Recursos de colección

Caltech Authors (127.467 recursos)

Repository of works by Caltech published authors.

Type = Conference or Workshop Item

Mostrando recursos 1 - 20 de 643

  1. Roving Reference: Getting out in the Wild

    Painter, Joy A.
    [no abstract]

  2. Droplet Breakup in High-Speed Gas Flows

    Meng, Jomela C.; Colonius, Tim
    Numerical simulations are performed to study the breakup of water cylinders in the flow behind normal shocks. The computational setup is similar to previous experiments (Igra and Takayama, 2001, 2003). We examine the qualitative features of the so-called stripping breakup observed in the numerical results. Two interesting flow features are discussed: the existence of recirculation regions and an upstream jet in the wake. Various integral quantities associated with the cylinder’s deformation and acceleration are computed and compared with the experimental results, with generally good agreement. Furthermore, calculations of the velocity and acceleration of the cylinder’s center of mass provide an...

  3. Using the Research of Others Responsibly: An Overview of Attribution, Copyright, and Authorship Ethics

    Clement, Gail P.; Wrublewski, Donna
    [no abstrac]

  4. Natural and non-canonical mutagenesis studies of receptor gating in 5-HT3A receptors

    Mosesso, Richard; Lummis, Sarah C. R.; Dougherty, Dennis A.
    The 5-HT_(3A) receptor is a homopentameric ligand-gated ion channel belonging to the Cys-loop family of receptors, members of which have many functions and are important targets for a variety of diseases. Previously, our lab has elucidated key binding interactions between these receptors and their ligands. However, the "gating" events that link binding of ligand to receptor activation are less well characterized. While obtaining high-resoln. crystal structures of transmembrane proteins can be difficult, a recent crystal structure of the mouse 5-HT_(3A) receptor has guided our search for intramol. interactions involved in gating. Focusing on regions identified to be important for gating in homologous receptors, we have...

  5. Evidence for in situ catalyst modification in atom transfer radical reactions with ruthenium benzylidene complexes

    Lee, Juneyoung; Grandner, Jessica M.; Engle, Keary; Houk, Kendall N.; Grubbs, Robert H.
    Since the first report of ruthenium- based catalysts in atom transfer radical addn. (ATRA, also called Kharasch addn.) and atom transfer radical polymn. (ATRP) , this area of research has attracted widespread interest. Well- defined ruthenium benzylidene complexes, commonly used as olefin metathesis catalysts, have also been reported to catalyze ATRA and ATRP. The ability of ruthenium benzylidene complexes to promote two reactions with such markedly different mechanisms has been utilized in various tandem reactions in which olefin metathesis and atom transfer radical (ATR) reactions take place in one pot. While the mechanism by which ruthenium benzylidenes initiate and catalyze olefin metathesis has been studied...

  6. Mechanistic investigation of proton reduction by cobaloximes: Insight from H2 oxidation kinetics

    Del Ciello, Sarah A.; Winkler, Jay R.; Peters, Jonas C.; Gray, Harry B.
    Cobaloximes are a class of earth- abundant proton redn. catalysts that have been known since the 1980's. Previous studies have come to conflicting conclusions about the mechanism of proton redn. by these catalysts, with evidence existing for both a homolytic and heterolytic mechanism. In this work, kinetic anal. of the reverse reaction is used to gain further insight.

  7. Cation-π interactions: Computational analyses of the aromatic box motif and the fluorination strategy for experimental evaluation of cys-loop receptors and related structures

    Davis, Matthew R.; Dougherty, Dennis A.
    Cation-π interactions are common in biol. systems, in particular ligand- gated ion channels (LGICs). Our own studies, in addn. to more recent structural studies, have revealed the arom. box as a common motif for binding cationic ligands. With the aim of understanding the nature of the arom. box, several computational methods were evaluated for their ability to reproduce exptl. cation-π binding energies. We find the DFT method M06 with the 6-31G(d, p) basis set performs best of several methods tested. The binding of benzene to a no. of different cations (sodium, potassium, ammonium, tetramethylammonium, and guanidinium) was studied. In addn., the binding of the org....

  8. Chemically specific dynamic bond percolation model for computational screening of polymer electrolytes

    Webb, Michael; Savoie, Brett; Wang, Zhen-Gang; Miller, Thomas
    Polymer electrolytes have significant promise for many lithium-ion battery applications because they are non-flammable, electrochem. stable, and easily manufd. However, significant improvements in the ionic cond. of even state- of-the-art polymer electrolytes is needed for technol. viability. The computationally- guided design of more conductive polymer electrolytes would save significant time and monetary resources, but these efforts require both a better understanding of ion- transport mechanisms in polymers and the development of tools for screening candidate polymers prior to synthesis and characterization. Using atomistic mol. dynamics (MD) simulations, we provide new insights into the mechanisms of lithium-ion diffusion in polymer electrolyte materials, including that the spatial distribution...

