Physics Commons^™

Surface Plasmon Induced Enhancement In Selective Laser Melting Processes, Dentcho A. Genov, Raj K. Vinnakota

Dentcho Genov

Infinite-Randomness Fixed Point Of The Quantum Superconductor-Metal Transitions In Amorphous Thin Films, Nicholas A. Lewellyn, Ilana M. Percher, J. J. Nelson, Javier Garcia-Barriocanal, Irina Volotsenko, Aviad Frydman, Thomas Vojta, Allen M. Goldman

Physics Faculty Research & Creative Works

The magnetic-field-tuned quantum superconductor-insulator transitions of disordered amorphous indium oxide films are a paradigm in the study of quantum phase transitions and exhibit power-law scaling behavior. For superconducting indium oxide films with low disorder, such as the ones reported on here, the high-field state appears to be a quantum-corrected metal. Resistance data across the superconductor-metal transition in these films are shown here to obey an activated scaling form appropriate to a quantum phase transition controlled by an infinite-randomness fixed point in the universality class of the random transverse-field Ising model. Collapse of the field-dependent resistance vs temperature data is obtained …

Lithography-Free, Omnidirectional, Cmos-Compatible Alcu Alloys For Thin-Film Superabsorbers, Mariama Rebello De Sousa Dias, Chen Gong, Zachary A. Benson, Marina S. Leite

Physics Faculty Publications

Superabsorbers based on metasurfaces have recently enabled the control of light at the nanoscale in unprecedented ways. Nevertheless, the sub‐wavelength features needed to modify the absorption band usually require complex fabrication methods, such as electron‐beam lithography. To overcome the scalability limitations associated with the fabrication of metallic nanostructures, engineering the optical response of superabsorbers by metal alloying is proposed, instead of tuning the geometry/size of the nanoscale building blocks. The superior performance of thin film AlCu alloys as the metallic component of planar bilayer superabsorbers is numerically demonstrated. This alloy outperforms its pure constituents as well as other metals, such …

Molecules And Metals In The Distant Universe: Sub-Mm And Optical Spectroscopy Of Quasar Absorbers, Sean Stephen Morrison

Theses and Dissertations

In order to gain a complete understanding of galaxy formation and evolution, knowledge of the atomic and molecular gas in the interstellar medium (ISM) is required. Absorption-line spectroscopy of quasars offers a powerful and luminosity independent probe of gas in distant galaxies. The Damped Lyman- systems (DLAs; 20.3 . log NHI ), are the highest neutral hydrogen column density quasar absorbers and contain a substantial fraction of the neutral gas available for star formation in the high-redshift Universe. This thesis presents a study of the metal content in some DLAs, based on optical spectroscopy, and a search for molecules based …

Combinatorial Computational Chemistry Approach To The Design Of Metal Oxide Electronics Materials, B. Rodion, Salai Ammal, Y. Inaba, Y. Oumi, S. Takami, M. Kubo, A. Miyamoto, M. Kawasaki, M. Yoshimoto, H. Koinuma

Salai C. Ammal

Combinatorial chemistry has been developed as an experimental method where it is possible to synthesize hundreds of samples all at once and examine their properties. Recently, we introduced the concept of combinatorial approach to computational chemistry for material design and proposed a new method called `a combinatorial computational chemistry'. In this approach, the effects of large number of dopants, substrates, and buffer layers on the structures, electronic states, and properties of metal oxide electronics material is estimated systematically using computer simulations techniques, in order to predict the best dopant, substrate, and buffer layer for each metal oxide electronics materials.

Converting Glx2-1 Into An Active Glyoxalase Ii, Pattraranee Limphong, Nicole E. Adams, Matthew F. Rouhier, Ross M. Mckinney, Melissa Naylor, Brian Bennett, Christopher A. Makaroff, Michael W. Crowder

Physics Faculty Research and Publications

Arabidopsis thaliana glyoxalase 2-1 (GLX2-1) exhibits extensive sequence similarity with GLX2 enzymes but is catalytically inactive with SLG, the GLX2 substrate. In an effort to identify residues essential for GLX2 activity, amino acid residues were altered at positions 219, 246, 248, 325, and 328 in GLX2-1 to be the same as those in catalytically active human GLX2. The resulting enzymes were overexpressed, purified, and characterized using metal analyses, fluorescence spectroscopy, and steady-state kinetics to evaluate how these residues affect metal binding, structure, and catalysis. The R246H/N248Y double mutant exhibited low level S-lactoylglutathione hydrolase activity, while the R246H/N248Y/Q325R/R328K mutant exhibited …

