NMR and EPR

Molecular systems important to biology, environmental remediation and sustainability are studied using a suite of nuclear magnetic resonance (NMR) spectrometers with frequencies ranging from 300 to 850 MHz. A pair of electron paramagnetic resonance (EPR) spectrometers complement the capability. See a complete list of NMR and EPR instruments.

Description

Interfacial and in situ biology—Innovative NMR instrumentation and techniques for probing properties of macromolecular cellular assemblies and in situ and ex situ metabolic processes, as well as for exploring biological membrane proteins in the solid state. Unique EPR and variable-temperature NMR approaches to explore structure and properties of redox metal centers critical catalysis, environmental chemistry and cell biology.

Environmental chemistry— EMSL offers a unique NMR system for radiological studies. Users can perform magic angle spinning of highly radioactive samples with a novel hermetically sealed 3.2mm NMR probe. These tools allow users to apply NMR techniques to critical areas of radiological research, including the study of radioactive waste processing and storage.

Interfacial and in situ chemistry—Leading-edge solid-state NMR probe technology to analyze and quantify properties of advanced energy materials, fuel cells and real-time catalytic processes. High power pulsed field gradient diffusion capabilities for liquid and solid samples.

EMSL offers unique and custom NMR and EPR tools, including probes for specialized studies.

  • NMR spectrometers, ranging from 300 MHz to 850 MHz for high-field liquid-state, solid-state and micro-imaging techniques
  • W- and X-band pulsed EPR spectremeter for probing metal centers in biological and materials systems
  • NMR metabolomics capabilities
  • Extreme-temperature probes, both high and low temperatures
  • Virtual NMR tools for remote access to spectrometer systems.

Instruments

Highlighted Research Applications Structural biology Protein structure and dynamics Nuclei acid structure and dynamics. Metabolomics Eukaryotic and...
Custodian(s): Sarah D Burton, David Hoyt
Highlighted Research Applications Structural biology Protein structure and dynamics Nuclei acid structure and dynamics Metabolomics Eukaryotic and...
Custodian(s): David Hoyt, Nancy Isern
Highlighted Research Applications Characterization of quadrupolar nuclei for materials and biological samples In situ catalysis investigations via...
Research applications Samples containing paramagnetics Soils (SOM and NOM) Metal oxide materials for catalysis applications Researchers may operate...
Custodian(s): Nancy Washton, Sarah D Burton
Highlighted Research Applications Characterization of natural and soil organic matter (NOM and SOM) CO2 sequestration investigations via high-...
Custodian(s): Sarah D Burton, David Hoyt

Publications

A hydrogen-evolving homogeneous Ni(P2N2)2 electrocatalyst with peripheral ester groups has been covalently attached to a 1,2,3-triazolyllithium-...
The altered layer (i.e., amorphous hydrated surface layer and crystalline reaction products)represents a complex region, both physically and...
Bacterial species in the Enterobacteriaceae typically contain multiple paralogues of a small domain of unknown function (DUF1471) from a family of...
A major bottleneck to fully understanding the functional aspects of lysine acetylation is the lack of stoichiometry information. Here we describe a...
Melanoma is a malignant tumor of melanocytes with high capability of invasion and rapid metastasis to other organs. Malignant melanoma is the most...

Science Highlights

Posted: March 02, 2015
A new zinc-polyiodide redox flow battery developed at Pacific Northwest National Laboratory with EMSL resources uses an electrolyte with more than...
Posted: January 15, 2015
A team of scientists with Pacific Northwest National Laboratory, EMSL, Marine Biological Laboratory and The Pennsylvania State University grew two...
Posted: November 21, 2014
The Science Carbon dioxide (CO2) sequestration in deep subsurface environments has received significant attention and investment as a way to reduce...
Posted: August 14, 2014
Industry uses zeolites as an ion exchange material and solid acid to catalyze a broad range of chemical reactions. Zeolites are also promising...
Posted: June 23, 2014
Congratulations to Pacific Northwest National Laboratory and EMSL researchers on being named highly cited authors for 2012-2013 by the Journal of...

Molecular systems important to biology, environmental remediation and sustainability are studied using a suite of nuclear magnetic resonance (NMR) spectrometers with frequencies ranging from 300 to 850 MHz. A pair of electron paramagnetic resonance (EPR) spectrometers complement the capability. See a complete list of NMR and EPR instruments.