  9. Reduction of CO2 on Cu and Au/W electrode surfaces: A study by differential electrochemical mass spectrometry

    Javier, Alnald; Baricuatro, Jack; Kim, Youn-Geun; Soriaga, Manuel
    This work describes results from an attempt to employ differential electrochem. mass spectrometry (DEMS) of selectively pre-adsorbed reactants and (postulated) intermediates as a supplementary exptl. approach in the study of the reaction mechanism of the Cu-catalyzed electrochem. redn. of CO2. The results prompt the following empirical inferences: (i) CO is the first product of CO2 redn., as well as the first intermediate in more advanced reactions that include formation of pure and oxygenated hydrocarbons; this is in conformity with the (almost) unanimously held view. (ii) HCHO is not a precursor for C=C double-bond formation. (iii) HCHO is an intermediate for the prodn. of methane...

  10. Observation and reactivity studies of an unusual RhI intermediate in H2 evolution catalysis

    Aguirre Quintana, Luis; Gray, Harry; Winkler, Jay; Blakemore, James
    Understanding mechanisms of hydrogen evolution is important for improving catalysts that generate clean fuels. Catalysts often operate via unknown mechanism(s) due to the difficulty of observing or isolating key intermediates in the 2e-/2H+ redn. process. For our study, we prepd. a family of RhI complexes bearing the pentamethylcyclopentadienyl (η5-Cp*) ligand in addn. to derivs. of 4,4'- bipyridyl or 1,10- phenanthroline (bound in the κ2 mode). Under carefully chosen conditions, these compds. formed intermediate species that suggest a previously unknown mechanism of H2 evolution involving protonhydride tautomerism driven by the Cp* ligand. This intermediate complex could be isolated in a MeCN soln., and even as a solid,...

  11. Effects of the μ4-bridging atom in a tetranuclear iron cluster on the activation of nitric oxide

    Reed, Christopher; Agapie, Theodor
    A series of tetrairon μ_4-fluoride clusters, [LFe_3F(PhPz)_3Fe][OTf]_n (n=1-3), was synthesized using the previously reported 1,3,5- triarylbenzene framework, a multinucleating ligand contg. pyridine and alkoxide donors, which bind three of the four metal centers. These three metal sites contain six-coordinate iron atoms. 3-phenyl-pyrazolate ligands (PhPz) bridge the triiron core to a four-coordinate, site-differentiated iron center. These clusters have notably different redox properties than the closely related μ_4-oxo analogs, [LFe_3O(PhPz)_3Fe][OTf]_n (n=0-3). While for [LFe_3O(PhPz)_3Fe][OTf]_2 three reversible redox events are obsd. at -1.73 V (vs. Fc /Fc+), -0.72 V, and +0.02 V (Fe^(II)_4 Fe^(II)Fe^(III)_3), only two redox events are obsd. for the fluoride-bridged cluster, [LFe_3F(PhPz)_3Fe][OTf], at -0.52 V (Fe^(II)_4...

  12. Scalable models of ion transport for electrolyte materials discovery

    Savoie, Brett M.; Miller, Thomas F.
    Solid polymeric electrolytes have the potential to greatly improve battery efficiency and stability, but ions like Li simply diffuse too slowly in current materials for them to be viable. The challenge for computationally designing new polymers lies in accurately modeling both the long- timescale of ion transport and the chem. specific ion- polymer couplings that govern ion motion. In this talk, I will show how short atomistic simulations can be combined with a generalizable mesoscopic ion transport model to reliably predict ion diffusivity across many chem. classes of polymers. This model has now been used to characterize several hundred new materials and the talk will...

  13. Probing binding interactions of agonists at a nicotinic acetylcholine receptor subtype important to addiction and Parkinson's disease

    Post, Michael R.; Lester, Henry; Dougherty, Dennis A.
    Nicotine addiction is still a major problem in American society. Sixteen percent of adults report smoking regularly, resulting in 96 billion dollars in healthcare costs per yr. Parkinson's disease is incurable, with 6,000 new diagnoses each year - it is the 14th leading cause of death in the US. Parkinson's disease and nicotine addiction are disorders of the dopamine pathway, making α6β2- contg. subtypes of the nicotinic acetylcholine receptor (nAChR) , which are ligand gated ion channels localized to dopaminergic neurons, an attractive target. Advanced knowledge of the binding site, which sits at the interface of α6 and β2, could lead to design of agonists...

  14. Electrochemical CO2 reduction catalyzed by Mn catalysts: DFT investigations point to strategies for overpotential reduction and activity improvement

    Lam, Yan Choi; Nielsen, Robert J.; Goddard, William A.; Gray, Harry B.
    Exptl., [(L) Mn(CO)_3]- (where L = bis alkyl- substituted bipyridine) has been obsd. to catalyze the electrochem. redn. of CO_2 to CO in the presence of trifluoroethanol (TFEH). Our DFT calcns. (B3LYP- d3 with continuum solvation) of the free energies of reaction and activation show that the highly exergonic hydrogen bonding between TFEH and TFE (homoconjugation) plays a crit. role in reaction thermodn. and kinetics. The analgous 2,2'- bipyrimidine complex is predicted to have a lower (by ca. 0.5 V) onset overpotential, but at the expense of max. catalytic activity. As a strategy to improve catalytic activity and onset overpotential, a series of 2,2'- and...