In Search Of The Elusive Lossless Metal, Jacob B. Khurgin, Greg Sun

Physics Faculty Publications

We show that when one looks beyond the Drude model of metal conductivity, the metals that may be extremely lossy for low frequency electromagnetic waves can become perfectly lossless in the mid-IR region or higher, while retaining the essential metallic characteristic of negative permittivity even at those frequencies. We identify that the transition to the lossless regime occurs when the interatomic distances in the lattice exceed certain values, typically a factor of two larger than those occurring in nature. We believe that advances in nanoassembly may render lossless metals feasible with revolutionary implications for the fields of plasmonics and metamaterials.

Measured Optical Constants Of Copper From 10 Nm To 35 Nm, David D. Allred, Nicole Brimhall, Nicholas Herrick, Justin Peatross, R. Steven Turley, Michael Ware

Faculty Publications

We use laser high-order harmonics and a polarization-ratioreflectance technique to determine the optical constants of copper and oxidized copper in the wavelength range 10-35 nm. This measurement resolves previously conflicting data sets, where disagreement on optical constants of copper in the extreme ultraviolet most likely arises from inadvertent oxidation of samples before measurement.

How Much Can Guided Modes Enhance Absorption In Thin Solar Cells?, Peter N. Saeta, Vivian E. Ferry, Domenico Pacifici, Jeremy N. Munday, Harry A. Atwater

All HMC Faculty Publications and Research

Absorption enhancement in thin metal-backed solar cells caused by dipole scatterers embedded in the absorbing layer is studied using a semi-analytical approach. The method accounts for changes in the radiation rate produced by layers above and below the dipole, and treats incoherently the subsequent scattering of light in guided modes from other dipoles. We find large absorption enhancements for strongly coupled dipoles, exceeding the ergodic limit in some configurations involving lossless dipoles. An antireflection-coated 100-nm layer of a-Si:H on Ag absorbs up to 87% of incident above-gap light. Thin layers of both strong and weak absorbers show similar strongly enhanced …

Human Glyoxalase Ii Contains An Fe(Ii)Zn(Ii) Center But Is Active As A Mononuclear Zn(Ii) Enzyme, Pattraranee Limphong, Ross M. Mckinney, Nicole E. Adams, Brian Bennett, Christopher A. Makaroff, Thusitha Gunasekera, Michael W. Crowder

Physics Faculty Research and Publications

Human glyoxalase II (Glx2) was overexpressed in rich medium and in minimal medium containing zinc, iron, or cobalt, and the resulting Glx2 analogues were characterized using metal analyses, steady-state and pre-steady-state kinetics, and NMR and EPR spectroscopies to determine the nature of the metal center in the enzyme. Recombinant human Glx2 tightly binds nearly 1 equiv each of Zn(II) and Fe. In contrast to previous reports, this study demonstrates that an analogue containing 2 equiv of Zn(II) cannot be prepared. EPR studies suggest that most of the iron in recombinant Glx2 is Fe(II). NMR studies show that Fe(II) binds to …

Structure And Mechanism Of Copper- And Nickel-Substituted Analogues Of Metallo-Β-Lactamase L1, Zhenxin Hu, Lauren J. Spadafora, Christine E. Hajdin, Brian Bennett, Michael W. Crowder

Physics Faculty Research and Publications

In an effort to further probe metal binding to metallo-β-lactamase L1 (mβl L1), Cu- (Cu-L1) and Ni-substituted (Ni-L1) L1 were prepared and characterized by kinetic and spectroscopic studies. Cu-L1 bound 1.7 equiv of Cu and small amounts of Zn(II) and Fe. The EPR spectrum of Cu-L1 exhibited two overlapping, axial signals, indicative of type 2 sites with distinct affinities for Cu(II). Both signals indicated multiple nitrogen ligands. Despite the expected proximity of the Cu(II) ions, however, only indirect evidence was found for spin−spin coupling. Cu-L1 exhibited higher k_cat (96 s⁻¹) and K_m (224 μM) values, as …

