TY - JOUR T1 - Ultrafast electronic relaxation and charge-carrier localization in CdS/CdSe/CdS quantum-dot quantum-well heterostructures JF - Nano Letters Y1 - 2006 A1 - Schill, A. W. A1 - Gaddis, C. S. A1 - Qian, Wei A1 - El-Sayed, Mostafa A A1 - Cai, Y. A1 - Milam, V. T. A1 - Sandhage, K. AB - The relaxation and localization times of excited electrons in CdS/CdSe/CdS colloidal quantum wells were measured using subpicosecond spectroscopy. HRTEM analysis and steady-state PL demonstrate a narrow size distribution of 5-6 nm epitaxial crystallites. By monitoring the rise time of the stimulated emission as a function of pump intensity, the relaxation times of the electron from the CdS core into the CdSe well are determined and assigned. Two-component rise times in the stimulated emission are attributed to intraband relaxation of carriers generated directly within the CdSe well ( fast component) and charge transfer of core-localized carriers across the CdS/CdSe interface ( slow component). This is the first reported observation of simultaneous photon absorption in the core and well of a quantum-dot heterostructure. With increasing pump intensity, the charge-transfer channel between the CdS core CdSe well contributes less to the stimulated emission signal because of filling and saturation of the CdSe well state, making the interfacial charge-transfer component less efficient. The interfacial charge-transfer time of the excited electron was determined from the slow component of the stimulated emission build-up time and is found to have a value of 1.2 ps. VL - 6 SN - 1530-6984 N1 - Schill, Alexander W. Gaddis, Christopher S. Qian, Wei El-Sayed, Mostafa A. Cai, Ye Milam, Valeria T. Sandhage, Kenneth M3 - 10.1021/nl061054v ER - TY - JOUR T1 - Growth and fragmentation of silver nanoparticles in their synthesis with a fs laser and CW light by photo-sensitization with benzophenone JF - Photochemical & Photobiological Sciences Y1 - 2005 A1 - Eustis, Susie A1 - Krylova, G. A1 - Eremenko, A. A1 - Smirnova, N. A1 - Schill, A. W. A1 - El-Sayed, Mostafa A AB - The photo-sensitization synthetic technique of making silver nanoparticles using benzophenone is studied using both a laser and a mercury lamp as light sources. The power and irradiation time dependence of the synthesized nanoparticle absorption spectra and their size distribution [as determined by transmission electron microscopy (TEM)] are studied in each method and compared. In the laser synthesis, as either the laser power or the irradiation time increases, the intensity of the surface plasmon resonance absorption at 400 nm is found to increase linearly first, followed by a reduction of the red edge of the plasmon resonance absorption band. The TEM results showed that in the laser synthesis low powers and short irradiation times produce nanoparticles around 20 nm in diameter. Increasing the power or irradiation time produces a second population of nanoparticles with average size of 5 nm in diameter. These small particles are believed to be formed from the surface ablation of the large particles. The surface plasmon absorption band is found to be narrower when the nanoparticles are produced with laser irradiation. Throughout the exposure time with the CW lamp, the plasmon resonance absorption band of the particles formed first grows in intensity, then blue shifts and narrows, and finally red shifts while decreasing in intensity. The TEM results for lamp samples showed particle formation and growth, followed by small nanoparticle formation. The above results are discussed in terms of a mechanism in which, the excited benzophenone forms the ketal radical, which reduces Ag+ in solution and on the Ag nanoparticle surface. As the time of irradiation or the light energy increases the benzophenone is consumed, which is found to be the limiting reagent. This stops the formation of the normal large nanoparticles while their photo-ablation continues to make the small particles. PB - Royal Society of Chemistry VL - 4 CP - 1 M3 - 10.1039/B411488D ER - TY - JOUR T1 - The protonation-deprotonation kinetics of the