Louis-S. Bouchard

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Name: Bouchard, Louis
Organization: University of California at Los Angeles , USA
Department: Department of Chemistry and Biochemistry
Title: (PhD)

TOPICS

Co-reporter:S. Glöggler, A. M. Grunfeld, Y. N. Ertas, J. McCormick, S. Wagner and L.-S. Bouchard  
Chemical Communications 2016 vol. 52(Issue 3) pp:605-608
Publication Date(Web):10 Nov 2015
DOI:10.1039/C5CC08648E
para-Hydrogen induced polarization is a technique of magnetic resonance hyperpolarization utilizing hydrogen's para-spin state for generating signal intensities at magnitudes far greater than state-of-the-art magnets. Platinum nanoparticle-catalysts with cysteine-capping are presented. The measured polarization is the highest reported to date in water, paving pathways for generating medical imaging contrast agents.
Co-reporter:S. Glöggler, S. Wagner and L.-S. Bouchard  
Chemical Science 2015 vol. 6(Issue 7) pp:4261-4266
Publication Date(Web):26 May 2015
DOI:10.1039/C5SC00503E
We report on the successful synthesis and hyperpolarization of N-unprotected α-amino acid ethyl propionate esters and extensively, on an alanine derivative hyperpolarized by PHIP (4.4 ± 1.0% 13C-polarization), meeting required levels for in vivo detection. Using water as solvent increases biocompatibility and the absence of N-protection is expected to maintain biological activity.
Co-reporter:Dr. Stefan Glöggler;Alexer M. Grunfeld;M.Sc. Yavuz N. Ertas;M.Sc. Jeffrey McCormick; Shawn Wagner;Dipl.-Chem. P. Philipp M. Schleker; Louis-S. Bouchard
Angewandte Chemie 2015 Volume 127( Issue 8) pp:2482-2486
Publication Date(Web):
DOI:10.1002/ange.201409027

Abstract

Para-hydrogen-induced polarization (PHIP) is a technique capable of producing spin polarization at a magnitude far greater than state-of-the-art magnets. A significant application of PHIP is to generate contrast agents for biomedical imaging. Clinically viable and effective contrast agents not only require high levels of polarization but heterogeneous catalysts that can be used in water to eliminate the toxicity impact. Herein, we demonstrate the use of Pt nanoparticles capped with glutathione to induce heterogeneous PHIP in water. The ligand-inhibited surface diffusion on the nanoparticles resulted in a 1H polarization of P=0.25 % for hydroxyethyl propionate, a known contrast agent for magnetic resonance angiography. Transferring the 1H polarization to a 13C nucleus using a para-hydrogen polarizer yielded a polarization of 0.013 %. The nuclear-spin polarizations achieved in these experiments are the first reported to date involving heterogeneous reactions in water.

Co-reporter:Dr. Stefan Glöggler;Alexer M. Grunfeld;M.Sc. Yavuz N. Ertas;M.Sc. Jeffrey McCormick; Shawn Wagner;Dipl.-Chem. P. Philipp M. Schleker; Louis-S. Bouchard
Angewandte Chemie International Edition 2015 Volume 54( Issue 8) pp:2452-2456
Publication Date(Web):
DOI:10.1002/anie.201409027

Abstract

Para-hydrogen-induced polarization (PHIP) is a technique capable of producing spin polarization at a magnitude far greater than state-of-the-art magnets. A significant application of PHIP is to generate contrast agents for biomedical imaging. Clinically viable and effective contrast agents not only require high levels of polarization but heterogeneous catalysts that can be used in water to eliminate the toxicity impact. Herein, we demonstrate the use of Pt nanoparticles capped with glutathione to induce heterogeneous PHIP in water. The ligand-inhibited surface diffusion on the nanoparticles resulted in a 1H polarization of P=0.25 % for hydroxyethyl propionate, a known contrast agent for magnetic resonance angiography. Transferring the 1H polarization to a 13C nucleus using a para-hydrogen polarizer yielded a polarization of 0.013 %. The nuclear-spin polarizations achieved in these experiments are the first reported to date involving heterogeneous reactions in water.

