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Sample records for hr mas nmr

  1. Slow-spinning low-sideband HR-MAS NMR spectroscopy: delicate analysis of biological samples

    PubMed Central

    Renault, Marie; Shintu, Laetitia; Piotto, Martial; Caldarelli, Stefano

    2013-01-01

    High-Resolution Magic-Angle Spinning (HR-MAS) NMR spectroscopy has become an extremely versatile analytical tool to study heterogeneous systems endowed with liquid-like dynamics. Spinning frequencies of several kHz are however required to obtain NMR spectra, devoid of spinning sidebands, with a resolution approaching that of purely isotropic liquid samples. An important limitation of the method is the large centrifugal forces that can damage the structure of the sample. In this communication, we show that optimizing the sample preparation, particularly avoiding air bubbles, and the geometry of the sample chamber of the HR-MAS rotor leads to high-quality low-sideband NMR spectra even at very moderate spinning frequencies, thus allowing the use of well-established solution-state NMR procedures for the characterization of small and highly dynamic molecules in the most fragile samples, such as live cells and intact tissues. PMID:24284435

  2. Slow-spinning low-sideband HR-MAS NMR spectroscopy: delicate analysis of biological samples

    NASA Astrophysics Data System (ADS)

    Renault, Marie; Shintu, Laetitia; Piotto, Martial; Caldarelli, Stefano

    2013-11-01

    High-Resolution Magic-Angle Spinning (HR-MAS) NMR spectroscopy has become an extremely versatile analytical tool to study heterogeneous systems endowed with liquid-like dynamics. Spinning frequencies of several kHz are however required to obtain NMR spectra, devoid of spinning sidebands, with a resolution approaching that of purely isotropic liquid samples. An important limitation of the method is the large centrifugal forces that can damage the structure of the sample. In this communication, we show that optimizing the sample preparation, particularly avoiding air bubbles, and the geometry of the sample chamber of the HR-MAS rotor leads to high-quality low-sideband NMR spectra even at very moderate spinning frequencies, thus allowing the use of well-established solution-state NMR procedures for the characterization of small and highly dynamic molecules in the most fragile samples, such as live cells and intact tissues.

  3. Distinction between a transgenic and a conventional common bean genotype by 1H HR-MAS NMR.

    PubMed

    Choze, Rafael; Alcantara, Glaucia B; Alves Filho, Elenilson de G; e Silva, Lorena Mara A; Faria, Josias C; Lião, Luciano M

    2013-12-01

    In this work, it is proposed a methodology which allows to differentiate a conventional and a specific transgenic common beans, grown in greenhouse or under field conditions, based on modifications in chemical composition using (1)H HR-MAS NMR. It is demonstrated that the influence of typical variables from field planting conditions had no significant influence on the ability to set apart transgenic from conventional. This methodology was corroborated by multivariate data analysis of the (1)H NMR and IR spectra. This study also points out the simplicity of using the HR-MAS NMR technique for food analyses. The measurement is highly simplified because it does not require any pretreatment of the sample apart from the addition of a small amount of D2O necessary to produce homogeneous dough and a field frequency lock. Moreover, due to the high concentration of the sample, measurement time in HR-MAS NMR is very short. PMID:23871032

  4. High resolution magic angle spinning (HR-MAS) NMR spectroscopy of human osteoarthritic cartilage

    PubMed Central

    Shet, Keerthi; Siddiqui, Sarmad M.; Yoshihara, Hikari; Kurhanewicz, John; Ries, Michael; Li, Xiaojuan

    2011-01-01

    Osteoarthritis (OA) is a degenerative disease of the joint and results in changes in the biochemical composition of cartilage. Studies have been undertaken in the past that have used high resolution NMR spectroscopy to study the biochemical composition of porcine, canine and bovine cartilage. In this study high resolution magical angle spinning (HRMAS) NMR spectroscopy at 11.7 T has been used to characterize metabolites and detect differences in the spectral signature of human knee articular cartilage from non-OA healthy cadaver knees and samples acquired from severe OA patients at the time of total knee replacement surgery. A statistically significant difference in the alanine (1.47 ppm), N-acetyl (2.04 ppm), choline (3.25 ppm) and glycine (3.55 ppm) metabolite levels is observed between healthy and OA specimens. The results of the study indicate that a decrease in the intensity of N-acetyl resonance occurs in later stages of OA. A positive correlation of the N-acetyl levels as measured by 1H HR-MAS NMR spectroscopy with the total proteoglycan content in the same cartilage specimens as measured by the GAG assay was observed. This indicates that N-acetyl can serve as an important bio-marker of OA disease progression. A decrease in the alanine concentration in OA may be attributed to the degradation of the collagen framework with disease progression and eventual loss of the degradation products that are transported from cartilage into the synovial cavity. PMID:21850648

  5. HR-MAS NMR tissue metabolomic signatures cross-validated by mass spectrometry distinguish bladder cancer from benign disease.

    PubMed

    Tripathi, Pratima; Somashekar, Bagganahalli S; Ponnusamy, M; Gursky, Amy; Dailey, Stephen; Kunju, Priya; Lee, Cheryl T; Chinnaiyan, Arul M; Rajendiran, Thekkelnaycke M; Ramamoorthy, Ayyalusamy

    2013-07-01

    Effective diagnosis and surveillance of bladder cancer (BCa) is currently challenged by detection methods that are of poor sensitivity, particularly for low-grade tumors, resulting in unnecessary invasive procedures and economic burden. We performed HR-MAS NMR-based global metabolomic profiling and applied unsupervised principal component analysis (PCA) and hierarchical clustering performed on NMR data set of bladder-derived tissues and identified metabolic signatures that differentiate BCa from benign disease. A partial least-squares discriminant analysis (PLS-DA) model (leave-one-out cross-validation) was used as a diagnostic model to distinguish benign and BCa tissues. Receiver operating characteristic curve generated either from PC1 loadings of PCA or from predicted Y-values resulted in an area under curve of 0.97. Relative quantification of more than 15 tissue metabolites derived from HR-MAS NMR showed significant differences (P < 0.001) between benign and BCa samples. Noticeably, striking metabolic signatures were observed even for early stage BCa tissues (Ta-T1), demonstrating the sensitivity in detecting BCa. With the goal of cross-validating metabolic signatures derived from HR-MAS NMR, we utilized the same tissue samples to analyze 8 metabolites through gas chromatography-mass spectrometry (GC-MS)-targeted analysis, which undoubtedly complements HR-MAS NMR-derived metabolomic information. Cross-validation through GC-MS clearly demonstrates the utility of a straightforward, nondestructive, and rapid HR-MAS NMR technique for clinical diagnosis of BCa with even greater sensitivity. In addition to its utility as a diagnostic tool, these studies will lead to a better understanding of aberrant metabolic pathways in cancer as well as the design and implementation of personalized cancer therapy through metabolic modulation. PMID:23731241

  6. DRIFT and HR MAS NMR characterization of humic substances from a soil treated with different organic and mineral fertilizers

    NASA Astrophysics Data System (ADS)

    Ferrari, Erika; Francioso, Ornella; Nardi, Serenella; Saladini, Monica; Ferro, Nicola Dal; Morari, Francesco

    2011-07-01

    In this study, using DRIFT and HR MAS NMR, we analyzed the humic substances isolated from a soil treated, over 40 years, with different organic, mineral and organic plus mineral treatments and cultivated with maize as the main crop. As expected, the structure of humic substances was very complex but by combining both techniques (DRIFT and HR MAS NMR) additional information was obtained on aromatic and aliphatic components, the most recalcitrant parts of these macromolecules. In so doing we wanted to investigate the relationship between HS structure and long-term management practices. An elevated content of lignin, aminoacids, peptides and proteins was observed mainly for farmyard manure treatments with respect to mineral or liquid manure amendments; this supports how the different management practices have greatly influenced the humification process of cultivated soils.

  7. 1H HR-MAS NMR Spectroscopy and the Metabolite Determination of Typical Foods in Mediterranean Diet

    PubMed Central

    Corsaro, Carmelo; Mallamace, Domenico; Vasi, Sebastiano; Ferrantelli, Vincenzo; Dugo, Giacomo; Cicero, Nicola

    2015-01-01

    NMR spectroscopy has become an experimental technique widely used in food science. The experimental procedures that allow precise and quantitative analysis on different foods are relatively simple. For a better sensitivity and resolution, NMR spectroscopy is usually applied to liquid sample by means of extraction procedures that can be addressed to the observation of particular compounds. For the study of semisolid systems such as intact tissues, High-Resolution Magic Angle Spinning (HR-MAS) has received great attention within the biomedical area and beyond. Metabolic profiling and metabolism changes can be investigated both in animal organs and in foods. In this work we present a proton HR-MAS NMR study on the typical vegetable foods of Mediterranean diet such as the Protected Geographical Indication (PGI) cherry tomato of Pachino, the PGI Interdonato lemon of Messina, several Protected Designation of Origin (PDO) extra virgin olive oils from Sicily, and the Traditional Italian Food Product (PAT) red garlic of Nubia. We were able to identify and quantify the main metabolites within the studied systems that can be used for their characterization and authentication. PMID:26495154

  8. The Effect of Antitumor Glycosides on Glioma Cells and Tissues as Studied by Proton HR-MAS NMR Spectroscopy

    PubMed Central

    García-Álvarez, Isabel; Garrido, Leoncio; Romero-Ramírez, Lorenzo; Nieto-Sampedro, Manuel; Fernández-Mayoralas, Alfonso; Campos-Olivas, Ramón

    2013-01-01

    The effect of the treatment with glycolipid derivatives on the metabolic profile of intact glioma cells and tumor tissues, investigated using proton high resolution magic angle spinning (1H HR-MAS) nuclear magnetic resonance (NMR) spectroscopy, is reported here. Two compounds were used, a glycoside and its thioglycoside analogue, both showing anti-proliferative activity on glioma C6 cell cultures; however, only the thioglycoside exhibited antitumor activity in vivo. At the drug concentrations showing anti-proliferative activity in cell culture (20 and 40 µM), significant increases in choline containing metabolites were observed in the 1H NMR spectra of the same intact cells. In vivo experiments in nude mice bearing tumors derived from implanted C6 glioma cells, showed that reduction of tumor volume was associated with significant changes in the metabolic profile of the same intact tumor tissues; and were similar to those observed in cell culture. Specifically, the activity of the compounds is mainly associated with an increase in choline and phosphocholine, in both the cell cultures and tumoral tissues. Taurine, a metabolite that has been considered a biomarker of apoptosis, correlated with the reduction of tumor volume. Thus, the results indicate that the mode of action of the glycoside involves, at least in part, alteration of phospholipid metabolism, resulting in cell death. PMID:24194925

  9. LC/ESI-MS n and 1H HR-MAS NMR analytical methods as useful taxonomical tools within the genus Cystoseira C. Agardh (Fucales; Phaeophyceae).