Kinetic And Spectroscopic Analysis Of The Catalytic Role Of H79 In The Methionine Aminopeptidase From Escherichia Coli, Sarah J. Watterson, Sanghamitra Mitra, Sabina I. Swierczek, Brian Bennett, Richard C. Holz

Physics Faculty Research and Publications

To gain insight into the role of the strictly conserved histidine residue, H79, in the reaction mechanism of the methionyl aminopeptidase from Escherichia coli (EcMetAP-I), the H79A mutated enzyme was prepared. Co(II)-loaded H79A exhibits an overall >7000-fold decrease in specific activity. The almost complete loss of activity is primarily due to a >6000-fold decrease in k_cat. Interestingly, the K_m value obtained for Co(II)-loaded H79A was approximately half the value observed for wild-type (WT) EcMetAP-I. Consequently, k_cat/K_m values decreased only 3000-fold. On the other hand, the observed specific activity of Mn(II)-loaded …

Metal Content Of Metallo-Β-Lactamase L1 Is Determined By The Bioavailability Of Metal Ions, Zhenxin Hu, Thusitha S. Gunasekera, Lauren J. Spadafora, Brian Bennett, Michael W. Crowder

Physics Faculty Research and Publications

In an effort to probe whether the metal content of metallo-β-lactamase L1 is affected by metal ion bioavailability, L1 was overexpressed as mature protein (M-L1) and full-length (FL-L1) analogues, and the analogues were characterized with metal analyses, kinetics, and EPR spectroscopy. FL-L1, containing the putative leader sequence, was localized in the periplasm of Escherichia coli and shown to bind Zn(II) preferentially. The metal content of FL-L1 could be altered if the enzyme was overexpressed in minimal medium containing Fe and Mn, and surprisingly, an Fe-binding analogue was obtained. On the other hand, M-L1, lacking the putative leader sequence, was localized …

Effects Of Htert On Genomic Instability Caused By Either Metals Or Radiation Or Combined Exposure, Antonino Glaviano

Doctoral

There is currently a great interest in delayed chromosomal damage and other damaging effects of low-dose exposure to a variety of agents, which appear collectively to act through induction of stress-response pathways related to oxidative stress (and aging). These agents have been studied mostly in the radiation field but evidence is accumulating that chemicals, especially heavy metals, can also act in the same manner. Therefore, this work investigated the effects of metals and/or radiation in human fibroblasts in vitro. Humans are exposed to metals, including chromium (CR) VI) and vanadium (V) (V) from the environment, industry and surgical implants. Thus …

Sequential Binding Of Cobalt(Ii) To Metallo-Β-Lactamase Ccra, Gopal R. Periyannan, Alison L. Costello, David L. Tierney, Ke-Wu Yang, Brian Bennett, Michael W. Crowder

Physics Faculty Research and Publications

In an effort to probe Co(II) binding to metallo-β-lactamase CcrA, EPR, EXAFS, and ¹H NMR studies were conducted on CcrA containing 1 equiv (1-Co(II)-CcrA) and 2 equiv (Co(II)Co(II)-CcrA) of Co(II). The EPR spectra of 1-Co(II)-CcrA and Co(II)Co(II)-CcrA are distinct and indicate 5/6-coordinate Co(II) ions. The EPR spectra also reveal the absence of significant spin-exchange coupling between the Co(II) ions in Co(II)Co(II)-CcrA. EXAFS spectra of 1-Co(II)-CcrA suggest 5/6-coordinate Co(II) with two or more histidine ligands. EXAFS spectra of Co(II)Co(II)-CcrA also indicate 5/6 ligands at a similar average distance to 1-Co(II)-CcrA, including an average of about two histidines per Co(II). ^{1 …}

Spectroscopic And Thermodynamic Characterization Of The E151d And E151a Altered Leucine Aminopeptidases From Aeromonas Proteolytica, Krzysztof P. Bzymek, Sabina I. Swierczek, Brian Bennett, Richard C. Holz

Physics Faculty Research and Publications

Previous kinetic characterization of the glutamate 151 (E151)-substituted forms of the leucine aminopeptidase from Aeromonas proteolytica (Vibrio proteolyticus; AAP) has provided critical evidence that this residue functions as the general acid/base. The close proximity of similar glutamate residues to the bridging water/hydroxide of the dinuclear active sites of metalloenzymes (2.80 and 3.94 Å in carboxypeptidase G₂ and 3.30 and 3.63 Å in AAP), suggests it may also be involved in stabilizing the active-site metal ions. Therefore, the structural perturbations of the dinuclear active site of AAP were examined for two E151-substituted forms, namely E151D-AAP and E151A-AAP, by …