protonated Schiff base in bicelle bacteriorhodopsin crystals JF - Biophysical Journal Y1 - 2005 A1 - Sanii, L. S. A1 - Schill, A. W. A1 - Moran, C. E. A1 - El-Sayed, Mostafa A AB - In the recently published x-ray crystal structure of the "bicelle" bacteriorhodopsin (bbR) crystal, the protein has quite a different structure from the native and the in cubo bacteriorhodopsin (cbR) crystal. Instead of packing in parallel trimers as do the native membrane and the cbR crystals, in the bbR crystal the protein packs as antiparallel monomers. To date, no functional studies have been performed, to our knowledge, to investigate if the photocycle is observed in this novel protein packing structure. In this study, both Raman and time-resolved transient absorption spectroscopy are used to both confirm the presence of the photocycle and investigate the deprotonation-reprotonation kinetics of the Schiff base proton in the bbR crystal. The observed rates of deprotonation and reprotonation processes of its Schiff base have been compared to those observed for native bR under the same conditions. Unlike the previously observed similarity of the rates of these processes for cbR crystals and those for native bacteriorhodopsin (bR), in bbR crystals the rate of deprotonation has increased by 300%, and the rate of reprotonation has decreased by nearly 700%. These results are discussed in light of the changes observed when native bR is delipidated or monomerized by detergents. Both the change of the hydrophobicity of the environment around the protonated Schiff base and Asp(85) and Asp(96) (which could change the pK(a) values of proton donor-acceptor pairs) and the water structure in the bbR crystal are offered as possible explanations for the different observations. VL - 89 SN - 0006-3495 N1 - Sanii, LS Schill, AW Moran, CE El-Sayed, MA M3 - 10.1529/biophysj.105.059675 ER - TY - JOUR T1 - Wavelength-dependent hot electron relaxation in PVP capped CdS/HgS/CdS quantum dot quantum well nanocrystals JF - Journal of Physical Chemistry B Y1 - 2004 A1 - Schill, A. W. A1 - El-Sayed, Mostafa A AB - Subpicosecond pump-probe transient absorption spectroscopy has been used to examine the probe wavelength-dependent kinetics of PVP capped CdS/HgS/CdS quantum dot quantum well nanoparticles. Using 398- and 520-nm excitations, the relaxation of the excited hot electrons above the band gap state is characterized by both rapid electronic nonradiative relaxation and slower thermal relaxation processes. The wavelength dependence of both the fast rise and fast decay of the transient bleach is discussed in terms of electronic relaxation processes involving mixed CdS/HgS states at short probe wavelengths or pure HgS states at long probe wavelengths. The slow decay of the transient bleach is discussed in terms of a thermal relaxation process leading to the dissipation of heat from the hot nanoparticle lattice to the surrounding medium. VL - 108 SN - 1520-6106 N1 - Schill, AW El-Sayed, MA M3 - 10.1021/jp047832u ER - TY - JOUR T1 - Why is the thermalization of excited electrons in semiconductor nanoparticles so rapid? Studies on CdSe nanoparticles JF - Chemical Physics Letters Y1 - 2003 A1 - Darugar, Q. A1 - Landes, Christy F. A1 - Link, Stephan A1 - Schill, A. W. A1 - El-Sayed, Mostafa A AB - Quantum confinement of electronic motion in semiconductor nanoparticles leads to quantization of its band continua of the bulk. The relaxation between the resulting quantized levels by electron phonon coupling was expected, but not found, to be slow due to the small phonon frequencies (phonon bottleneck). Studying the electronic relaxation from the band gap and a higher excited state in CdSe dots and rods under different perturbations suggest the importance of coupling the excited electron to the surface. The surface species act as an efficient heat bath or as electron trapping sites in the linear or nonlinear (Auger) relaxation processes. (C) 2003 Elsevier Science B.V. All rights reserved. VL - 373 SN - 0009-2614 N1 - Darugar, Q Landes, C Link, S Schill, A El-Sayed, MA M3 - 10.1016/s0009-2614(03)00213-6 ER -