    PubMed

    Jégou, Camille; Culioli, Gérald; Kervarec, Nelly; Simon, Gaëlle; Stiger-Pouvreau, Valérie

    2010-12-15

    Species of the genus Cystoseira are particularly hard to discriminate, due to the complexity of their morphology, which can be influenced by their phenological state and ecological parameters. Our study emphasized on the relevance of two kinds of analytical tools, (1) LC/ESI-MS(n) and (2) (1)H HR-MAS NMR, also called in vivo NMR, to identify Cystoseira specimens at the specific level and discuss their taxonomy. For these analyses, samples were collected at several locations in Brittany (France), where Cystoseira baccata, C. foeniculacea, C. humilis, C. nodicaulis and C. tamariscifolia were previously reported. To validate our chemical procedure, the sequence of the ITS2 has been obtained for each species to investigate their phylogenetic relationships at a molecular level. Our study highlighted the consistency of the two physico-chemical methods, compared to "classical" molecular approach, in studying taxonomy within the genus Cystoseira. Especially, LC/ESI-MS(n) and phylogenetic analyses converged into the discrimination of two taxonomical groups among the 5 species. The occurrence of some specific signals in the (1)H HR-MAS NMR spectra and/or some characteristic chemical compounds during LC/ESI-MS(n) analysis could be regarded as discriminating factors. LC/ESI-MS(n) and (1)H HR-MAS NMR turned out to be two relevant and innovative techniques to discriminate taxonomically this complex genus. PMID:21111182

  10. The metabolic profile of lemon juice by proton HR-MAS NMR: the case of the PGI Interdonato Lemon of Messina.

    PubMed

    Cicero, Nicola; Corsaro, Carmelo; Salvo, Andrea; Vasi, Sebastiano; Giofré, Salvatore V; Ferrantelli, Vincenzo; Di Stefano, Vita; Mallamace, Domenico; Dugo, Giacomo

    2015-01-01

    We have studied by means of High Resolution Magic Angle Spinning Nuclear Magnetic Resonance (HR-MAS NMR) the metabolic profile of the famous Sicilian lemon known as 'Interdonato Lemon of Messina PGI'. The PGI Interdonato Lemon of Messina possesses high organoleptic and healthy properties and is recognised as one of the most nutrient fruits. In particular, some of its constituents are actively studied for their chemo-preventive and therapeutic properties. In this paper, we have determined by means of HR-MAS NMR spectroscopy the molar concentration of the main metabolites constituent the juice of PGI Interdonato Lemon of Messina in comparison with that of the not-PGI Interdonato Lemon of Turkey. Our aim is to develop an analytical technique, in order to determine a metabolic fingerprint able to reveal commercial frauds in national and international markets. PMID:25702767

  11. Proton HR-MAS NMR spectroscopic characterization of metabolites in various human organ tissues: pancreas, brain and liver from trauma cases.

    PubMed

    Misra, Divya; Gupta, Vivek; Sonkar, Abhinav A; Bajpai, Usha; Roy, Raja

    2008-01-01

    High-Resolution Magic Angle Spinning (HR-MAS) NMR has been employed to characterize various metabolites of human pancreas, liver and brain tissues from trauma cases. The potential usefulness of NMR in identifying the metabolites in human tissues has been explored using a combination of one- and two-dimensional experiments. The complete resonance assignments of pancreas tissue have been carried out for the first time. Two new metabolites, alpha-hydroxyisovalarate and alpha-hydroxybutarate were identified in all the tissue specimens. The metabolites information of these human tissues can further be utilized in correlating several diseases associated with pathological manifestations as well in distinguishing traumatic tissues along with control tissues of pancreas, liver and brain. PMID:20070041

  12. 1H HR-MAS NMR Based Metabolic Profiling of Cells in Response to Treatment with a Hexacationic Ruthenium Metallaprism as Potential Anticancer Drug

    PubMed Central

    Vermathen, Martina; Paul, Lydia E. H.; Diserens, Gaëlle

    2015-01-01

    1H high resolution magic angle spinning (HR-MAS) NMR spectroscopy was applied in combination with multivariate statistical analyses to study the metabolic response of whole cells to the treatment with a hexacationic ruthenium metallaprism [1]6+ as potential anticancer drug. Human ovarian cancer cells (A2780), the corresponding cisplatin resistant cells (A2780cisR), and human embryonic kidney cells (HEK-293) were each incubated for 24 h and 72 h with [1]6+ and compared to untreated cells. Different responses were obtained depending on the cell type and incubation time. Most pronounced changes were found for lipids, choline containing compounds, glutamate and glutathione, nucleotide sugars, lactate, and some amino acids. Possible contributions of these metabolites to physiologic processes are discussed. The time-dependent metabolic response patterns suggest that A2780 cells on one hand and HEK-293 cells and A2780cisR cells on the other hand may follow different cell death pathways and exist in different temporal stages thereof. PMID:26024484

  13. Identification of Streptococcus pneumoniae Serotype 11E, Serovariant 11Av and Mixed Populations by High-Resolution Magic Angle Spinning Nuclear Magnetic Resonance (HR-MAS NMR) Spectroscopy and Flow Cytometric Serotyping Assay (FCSA)

    PubMed Central

    Camilli, Romina; Spencer, Brady L.; Moschioni, Monica; Pinto, Vittoria; Berti, Francesco; Nahm, Moon H.; Pantosti, Annalisa

    2014-01-01

    Background Recent studies have identified Streptococcus pneumoniae serotype 11E and serovariant 11Av among isolates previously typed as 11A by classical serotyping methods. Serotype 11E and serovariant 11Av differ from serotype 11A by having totally or partially inactive wcjE, a gene in cps locus coding for an O-acetyl transferase. Serotype 11E is rare among carriage isolates but common among invasive isolates suggesting that it survives better during invasion. Aim of this work was to investigate the epidemiology of serotype 11A in a pneumococcal collection using a new serotyping approach based on High-Resolution Magic Angle Spinning Nuclear Magnetic Resonance (HR-MAS NMR) spectroscopy to distinguish serotypes 11A and 11E. Methods A collection of 48 (34 invasive and 14 carriage) S. pneumoniae isolates from Italy, previously identified as serotype 11A by the Quellung reaction, were investigated by wcjE sequencing, HR-MAS NMR spectroscopy and the reference flow cytometric serotyping assay (FCSA) based on monoclonal antibodies. Results HR-MAS NMR spectra from serotypes 11A and 11E showed different NMR peaks indicating that HR-MAS NMR could be used to distinguish these serotypes, although HR-MAS NMR could not distinguish serotype 11Av from serotype 11E unambiguously. Thirty-eight isolates were confirmed to be serotype 11A, 8 isolates with a mutated wcjE were serotype 11E, 1 isolate belonged to serovariant 11Av, and 1 isolate was a mixed population 11A/11Av. All 11E isolates were identified among invasive isolates. Conclusions We proved that HR-MAS NMR can be of potential use for pneumococcal serotyping. The detection of serotype 11E among invasive isolates in our collection, supports previous epidemiological studies suggesting that mutations in wcjE can represent a mechanism promoting pneumococcal survival during invasion. The discovery of a spectrum of immunochemical diversity within established serotypes should stimulate efforts to develop new serotyping approaches. PMID:24967818

  14. 1H HR-MAS NMR spectroscopy of tumor-induced local metabolic "field-effects" enables colorectal cancer staging and prognostication.

    PubMed

    Jiménez, Beatriz; Mirnezami, Reza; Kinross, James; Cloarec, Olivier; Keun, Hector C; Holmes, Elaine; Goldin, Robert D; Ziprin, Paul; Darzi, Ara; Nicholson, Jeremy K

    2013-02-01

    Colorectal cancer (CRC) is a major cause of morbidity and mortality in developed countries. Despite operative advances and the widespread adoption of combined-modality treatment, the 5-year survival rarely exceeds 60%. Improving our understanding of the biological processes involved in CRC development and progression will help generate new diagnostic and prognostic approaches. Previous studies have identified altered metabolism as a common feature in carcinogenesis, and quantitative measurement of this altered activity (metabonomics/metabolomics) has the potential to generate novel metabolite-based biomarkers for CRC diagnosis, staging and prognostication. In the present study we applied high-resolution magic angle spinning nuclear magnetic resonance (HR-MAS NMR) spectroscopy to analyze metabolites in intact tumor samples (n = 83) and samples of adjacent mucosa (n = 87) obtained from 26 patients undergoing surgical resection for CRC. Orthogonal partial least-squares discriminant analysis (OPLS-DA) of metabolic profiles identified marked biochemical differences between cancer tissue and adjacent mucosa (R(2) = 0.72; Q(2) = 0.45; AUC = 0.91). Taurine, isoglutamine, choline, lactate, phenylalanine, tyrosine (increased concentrations in tumor tissue) together with lipids and triglycerides (decreased concentrations in tumor tissue) were the most discriminant metabolites between the two groups in the model. In addition, tumor tissue metabolic profiles were able to distinguish between tumors of different T- and N-stages according to TNM classification. Moreover, we found that tumor-adjacent mucosa (10 cm from the tumor margin) harbors unique metabolic field changes that distinguish tumors according to T- and N-stage with higher predictive capability than tumor tissue itself and are accurately predictive of 5-year survival (AUC = 0.88), offering a highly novel means of tumor classification and prognostication in CRC. PMID:23240862

  15. Investigation of relative metabolic changes in the organs and plasma of rats exposed to X-ray radiation using HR-MAS (1) H NMR and solution (1) H NMR.

    PubMed

    Jang, Won Gyo; Park, Ju Yeon; Lee, Jueun; Bang, Eunjung; Kim, So Ra; Lee, Eun Kyeong; Yun, Hyun Jin; Kang, Chang-Mo; Hwang, Geum-Sook

    2016-04-01

    Excess exposure to ionizing radiation generates reactive oxygen species and increases the cellular inflammatory response by modifying various metabolic pathways. However, an investigation of metabolic perturbations and organ-specific responses based on the amount of radiation during the acute phase has not been conducted. In this study, high-resolution magic-angle-spinning (HR-MAS) NMR and solution NMR-based metabolic profiling were used to investigate dose-dependent metabolic changes in multiple organs and tissues - including the jejunum, spleen, liver, and plasma - of rats exposed to X-ray radiation. The organs, tissues, and blood samples were obtained 24, 48, and 72 h after exposure to low-dose (2 Gy) and high-dose (6 Gy) X-ray radiation and subjected to metabolite profiling and multivariate analyses. The results showed the time course of the metabolic responses, and many significant changes were detected in the high-dose compared with the low-dose group. Metabolites with antioxidant properties showed acute responses in the jejunum and spleen after radiation exposure. The levels of metabolites related to lipid and protein metabolism were decreased in the jejunum. In addition, amino acid levels increased consistently at all post-irradiation time points as a consequence of activated protein breakdown. Consistent with these changes, plasma levels of tricarboxylic acid cycle intermediate metabolites decreased. The liver did not appear to undergo remarkable metabolic changes after radiation exposure. These results may provide insight into the major metabolic perturbations and mechanisms of the biological systems in response to pathophysiological damage caused by X-ray radiation. Copyright © 2016 John Wiley & Sons, Ltd. PMID:26871685

  16. MAS NMR of HIV-1 protein assemblies

    NASA Astrophysics Data System (ADS)

    Suiter, Christopher L.; Quinn, Caitlin M.; Lu, Manman; Hou, Guangjin; Zhang, Huilan; Polenova, Tatyana

    2015-04-01

    The negative global impact of the AIDS pandemic is well known. In this perspective article, the utility of magic angle spinning (MAS) NMR spectroscopy to answer pressing questions related to the structure and dynamics of HIV-1 protein assemblies is examined. In recent years, MAS NMR has undergone major technological developments enabling studies of large viral assemblies. We discuss some of these evolving methods and technologies and provide a perspective on the current state of MAS NMR as applied to the investigations into structure and dynamics of HIV-1 assemblies of CA capsid protein and of Gag maturation intermediates.

