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Posterminaries: More Or Less Modern, Alexander H. King Nov 2007

Posterminaries: More Or Less Modern, Alexander H. King

Alexander H. King

It is yet another sign that I am aging. More and more often when young researchers hand me a written report of their research, I find myself criticizing their introductory section: “You need to start your literature survey with the original papers on this topic. Go and read…” followed by a citation to some classic of the learned literature.


Non-Destructive Horseradish Peroxidase Immobilization In Porous Silica Nanoparticles, Rebecca Voss, Michael A. Brook, Jordan Thompson, Yang Chen, Robert H. Pelton, John D. Brennan Sep 2007

Non-Destructive Horseradish Peroxidase Immobilization In Porous Silica Nanoparticles, Rebecca Voss, Michael A. Brook, Jordan Thompson, Yang Chen, Robert H. Pelton, John D. Brennan

Rebecca Cademartiri

The preparation of protein doped silica particles is impeded by the difficulty of incorporating proteins within the silica mesostructure under conditions that do not lead to denaturation. Herein, the synthesis of spherical silica particles (diameter 150 nm–550 nm) under protein friendly conditions in a one step process is described. Diglyceroxysilane (DGS) was reacted in ethanol and methanol-free conditions in pure water or in buffer solutions with or without the presence of additional glycerol. Stabilization of the particles, consistent with steric stabilization, was obtained using poly(ethylene glycol) (PEG) of various molecular weights and with various end groups, including allyl and (CH2)3Si(OEt)3 …


Control Of Porosity In Fluoride Thin Films Prepared By Vapor Deposition, Alexander H. King Jul 2007

Control Of Porosity In Fluoride Thin Films Prepared By Vapor Deposition, Alexander H. King

Alexander H. King

We have measured the porosity in thin films of lithium fluoride (LiF), magnesium fluoride (MgF2), barium fluoride (BaF2), and calcium fluoride (CaF2) as a function of the substrate temperature for films deposited by thermal evaporation onto glass substrates. The amount of porosity in the thin films was measured using an atomic force microscope and a quartz crystal thickness monitor. The porosity was very sensitive to the substrate temperature and decreased as the substrate temperature increased. Consistent behavior was observed among all of the materials in this study.


Posterminaries: Full Circle, Alexander H. King Jul 2007

Posterminaries: Full Circle, Alexander H. King

Alexander H. King

A few years ago, I was walking near the old Union Station in Pittsburgh with a colleague only slightly younger than myself, when we happened upon some large-scale relics of the steel industry displayed for public viewing. “You don’t see too many of those in public parking lots,” I offered. “Um… what is it?” was the response. I suppose I was just a little surprised that a prominent materials scientist did not recognize a Bessemer converter—arguably the principal source of wealth during the U.S. industrial revolution—but this conversation took place back when steel was in decline, and many university Materials …


Thermal Effects On Mechanical Grinding-Induced Surface Texture In Tetragonal Piezoelectrics, Wonyoung Chang, Alexander H. King, Keith J. Bowman Jan 2007

Thermal Effects On Mechanical Grinding-Induced Surface Texture In Tetragonal Piezoelectrics, Wonyoung Chang, Alexander H. King, Keith J. Bowman

Alexander H. King

The effect of temperature on grinding-induced texture in tetragonal lead zirconate titanate (PZT) and lead titanate (PT) has been investigated using in situ x-ray diffraction (XRD) with an area detector. In contrast with previous results on electrical poling, mechanically-ground PT and soft PZT materials retain strong ferroelastic textures during thermal cycling, even after excursions to temperatures slightly above the Curie temperature. The relationship between the residual stresses in the surface region, caused by grinding, and those resulting from domain wall motion is elucidated by in situ texture measurements obtained during thermal cycling.


How Surface Stresses Lead To Size-Dependent Mechanics Of Tensile Deformation In Nanowires, M. Ravi Shankar, Alexander H. King Jan 2007

How Surface Stresses Lead To Size-Dependent Mechanics Of Tensile Deformation In Nanowires, M. Ravi Shankar, Alexander H. King

Alexander H. King

It has been proposed that surface and interface stresses can modify the elastic behavior in nanomaterials such as nanowires. The authors show that surface stresses modify the tensile response of nanowires only when nonlinear elastic effects become important leading to cross terms between the applied stress and the surface stress. These effects are only significant when the radius of the nanowire is of the order of a few nanometers. The resulting alteration of tensile stiffness, though effected in part by the nonlinear elastic modulus, is particularly wrought by a modification of the stress state in the deformed nanowire.