A Hydrogen-Evolving Ni(P2N2)2 Electrocatalyst Covalently Attached to a Glassy Carbon Electrode: Preparation, Characterization,

Abstract: 

A hydrogen-evolving homogeneous Ni(P2N2)2 electrocatalyst with peripheral ester groups has been covalently attached to a 1,2,3-triazolyllithium-terminated glassy carbon electrode. The surface-confined complex is an electroctalyst for hydrogen evolution, showing onset of catalytic current at the same potential as the soluble parent complex. X-ray photoemission spectra show excellent agreement between the coupled and homogeneous species. Coverage approaches a dense monolayer. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy. The XPS measurements were performed at EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.

Citation: 
Das AK, MH Engelhard, RM Bullock, and JA Roberts.2014."A Hydrogen-Evolving Ni(P2N2)2 Electrocatalyst Covalently Attached to a Glassy Carbon Electrode: Preparation, Characterization, and Catalysis. Comparisons With the Homogeneous Analog."Inorganic Chemistry 53(13):6875-6885. doi:10.1021/ic500701a
Authors: 
AK Das
MH Engelhard
RM Bullock
JA Roberts
Facility: 
Volume: 
53
Issue: 
13
Pages: 
6875-6885
Publication year: 
2014

Structural and Functional Characterization of DUF1471 Domains of Salmonella Proteins SrfN, YdgH/SssB, and YahO.

Abstract: 

Bacterial species in the Enterobacteriaceae typically contain multiple paralogues of a small domain of unknown function (DUF1471) from a family of conserved proteins also known as YhcN or BhsA/McbA. Proteins containing DUF1471 may have a
single or three copies of this domain. Representatives of this family have been demonstrated to play roles in several cellular processes including stress response, biofilm formation, and pathogenesis. We have conducted NMR and X-ray crystallographic studies of four DUF1471 domains from Salmonella representing three different paralogous DUF1471 subfamilies: SrfN, YahO, and SssB/YdgH (two of its three DUF1471 domains: the N-terminal domain I (residues 21–91), and the C-terminal domain III (residues 244–314)). Notably, SrfN has been shown to have a role in intracellular infection by Salmonella Typhimurium. These domains share less than 35% pairwise sequence identity. Structures of all four domains show a mixed a+b fold that is most similar to that of bacterial lipoprotein RcsF. However, all four DUF1471 sequences lack the redox sensitive cysteine residues essential for RcsF activity in a phospho-relay pathway, suggesting that DUF1471 domains perform a different function(s). SrfN forms a dimer in contrast to YahO and SssB domains I and III, which are monomers in solution. A putative binding site for oxyanions such as phosphate and sulfate was identified in SrfN, and an interaction between the SrfN dimer and sulfated polysaccharides was demonstrated, suggesting a direct role for this DUF1471 domain at the host-pathogen interface.

Citation: 
Eletsky A, K Michalska, S Houliston, Q Zhang, MD Daily, X Xu, H Cui, A Yee, A Lemak, B Wu, M Garcia, MC Burnet, KM Meyer, UK Aryal, O Sanchez, C Ansong, R Xiao, T Acton, JN Adkins, G Montelione, A Joachimiak, CH Arrowsmith, A Savchenko, T Szyperski, and JR Cort.2014."Structural and Functional Characterization of DUF1471 Domains of Salmonella Proteins SrfN, YdgH/SssB, and YahO."PLoS One 9(7):Article No. e101787. doi:10.1371/journal.pone.0101787
Authors: 
A Eletsky
K Michalska
S Houliston
Q Zhang
MD Daily
X Xu
H Cui
A Yee
A Lemak
B Wu
M Garcia
MC Burnet
KM Meyer
UK Aryal
O Sanchez
C Ansong
R Xiao
T Acton
JN Adkins
G Montelione
A Joachimiak
CH Arrowsmith
A Savchenko
T Szyperski
JR Cort
Facility: 
Volume: 
Issue: 
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Publication year: 
2014

Modeling Interfacial Glass-Water Reactions: Recent Advances and Current Limitations.

Abstract: 

The altered layer (i.e., amorphous hydrated surface layer and crystalline reaction products)represents a complex region, both physically and chemically, sandwiched between two distinct boundaries - pristine glass surface at the inner most interface and aqueous solution at the outer most. The physico-chemical processes that control the development of this region have a significant impact on the long-term glass-water reaction. Computational models, spanning different length and time-scales, are currently being developed to improve our understanding of this complex and dynamic process with the goal of accurately describing the pore-scale changes that occur as the system evolves. These modeling approaches include Geochemical Reaction Path simulations, Glass Reactivity in Allowance for Alteration Layer simulations, Monte Carlo simulations, and Molecular Dynamics methods. Discussed in this manuscript are the advances and limitations of each modeling approach placed in the context of the glass water reaction and how collectively these approaches provide insights into the mechanisms that control the formation and evolution of altered layers; thus providing the fundamental data needed to develop pore-scale equations that enable more accurate predictions of nuclear waste glass corrosion in a geologic repository.