  17. Sealed rotors for in situ high temperature high pressure MAS NMR

    SciTech Connect

    Hu, Jian Z.; Hu, Mary Y.; Zhao, Zhenchao; Xu, Souchang; Vjunov, Aleksei; Shi, Hui; Camaioni, Donald M.; Peden, Charles H. F.; Lercher, Johannes A.

    2015-07-06

    Magic angle spinning (MAS) nuclear magnetic resonance (NMR) investigations on heterogeneous samples containing solids, semi-solids, liquid and gases or a mixture of them under non-conventional conditions of a combined high pressure and high temperature, or cold temperature suffer from the unavailability of a perfectly sealed rotor. Here, we report the design of reusable and perfectly-sealed all-zircornia MAS rotors. The rotors are easy to use and are suitable for operation temperatures from below 0 to 250 °C and pressures up to 100 bar. As an example of potential applications we performed in situ MAS NMR investigations of AlPO?-5 molecular sieve crystallization, a kinetic study of the cyclohexanol dehydration reaction using 13C MAS NMR, and an investigation of the metabolomics of intact biological tissue at low temperature using 1H HR-MAS NMR spectroscopy. The in situ MAS NMR experiments performed using the reported rotors allowed reproduction of the results from traditional batch reactions, while offering more detailed quantitative information at the molecular level, as demonstrated for the molecular sieve synthesis and activation energy measurements for cyclohexanol dehydration. The perfectly sealed rotor also shows promising application for metabolomics studies using 1H HR-MAS NMR.

  18. An HR-MAS MR Metabolomics Study on Breast Tissues Obtained with Core Needle Biopsy

    PubMed Central

    Cho, Nariya; Chang, Jung Min; Koo, Hye Ryoung; Yi, Ann; Kim, Hyeonjin; Park, Sunghyouk; Moon, Woo Kyung

    2011-01-01

    Background Much research has been devoted to the development of new breast cancer diagnostic measures, including those involving high-resolution magic angle spinning (HR-MAS) magnetic resonance (MR) spectroscopic techniques. Previous HR-MAS MR results have been obtained from post-surgery samples, which limits their direct clinical applicability. Methodology/Principal Findings In the present study, we performed HR-MAS MR spectroscopic studies on 31 breast tissue samples (13 cancer and 18 non-cancer) obtained by percutaneous core needle biopsy. We showed that cancer and non-cancer samples can be discriminated very well with Orthogonal Projections to Latent Structure-Discriminant Analysis (OPLS-DA) multivariate model on the MR spectra. A subsequent blind test showed 69% sensitivity and 94% specificity in the prediction of the cancer status. A spectral analysis showed that in cancer cells, taurine- and choline-containing compounds are elevated. Our approach, additionally, could predict the progesterone receptor statuses of the cancer patients. Conclusions/Significance HR-MAS MR metabolomics on intact breast tissues obtained by core needle biopsy may have a potential to be used as a complement to the current diagnostic and prognostic measures for breast cancers. PMID:22028780

  19. Zur Bestimmung chemischer Verschiebungen der NMR-Frequenzen bei Quadrupolkernen aus den MAS-NMR-Spektren

    NASA Astrophysics Data System (ADS)

    Müller, D.

    Die allgemeinen Ausdrücke für den NMR-Zentralübergang für Quadrupolkerne mit halbzahligem Spin bei Probenrotation, die von BEHRENS [1, 2] unter Berücksichtigung von Quadrupolwechselwirkungseffekten 2. Ordnung für beliebige Neigungswinkel der Rotationsachse abgeleitet wurden, werden für den praktisch interessierenden Fall der Probenrotation um den magischen Winkel (magic angle spinning, MAS) in einer den Ausgangsformeln für das Ruhespektrum (ohne Probenrotation) analogen Form dargestellt. Am Beispiel der 27Al-NMR-Spektren zweier Aluminate wird die Theorie überprüft und zur exakten Ermittlung der chemischen Verschiebungswerte aus den MAS-Spektren eingesetzt.Translated AbstractDetermination of Chemical Shifts of NMR-Frequencies of Quadrupolar Nuclei from the MAS-NMR SpectraThe general expressions for the NMR central transition of rotating samples with quadrupolar nuclei of half-integer spins, derived by BEHRENS [1, 2] for arbitrary angles of inclination of the spinning axis considering second-order quadrupolar effects, are presented for the practically interesting case of magic angle spinning (MAS) in a form analogous to the expressions for the resting sample. The theory is tested and used for the exact determination of the chemical shift values from the MAS-27Al-NMR spectra of two representative aluminates.

  20. Broadband solid-state MAS NMR of paramagnetic systems.

    PubMed

    Pell, Andrew J; Pintacuda, Guido

    2015-02-01

    The combination of new magnet and probe technology with increasingly sophisticated pulse sequences has resulted in an increase in the number of applications of solid-state nuclear magnetic resonance (NMR) spectroscopy to paramagnetic materials and biomolecules. The interaction between the paramagnetic metal ions and the NMR-active nuclei often yields crucial structural or electronic information about the system. In particular the application of magic-angle spinning (MAS) has been shown to be crucial to obtaining resolution that is sufficiently high for studying complex systems. However such systems are generally extremely difficult to study as the shifts and shift anisotropies resulting from the same paramagnetic interaction broaden the spectrum beyond excitation and detection, and the paramagnetic relaxation enhancement (PRE) shortens the lifetimes of the excited signals considerably. One specific area that has therefore been receiving significant attention in recent years, and for which great improvements have been seen, is the development of broadband NMR sequences. The development of new excitation and inversion sequences for paramagnetic systems under MAS has often made the difference between the spectrum being unobtainable, and a complete NMR study being possible. However the development of the new sequences must explicitly take account of the modulation of the anisotropic shift interactions due to the sample rotation, with the resulting spin dynamics often being complicated considerably. The NMR sequences can either be helped or hindered by MAS, with the efficiency of some pulse schemes being destroyed, and others being greatly enhanced. This review describes the pulse sequences that have recently been proposed for broadband excitation, inversion, and refocussing of the signal components of paramagnetic systems. In doing so we define exactly what is meant by "broadband" under spinning conditions, and what the perfect pulse scheme should deliver. We also give a unified description of the spin dynamics under MAS which highlights the strengths and weaknesses of the various schemes, and which can be used as guidance for future research in this area. All the reviewed pulse schemes are evaluated both with simulations and experimental data obtained on the battery material LiFe(0.5)Mn(0.5)PO(4) which is typical of the complexity of the paramagnetic systems that are currently under study. PMID:25669740

  1. Solid-state 33S MAS NMR of inorganic sulfates.

    PubMed

    Wagler, Todd A; Daunch, William A; Panzner, Matthew; Youngs, Wiley J; Rinaldi, Peter L

    2004-10-01

    Solid-state (33)S MAS NMR spectra of a variety of inorganic sulfates have been obtained at magnetic field strengths of 4.7, 14.1, 17.6, and 18.8 T. Some of the difficulties associated with obtaining natural abundance (33)S NMR spectra have been overcome by using a high magnetic field strength and magic angle spinning (MAS). Multiple factors were considered when analyzing the spectral linewidths, including magnetic field inhomogeneity, dipolar coupling, chemical shift anisotropy, chemical shift dispersion, and quadrupolar coupling. In most of these sulfate samples, quadrupolar coupling was the dominant line broadening mechanism. Nuclear electric quadrupolar coupling constants (C(q)) as large as 2.05 MHz were calculated using spectral simulation software. Spectral information from these new data are compared with X-ray measurements and GAUSSIAN 98W calculations. A general correlation was observed between the magnitude of the C(q) and the increasing difference between S-O bond distances within the sulfate groups. Solid-state (33)S spin-lattice (T(1)) relaxation times were measured and show a significant reduction in T(1) for the hydrated sulfates. This is most likely the result of the modulation of the time-dependent electric field gradient at the nuclear site by motion of water molecules. This information will be useful in future efforts to use (33)S NMR in the compositional and structural analysis of sulfur containing materials. PMID:15388098

  2. Neutron diffraction and MAS NMR of Cesium Tungstate defect pyrochlores

    SciTech Connect

    Whittle, K.R. . E-mail: kwhi02@esc.cam.ac.uk; Lumpkin, G.R.; Ashbrook, S.E.

    2006-02-15

    Defect-pyrochlores based on the formulation CsM {sub 0.5}W{sub 1.5}O{sub 6} (M=Ti, Ti/Zr, Zr and Hf) have been studied using neutron diffraction and magic-angle spinning nuclear magnetic resonance (MAS NMR). The results show that structural changes are linearly linked to the change in ionic-radius for the B-site, e.g. the unit cell changes from 10.2763 A for CsTi{sub 0.5}W{sub 1.5}O{sub 6} to 10.3820 A for CsZr{sub 0.4}W{sub 1.6}O{sub 6}. Changes in the NMR chemical shift correlate with the change in electronegativity on the B-site, and show the presence of only one Cs crystal site.

  3. Coherence selection in double CP MAS NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Yang, Jen-Hsien; Chou, Fang-Chieh; Tzou, Der-Lii M.

    2008-11-01

    Applications of double cross-polarization (CP) magic-angle spinning (MAS) NMR spectroscopy, via 1H/ 15N and then 15N/ 13C coherence transfers, for 13C coherence selection are demonstrated on a 15N/ 13C-labeled N-acetyl-glucosamine (GlcNAc) compound. The 15N/ 13C coherence transfer is very sensitive to the settings of the experimental parameters. To resolve explicitly these parameter dependences, we have systematically monitored the 13C{ 15N/ 1H} signal as a function of the rf field strength and the MAS frequency. The data reveal that the zero-quantum coherence transfer, with which the 13C effective rf field is larger than that of the 15N by the spinning frequency, would give better signal sensitivity. We demonstrate in one- and two-dimensional double CP experiments that spectral editing can be achieved by tailoring the experimental parameters, such as the rf field strengths and/or the MAS frequency.

  4. Visibility of lipid resonances in HR-MAS spectra of brain biopsies subject to spinning rate variation.

    PubMed

    Precht, C; Diserens, G; Oevermann, A; Vermathen, M; Lang, J; Boesch, C; Vermathen, P

    2015-12-01

    Lipid resonances from mobile lipids can be observed by ¹H NMR spectroscopy in multiple tissues and have also been associated with malignancy. In order to use lipid resonances as a marker for disease, a reference standard from a healthy tissue has to be established taking the influence of variable factors like the spinning rate into account. The purpose of our study was to investigate the effect of spinning rate variation on the HR-MAS pattern of lipid resonances in non-neoplastic brain biopsies from different regions and visualize polar and non-polar lipids by fluorescence microscopy using Nile Red staining. ¹H HR-MAS NMR spectroscopy demonstrated higher lipid peak intensities in normal sheep brain pure white matter biopsies compared to mixed white and gray matter biopsies and pure gray matter biopsies. High spinning rates increased the visibility particularly of the methyl resonances at 1.3 and the methylene resonance at 0.89 ppm in white matter biopsies stronger compared to thalamus and brainstem biopsies, and gray matter biopsies. The absence of lipid droplets and presence of a large number of myelin sheaths observed in white matter by Nile Red fluorescence microscopy suggest that the observed lipid resonances originate from the macromolecular pool of lipid protons of the myelin sheath's plasma membranes. When using lipid contents as a marker for disease, the variable behavior of lipid resonances in different neuroanatomical regions of the brain and at variable spinning rates should be considered. The findings may open up interesting possibilities for investigating lipids in myelin sheaths. PMID:26391918

  5. A General Protocol for Temperature Calibration of MAS NMR Probes at Arbitrary Spinning Speeds

    PubMed Central

    Guan, Xudong; Stark, Ruth E.