Co-reporter:Dimitrios Koumoulis;Belinda Leung;Thomas C. Chasapis;Robert Taylor;Daniel King Jr.;Mercouri G. Kanatzidis
Advanced Functional Materials 2014 Volume 24( Issue 11) pp:1519-1528
Publication Date(Web):
DOI:10.1002/adfm.201302673

Non-invasive local probes are needed to characterize bulk defects in binary and ternary chalcogenides. These defects contribute to the non-ideal behavior of topological insulators. The bulk electronic properties are studied via 125Te NMR in Bi2Te3, Sb2Te3, Bi0.5Sb1.5Te3, Bi2Te2Se, and Bi2Te2S. A distribution of defects gives rise to asymmetry in the powder lineshapes. The Knight shift, line shape, and spin-lattice relaxation are investigated in terms of how they affect carrier density, spin-orbit coupling, and phase separation in the bulk. The present study confirms that the ordered ternary compound Bi2Te2Se is the best topological insulator candidate material at the present time. These results, which are in good agreement with transport and angle-resolved photoemission spectroscopy studies, help establish the NMR probe as a valuable method to characterize the bulk properties of these materials.

Co-reporter:Julia J. Mack, Khalid Youssef, Onika D.V. Noel, Michael P. Lake, Ashley Wu, M. Luisa Iruela-Arispe, Louis-S. Bouchard
Biomaterials 2013 34(8) pp: 1980-1986
Publication Date(Web):
DOI:10.1016/j.biomaterials.2012.11.030
Co-reporter:Robert E. Taylor, Fahri Alkan, Dimitrios Koumoulis, Michael P. Lake, Daniel King, Cecil Dybowski, and Louis-S. Bouchard
The Journal of Physical Chemistry C 2013 Volume 117(Issue 17) pp:8959-8967
Publication Date(Web):April 10, 2013
DOI:10.1021/jp3101877
In this study we present an alternative approach to separating contributions to the NMR shift originating from the Knight shift and chemical shielding by a combination of experimental solid-state NMR results and ab initio calculations. The chemical and Knight shifts are normally distinguished through detailed studies of the resonance frequency as a function of temperature and carrier concentration, followed by extrapolation of the shift to zero carrier concentration. This approach is time-consuming and requires studies of multiple samples. Here, we analyzed 207Pb and 125Te NMR spin–lattice relaxation rates and NMR shifts for bulk and nanoscale PbTe. The shifts are compared with calculations of the 207Pb and 125Te chemical shift resonances to determine the chemical shift at zero charge carrier concentration. The results are in good agreement with literature values from carrier concentration-dependent studies. The measurements are also compared to literature reports of the 207Pb and 125Te Knight shifts of n- and p-type PbTe semiconductors. The literature data have been converted to the currently accepted shift scale. We also provide possible evidence for the “self-cleaning effect” property of PbTe nanocrystals whereby defects are removed from the core of the particles while preserving the crystal structure.
Co-reporter:Robert E. Taylor, Belinda Leung, Michael P. Lake, and Louis-S. Bouchard
The Journal of Physical Chemistry C 2012 Volume 116(Issue 32) pp:17300-17305
Publication Date(Web):July 23, 2012
DOI:10.1021/jp307051z
Bismuth chalcogenides Bi2Se3 and Bi2Te3 are semiconductors that can be both thermoelectric materials (TEs) and topological insulators (TIs). Lattice defects arising from vacancies, impurities, or dopants in these materials are important in that they provide the charge carriers in TE applications and compromise the performance of these materials as TIs. We present the first solid-state nuclear magnetic resonance (NMR) study of the 77Se and 125Te NMR resonances in polycrystalline powders of Bi2Se3 and Bi2Te3, respectively. The spin–lattice (T1) relaxation is modeled by at most two exponentials. Within the framework of this model, the NMR measurement is sensitive to the distribution of native defects within these materials. One component corresponds to a stoichiometric