El-Sayed, Mostafa A %X Gold nanorods have been found to change their shape after excitation with intense pulsed laser irradiation. The final irradiation products strongly depend on the energy of the laser pulse as well as on its width. We performed a series of measurements in which the excitation power was varied over the range of the output power of an amplified femtosecond laser system producing pulses of 100 fs duration and a nanosecond optical parametric oscillator (OPO) laser system having a pulse width of 7 ns. The shape transformations of the gold nanorods are followed by two techniques: (1) visible absorption spectroscopy by monitoring the changes in the plasmon absorption bands characteristic for gold nanoparticles; (2) transmission electron microscopy (TEM) in order to analyze the final shape and size distribution. While at high laser fluences (similar to 1 J cm(-2)) the gold nanoparticles fragment, a melting of the nanorods into spherical nanoparticles (nanodots) is observed when the laser energy is lowered. Upon decreasing the energy of the excitation pulse, only partial melting of the nanorods takes place. Shorter but wider nanorods are observed in the final distribution as well as a higher abundance of particles having odd shapes (bent, twisted, phi-shaped, etc.). The threshold for complete melting of the nanorods with femtosecond laser pulses is about 0.01 J cm(-2). Comparing the results obtained using the two different types of excitation sources (femtosecond vs nanosecond laser), it is found that the energy threshold for a complete melting of the nanorods into nanodots is about 2 orders of magnitude higher when using nanosecond laser pulses than with femtosecond laser pulses. This is explained in terms of the successful competitive cooling process of the nanorods when the nanosecond laser pulses are used. For nanosecond pulse excitation, the absorption of the nanorods decreases during the laser pulse because of the bleaching of the longitudinal plasmon band. In addition, the cooling of the lattice occurring on the 100 ps time scale can effectively compete with the rate of absorption in the case of the nanosecond pulse excitation but not for the femtosecond pulse excitation. When the excitation source is a femtosecond laser pulse, the involved precesses (absorption of the photons by the electrons (100 fs), heat transfer between the hot electrons and the lattice (<10 ps), melting (30 ps), and heat loss to the surrounding solvent (>100 ps) are clearly separated in time. %B Journal of Physical Chemistry B %V 104 %P 6152-6163 %8 Jul %@ 1089-5647 %G eng %M WOS:000088057100012 %R 10.1021/jp000679t %0 Journal Article %J Journal of Chemical Physics %D 1999 %T Electron dynamics in gold and gold-silver alloy nanoparticles: The influence of a nonequilibrium electron distribution and the size dependence of the electron-phonon relaxation %A Link, Stephan %A Burda, Clemens %A Wang, Z.L. %A El-Sayed, Mostafa A %X Electron dynamics in gold nanoparticles with an average diameter between 9 and 48 nm have been studied by femtosecond transient absorption spectroscopy. Following the plasmon bleach recovery after low power excitation indicates that a non-Fermi electron distribution thermalizes by electron-electron relaxation on a time scale of 500 fs to a Fermi distribution. This effect is only observed at low excitation power and when the electron distribution is perturbed by mixing with the intraband transitions within the conduction band (i.e., when the excitation wavelength is 630 or 800 nm). However, exciting the interband transitions at 400 nm does not allow following the early electron thermalization process. Electron thermalization with the lattice of the nanoparticle by electron-phonon interactions occurs within 1.7 ps under these conditions, independent of the excitation wavelength. In agreement with the experiments, simulations of the optical response arising from thermalized and nonthermalized electron distributions show that a non-Fermi electron distribution leads to a less intense bleach of the plasmon absorption. Furthermore, the difference between the response from the two electron distributions is greater for small temperature changes of the electron gas (low excitation powers). No size dependence of the electron thermalization dynamics is observed for gold nanoparticles with diameters between 9 and 48 nm. High-resolution transmission electron microscopy (HRTEM) reveals that these gold nanoparticles possess defect structures. The effect of this on the electron-phonon relaxation processes is discussed. 