    2010-01-01

    A protocol using 207Pb NMR of solid lead nitrate was developed to determine the temperature of magic-angle spinning (MAS) NMR probes over a range of nominal set temperatures and spinning speeds. Using BioMAS and fastMAS probes with typical sample spinning rates of 8 and 35 kHz, respectively, empirical equations were devised to predict the respective sample temperatures. These procedures provide a straightforward recipe for temperature calibration of any MAS probe. PMID:21036557

  6. A general protocol for temperature calibration of MAS NMR probes at arbitrary spinning speeds.

    PubMed

    Guan, Xudong; Stark, Ruth E

    2010-01-01

    A protocol using (207)Pb NMR of solid lead nitrate was developed to determine the temperature of magic-angle spinning (MAS) NMR probes over a range of nominal set temperatures and spinning speeds. Using BioMAS and FastMAS probes with typical sample spinning rates of 8 and 35 kHz, respectively, empirical equations were devised to predict the respective sample temperatures. These procedures provide a straightforward recipe for temperature calibration of any MAS probe. PMID:21036557

  7. Bandwidth in double cross-polarization MAS NMR spectroscopy.

    PubMed

    Tzou, Der-Lii M

    2012-01-01

    The signal intensity in double cross-polarization (DCP) NMR experiments is critically dependent on the experimental parameters, which include the rf field strength, carrier frequency, and magic-angle spinning (MAS) frequency. In this systematic study, we have monitored {(1)H}/(31)P/(13)C DCP signals from monosaccharide ?-D-[UL-(13)C(6)] galactopyranosyl 1-phosphate (GalP) at a MAS frequency of 13 kHz, at which only double quantum cross-polarization (CP) coherence transfer is allowed. To lessen the stringent requirements for these experimental parameters, we have implemented linear ramp pulse, adiabatic ramp-shaped pulse, and block pulse during the period of (31)P/(13)C CP. We unravel the CP matching profiles with respect to these parameters by monitoring the (31)P/(13)C signal while varying the rf field strength and carrier frequency. For comparison, we extracted the selectivity bandwidth from the full width at half maximum (FWHM) of the matching profiles, in units of frequency (kHz), and found bandwidths of 1.1, 14, and 22 kHz for the matching profiles of the (13)C rf field strength and the (13)C and (31)P carrier frequencies, respectively, for a linear ramp pulse CP. These bandwidths are broader than the measured values in an adiabatic-shaped pulse CP (0.8, 10, and 12 kHz), as well as in block CP (0.3, 7, and 10 kHz) experiments. We demonstrate that the linear ramp pulse CP is superior to both block CP and adiabatic-shaped CP in lessening the stringent requirements of the aforementioned experimental settings for DCP experiments. PMID:22925494

  8. HR-MAS MR Spectroscopy of Breast Cancer Tissue Obtained with Core Needle Biopsy: Correlation with Prognostic Factors

    PubMed Central

    Choi, Ji Soo; Baek, Hyeon-Man; Kim, Suhkmann; Kim, Min Jung; Youk, Ji Hyun; Moon, Hee Jung; Kim, Eun-Kyung; Han, Kyung Hwa; Kim, Dong-hyun; Kim, Seung Il; Koo, Ja Seung

    2012-01-01

    The purpose of this study was to examine the correlation between high-resolution magic angle spinning (HR-MAS) magnetic resonance (MR) spectroscopy using core needle biopsy (CNB) specimens and histologic prognostic factors currently used in breast cancer patients. After institutional review board approval and informed consent were obtained for this study, CNB specimens were collected from 36 malignant lesions in 34 patients. Concentrations and metabolic ratios of various choline metabolites were estimated by HR-MAS MR spectroscopy using CNB specimens. HR-MAS spectroscopic values were compared according to histopathologic variables [tumor size, lymph node metastasis, histologic grade, status of estrogens receptor (ER), progesterone receptor (PR), HER2 (a receptor for human epidermal growth factor), and Ki-67, and triple negativity]. Multivariate analysis was performed with Orthogonal Projections to Latent Structure-Discriminant Analysis (OPLS-DA). HR-MAS MR spectroscopy quantified and discriminated choline metabolites in all CNB specimens of the 36 breast cancers. Several metabolite markers [free choline (Cho), phosphocholine (PC), creatine (Cr), taurine, myo-inositol, scyllo-inositol, total choline (tCho), glycine, Cho/Cr, tCho/Cr, PC/Cr] on HR-MAS MR spectroscopy were found to correlate with histologic prognostic factors [ER, PR, HER2, histologic grade, triple negativity, Ki-67, poor prognosis]. OPLS-DA multivariate models were generally able to discriminate the status of histologic prognostic factors (ER, PR, HER2, Ki-67) and prognosis groups. Our study suggests that HR-MAS MR spectroscopy using CNB specimens can predict tumor aggressiveness prior to surgery in breast cancer patients. In addition, it may be helpful in the detection of reliable markers for breast cancer characterization. PMID:23272149

  9. MAS NMR studies of nanoporous matrices filled with sodium nitrite

    NASA Astrophysics Data System (ADS)

    Gorchakov, A. G.; Sedykh, P. S.; Charnaya, E. V.; Baryshnikov, S. V.; Tien, Cheng; Michel, D.

    2009-10-01

    The sodium nitrite NaNO2 incorporated into MCM-41 molecular sieves with pore sizes of 20, 26, and 37 Å has been investigated by 23Na magic-angle spinning NMR spectroscopy. It has been demonstrated that the structure of the crystalline phase of the nitrite in a confined geometry is similar to the structure of bulk nitrite NaNO2. The direct proof of the diffuse melting of sodium nitrite in the pores has been obtained. The NMR signal of the molten sodium nitrite phase has been observed at temperatures close to the completion of the melting.

  10. Measuring proton shift tensors with ultrafast MAS NMR.

    PubMed

    Miah, Habeeba K; Bennett, David A; Iuga, Dinu; Titman, Jeremy J

    2013-10-01

    A new proton anisotropic-isotropic shift correlation experiment is described which operates with ultrafast MAS, resulting in good resolution of isotropic proton shifts in the detection dimension. The new experiment makes use of a recoupling sequence designed using symmetry principles which reintroduces the proton chemical shift anisotropy in the indirect dimension. The experiment has been used to measure the proton shift tensor parameters for the OH hydrogen-bonded protons in tyrosine·HCl and citric acid at Larmor frequencies of up to 850 MHz. PMID:23911900

  11. Advanced instrumentation for DNP-enhanced MAS NMR for higher magnetic fields and lower temperatures

    NASA Astrophysics Data System (ADS)

    Matsuki, Yoh; Idehara, Toshitaka; Fukazawa, Jun; Fujiwara, Toshimichi

    2016-03-01

    Sensitivity enhancement of MAS NMR using dynamic nuclear polarization (DNP) is gaining importance at moderate fields (B0 < 9 T) and temperatures (T > 90 K) with potential applications in chemistry and material sciences. However, considering the ever-increasing size and complexity of the systems to be studied, it is crucial to establish DNP under higher field conditions, where the spectral resolution and the basic NMR sensitivity tend to improve. In this perspective, we overview our recent efforts on hardware developments, specifically targeted on improving DNP MAS NMR at high fields. It includes the development of gyrotrons that enable continuous frequency tuning and rapid frequency modulation for our 395 GHz-600 MHz and 460 GHz-700 MHz DNP NMR spectrometers. The latter 700 MHz system involves two gyrotrons and a quasi-optical transmission system that combines two independent sub-millimeter waves into a single dichromic wave. We also describe two cryogenic MAS NMR probe systems operating, respectively, at T ∼100 K and ∼30 K. The latter system utilizes a novel closed-loop helium recirculation mechanism, achieving cryogenic MAS without consuming any cryogen. These instruments altogether should promote high-field DNP toward more efficient, reliable and affordable technology. Some experimental DNP results obtained with these instruments are presented.

  12. Advanced instrumentation for DNP-enhanced MAS NMR for higher magnetic fields and lower temperatures.

    PubMed

    Matsuki, Yoh; Idehara, Toshitaka; Fukazawa, Jun; Fujiwara, Toshimichi

    2016-03-01

    Sensitivity enhancement of MAS NMR using dynamic nuclear polarization (DNP) is gaining importance at moderate fields (B0<9T) and temperatures (T>90K) with potential applications in chemistry and material sciences. However, considering the ever-increasing size and complexity of the systems to be studied, it is crucial to establish DNP under higher field conditions, where the spectral resolution and the basic NMR sensitivity tend to improve. In this perspective, we overview our recent efforts on hardware developments, specifically targeted on improving DNP MAS NMR at high fields. It includes the development of gyrotrons that enable continuous frequency tuning and rapid frequency modulation for our 395GHz-600MHz and 460GHz-700MHz DNP NMR spectrometers. The latter 700MHz system involves two gyrotrons and a quasi-optical transmission system that combines two independent sub-millimeter waves into a single dichromic wave. We also describe two cryogenic MAS NMR probe systems operating, respectively, at T ?100K and ?30K. The latter system utilizes a novel closed-loop helium recirculation mechanism, achieving cryogenic MAS without consuming any cryogen. These instruments altogether should promote high-field DNP toward more efficient, reliable and affordable technology. Some experimental DNP results obtained with these instruments are presented. PMID:26920836

  13. Identification of Metastasis-Associated Metabolic Profiles of Tumors by 1H-HR-MAS-MRS123

    PubMed Central

    Gorad, Saurabh S.; Ellingsen, Christine; Bathen, Tone F.; Mathiesen, Berit S.; Moestue, Siver A.; Rofstad, Einar K.