fraction, an insulator with a very long T1, whereas the other component is attributed to a sample fraction with high defect content with a short T1 resulting from interaction with the conduction carriers. The absence of a very long T1 in the bismuth telluride suggests defects throughout the sample. For the bismuth selenide, defect regions segregate into domains. We also find a substantial difference in the short T1 component for 125Te nuclei (76 ms) and 77Se (0.63 s) despite the fact that these materials have nearly identical lattice structures and chemical and physical properties. Investigations of the NMR shift and Korringa law indicate that the coupling to the conduction band electrons at the chalcogenide sites is much stronger in the telluride. The results are consistent with a stronger spin–orbit coupling (SOC) to the p-band electrons in the telluride. If most parameters of a given material are kept equal, then this type of experiment could provide a useful probe of SOC in engineered TI materials.
Co-reporter:Ramesh Sharma ; Robert. E. Taylor
The Journal of Physical Chemistry C 2011 Volume 115(Issue 8) pp:3297-3303
Publication Date(Web):February 4, 2011
DOI:10.1021/jp110686a
The knowledge of intramolecular dynamics, geo-metric confinement, and structure of surface-bound ligands are important factors for understanding surface chemistry, catalysis, and design of catalytically optimized nanoparticles. In this report, intramolecular dynamics of perdeuterated triphenylphosphine ligands, d15-(PPh3), bound to the surface of gold nanoparticles (AuNPs) are characterized by pulsed deuteron nuclear magnetic resonance (2H NMR) in the solid state. The 2H quadrupolar echo Fourier transform NMR line shapes indicate fast 180° flip dynamics (π flip) of phenyl rings in surface-bound d15-(PPh3) ligands about the P−C bond at the rate of k ≥ 7 × 107 s−1. In contrast, the d15-(PPh3)AuCl complex, a model compound that is also present in this nanoparticle system, does not exhibit measurable π flips on the time scale sampled by the experiment (∼10−5 s). Its phenyl rings appear rigid from ambient temperature up to 386 K. The experimental 2H NMR line shape results are consistent with a theoretical model of phenyl rings undergoing rapid π flips. The deuterons of the phenyl ring experiencing the rapid motion of surface-bound d15-(PPh3) ligands in a high magnetic field exhibit substantially shortened spin−lattice (T1) relaxation times of 44 ms in the ortho and meta positions and 2.5 s for the para position in comparison to the very long T1 time in excess of 103 s observed in the rigid d15-(PPh3)AuCl complex. The difference in T1 by several orders of magnitude further confirms the rapid phenyl ring dynamics of ligands bound through gold−phosphorus bond on the surfaces. The observation of uninterrupted rapid motion in phenyl rings suggests the presence of well-separated ligands and availability of low-coordinated surface gold atoms. These parameters are critically important in the catalytic activity of ligand-capped nanoparticles.
Co-reporter:Louis-S. Bouchard;M. Sabieh Anwar;Gang L. Liu;Z. Harry Xie;Alexander Pines;Joe W. Gray;Byron Hann;Xueding Wang;Fanqing Frank Chen
PNAS 2009 Volume 106 (Issue 11 ) pp:4085-4089
Publication Date(Web):2009-03-17
DOI:10.1073/pnas.0813019106
Multimodality imaging based on complementary detection principles has broad clinical applications and promises to improve the accuracy of medical diagnosis. This means that a tracer particle advantageously incorporates multiple functionalities into a single delivery vehicle. In the present work, we explore a unique combination of MRI and photoacoustic tomography (PAT) to detect picomolar concentrations of nanoparticles. The nanoconstruct consists of ferromagnetic (Co) particles coated with gold (Au) for biocompatibility and a unique shape that enables optical absorption over a broad range of frequencies. The end result is a dual-modality probe useful for the detection of trace amounts of nanoparticles in biological tissues, in which MRI provides volume detection, whereas PAT performs edge detection.