Citation: 
Pierce EM, P Frugier, LJ Criscenti, KD Kwon, and SN Kerisit.2014."Modeling Interfacial Glass-Water Reactions: Recent Advances and Current Limitations."International Journal of Applied Glass Science 5(4):421-435. doi:10.1111/ijag.12077
Authors: 
EM Pierce
P Frugier
LJ Criscenti
KD Kwon
SN Kerisit
Volume: 
5
Issue: 
4
Pages: 
421-435
Publication year: 
2014

Metastatic Melanoma Induced Metabolic Changes in C57BL/6J Mouse Stomach Measured by 1H NMR Spectroscopy.

Abstract: 

Melanoma is a malignant tumor of melanocytes with high capability of invasion and rapid metastasis to other organs. Malignant melanoma is the most common metastatic malignancy found in gastrointestinal tract (GI). To the best of our knowledge, previous studies of melanoma in gastrointestinal tract are all clinical case reports. In this work, 1H NMR-based metabolomics approach is used to investigate the metabolite profiles differences of stomach tissue extracts of metastatic B16-F10 melanoma in C57BL/6J mouse and search for specific metabolite biomarker candidates. Principal Component Analysis (PCA), an unsupervised multivariate data analysis method, is used to detect possible outliers, while Orthogonal Projection to Latent Structure (OPLS), a supervised multivariate data analysis method, is employed to evaluate important metabolites responsible for discriminating the control and the melanoma groups. Both PCA and OPLS results reveal that the melanoma group can be well separated from its control group. Among the 50 identified metabolites, it is found that the concentrations of 19 metabolites are statistically and significantly changed with the levels of O-phosphocholine and hypoxanthine down-regulated while the levels of isoleucine, leucine, valine, isobutyrate, threonine, cadaverine, alanine, glutamate, glutamine, methionine, citrate, asparagine, tryptophan, glycine, serine, uracil, and formate up-regulated in the melanoma group. These significantly changed metabolites are associated with multiple biological pathways and may be potential biomarkers for metastatic melanoma in stomach.

Citation: 
Wang X, MY Hu, M Liu, and JZ Hu.2014."Metastatic Melanoma Induced Metabolic Changes in C57BL/6J Mouse Stomach Measured by 1H NMR Spectroscopy."Metabolomics 4(2):135. doi:10.4172/2153-0769.1000135
Authors: 
X Wang
MY Hu
M Liu
JZ Hu
Capabilities: 
Volume: 
Issue: 
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Publication year: 
2014

A Method to determine lysine acetylation stoichiometries.

Abstract: 

A major bottleneck to fully understanding the functional aspects of lysine acetylation is the lack of stoichiometry information. Here we describe a mass spectrometry method using a combination of isotope labeling and detection of a diagnostic fragment ion to determine the stoichiometry of lysine acetylation on proteins globally. Using this technique, we determined the modification occupancy on hundreds of acetylated peptides from cell lysates and cross-validated the measurements via immunoblotting.

Citation: 
Nakayasu ES, S Wu, MA Sydor, AK Shukla, KK Weitz, RJ Moore, KK Hixson, JS Kim, VA Petyuk, ME Monroe, L Pasa-Tolic, W Qian, RD Smith, JN Adkins, and C Ansong.2014."A Method to determine lysine acetylation stoichiometries."International Journal of Proteomics 2014:Article No. 730725. doi:10.1155/2014/730725
Authors: 
ES Nakayasu
S Wu
MA Sydor
AK Shukla
KK Weitz
RJ Moore
KK Hixson
JS Kim
VA Petyuk
ME Monroe
L Pasa-Tolic
W Qian
RD Smith
JN Adkins
C Ansong
Capabilities: 
Facility: 
Volume: 
Issue: 
Pages: 
Publication year: 
2014

An Electrically Switchable Metal-Organic Framework.

Abstract: 

Crystalline metal organic framework (MOF) materials containing interconnected porosity can be chemically modified to promote stimulus-driven (light, magnetic or electric fields) structural transformations that can be used in a number of devices. Innovative research strategies are now focused on understanding the role of chemical bond manipulation to reversibly alter the free volume in such structures of critical importance for electro-catalysis, molecular electronics, energy storage technologies, sensor devices and smart membranes. In this letter, we study the mechanism for which an electrically switchable MOF composed of Cu(TCNQ) (TCNQ 5 7,7,8,8-tetracyanoquinodimethane) transitions from a high-resistance state to a conducting state in a reversible fashion by an applied potential. The actual mechanism for this reversible electrical switching is still not understood even though a number of reports are available describing the application of electric-field-induced switching of Cu(TCNQ) in device fabrication.