    2015-01-01

    Tumors develop an abnormal microenvironment during growth, and similar to the metastatic phenotype, the metabolic phenotype of cancer cells is tightly linked to characteristics of the tumor microenvironment (TME). In this study, we explored relationships between metabolic profile, metastatic propensity, and hypoxia in experimental tumors in an attempt to identify metastasis-associated metabolic profiles. Two human melanoma xenograft lines (A-07, R-18) showing different TMEs were used as cancer models. Metabolic profile was assessed by proton high resolution magic angle spinning magnetic resonance spectroscopy (1H-HR-MAS-MRS). Tumor hypoxia was detected in immunostained histological preparations by using pimonidazole as a hypoxia marker. Twenty-four samples from 10 A-07 tumors and 28 samples from 10 R-18 tumors were analyzed. Metastasis was associated with hypoxia in both A-07 and R-18 tumors, and 1H-HR-MAS-MRS discriminated between tissue samples with and tissue samples without hypoxic regions in both models, primarily because hypoxia was associated with high lactate resonance peaks in A-07 tumors and with low lactate resonance peaks in R-18 tumors. Similarly, metastatic and non-metastatic R-18 tumors showed significantly different metabolic profiles, but not metastatic and non-metastatic A-07 tumors, probably because some samples from the metastatic A-07 tumors were derived from tumor regions without hypoxic tissue. This study suggests that 1H-HR-MAS-MRS may be a valuable tool for evaluating the role of hypoxia and lactate in tumor metastasis as well as for identification of metastasis-associated metabolic profiles. PMID:26585232

  14. Analysis of electron donors in photosystems in oxygenic photosynthesis by photo-CIDNP MAS NMR.

    PubMed

    Najdanova, M; Janssen, G J; de Groot, H J M; Matysik, J; Alia, A

    2015-11-01

    Both photosystem I and photosystem II are considerably similar in molecular architecture but they operate at very different electrochemical potentials. The origin of the different redox properties of these RCs is not yet clear. In recent years, insight was gained into the electronic structure of photosynthetic cofactors through the application of photochemically induced dynamic nuclear polarization (photo-CIDNP) with magic-angle spinning NMR (MAS NMR). Non-Boltzmann populated nuclear spin states of the radical pair lead to strongly enhanced signal intensities that allow one to observe the solid-state photo-CIDNP effect from both photosystem I and II from isolated reaction center of spinach (Spinacia oleracea) and duckweed (Spirodela oligorrhiza) and from the intact cells of the cyanobacterium Synechocystis by (13)C and (15)N MAS NMR. This review provides an overview on the photo-CIDNP MAS NMR studies performed on PSI and PSII that provide important ingredients toward reconstruction of the electronic structures of the donors in PSI and PSII. PMID:26282679

  15. Decomposition of adsorbed VX on activated carbons studied by {sup 31}P MAS NMR

    SciTech Connect

    Ishay Columbus; Daniel Waysbort; Liora Shmueli; Ido Nir; Doron Kaplan

    2006-06-15

    The fate of the persistent OP nerve agent O-ethyl S-(2-(diisopropylamino)ethyl) methylphosphonothioate (VX) on granular activated carbons that are used for gas filtration was studied by means of 31P magic angle spinning (MAS) NMR spectroscopy. Four types of activated carbon were used, including coal-based BPL. VX as vapor or liquid was adsorbed on carbon granules, and MAS NMR spectra were recorded periodically. The results show that at least 90% of the adsorbed VX decomposes within 20 days or less to the nontoxic ethyl methylphosphonic acid (EMPA) and bis(S-2-diisopropylaminoethane) ((DES){sub 2}). Decomposition occurred irrespective of the phase from which VX was loaded, the presence of metal impregnation on the carbon surface, and the water content of the carbon. Theoretical and practical aspects of the degradation are discussed. 17 refs., 6 figs., 3 tabs.

  16. Effects of fluoride on in vitro enamel demineralization analyzed by ¹?F MAS-NMR.

    PubMed

    Mohammed, N R; Kent, N W; Lynch, R J M; Karpukhina, N; Hill, R; Anderson, P

    2013-01-01

    The mechanistic action of fluoride on inhibition of enamel demineralization was investigated using (19)F magic angle spinning nuclear magnetic resonance (MAS-NMR). The aim of this study was to monitor the fluoride-mineral phase formed on the enamel as a function of the concentration of fluoride ions [F(-)] in the demineralizing medium. The secondary aim was to investigate fluorapatite formation on enamel in the mechanism of fluoride anti-caries efficacy. Enamel blocks were immersed into demineralization solutions of 0.1 M acetic acid (pH 4) with increasing concentrations of fluoride up to 2,262 ppm. At and below 45 ppm [F(-)] in the solution, (19)F MAS-NMR showed fluoride-substituted apatite formation, and above 45 ppm, calcium fluoride (CaF2) formed in increasing proportions. Further increases in [F(-)] caused no further reduction in demineralization, but increased the proportion of CaF2 formed. Additionally, the combined effect of strontium and fluoride on enamel demineralization was also investigated using (19)F MAS-NMR. The presence of 43 ppm [Sr(2+)] in addition to 45 ppm [F(-)] increases the fraction of fluoride-substituted apatite, but delays formation of CaF2 when compared to the demineralization of enamel in fluoride-only solution. PMID:23712030

  17. (11)B MAS NMR and First-Principles Study of the [OBO3] Pyramids in Borates.

    PubMed

    Zhou, Bing; Sun, Wei; Zhao, Biao-Chun; Mi, Jin-Xiao; Laskowski, Robert; Terskikh, Victor; Zhang, Xi; Yang, Lingyun; Botis, Sanda M; Sherriff, Barbara L; Pan, Yuanming

    2016-03-01

    Borates are built from the [Bϕ3] planar triangles and the [Bϕ4] tetrahedral groups, where ϕ denotes O or OH. However, the [Bϕ4] groups in some borates are highly distorted to include three normal B-O bonds and one anomalously long B-O bond and, therefore, are best described as the [OBO3] pyramids. Four synthetic borates of the boracite-type structures (Mg3B7O13Br, Cu3B7O13Br, Zn3B7O13Cl, and Mg3B7O13Cl) containing a range of [OBO3] pyramids were investigated by multifield (7.05, 14.1, and 21.1 T) (11)B magic-angle spinning nuclear magnetic resonance (MAS NMR), triple quantum (3Q) MAS NMR experiments, as well as density functional theory calculations. The high-resolution (11)B MAS NMR spectra supported by theoretical predictions show that the [OBO3] pyramids are characterized by isotropic chemical shifts δiso((11)B) from 1.4(1) to 4.9(1) ppm and nuclear quadrupole parameters CQ((11)B) up to 1.3(1) MHz, both significantly different from those of the [BO4] and [BO3] groups in borates. These δiso((11)B) and CQ((11)B) values indicate that the [OBO3] pyramids represent an intermediate state between the [BO4] tetrahedra and [BO3] triangles and demonstrate that the (11)B NMR parameters of four-coordinate boron oxyanions are sensitive to local structural environments. The orientation of the calculated unique electronic field gradient tensor element Vzz of the [OBO3] pyramids is aligned approximately along the direction of the anomalously long B-O bond, corresponding to B-2pz with the lowest electron density. PMID:26914372

  18. 1H fast MAS NMR studies of hydrogen-bonding interactions in self-assembled monolayers.

    PubMed

    Pawsey, Shane; McCormick, Mark; De Paul, Susan; Graf, Robert; Lee, Y S; Reven, Linda; Spiess, Hans W

    2003-04-01

    The structures formed by the adsorption of carboxyalkylphosphonic acids on metal oxides were investigated by (1)H fast magic angle spinning (MAS), heteronuclear correlation (HETCOR), and (1)H double-quantum (DQ) MAS solid-state NMR experiments. The diacids HO(2)C(CH(2))(n)PO(3)H(2) (n = 2, 3, 11, and 15) were adsorbed on TiO(2) and two types of ZrO(2) powders having average particle sizes of 20, 30, and 5 nm, respectively. Carboxyalkylphosphonic acids bind selectively via the phosphonate group, forming monolayers with pendant carboxylic acid groups. Whereas dipolar coupled P-OH protons are detected on TiO(2), there are only isolated residual P-OH groups on ZrO(2), reflecting the relative binding strengths of phosphonic acids on these two substrates. From a comparative (1)H MAS NMR study with an analogous monolayer system, HO(2)C(CH(2))(7)SH coated gold nanoparticles, the hydrogen-bonding network at the monolayer/air interface is found to be quite disordered, at least for SAMs deposited on nonplanar substrates. Whereas only hydrogen-bonded homodimers occur in the bulk diacids, hydrogen bonding between the carboxylic and phosphonic acid groups is present in multilayers of the diacids on the ZrO(2) nanopowder. PMID:12670240

  19. CP-MAS NMR and in-situ FTIR study of AlN surface reactivity

    SciTech Connect

    Monie, S.A.; Aurentz, D.J.; Pantano, C.G.

    1996-12-31

    The hydrolytic stability of aluminum nitride (AlN) is an important issue from the standpoint of technology developments of AlN as an electronic packaging material. Although numerous studies have been made of the hydrolysis of AlN and characterization of the reaction products, an understanding of the interaction between surface sites and molecular species is still lacking. A combination of Magic-Angle-Spinning Nuclear Magnetic Resonance (MAS NMR) and in-situ Fourier Transform Infrared (FTIR) spectroscopies was used to study the surface reactivity of AlN. The specimens used were specially fabricated self-supported AlN films of high-surface-area ({approximately} 25 m{sup 2}/g), made by nitridation of sol-gel derived pseudoboehmite (AlO(OH)). The in-situ FTIR spectra suggest the formation of a surface layer on the AlN films upon storage. MAS NMR was used to further characterize the surface layer. Using the chemical shifts obtained by {sup 1}H-{sup 27}Al Cross Polarization (CP) MAS NMR experiments, the authors were able to identify the surface cation sites. The assignment of these sites to Al{sup 3+} cations in either tetrahedral coordination with nitrogen or octahedral coordination with oxygen was used to monitor the evolution of the surface upon exposure to the atmosphere. The results indicate that high-surface-area AlN rapidly acquires a surface layer (probably AlO(OH)/Al(OH){sub 3}) upon exposure to the atmosphere.

  20. Effects of nucleotide binding to LmrA: A combined MAS-NMR and solution NMR study.

    PubMed

    Hellmich, Ute A; Mönkemeyer, Leonie; Velamakanni, Saroj; van Veen, Hendrik W; Glaubitz, Clemens

    2015-12-01

    ABC transporters are fascinating examples of fine-tuned molecular machines that use the energy from ATP hydrolysis to translocate a multitude of substrates across biological membranes. While structural details have emerged on many members of this large protein superfamily, a number of functional details are still under debate. High resolution structures yield valuable insights into protein function, but it is the combination of structural, functional and dynamic insights that facilitates a complete understanding of the workings of their complex molecular mechanisms. NMR is a technique well-suited to investigate proteins in atomic resolution while taking their dynamic properties into account. It thus nicely complements other structural techniques, such as X-ray crystallography, that have contributed high-resolution data to the architectural understanding of ABC transporters. Here, we describe the heterologous expression of LmrA, an ABC exporter from Lactococcus lactis, in Escherichia coli. This allows for more flexible isotope labeling for nuclear magnetic resonance (NMR) studies and the easy study of LmrA's multidrug resistance phenotype. We use a combination of solid-state magic angle spinning (MAS) on the reconstituted transporter and solution NMR on its isolated nucleotide binding domain to investigate consequences of nucleotide binding to LmrA. We find that nucleotide binding affects the protein globally, but that NMR is also able to pinpoint local dynamic effects to specific residues, such as the Walker A motif's conserved lysine residue. PMID:26449340

  1. An experimental study of decoupling sequences for multiple-quantum and high-resolution MAS experiments in solid-state NMR.

    PubMed

    Thakur, Rajendra Singh; Kurur, Narayanan D; Madhu, P K

    2008-02-01

    Recently, a sequence for heteronuclear dipolar decoupling in solid-state NMR, namely SWf-TPPM, was introduced by us. Under magic-angle spinning (MAS), the decoupling efficiency of the sequence was unaffected over a range of values for various experimental parameters such as the pulse length, pulse phase, and 1H resonance offset. We here demonstrate its use in multiple-quantum (MQ) and high-resolution (HR) MAS experiments. This sequence further improves the MQMAS spectra compared to the earlier reported decoupling sequences with improved immunity to any missets of the pulse length, pulse phase and decoupler offset. In contrast, for HRMAS, the simple CW scheme is as efficient as any of the decoupling schemes that were studied. PMID:18098152

  2. 1H high resolution magic-angle coil spinning (HR-MACS) ?NMR metabolic profiling of whole Saccharomyces cervisiae cells: a demonstrative study

    PubMed Central

    Wong, Alan; Boutin, Céline; Aguiar, Pedro M.