  15. Variable binding modes of pyridine in molybdenum complexes supported by novel P-pyridine-P ligands

    Wan, Ruomeng; Horak, Kyle; Buss, Joshua A.; Agapie, Theodor
    Low oxidn. state molybdenum complexes bind N_2 and in some cases reduce it to NH_3. We have previously demonstrated that molybdenum complexes supported by terphenyl diphosphine ligand platforms bind and activate small mols. We report herein the synthesis and characterization of mononuclear Mo complexes supported by two isomers of a novel ligand framework: 3,5-bis(2-(diisopropylphosphino)phenyl)pyridine (PNP^(3,5)) and 2, 6-bis(2-(diisopropylphosphino) phenyl) pyridine (PNP^(2,6)). Metalation of the phosphines with Mo(CO)_3 (MeCN)_3 results in the formation of MoPNP(CO)_3 complexes. The PNP^(3,5) isomer shows binding via the pyridine π system, while the PNP^(2,6) via the nitrogen lone pair. Oxidn. results in Mo species. Upon photolysis, CO ligand substitution occurs to give...

  16. Multi-layer anode for saline wastewater treatment: Manipulating oxidant generation pathway by TiO_2 thin film deposition

    Yang, Yang; Hoffmann, Michael R.
    Nowadays, both developed and developing countries are suffering from water scarcity due to the rapid urbanization and global climate change. The on-site reuse of water is a possible soln., which calls for the development of various decentralized wastewater treatment techniques. Electrochem. oxidn. is a promising candidate due to its modular design, convenient operation, and small carbon footprint. In the past decades, the IrO_x based DSA electrode showed excellent performance on saline wastewater treatment. However, the high cost and low energy efficiency impede the widespread application. In this study, uniform TiO_2 thin film was deposited onto the IrO_x electrode by novel spray- pyrolysis process. Instead of...

  17. Selective two-electron reduction of carbon monoxide mediated by molybdenum complexes supported on an asymmetric phenol phosphine ligand

    Riduan, Siti Nurhanna; Buss, Joshua A.; Agapie, Theodor
    Our group has recently reported a monometallic Molybdenum complex supported by a terphenyl diphosphine ligand capable of undergoing multielectron reductive processes. Various oxidn. states of the metal center are stabilized by the ability of the ligand to accommodate different binding modes. For example, the arene π-system displays η^2, η^4, η^6 binding while one of the phosphine arms reversibly dissocs. To further study the significance of the hemilability of the ligand donor arms, a monometallic Mo dicarbonyl complex supported by an asym. terphenyl phosphine- phenol ligand (POH) framework has been isolated. Deprotonation and treatment of the (PMo(CO)_2OH) complex with KC_8 or K(C_(10)H_8) yields a reduced Mo...

  18. Rolling revolution in analytical isotope geochemistry

    Eiler, John
    The many subjects of isotope geochem. have two things in common: they generally require anal. of isotope ratios at low natural abundances (∼10^(-2)-10^(-6)) and high precision (∼10^(-3)-10(-6)). For the first 50 years of this field (ca. 1950-2000), these requirements were met by a narrow range of technologies - mostly low mass resoln. (M/ΔM of a few hundred) TIMS and gas source IRMS - that limited the field to a few simple mols. and elements. Over the last 15 years this field has been transformed by the emergence of a wide range of new instruments and methods: plasma-source, high-resoln. MC-ICPMS has dramatically expanded the list of...

  19. Towards an energy landscape of G protein-coupled receptor (GPCR) activation using hybrid methods

    Dong, Sijia S.; Abrol, Ravinder; Goddard, William A.
    The prediction of various GPCR conformations along their activation pathways has been a challenge for computational biophysicists. The shortage of exptl. active structures has impaired the study of GPCR activation mechanisms. We have developed a hybrid computational method that predicts multiple GPCR conformations systematically, including the active ones. This is one of the very few methods that can predict the high-energy active conformations, capable of coupling to the G protein, starting from an inactive conformation. We are also able to generate, to the best of our knowledge, the first quant. energy profile of GPCR activation consistent with the qual. energy landscape from expts. Our hybrid...

  20. Homogeneous Ta/Ir tandem catalytic alkane/alkene coupling

    Bercaw, John E.; Labinger, Jay A.; Leitch, David; Steelman, Keith
    Light alkanes and alkenes are abundant but under-utilized energy carriers due to their high volatility and low energy d. A tandem catalytic approach for the coupling of alkanes and alkenes has been developed in order to upgrade these light hydrocarbons into heavier fuel mols. This process involves alkane dehydrogenation by pincer- ligated iridium complexes, and alkene dimerization by a Cp*TaCl_2(alkene) catalyst. These two homogeneous catalysts operate with up to 60 /30 cooperative turnovers (Ir/Ta) in the dimerization of 1- hexene /n- heptane, giving C_(13)/C_(14) products in 40 % yield. Because there is no kinetically relevant interaction between the two catalysts, the tandem mechanism can be...

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