Spectroscopic Studies On Cobalt(Ii)-Substituted Metallo-Β-Lactamase Imis From Aeromonas Veronii Bv. Sobria, Patrick A. Crawford, Ke-Wu Yang, Narayan Sharma, Brian Bennett, Michael W. Crowder

Physics Faculty Research and Publications

In an effort to probe the structure of a group Bb metallo-β-lactamase, Co(II)-substituted ImiS was prepared and characterized by electronic absorption, NMR, and EPR spectroscopies. ImiS containing 1 equiv of Co(II) (Co(II)₁-ImiS) was shown to be catalytically active. Electronic absorption studies of Co(II)₁-ImiS revealed the presence of two distinct features:  (1) an intense sulfur to Co(II) ligand to metal charge transfer band and (2) less intense, Co(II) ligand field transitions that suggest 4-coordinate Co(II) in Co(II)₁-ImiS. ¹H NMR studies of Co(II)₁-ImiS suggest that one histidine, one aspartic acid, and one cysteine …

Both Nucleophile And Substrate Bind To The Catalytic Fe(Ii)-Center In The Type-Ii Methionyl Aminopeptidase From Pyrococcus Furiosus, Alicja J. Copik, Sarah Waterson, Sabina I. Swierczek, Brian Bennett, Richard C. Holz

Physics Faculty Research and Publications

Metalloproteases utilize their active site divalent metal ions to generate a nucleophilic water/hydroxide. For methionine aminopeptidases (MetAPs), the exact location of this nucleophile, as well as of the substrate, with respect to the active site metal ion is unknown. In order to address this issue, we have examined the catalytically competent Fe(II)-loaded form of PfMetAP-II ([Fe(PfMetAP-II)]) in the absence and presence of both nitric oxide (NO) and the substrate-analogue inhibitor butaneboronic acid (BuBA) by kinetic and spectroscopic (EPR, UV−vis) methods. NO binds to [Fe(PfMetAP−II)] with a K_d of 200 μM forming an {FeNO}^{7 …}

Direct Evidence That The Reaction Intermediate Of Metallo-Β-Lactamase L1 Is Metal Bound, James D. Garrity, Brian Bennett, Michael W. Crowder

Physics Faculty Research and Publications

In an effort to probe the structure of the reaction intermediate of metallo-β-lactamase L1 when reacted with nitrocefin and other β-lactams, time-dependent absorption and rapid-freeze-quench (RFQ) EPR spectra were obtained using the Co(II)-substituted form of the enzyme. When using nitrocefin as the substrate, time-dependent absorption spectra demonstrate that Co(II)-substituted L1 utilizes a reaction mechanism, similar to that of the native Zn(II) enzyme, in which a short-lived intermediate forms. RFQ-EPR spectra of this intermediate demonstrate that the binding of substrate results in a change in the electronic properties of one or both of the Co(II)'s in the enzyme …

Spectroscopic And X-Ray Crystallographic Characterization Of Bestatin Bound To The Aminopeptidase From Aeromonas (Vibrio) Proteolytica, Carin C. Stamper, David L. Bienvenue, Brian Bennett, Dagmar Ringe, Gregory A. Petsko, Richard C. Holz

Physics Faculty Research and Publications

Binding of the competitive, slow-binding inhibitor bestatin ([(2S,3R)-3-amino-2-hydroxy-4-phenylbutanoy]-leucine) to the aminopeptidase from Aeromonas proteolytica (AAP) was examined by both spectroscopic and crystallographic methods. Electronic absorption spectra of the catalytically competent [Co_(AAP)], [CoCo(AAP)], and [ZnCo(AAP)] enzymes recorded in the presence of bestatin revealed that both of the divalent metal ions in AAP are involved in binding bestatin. The electron paramagnetic resonance (EPR) spectrum of the [CoCo(AAP)]−bestatin complex exhibited no observable perpendicular- or parallel-mode signal. These data indicate that the two Co^II ions in AAP are antiferromagnetically coupled yielding an S = 0 ground state and suggest …