    2014-01-01

    The low sensitivity and thus need for large sample volume is one of the major drawbacks of Nuclear Magnetic Resonance (NMR) spectroscopy. This is especially problematic for performing rich metabolic profiling of scarce samples such as whole cells or living organisms. This study evaluates a 1H HR-MAS approach for metabolic profiling of small volumes (250 nl) of whole cells. We have applied an emerging micro-NMR technology, high-resolution magic-angle coil spinning (HR-MACS), to study whole Saccharomyces cervisiae cells. We find that high-resolution high-sensitivity spectra can be obtained with only 19 million cells and, as a demonstration of the metabolic profiling potential, we perform two independent metabolomics studies identifying the significant metabolites associated with osmotic stress and aging. PMID:24971307

  3. Higher order amyloid fibril structure by MAS NMR and DNP spectroscopy.

    PubMed

    Debelouchina, Galia T; Bayro, Marvin J; Fitzpatrick, Anthony W; Ladizhansky, Vladimir; Colvin, Michael T; Caporini, Marc A; Jaroniec, Christopher P; Bajaj, Vikram S; Rosay, Melanie; Macphee, Cait E; Vendruscolo, Michele; Maas, Werner E; Dobson, Christopher M; Griffin, Robert G

    2013-12-26

    Protein magic angle spinning (MAS) NMR spectroscopy has generated structural models of several amyloid fibril systems, thus providing valuable information regarding the forces and interactions that confer the extraordinary stability of the amyloid architecture. Despite these advances, however, obtaining atomic resolution information describing the higher levels of structural organization within the fibrils remains a significant challenge. Here, we detail MAS NMR experiments and sample labeling schemes designed specifically to probe such higher order amyloid structure, and we have applied them to the fibrils formed by an eleven-residue segment of the amyloidogenic protein transthyretin (TTR(105-115)). These experiments have allowed us to define unambiguously not only the arrangement of the peptide ?-strands into ?-sheets but also the ?-sheet interfaces within each protofilament, and in addition to identify the nature of the protofilament-to-protofilament contacts that lead to the formation of the complete fibril. Our efforts have resulted in 111 quantitative distance and torsion angle restraints (10 per residue) that describe the various levels of structure organization. The experiments benefited extensively from the use of dynamic nuclear polarization (DNP), which in some cases allowed us to shorten the data acquisition time from days to hours and to improve significantly the signal-to-noise ratios of the spectra. The ?-sheet interface and protofilament interactions identified here revealed local variations in the structure that result in multiple peaks for the exposed N- and C-termini of the peptide and in inhomogeneous line-broadening for the residues buried within the interior of the fibrils. PMID:24304221

  4. Higher Order Amyloid Fibril Structure by MAS NMR and DNP Spectroscopy

    PubMed Central

    Debelouchina, Galia T.; Bayro, Marvin J.; Fitzpatrick, Anthony W.; Ladizhansky, Vladimir; Colvin, Michael T.; Caporini, Marc A.; Jaroniec, Christopher P.; Bajaj, Vikram S.; Rosay, Melanie; MacPhee, Cait E.; Vendruscolo, Michele; Maas, Werner E.; Dobson, Christopher M.; Griffin, Robert G.

    2014-01-01

    Protein magic angle spinning (MAS) NMR spectroscopy has generated structural models of several amyloid fibril systems, thus providing valuable information regarding the forces and interactions that confer the extraordinary stability of the amyloid architecture. Despite these advances, however, obtaining atomic resolution information describing the higher levels of structural organization within the fibrils remains a significant challenge. Here, we detail MAS NMR experiments and sample labeling schemes designed specifically to probe such higher order amyloid structure and we have applied them to the fibrils formed by an eleven-residue segment of the amyloidogenic protein transthyretin (TTR(105-115)). These experiments have allowed us to define unambiguously not only the arrangement of the peptide β-strands into β-sheets but also the β-sheet interfaces within each protofilament, and in addition to identify the nature of the protofilament-to-protofilament contacts that lead to the formation of the complete fibril. Our efforts have resulted in 111 quantitative distance and torsion angle restraints (10 per residue) that describe the various levels of structure organization. The experiments benefited extensively from the use of dynamic nuclear polarization (DNP), which in some cases allowed us to shorten the data acquisition time from days to hours and to improve significantly the signal-to-noise ratios of the spectra. The β-sheet interface and protofilament interactions identified here revealed local variations in the structure that result in multiple peaks for the exposed N- and C-termini of the peptide and in inhomogeneous line-broadening for the side-chains buried within the interior of the fibrils. PMID:24304221

  5. Dynamic Nuclear Polarization Enhanced MAS NMR Spectroscopy for Structural Analysis of HIV-1 Protein Assemblies.

    PubMed

    Gupta, Rupal; Lu, Manman; Hou, Guangjin; Caporini, Marc A; Rosay, Melanie; Maas, Werner; Struppe, Jochem; Suiter, Christopher; Ahn, Jinwoo; Byeon, In-Ja L; Franks, W Trent; Orwick-Rydmark, Marcella; Bertarello, Andrea; Oschkinat, Hartmut; Lesage, Anne; Pintacuda, Guido; Gronenborn, Angela M; Polenova, Tatyana

    2016-01-21

    Mature infectious HIV-1 virions contain conical capsids composed of CA protein, generated by the proteolytic cleavage cascade of the Gag polyprotein, termed maturation. The mechanism of capsid core formation through the maturation process remains poorly understood. We present DNP-enhanced MAS NMR studies of tubular assemblies of CA and Gag CA-SP1 maturation intermediate and report 20-64-fold sensitivity enhancements due to DNP at 14.1 T. These sensitivity enhancements enabled direct observation of spacer peptide 1 (SP1) resonances in CA-SP1 by dipolar-based correlation experiments, unequivocally indicating that the SP1 peptide is unstructured in assembled CA-SP1 at cryogenic temperatures, corroborating our earlier results. Furthermore, the dependence of DNP enhancements and spectral resolution on magnetic field strength (9.4-18.8 T) and temperature (109-180 K) was investigated. Our results suggest that DNP-based measurements could potentially provide residue-specific dynamics information by allowing for the extraction of the temperature dependence of the anisotropic tensorial or relaxation parameters. With DNP, we were able to detect multiple well-resolved isoleucine side-chain conformers; unique intermolecular correlations across two CA molecules; and functionally relevant conformationally disordered states such as the 14-residue SP1 peptide, none of which are visible at ambient temperatures. The detection of isolated conformers and intermolecular correlations can provide crucial constraints for structure determination of these assemblies. Overall, our results establish DNP-based MAS NMR spectroscopy as an excellent tool for the characterization of HIV-1 assemblies. PMID:26709853

  6. Structural characteristics for phase transitions of [N(CH3)4]2CuCl4 by (13)C CP/MAS NMR and (14)N NMR.

    PubMed

    Hee Kim, Nam; Lim, Ae Ran

    2015-09-01

    Structure geometry changes in [N(CH3)4]2CuCl4 near the phase transition temperature were studied by (13)C CP/MAS NMR and (14)N NMR spectrum. We distinguished the two chemically inequivalent N(1)(CH3)4 and N(2)(CH3)4 groups by (13)C CP/MAS NMR and (14)N NMR spectrum. The abrupt changes in chemical shifts and the split of the NMR signals near the phase transition temperatures for (13)C and (14)N are explained by a structural phase transition, implying that the structural geometry depends on the temperature. The mechanism behind this phase transition is based on ferroelasticity, and is also mainly related to the (14)N ions in N(CH3)4 ions. Furthermore, both phases III and IV exhibit ferroelastic properties with identical orientational domains. PMID:26163466

  7. 1H, 13C MAS NMR and GIAO-CPHF calculations of chloramphenicol, thiamphenicol and their pyrrole analogues

    NASA Astrophysics Data System (ADS)

    ?o?ek, Teresa; Paradowska, Katarzyna; Krajewska, Dorota; Ró?a?ski, Andrzej; Wawer, Iwona

    2003-02-01

    The 13C CP MAS and 1H MAS NMR and ab initio (GIAO-CPHF) calculations were used to obtain structural information on two known antibiotics: chloramphenicol, and thiamphenicol, and two new analogues: DL- threo-1-(1-methyl-4-nitro-pyrrole-2-yl)-2-dichloroacetamidopropane-1,3-diol and DL- threo-1-(1-methylsulfonylpyrrole-3-yl)-2-dichloroacetamidopropane-1,3-diol.

  8. Investigations of Li-containing SiCN(O) ceramics via 7Li MAS NMR.

    PubMed

    Gumann, Sina; Nestle, Nikolaus; Liebau-Kunzmann, Verena; Riedel, Ralf

    2007-04-01

    Lithium-containing silicon (oxy)carbonitride ceramics (SiCN(O):Li) were synthesized via precursor-to-ceramic-transformation of Li-containing (poly)silazanes. The precursors were obtained by lithiation of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane with n-butyllithium and by reaction of a commercial poly(organosilazane) VL20 with metallic lithium. The annealing treatment was carried out at temperatures between 200 and 1400 degrees C in argon (DeltaT=200 degrees C) and yielded Li-containing silicon (oxy)carbonitride. X-ray powder diffraction revealed that the resulting SiCN(O):Li ceramics were basically amorphous up to temperatures of 1000 degrees C and formed LiSi(2)N(3), graphite and silicon carbide as crystalline phases at higher temperatures. (7)Li MAS NMR spectroscopy was carried out to investigate the structure of the Li-containing phases and to study the reaction path of metallic Li with polysilazane. Based on the NMR spectra, there is almost no difference found in the chemical shift of the SiCN(O):Li ceramics obtained at different temperatures. Accordingly, Li is assigned to be mainly coordinated to N and O present as contaminant element. Relaxation time measurements showed that the most mobile Li(+) species seems to be present in the product obtained in the pyrolysis temperature range between 600 and 1000 degrees C. PMID:17418540

  9. Broadband inversion for MAS NMR with single-sideband-selective adiabatic pulses.

    PubMed

    Pell, Andrew J; Kervern, Gwendal; Emsley, Lyndon; Deschamps, Michaäl; Massiot, Dominique; Grandinetti, Philip J; Pintacuda, Guido

    2011-01-14

    We explain how and under which conditions it is possible to obtain an efficient inversion of an entire sideband family of several hundred kHz using low-power, sideband-selective adiabatic pulses, and we illustrate with some experimental results how this framework opens new avenues in solid-state NMR for manipulating spin systems with wide spinning-sideband (SSB) manifolds. This is achieved through the definition of the criteria of phase and amplitude modulation for designing an adiabatic inversion pulse for rotating solids. In turn, this is based on a framework for representing the Hamiltonian of the spin system in an NMR experiment under magic angle spinning (MAS). Following earlier ideas from Caravatti et al. [J. Magn. Reson. 55, 88 (1983)], the so-called "jolting frame" is used, which is the interaction frame of the anisotropic interaction giving rise to the SSB manifold. In the jolting frame, the shift modulation affecting the nuclear spin is removed, while the Hamiltonian corresponding to the RF field is frequency modulated and acquires a spinning-sideband pattern, specific for each crystallite orientation. PMID:21241090

  10. Low Temperature 1H MAS NMR Spectroscopy Studies of Proton Motion in Zeolite

    SciTech Connect

    Huo, H.; Peng, L; Grey, C

    2009-01-01

    Low temperature {sup 1}H MAS NMR spectroscopy is used to study protonic motion in zeolite HZSM-5 in both samples that have been dried using procedures that are standard in the literature and samples that have been more carefully dehydrated. A significant enhancement of proton mobility is seen for the ''standard'' dehydrated HZSM-5 sample in comparison to that seen for the much drier sample. This is ascribed to a vehicle-hopping mechanism involving the residual water that is present in these zeolites. A gradual change of the framework structure is observed on cooling to approximately 213 K, as monitored via the change in {sup 1}H chemical shift values of the Broensted acid resonances and by X-ray diffraction. A more sudden change in structure is seen by differential scanning calorimetry and NMR at approximately 220?230 K, which is associated with changes in both the mobility and the modes of binding of the residual water to the Broensted acid sites and the zeolite framework.