Citation: 
Fernandez CA, PF Martin, HT Schaef, ME Bowden, PK Thallapally, LX Dang, W Xu, X Chen, and BP McGrail.2014."An Electrically Switchable Metal-Organic Framework."Scientific Reports 12(3):Article No. 6114 . doi:10.1038/srep06114
Authors: 
CA Fernez
PF Martin
HT Schaef
ME Bowden
PK Thallapally
LX Dang
W Xu
X Chen
BP McGrail
Facility: 
Volume: 
Issue: 
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Publication year: 
2014

Molecular Characterization of Organosulfates in Organic Aerosols from Shanghai and Los Angeles Urban Areas by Nanospray

Abstract: 

Aerosol samples collected in the urban areas of Shanghai and Los Angeles were analyzed by nanospray-desorption electrospray ionization mass spectrometry (nano-DESI MS) with high mass resolution (m/m=100,000). Solvent mixtures of acetonitrile/water and acetonitrile/toluene were used to extract and ionize polar and non-polar compounds, respectively. A diverse mixture of oxygenated hydrocarbons, organosulfates, organonitrates, and organics with reduced nitrogen were detected in the Los Angeles sample. Majority of the organics in the Shanghai sample were detected as organosulfates. The dominant organosulfates in the two samples have distinctly different molecular characteristics. Specifically, organosulfates in the Los Angeles sample were dominated by isoprene- or monoterpene-derived products, while organosulfates of yet unknown origin in the Shanghai sample had distinctive characteristics of long aliphatic carbon chains and low degree of oxidation and unsaturation. The use of acetonitrile/toluene solvent facilitated identification of this type of organosulfates, suggesting they could be missed in previous studies relying on sample extraction using common polar solvents. The high molecular weight and low degree of unsaturation and oxidization of the organosulfates detected in the Shanghai sample suggest that they may act as surfactants, and plausibly affect the surface tension and hygroscopicity of the atmospheric particulate matter. We propose that direct esterification of carbonyl or hydroxyl compounds by sulfates or sulfuric acid in liquid phase could be the formation pathway of these special organosulfates. Long-chain alkanes from vehicle emissions might be their precursors.

Citation: 
Tao S, X Lu, NA Levac, AP Bateman, TB Nguyen, DL Bones, S Nizkorodov, J Laskin, A Laskin, and X Yang.2014."Molecular Characterization of Organosulfates in Organic Aerosols from Shanghai and Los Angeles Urban Areas by Nanospray-Desorption Electrospray Ionization High-Resolution Mass Spectrometry."Environmental Science & Technology 48(18):10993-11001. doi:10.1021/es5024674
Authors: 
S Tao
X Lu
NA Levac
AP Bateman
TB Nguyen
DL Bones
S Nizkorodov
J Laskin
A Laskin
X Yang
Volume: 
48
Issue: 
18
Pages: 
10993-11001
Publication year: 
2014

Excited States and Luminescent Properties of UO2F2 and Its Solvated Complexes in Aqueous Solution.

Abstract: 

The electronic absorption and emission spectra of free UO2F2 and its water solvated complexes below 32,000 cm1 are investigated at the levels of ab initio CASPT2 and CCSD(T) with inclusion of scalar relativistic and spin-orbit coupling effects. The influence of the water coordination on the electronic spectra of UO2F2 is explored by investigating the excited states of solvated complexes (H2O)nUO2F2 (n = 13). In these uranyl-complexes, water coordination is found to have appreciable influence on the 3 ( = 1g) character of the luminescent state and on the electronic spectral shape. The simulated luminescence spectral curves based on the calculated spectral parameters of (H2O)nUO2F2 from CCSD(T) approach agree well with experimental spectra in aqueous solution at both near liquid helium temperature and room temperature. The possible luminescence spectra of free UO2F2 in gas phase are predicted based on CASPT2 and CCSD(T) results, respectively, by considering three symmetric vibration modes. The effect of competition between spin-orbital coupling and ligand field repulsion on the luminescent state properties is discussed.

Citation: 
Su J, Z Wang, D Pan, and J Li.2014."Excited States and Luminescent Properties of UO2F2 and Its Solvated Complexes in Aqueous Solution."Inorganic Chemistry 53(14):7340-7350. doi:10.1021/ic5006852
Authors: 
Su J
Z Wang
D Pan
J Li
Volume: 
53
Issue: 
14
Pages: 
7340-7350
Publication year: 
2014

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