18 nm gold-silver alloy nanoparticles with a gold mole fraction of 0.8 are compared to 15 nm gold nanoparticles. While mixing silver leads to a blue-shift of the plasmon absorption in the ground-state absorption spectrum, no difference is observed in the femtosecond dynamics of the system. (C) 1999 American Institute of Physics. [S0021-9606(99)71427-3]. %B Journal of Chemical Physics %V 111 %P 1255-1264 %8 Jul %@ 0021-9606 %G eng %M WOS:000081309100051 %R 10.1063/1.479310 %0 Journal Article %J The Journal of Physical Chemistry B %D 1999 %T Electron Shuttling Across the Interface of CdSe Nanoparticles Monitored by Femtosecond Laser Spectroscopy %A Burda, Clemens %A Green, T.C. %A Link, Stephan %A El-Sayed, Mostafa A %X The formation and decay of the optical hole (bleach) for 4 nm CdSe nanoparticles (NPs) with adsorbed electron acceptors (1,4-benzoquinone and 1,2-naphthoquinone) and the rise and decay of the reduced electron acceptors formed after interfacial electron transfer from the CdSe NPs were investigated by femtosecond laser spectroscopy. The ultrashort (200?400 fs) rise times of the bleach at the band-gap energy of the CdSe NP as well as of the acceptor radical anion are found to increase with increasing the excitation energy. This suggests that the electron transfer from the CdSe NP to the quinone electron acceptor occurs after thermalization of the excited hot electrons. The decay times of the transient absorption for the electron acceptor radical anions are found to be comparable to that of the CdSe NP bleach recovery time (3 ps). This suggests that the surface quinones shuttle the electron from the conduction band to the valence band of the excited NP. We contrast this behavior with the excited-state dynamics of the recently investigated CdS?MV2+ system in which the electron acceptor does not shuttle the accepted electron back to the hole in CdS.The formation and decay of the optical hole (bleach) for 4 nm CdSe nanoparticles (NPs) with adsorbed electron acceptors (1,4-benzoquinone and 1,2-naphthoquinone) and the rise and decay of the reduced electron acceptors formed after interfacial electron transfer from the CdSe NPs were investigated by femtosecond laser spectroscopy. The ultrashort (200?400 fs) rise times of the bleach at the band-gap energy of the CdSe NP as well as of the acceptor radical anion are found to increase with increasing the excitation energy. This suggests that the electron transfer from the CdSe NP to the quinone electron acceptor occurs after thermalization of the excited hot electrons. The decay times of the transient absorption for the electron acceptor radical anions are found to be comparable to that of the CdSe NP bleach recovery time (3 ps). This suggests that the surface quinones shuttle the electron from the conduction band to the valence band of the excited NP. We contrast this behavior with the excited-state dynamics of the recently investigated CdS?MV2+ system in which the electron acceptor does not shuttle the accepted electron back to the hole in CdS. %B The Journal of Physical Chemistry B %I American Chemical Society %V 103 %P 1783 - 1788 %8 1999 %@ 1520-6106 %G eng %U http://dx.doi.org/10.1021/jp9843050 %N 11 %! J. Phys. Chem. B %R doi: 10.1021/jp9843050 %0 Journal Article %J Chemical Physics Letters %D 1999 %T How long does it take to melt a gold nanorod? A femtosecond pump-probe absorption spectroscopic study %A Link, Stephan %A Burda, Clemens %A Nikoobakht, Babak %A El-Sayed, Mostafa A %X Using pump-probe femtosecond transient absorption spectroscopy, we determined the rate of the bleach of absorption around 700-800 nm due to the longitudinal surface plasmon band of gold nanorods. Using TEM of