  11. Characterization of cation environments in polycrystalline forsterite by Mg-25 MAS, MQMAS, and QCPMG NMR

    SciTech Connect

    Davis, Michael C.; Brouwer, William J.; Lipton, Andrew S.; Gan, Zhehong; Mueller, Karl T.

    2010-11-01

    Forsterite (Mg2SiO4) is a silicate mineral frequently studied in the Earth sciences as it has a simple crystal structure and fast dissolution kinetics (elemental release rates under typical conditions on the order of 10-7 mol/m2/s1). During the dissolution process, spectroscopic techniques are often utilized to augment solution chemical analysis and to provide data for determining reaction mechanisms. Nuclear magnetic resonance (NMR) is able to interrogate the local bonding arrangement and coordination of a particular nuclide to obtain in structural information. Although previous NMR studies have focused on the silicon and oxygen environments in forsterite, studies focusing on the two nonequivalent magnesium environments in forsterite are limited to a few single-crystal studies. In this study, we present the results of 25Mg MAS, MQMAS, and static QCMG experiments performed on a powdered sample of pure synthetic forsterite. We also present spectral fits obtained from simulation software packages, which directly provide quadrupolar parameters for 25Mg nuclei occupying each of the two nonequivalent magnesium sites in the forsterite structure. These results are compared to calculations of the electric field gradient tenor conducted in previous ab initio studies to make definitive assignments correlating each peak to their respective magnesium site in the forsterite structure. Although previous NMR investigations of forsterite have focused on single-crystal samples, we have focused on powdered forsterite as the increased surface area of powdered samples makes them more amenable to laboratory-scale dissolution studies and, ultimately, the products from chemical weathering may be monitored an quantified.

  12. {207}Pb MAS NMR and conductivity identified anomalous phase transition in nanostructured PbF {2}

    NASA Astrophysics Data System (ADS)

    Thangadurai, P.; Ramasamy, S.; Manoharan, P. T.

    2004-02-01

    Lead fluoride, a superionic conductor was prepared in its nanostructured form by Inert Gas Condensation Technique (IGCT) using an Ultra High Vacuum (UHV) chamber. The average grain size was found to be in the range 9 to 43 nm. The existence of mixed phases (? and ?-PbF2) was identified using XRD. Solid state 207Pb MAS NMR was carried to average out the dipolar interaction and the resultant isotropic peaks were assigned to the corresponding phases. At high spinning frequencies, one isotropic peak emerged from the contribution of the grain boundary region. The relative intensity of this peak is reduced as the grain size is increased, independent of the concentration of the phases. This is related to the fact that the volume fraction of grain boundary atoms in nanostructured materials increases with the reduction of grain size. The width of the NMR resonance peak is found to be reduced as the grain size goes down. The structural phase transformations were identified at two different temperature regions. The first phase transformation from ? to ? phase in the annealing temperature range 573 K to 623 K is attributed to some anomalies related to the material microstructure and this has not been reported in earlier literatures. The second phase transformation from ? to ? in the temperature range 623 K to 673 K is similar to the already reported transformation. Electrical conductivity ? , of the samples was obtained from the complex impedance spectroscopy studies. Conduction species was identified as F- ion through anion vacancies. The magnitude of the conductivity varied according to the dominant phase available when the grain size is higher. But at lower grain sizes below 20 nm, it shows enhanced conductivity that is attributed to the grain size effect. The NMR and conductivity data have jointly supported the anomalous phase transition at the annealing temperature of 623 K.

  13. Magnetization-recovery experiments for static and MAS-NMR of I = 3/2 nuclei

    NASA Astrophysics Data System (ADS)

    Yesinowski, James P.

    2006-05-01

    Multifrequency pulsed NMR experiments on quadrupole-perturbed I = 3/2 spins in single crystals are shown to be useful for measuring spin-lattice relaxation parameters even for a mixture of quadrupolar plus magnetic relaxation mechanisms. Such measurements can then be related to other MAS-NMR experiments on powders. This strategy is demonstrated by studies of 71Ga and 69Ga (both I = 3/2) spin-lattice relaxation behavior in a single-crystal (film) sample of gallium nitride, GaN, at various orientations of the axially symmetric nuclear quadrupole coupling tensor. Observation of apparent single-exponential relaxation behavior in I = 3/2 saturation-recovery experiments can be misleading when individual contributing rate processes are neglected in the interpretation. The quadrupolar mechanism (dominant in this study) has both a single-quantum process ( T1Q1) and a double-quantum process ( T1Q2), whose time constants are not necessarily equal. Magnetic relaxation (in this study most likely arising from hyperfine couplings to unpaired delocalized electron spins in the conduction band) also contributes to a single-quantum process ( T1M). A strategy of multifrequency irradiation with observation of satellite and/or central transitions, incorporating different initial conditions for the level populations, provides a means of obtaining these three relaxation time constants from single-crystal 71Ga data alone. The 69Ga results provide a further check of internal consistency, since magnetic and quadrupolar contributions to its relaxation scale in opposite directions compared to 71Ga. For both perpendicular and parallel quadrupole coupling tensor symmetry axis orientations small but significant differences between T1Q1 and T1Q2 were measured, whereas for a tensor symmetry axis oriented at the magic-angle (54.74°) the values were essentially equal. Magic-angle spinning introduces a number of complications into the measurement and interpretation of the spin-lattice relaxation. Comparison of 71Ga and 69Ga MAS-NMR saturation-recovery curves with both central and satellite transitions completely saturated by a train of 90° pulses incommensurate with the rotor period provides the simplest means of assessing the contribution from magnetic relaxation, and yields results for the quadrupolar mechanism contribution that are consistent with those obtained from the film sample.

  14. Magnesium Silicate Dissolution Investigated by 29Si MAS, 1H-29Si CP MAS, 25Mg QCPMG, and 1H-25Mg CP QCPMG NMR

    SciTech Connect

    Davis, Michael C.; Brouwer, William J.; Wesolowski, David J.; Anovitz, Lawrence M.; Lipton, Andrew S.; Mueller, Karl T.

    2009-08-01

    Olivine has been the subject of frequent investigation in the earth sciences because of its simple structure and rapid dissolution kinetics. Several studies have observed a preferential release of magnesium with respect to silica during weathering under acidic conditions, which has been correlated to the formation of a silicon rich leached layer. While leached layer formation has been inferred through the changing solution chemistry, a thorough spectroscopic investigation of olivine reacted under acidic conditions has not been conducted. In particular, the fate of magnesium in the system is not understood and spectroscopic interrogations through nuclear magnetic resonance can elucidate the changing magnesium coordination and bonding environment. In this study, we combine analysis of the changing solution chemistry with advanced spectroscopic techniques (29Si MAS, 1H-29Si CP MAS, 25Mg QCPMG, and 1H-25Mg 2 CP QCPMG NMR) to probe leached layer formation and possible secondary phase precipitation during the dissolution of forsterite at 150 oC.

  15. Proton chemical shift tensors determined by 3D ultrafast MAS double-quantum NMR spectroscopy.

    PubMed

    Zhang, Rongchun; Mroue, Kamal H; Ramamoorthy, Ayyalusamy

    2015-10-14

    Proton NMR spectroscopy in the solid state has recently attracted much attention owing to the significant enhancement in spectral resolution afforded by the remarkable advances in ultrafast magic angle spinning (MAS) capabilities. In particular, proton chemical shift anisotropy (CSA) has become an important tool for obtaining specific insights into inter/intra-molecular hydrogen bonding. However, even at the highest currently feasible spinning frequencies (110-120 kHz), (1)H MAS NMR spectra of rigid solids still suffer from poor resolution and severe peak overlap caused by the strong (1)H-(1)H homonuclear dipolar couplings and narrow (1)H chemical shift (CS) ranges, which render it difficult to determine the CSA of specific proton sites in the standard CSA/single-quantum (SQ) chemical shift correlation experiment. Herein, we propose a three-dimensional (3D) (1)H double-quantum (DQ) chemical shift/CSA/SQ chemical shift correlation experiment to extract the CS tensors of proton sites whose signals are not well resolved along the single-quantum chemical shift dimension. As extracted from the 3D spectrum, the F1/F3 (DQ/SQ) projection provides valuable information about (1)H-(1)H proximities, which might also reveal the hydrogen-bonding connectivities. In addition, the F2/F3 (CSA/SQ) correlation spectrum, which is similar to the regular 2D CSA/SQ correlation experiment, yields chemical shift anisotropic line shapes at different isotropic chemical shifts. More importantly, since the F2/F1 (CSA/DQ) spectrum correlates the CSA with the DQ signal induced by two neighboring proton sites, the CSA spectrum sliced at a specific DQ chemical shift position contains the CSA information of two neighboring spins indicated by the DQ chemical shift. If these two spins have different CS tensors, both tensors can be extracted by numerical fitting. We believe that this robust and elegant single-channel proton-based 3D experiment provides useful atomistic-level structural and dynamical information for a variety of solid systems that possess high proton density. PMID:26472372

  16. Molybdenum modified phosphate glasses studied by 31P MAS NMR and Raman spectroscopy.

    PubMed

    Szumera, Magdalena

    2015-02-25

    Glasses have been synthesized in the system P2O5-SiO2-K2O-MgO-CaO modified by addition of MoO3. Glasses were prepared by conventional fusion method from 40 g batches. The influence of Mo-cations on the analysed glass structure was investigated by means of Raman and (31)P MAS-NMR techniques. It has been found that molybdate units can form Mo[MoO4/MoO6]-O-P and/or Mo[MoO4/MoO6]-O-Si bonds with non-bridging oxygens atoms of Q2 methaphosphate units, resulting in the transformation of chain methaphosphate structure into pyrophosphate and finally into orthophosphate structure. It has been also found that increasing amount of MoO3 in the structure of investigated glasses causes their gradual depolymerization and molybdenum ions in the analysed glass matrix act as modifying cations. PMID:25216461

  17. DNP-Enhanced MAS NMR of Bovine Serum Albumin Sediments and Solutions

    PubMed Central

    2015-01-01

    Protein sedimentation sans cryoprotection is a new approach to magic angle spinning (MAS) and dynamic nuclear polarization (DNP) nuclear magnetic resonance (NMR) spectroscopy of proteins. It increases the sensitivity of the experiments by a factor of ∼4.5 in comparison to the conventional DNP sample preparation and circumvents intense background signals from the cryoprotectant. In this paper, we investigate sedimented samples and concentrated frozen solutions of natural abundance bovine serum albumin (BSA) in the absence of a glycerol-based cryoprotectant. We observe DNP signal enhancements of ε ∼ 66 at 140 GHz in a BSA pellet sedimented from an aqueous solution containing the biradical polarizing agent TOTAPOL and compare this with samples prepared using the conventional protocol (i.e., dissolution of BSA in a glycerol/water cryoprotecting mixture). The dependence of DNP parameters on the radical concentration points to the presence of an interaction between TOTAPOL and BSA, so much so that a frozen solution sans cryoprotectant still gives ε ∼ 50. We have studied the interaction of BSA with another biradical, SPIROPOL, that is more rigid than TOTAPOL and has been reported to give higher enhancements. SPIROPOL was also found to interact with BSA, and to give ε ∼ 26 close to its maximum achievable concentration. Under the same conditions, TOTAPOL gives ε ∼ 31, suggesting a lesser affinity of BSA for SPIROPOL with respect to TOTAPOL. Altogether, these results demonstrate that DNP is feasible in self-cryoprotecting samples. PMID:24460530

  18. Proton-detected heteronuclear single quantum correlation NMR spectroscopy in rigid solids with ultra-fast MAS

    NASA Astrophysics Data System (ADS)

    Holland, Gregory P.; Cherry, Brian R.; Jenkins, Janelle E.; Yarger, Jeffery L.