Co-reporter:Trenton Otto, Nanette N. Jarenwattananon, Stefan Glöggler, Jonathan W. Brown, Arek Melkonian, Yavuz N. Ertas, Louis-S. Bouchard
Applied Catalysis A: General (November 2014) Volume 488() pp:
Publication Date(Web):1 November 2014
DOI:10.1016/j.apcata.2014.10.012
•Pd(CH3CN)2Cl2 was covalently bonded to IRMOF-3 to form a new palladium catalyst.•Optimal metal loading and specific surface were found for propylene hydrogenation.•Kinetics and diffusion measurements showed intra-particle diffusion limitations.•The operating temperature range for avoiding thermal degradation was identified.•Catalyst showed excellent reversibility to carbon monoxide poisoning.We investigated the performance of zinc-based metal-organic framework (MOF) catalysts that were post-synthetically modified with the homogeneous palladium catalyst Pd(CH3CN)2Cl2 for the hydrogenation of propylene in a packed-bed, tubular microreactor. The catalytic conversion and apparent reaction kinetics were analyzed across a range of metal loadings, reactant flow rates, feed concentrations, and reactor temperatures. The catalyst's deactivation in the presence of a common palladium catalyst poison, carbon monoxide, was also examined. The catalytic conversion was optimal at moderate metal loadings, stoichiometric excess of hydrogen, and relatively mild temperatures. The activity depended strongly on reactant feed composition but showed no dependence on total flow rate, indicating a diffusion-limited process. To investigate the effects of intra-particle diffusion limitations, internal diffusion coefficients for propylene in the MOF catalysts were measured with pulsed field gradient nuclear magnetic resonance (PFG NMR) and were incorporated into the kinetics analysis. Using these coefficients to compute effectiveness factors for heterogeneous catalytic reactions, diffusion-limited artifacts were accounted for to obtain intrinsic rate constants and activation energies from apparent kinetics data. The average intrinsic activation energy was found to be 51(6) kJ/mol. The MOF catalyst was also found to be reversible under carbon monoxide poisoning, suggesting a weak binding mechanism.Download high-res image (265KB)Download full-size image
Co-reporter:S. Glöggler, A. M. Grunfeld, Y. N. Ertas, J. McCormick, S. Wagner and L.-S. Bouchard
Chemical Communications 2016 - vol. 52(Issue 3) pp:NaN608-608
Publication Date(Web):2015/11/10
DOI:10.1039/C5CC08648E
para-Hydrogen induced polarization is a technique of magnetic resonance hyperpolarization utilizing hydrogen's para-spin state for generating signal intensities at magnitudes far greater than state-of-the-art magnets. Platinum nanoparticle-catalysts with cysteine-capping are presented. The measured polarization is the highest reported to date in water, paving pathways for generating medical imaging contrast agents.
Co-reporter:S. Glöggler, S. Wagner and L.-S. Bouchard
Chemical Science (2010-Present) 2015 - vol. 6(Issue 7) pp:NaN4266-4266
Publication Date(Web):2015/05/26
DOI:10.1039/C5SC00503E
We report on the successful synthesis and hyperpolarization of N-unprotected α-amino acid ethyl propionate esters and extensively, on an alanine derivative hyperpolarized by PHIP (4.4 ± 1.0% 13C-polarization), meeting required levels for in vivo detection. Using water as solvent increases biocompatibility and the absence of N-protection is expected to maintain biological activity.
IRMOF-3
MOF-5; IRMOF-1
Antimony bismuth telluride
Manganate(4-), chloro[[4,4',4'',4'''-(21H,23H-porphine-5,10,15,20-tetrayl-κN21,κN22,κN23,κN24)tetrakis[benzoato]](6-)]-, hydrogen (1:4), (SP-5-12)-
1,2-Ethanediol, monopropanoate
Oxirane, 2,3-diphenyl-
Selenium, isotope ofmass 77
Tin, isotope of mass119
Benzene, 1,1'-(1,2-ethenediyl)bis-
Lead, isotope of mass207