the spotted, completely irradiated solutions suggest that the dominant products of the photothermal conformation of the rods are spheres of comparable volume. This lead to the conclusion that the melting of the rods is at least 30-35 ps, independent of the power used (5-20 mu J) or the nanorod aspect ratio (1.9-3.7). (C) 1999 Elsevier Science B.V. All rights reserved. %B Chemical Physics Letters %V 315 %P 12-18 %8 Dec %@ 0009-2614 %G eng %M WOS:000084321900003 %R 10.1016/s0009-2614(99)01214-2 %0 Journal Article %J Journal of Physical Chemistry A %D 1999 %T Laser photothermal melting and fragmentation of gold nanorods: Energy and laser pulse-width dependence %A Link, Stephan %A Burda, Clemens %A Mohamed, MB %A Nikoobakht, Babak %A El-Sayed, Mostafa A %X We studied the shape transformation (by use of TEM and optical absorption spectroscopy) of gold nanorods in micellar solution by exposure to laser pulses of different pulse width (100 fs and 7 ns) and different energies (mu J to mJ) at 800 nm, where the longitudinal surface plasmon oscillation of the nanorods absorb. At moderate energies, the femtosecond irradiation melts the nanorods to near spherical particles of comparable volumes while the nanosecond pulses fragment them to smaller near-spherical particles. At high energies, fragmentation is also observed for the femtosecond irradiation. A mechanism involving the rate of energy deposition as compared to the rate of electron-phonon and phonon-phonon relaxation processes is proposed to determine the final fate of the laser-exposed nanorods, i.e., melting or fragmentation. %B Journal of Physical Chemistry A %V 103 %P 1165-1170 %8 Mar %@ 1089-5639 %G eng %M WOS:000079150000001 %R 10.1021/jp983141k %0 Journal Article %J Journal of Physical Chemistry B %D 1999 %T New transient absorption observed in the spectrum of colloidal CdSe nanoparticles pumped with high-power femtosecond pulses %A Burda, Clemens %A Link, Stephan %A Green, T.C. %A El-Sayed, Mostafa A %X The power dependence of the transient absorption spectrum of CdSe nanoparticle colloids with size distribution of 4.0 +/- 0.4 nm diameter is studied with femtosecond pump-probe techniques. At the lowest pump laser power, the absorption bleaching (negative spectrum) characteristic of the exciton spectrum is observed with maxima at 560 and 480 nm, As the pump laser power increases, two new transient absorptions at 510 and 590 nm with unresolved fast rise (<100 fs) and long decay times (much greater than 150 ps) are observed. The energy of each of the positive absorption is red shifted from that of the bleach bands by similar to 120 meV. The origin of this shift is discussed in terms of the effect of the internal electric field of the many electron-hole pairs formed within the quantum dot at the high pump intensity, absorption from a metastable excited state or the formation of biexcitons. %B Journal of Physical Chemistry B %V 103 %P 10775-10780 %8 Dec %@ 1089-5647 %G eng %M WOS:000084318600007 %R 10.1021/jp991503y %0 Journal Article %J Journal of Physical Chemistry A %D 1998 %T Charge separation effects on the rate of nonradiative relaxation processes in quantum dots quantum well heteronanostructures %A Little, Reginald %A Burda, Clemens %A Link, Stephan %A Logunov, Stephan L. %A El-Sayed, Mostafa A %X Using time-resolved optical hole (oh)-burning techniques with femtosecond lasers, the time dependence of the spectral diffusion of the oh is examined for both the CdS quantum dot (QD) and the CdS/HgS/CdS quantum dot quantum well (QDQW) nanoparticles. It is found that the nonradiative relaxation of the optical hole is at least 3 orders of magnitude slower in the QDQW than in the QD system. Analysis of the second derivative of the broad transient bleach spectrum of the QDQW system in the 1.6-2.5 eV energy region at 50 fs delay time is found to have a minimum at 2.1 eV, corresponding to a minimum in the radiative probability. Around this energy, the rise and decay times of the transient bleach in the spectrum an found to change greatly. These results suggest that spectral diffusion in the QDQW is a result of relaxation from high- to