Effect Of The Lattice Crystallinity On The Electron−Phonon Relaxation Rates In Gold Nanoparticles, Wenyu Huang, Wei Qian, Mostafa El-Sayed Jan 2007

Effect Of The Lattice Crystallinity On The Electron−Phonon Relaxation Rates In Gold Nanoparticles, Wenyu Huang, Wei Qian, Mostafa El-Sayed

Wenyu Huang

In order to study the importance of surface phonons on the electron−phonon relaxation in plasmonic nanoparticles, the effect of size, shape, and materials have recently been studied. Gold and silver nanoparticles have shown no dependence on size and shape while copper nanoparticles have shown some size dependence. This suggests that the bulk phonons, which are sensitive to the bulk-phase structure, are solely responsible for the relaxation of the hot electron in gold and silver plasmonic nanoparticles. The importance of bulk phonons should depend on the degree of crystallinity. In the present study, we have found that the electron−phonon relaxation rate …


On The Universal Scaling Behavior Of The Distance Decay Of Plasmon Coupling In Metal Nanoparticle Pairs: A Plasmon Ruler Equation, Prashant K. Jain, Wenyu Huang, Mostafa A. El-Sayed Jan 2007

On The Universal Scaling Behavior Of The Distance Decay Of Plasmon Coupling In Metal Nanoparticle Pairs: A Plasmon Ruler Equation, Prashant K. Jain, Wenyu Huang, Mostafa A. El-Sayed

Wenyu Huang

Localized surface plasmon resonances (LSPR) in lithographically fabricated gold (Au) nanodisc pairs are investigated using microabsorption spectroscopy and electrodynamic simulations. In agreement with previous work, we find that the fractional plasmon wavelength shift for polarization along the interparticle axis decays nearly exponentially with the interparticle gap. In addition, we find that the decay length is roughly about 0.2 in units of the particle size for different nanoparticle size, shape, metal type, or medium dielectric constant. The near-exponential distance decay and the interesting “universal” scaling behavior of interparticle plasmon coupling can be qualitatively explained on the basis of a dipolar-coupling model …


The Effect Of Plasmon Field On The Coherent Lattice Phonon Oscillation In Electron-Beam Fabricated Gold Nanoparticle Pairs, Wenyu Huang, Wei Qian, Prashant K. Jain, Mostafa El-Sayed Jan 2007

The Effect Of Plasmon Field On The Coherent Lattice Phonon Oscillation In Electron-Beam Fabricated Gold Nanoparticle Pairs, Wenyu Huang, Wei Qian, Prashant K. Jain, Mostafa El-Sayed

Wenyu Huang

By using electron beam lithography, we fabricated pairs of gold nanoparticles with varying interparticle separation. Double-beam femtosecond transient absorption spectroscopy was used to determine the coherent lattice oscillation frequency as a function of the interparticle separation in the presence of the plasmon field excited by the monitoring probe light. We found that the fractional shift in the coherent lattice phonon oscillation frequency follows an exponential decay with respect to the interparticle gap scaled by the disc diameter with the same decay constant as that previously observed for the fractional shift in the surface plasmon electronic oscillation resonance frequency. This strongly …


Carbazolyl Nitrenium Ion:  Electron Configuration And Antiaromaticity Assessed By Laser Flash Photolysis, Trapping Rate Constants, Product Analysis, And Computational Studies, Arthur Winter, Harry H. Gibson, Daniel E. Falvey Jan 2007

Carbazolyl Nitrenium Ion:  Electron Configuration And Antiaromaticity Assessed By Laser Flash Photolysis, Trapping Rate Constants, Product Analysis, And Computational Studies, Arthur Winter, Harry H. Gibson, Daniel E. Falvey

Arthur Winter

Laser flash photolysis of 1-(carbazol-9-yl)-2,4,6-trimethylpyridinium tetrafluoroborate generates the carbazolyl nitrenium ion (τ = 333 ns, kobs = 3.0 × 106 M-1s-1) having absorption bands at 570 and 620 nm in CH3CN. The nitrenium ion is found to have reactivity comparable to structurally similar closed-shell diarylnitrenium ions, but spectroscopic evidence favors an open-shell singlet diradical assignment for the observed nitrenium ion. The carbazolyl nitrenium ion is also more reactive than diarylnitrenium ions as a likely result of antiaromatic character. Ab initio and hybrid DFT calculations were performed to address the degree of antiaromaticity in this and similar nitrenium ions through analysis …


Benzylic Cations With Triplet Ground States:  Computational Studies Of Aryl Carbenium Ions, Silylenium Ions, Nitrenium Ions, And Oxenium Ions Substituted With Meta Π Donors, Arthur Winter, Daniel E. Falvey, Christopher J. Cramer, Benjamin F. Gherman Jan 2007

Benzylic Cations With Triplet Ground States:  Computational Studies Of Aryl Carbenium Ions, Silylenium Ions, Nitrenium Ions, And Oxenium Ions Substituted With Meta Π Donors, Arthur Winter, Daniel E. Falvey, Christopher J. Cramer, Benjamin F. Gherman

Arthur Winter

Density functional theory (B3LYP/6-31G(d,p)) was used to predict the effect of meta substitution on aryl cationic (Ar−X+) species, including aryloxenium ions, arylsilylenium ions, arylnitrenium ions, and arylcarbenium ions. Multireference second-order perturbation theory (CASPT2) calculations were used to benchmark the quantitative accuracy of the DFT calculations for representative systems. Substituting the meta positions on these species with π donors stabilizes a π,π* diradical state analogous to the well-known m-xylylene diradical. Notably, the 3,5-bis(N,N-dimethylamino)benzyl cation is predicted to have a triplet ground state by 1.9 kcal/mol by DFT and to have essentially degenerate singlet−triplet states at the CASPT2(10,9) level of theory. Adding …