Substrate Specificity, Metal Binding Properties, And Spectroscopic Characterization Of The Dape-Encoded N-Succinyl-L,L-Diaminopimelic Acid Desuccinylase From Haemophilus Influenzae, David L. Bienvenue, Danuta M. Gilner, Ryan S. Davis, Brian Bennett, Richard C. Holz

Physics Faculty Research and Publications

The catalytic and structural properties of divalent metal ion cofactor binding sites in the dapE-encoded N-succinyl-l,l-diaminopimelic acid desuccinylase (DapE) from Haemophilus influenzae were investigated. Co(II)-substituted DapE enzyme was 25% more active than the Zn(II)-loaded form of the enzyme. Interestingly, Mn(II) can activate DapE, but only to ∼20% of the Zn(II)-loaded enzyme. The order of the observed k_cat values are Co(II) > Zn(II) > Cd(II) > Mn(II) >Ni(II) ∼ Cu(II) ∼ Mg(II). DapE was shown to only hydrolyze l,l-N-succinyl-diaminopimelic acid (l,l-SDAP) and was inactive toward d,l-, l,d-, and d,d-SDAP. DapE was also inactive toward several acetylated amino acids as …

Inhibition Of The Aminopeptidase From Aeromonas Proteolytica By L-Leucinephosphonic Acid. Spectroscopic And Crystallographic Characterization Of The Transition State Of Peptide Hydrolysis, Carin Stamper, Brian Bennett, Tanya Edwards, Richard C. Holz, Dagmar Ringe, Gregory A. Petsko

Physics Faculty Research and Publications

The nature of the interaction of the transition-state analogue inhibitor l-leucinephosphonic acid (LPA) with the leucine aminopeptidase from Aeromonas proteolytica (AAP) was investigated. LPA was shown to be a competitive inhibitor at pH 8.0 with a K_i of 6.6 μM. Electronic absorption spectra, recorded at pH 7.5 of [CoCo(AAP)], [CoZn(AAP)], and [ZnCo(AAP)] upon addition of LPA suggest that LPA interacts with both metal ions in the dinuclear active site. EPR studies on the Co(II)-substituted forms of AAP revealed that the environments of the Co(II) ions in both [CoZn(AAP)] and [ZnCo(AAP)] become highly asymmetric and constrained upon the addition of …

Low-Temperature Ion Beam Mixing In Metals, S J. Kim, M A. Nicolet, R S. Averback, David Peak

All Physics Faculty Publications

A systematic study of ion-beam mixing of tracer impurities in thin metal films at low temperatures has been conducted. We have investigated the dependence of ion mixing on two matrix properties: atomic mass and cohesive energy. We have also studied the dependence of ion mixing on tracer impurity properties: its heat of mixing with the matrix and its thermal diffusivity in the matrix. The matrices investigated were thin films of C, Al, Ti, Fe, Ni, Cu, Mo, Ru, Ag, Hf, Ta, W, Pt, and Au. The tracer impurities, Al, Ti, Cr, Mn, Fe, Ni, Cu, Y, Nb, Mo, Ru, Ag, …

Measurement Of The Wear Properties Of Metallic Solids With A Falex Lubricant Testing Machine, Edward Boyd Hale, Chun-Ping John Meng, Ronald A. Kohser

Physics Faculty Research & Creative Works

A modified Falex Lubricant Testing Machine has been used to determine wear properties of metallic solids. In particular, wear mass loss, wear volume loss, wear rates, and other parameters have been determined for a basic steel, as heat treated and after ion implantation. Wear rate improvements of more than an order of magnitude were found in a nickel-chrome steel (SAE 3135) implanted with 2.5x10¹⁷ N⁺₂/cm². Wear tests were conducted with a cylinder-in-groove geometry in a mild lubricating oil with loads greater than 540 N, which corresponded to pressures which exceeded 10⁸N/m^{2 …}

A Study Of Light Metals And Alloys At Low Temperatures, Donald E. Higgins

Historical Dissertations & Theses

Although the determination of the strength of metals and alloys at ordinary temperatures is an everyday matter, very little work has been done to determine their strength and elasticity at very low temperatures. Mallock and Schaefer have investigated certain metals at the temperature of liquid air, and have deduced formulae to express the relation between elasticity and temperature, while Andrade has given an expression for the flow of metals under large constant stress. This work was intended in part to find out if their formulae would apply to the very light alloys used here. Another object was to find, if …