low-energy exciton states, involving an intervening dark state at an energy of similar to 2.0 eV. The energies of the maxima and minimum of the second-derivative curve are found to be in good agreement with recent theoretical calculations by Jaskolski and Bryant(1) of the energies of the radiative and dark charge-separated state, respectively. In the latter, the hole is in the CdS clad and the electron is in the HgS well. The slow nonradiative relaxation processes involving this state are expected to be slow owing to the large change in the charge carrier effective masses as they cross from the CdS clad to the HgS well. %B Journal of Physical Chemistry A %V 102 %P 6581-6584 %8 Aug %@ 1089-5639 %G eng %M WOS:000075509700001 %R 10.1021/jp9822687 %0 Journal Article %J MRS Proceedings %D 1998 %T Femtosecond Interfacial Electron Transfer Dynamics of CdSe Semiconductor Nanoparticles %A Burda, Clemens %A Green, T.C. %A Link, Stephan %A El-Sayed, Mostafa A %X The effect of the adsorption of an electron donor (thiophenol, TP) on the surface of CdSe nanoparticles (NPs) on the emission and electron-hole dynamics is studied. It is found that while the emission is completely quenched, the effect on the transient bleach recovery of the band gap absorption is only slight. This is explained by a mechanism in which the hole in the valence band of the NP is rapidly neutralized by electron transfer from the TP. However, the excited electron in the conduction band is not transferred to the TP cation, i. e. the electron does not shuttle via the organic moiety as it does when naphthoquinone is adsorbed [1]. The excited electron is rather trapped by surface states. Thus the rate of bleach recovery in the CdSe NP system is determined by the rate of electron trapping and not by hole trapping. Comparable conclusions resulted previously [2] for the CdS NP when the CdS-MV2+ system is studied. A comparative discussion of the electron-hole dynamics in these systems (CdSe-NQ, CdS-MV2+ and CdSe-TP) is given. %B MRS Proceedings %V 43 %P 419-424 %N 4 %R 10.1557/PROC-536-419 %0 Journal Article %J The Journal of Physical Chemistry %D 1996 %T Calcium and Magnesium Binding in Native and Structurally Perturbed Purple Membrane %A Griffiths, Jennifer A. %A King, John %A Yang, Difei %A Browner, Richard %A El-Sayed, Mostafa A %X The number and identity of the metal cations bound to wild-type bacteriorhodopsin (bR) are determined by using inductively coupled plasma mass spectrometry (ICP-MS) and ICP emission techniques. The results indicate that there at ≈2 total Ca2+ and Mg2+ per bR molecule with a ratio of ≈3:1 Ca2+ to Mg2+. This observed ratio is found to agree with the calculated ratio using previously determined binding constants for the two high affinity sites of Ca2+ to deionized bR (Zhang; et al. Biophys. J. 1992, 61, 1201). This suggests that the high-affinity binding sites in deionized bR are similar to those in native bR. Structural perturbation of the native membrane by cleavage of the C-terminus decreases the number of ions per bR to 1.4. The observed ratio of total ions in this sample to total ions in bR is found to agree with that calculated using known binding constants for each. The results on the number of metal cations/bR and their ratio in bacterio-opsin agrees with the calculated number using previously observed binding constants in deionized bO (Yang; et al. Biophys J., in press) only if one assumes that the second high-affinity site (not the first) is removed by retinal removal. Removal of 75% of the lipids from the purple membrane is found to greatly reduce the number of metal cations from 2 to 0.16. This suggest that if metal cations are in the two high-affinity sites (which are the only type of binding sites evident in our native bR sample), the removal of lipids, known to change the protein tertiary structure, changes also the metal ion binding sites.The number and identity of the metal cations bound to wild-type bacteriorhodopsin (bR) are determined by using inductively coupled plasma mass spectrometry (ICP-MS) and ICP emission techniques. The results indicate that there at ≈2 total Ca2+ and Mg2+ per bR molecule with a ratio of ≈3:1 Ca2+ to Mg2+. This observed ratio is found to agree with the calculated ratio using previously determined binding constants for the two high affinity sites of Ca2+ to deionized bR (Zhang; et al. Biophys. J. 1992, 61, 1201). This suggests that the high-affinity binding sites in deionized bR are similar to those in native bR. Structural perturbation of the native membrane by cleavage of the C-terminus decreases the number of ions per bR to 1.4. The observed ratio of total ions in this sample to total ions in bR is found to agree with that calculated using known binding constants for each. The results on the number of metal cations/bR and their ratio in bacterio-opsin agrees with the calculated number using previously observed binding constants in deionized bO (Yang; et al. Biophys J., in press) only if one assumes that the second high-affinity site (not the first) is removed by retinal removal. Removal of 75% of the lipids from the purple membrane is found to greatly reduce the number of metal cations from 2 to 0.16. This suggest that if metal cations are in the two high-affinity sites (which are the only type of binding sites evident in our native bR sample), the removal of lipids, known to change the protein tertiary structure, changes also the metal ion binding sites. %B The Journal of Physical Chemistry %I American Chemical Society %V 100 %P 929 - 933 %8 1996 %@ 0022-3654 %G eng %U http://dx.doi.org/10.1021/jp952951i %N 3 %! J. Phys. Chem. %R doi: 10.1021/jp952951i %0 Journal Article %J Proceedings of the National Academy of Sciences of the United States of America %D 1996 %T Detection of a Yb3+ binding site in regenerated bacteriorhodopsin that is coordinated with the protein and phospholipid head groups. %A Roselli, Cecile %A Boussac, A %A Mattioli, T A %A Griffiths, Jennifer A. %A El-Sayed, Mostafa A %K Bacteriorhodopsins %K Binding Sites %K Metals, Rare Earth %K Phospholipids %K Retinaldehyde %K Spectroscopy, Near-Infrared %X Near infrared Yb3+ vibronic sideband spectroscopy was used to characterize specific lanthanide binding sites in bacteriorhodopsin (bR) and retinal free bacteriorhodopsin (bO). The VSB spectra for deionized bO regenerated with a ratio of 1:1 and 2:1 ion to bO are identical. Application of a two-dimensional anti-correlation technique suggests that only a single Yb3+ site is observed. The Yb3+ binding site in bO is observed to consist of PO2- groups and carboxylic acid groups, both of which are bound in a bidentate manner. An additional contribution most likely arising from a phenolic group is also observed. This implies that the ligands for the observed single binding site are the lipid head groups and amino acid residues. The vibronic sidebands of Yb3+ in deionized bR regenerated at a ratio of 2:1 ion to bR are essentially identical to those in bO. The other high-affinity binding site is thus either not evident or its fluorescence is quenched. A discussion is given on the difference in binding of Ca2+ (or Mg2+) and lanthanides in phospholipid membrane proteins. %B Proceedings of the National Academy of Sciences of the United States of America %V 93 %P 14333-7 %8 1996 Dec 10 %G eng %N 25 %1 http://www.ncbi.nlm.nih.gov/pubmed/8962051?dopt=Abstract %0 Journal Article %J Advanced Materials %D 1993 %T Recording of transient gratings using the short lived bacteriorhodopsin photocycle intermediates %A Wu, Shuguang %A Bräuchle, Christoph %A El-Sayed, Mostafa A %X Bacteriorhodopsin, a light-transducing protein in the purple membrane of Halobacterium halobium, has unique properties that make it a potentially attractive material for use in optical imaging and processing. A transient diffraction grating based on the K intermediate of the bacteriorhodopsin photocycle has been produced on the nanosecond time scale. The diffraction efficiency, which would be sufficient for pattern recognition for example, was measured and the intensity dependence assessed. %B Advanced Materials %I WILEY-VCH Verlag GmbH %V 5 %P 838 - 842 %8 1993 %@ 1521-4095 %G eng %U http://dx.doi.org/10.1002/adma.19930051111 %N 11 %R 10.1002/adma.19930051111