    2010-01-01

    In this article, we show the potential for utilizing proton-detected heteronuclear single quantum correlation (HSQC) NMR in rigid solids under ultra-fast magic angle spinning (MAS) conditions. The indirect detection of carbon-13 from coupled neighboring hydrogen nuclei provides a sensitivity enhancement of 3- to 4-fold in crystalline amino acids over direct-detected versions. Furthermore, the sensitivity enhancement is shown to be significantly larger for disordered solids that display inhomogeneously broadened carbon-13 spectra. Latrodectus hesperus (Black Widow) dragline silk is given as an example where the sample is mass-limited and the sensitivity enhancement for the proton-detected experiment is 8- to 13-fold. The ultra-fast MAS proton-detected HSQC solid-state NMR technique has the added advantage that no proton homonuclear decoupling is applied during the experiment. Further, well-resolved, indirectly observed carbon-13 spectra can be obtained in some cases without heteronuclear proton decoupling.

  19. Characterization of the primary radical pair in reaction centers of Heliobacillus mobilis by 13C photo-CIDNP MAS NMR.

    PubMed

    Roy, Esha; Rohmer, Thierry; Gast, Peter; Jeschke, Gunnar; Alia, A; Matysik, Jörg

    2008-04-22

    Photochemically induced dynamic nuclear polarization (photo-CIDNP) has been observed in membrane fragments of heliobacterium Heliobacillus mobilis without further isolation by (13)C magic-angle spinning (MAS) solid-state NMR under continuous illumination with white light. In the (13)C photo-CIDNP MAS NMR spectra of heliobacterial membrane fragments, two sets of signals are observed, allowing characterization of the primary radical pair. One set, showing enhanced absorptive (positive) signals, arises from the BChl g donor, while the set of emissive (negative) signals is assigned to the 8(1)-hydroxy Chl a acceptor. Hence, under these sample conditions, both donor and acceptor sides are either monomeric or composed of identical cofactors. The occurrence of the differential relaxation (DR) mechanism suggests a donor triplet lifetime in the microsecond range. It appears that the occurrence of the solid-state photo-CIDNP effect is a general feature of primary radical pairs in natural photosynthesis. PMID:18370406

  20. Thermal maturity of type II kerogen from the New Albany Shale assessed by13C CP/MAS NMR

    USGS Publications Warehouse

    Werner-Zwanziger, U.; Lis, G.; Mastalerz, Maria; Schimmelmann, A.

    2005-01-01

    Thermal maturity of oil and gas source rocks is typically quantified in terms of vitrinite reflectance, which is based on optical properties of terrestrial woody remains. This study evaluates 13C CP/MAS NMR parameters in kerogen (i.e., the insoluble fraction of organic matter in sediments and sedimentary rocks) as proxies for thermal maturity in marine-derived source rocks where terrestrially derived vitrinite is often absent or sparse. In a suite of samples from the New Albany Shale (Middle Devonian to the Early Mississippian, Illinois Basin) the abundance of aromatic carbon in kerogen determined by 13C CP/MAS NMR correlates linearly well with vitrinite reflectance. ?? 2004 Elsevier Inc. All rights reserved.

  1. Proton-detected heteronuclear single quantum correlation NMR spectroscopy in rigid solids with ultra-fast MAS.

    PubMed

    Holland, Gregory P; Cherry, Brian R; Jenkins, Janelle E; Yarger, Jeffery L

    2010-01-01

    In this article, we show the potential for utilizing proton-detected heteronuclear single quantum correlation (HSQC) NMR in rigid solids under ultra-fast magic angle spinning (MAS) conditions. The indirect detection of carbon-13 from coupled neighboring hydrogen nuclei provides a sensitivity enhancement of 3- to 4-fold in crystalline amino acids over direct-detected versions. Furthermore, the sensitivity enhancement is shown to be significantly larger for disordered solids that display inhomogeneously broadened carbon-13 spectra. Latrodectus hesperus (Black Widow) dragline silk is given as an example where the sample is mass-limited and the sensitivity enhancement for the proton-detected experiment is 8- to 13-fold. The ultra-fast MAS proton-detected HSQC solid-state NMR technique has the added advantage that no proton homonuclear decoupling is applied during the experiment. Further, well-resolved, indirectly observed carbon-13 spectra can be obtained in some cases without heteronuclear proton decoupling. PMID:19857977

  2. Experimental aspects in acquisition of wide bandwidth solid-state MAS NMR spectra of low-? nuclei with different opportunities on two commercial NMR spectrometers.

    PubMed

    Jakobsen, Hans J; Bildsøe, Henrik; Gan, Zhehong; Brey, William W

    2011-08-01

    The acquisition and different appearances observed for wide bandwidth solid-state MAS NMR spectra of low-? nuclei, using (14)N as an illustrative nucleus and employing two different commercial spectrometers (Varian, 14.1T and Bruker, 19.6T), have been compared/evaluated and optimized from an experimental NMR and an electronic engineering point of view, to account for the huge differences in these spectra. The large differences in their spectral appearances, employing the recommended/standard experimental set-up for the two different spectrometers, are shown to be associated with quite large differences in the electronic design of the two types of preamplifiers, which are connected to their respective probes through a 50? cable, and are here completely accounted for. This has led to different opportunities for optimum performances in the acquisition of nearly ideal wide bandwidth spectra for low-? nuclei on the two spectrometers by careful evaluation of the length for the 50? probe-to-preamp cable for the Varian system and appropriate changes to the bandwidth (Q) of the NMR probe used on the Bruker spectrometer. Earlier, we reported quite distorted spectra obtained with Varian Unity INOVA spectrometers (at 11.4 and 14.1T) in several exploratory wide bandwidth (14)N MAS NMR studies of inorganic nitrates and amino acids. These spectra have now been compared/evaluated with fully analyzed (14)N MAS spectra correspondingly acquired at 19.6T on a Bruker spectrometer. It is shown that our upgraded version of the STARS simulation/iterative-fitting software is capable of providing identical sets for the molecular spectral parameters and corresponding fits to the experimental spectra, which fully agree with the electronic measurements, despite the highly different appearances for the MAS NMR spectra acquired on the Varian and Bruker spectrometers. PMID:21704544

  3. DETERMINATION OF BRANCHING RATIOS IN STARCH OF INTACT FLOURS BY GEL-STATE 1H MAS NMR SSPECTROSCOPY

    Technology Transfer Automated Retrieval System (TEKTRAN)

    1H MAS NMR was employed to determine the ratio of alpha 1-4 to alpha 1-6 branching in the starch of rice flour. Samples investigated were exchanged (2X) in D2O with freeze drying, gelatinized with 90/10 percent DMSO/ D2O freeze dried again, finally moistened with D2O, and placed in a spherical 4 mm ...

  4. Characterization of solid polymer dispersions of active pharmaceutical ingredients by 19F MAS NMR and factor analysis

    NASA Astrophysics Data System (ADS)

    Urbanova, Martina; Brus, Jiri; Sedenkova, Ivana; Policianova, Olivia; Kobera, Libor

    In this contribution the ability of 19F MAS NMR spectroscopy to probe structural variability of poorly water-soluble drugs formulated as solid dispersions in polymer matrices is discussed. The application potentiality of the proposed approach is demonstrated on a moderately sized active pharmaceutical ingredient (API, Atorvastatin) exhibiting extensive polymorphism. In this respect, a range of model systems with the API incorporated in the matrix of polvinylpyrrolidone (PVP) was prepared. The extent of mixing of both components was determined by T1(1H) and T1ρ(1H) relaxation experiments, and it was found that the API forms nanosized domains. Subsequently it was found out that the polymer matrix induces two kinds of changes in 19F MAS NMR spectra. At first, this is a high-frequency shift reaching 2-3 ppm which is independent on molecular structure of the API and which results from the long-range polarization of the electron cloud around 19F nucleus induced by electrostatic fields of the polymer matrix. At second, this is broadening of the signals and formation of shoulders reflecting changes in molecular arrangement of the API. To avoid misleading in the interpretation of the recorded 19F MAS NMR spectra, because both the contributions act simultaneously, we applied chemometric approach based on multivariate analysis. It is demonstrated that factor analysis of the recorded spectra can separate both these spectral contributions, and the subtle structural differences in the molecular arrangement of the API in the nanosized domains can be traced. In this way 19F MAS NMR spectra of both pure APIs and APIs in solid dispersions can be directly compared. The proposed strategy thus provides a powerful tool for the analysis of new formulations of fluorinated pharmaceutical substances in polymer matrices.

  5. Spectral editing through laser-flash excitation in two-dimensional photo-CIDNP MAS NMR experiments

    NASA Astrophysics Data System (ADS)

    Sai Sankar Gupta, Karthick Babu; Daviso, Eugenio; Jeschke, Gunnar; Alia, A.; Ernst, Matthias; Matysik, Jörg

    2014-09-01

    In solid-state photochemically induced dynamic nuclear polarization (photo-CIDNP) MAS NMR experiments, strong signal enhancement is observed from molecules forming a spin-correlated radical pair in a rigid matrix. Two-dimensional 13C-13C dipolar-assisted rotational resonance (DARR) photo-CIDNP MAS NMR experiments have been applied to obtain exact chemical shift assignments from those cofactors. Under continuous illumination, the signals are enhanced via three-spin mixing (TSM) and differential decay (DD) and their intensity corresponds to the electron spin density in pz orbitals. In multiple-13C labelled samples, spin diffusion leads to propagation of signal enhancement to all 13C spins. Under steady-state conditions, direct signal assignment is possible due to the uniform signal intensity. The original intensities, however, are inaccessible and the information of the local electron spin density is lost. Upon laser-flash illumination, the signal is enhanced via the classical radical pair mechanism (RPM). The obtained intensities are related to isotropic hyperfine interactions aiso and both enhanced absorptive and emissive lines can be observed due to differences in the sign of the local isotropic hyperfine interaction. Exploiting the mechanism of the polarization, selectivity can be increased by the novel time-resolved two-dimensional dipolar-assisted rotational resonance (DARR) MAS NMR experiment which simplifies the signal assignment compared to complex spectra of the same RCs obtained by continuous illumination. Here we present two-dimensional time-resolved photo-CIDNP MAS NMR experiments providing both directly: signal assignment and spectral editing by sign and strength of aiso. Hence, this experiment provides a direct key to the electronic structure of the correlated radical pair.

  6. Development of a rapid method for the quantification of cellulose in tobacco by (13)C CP/MAS NMR.

    PubMed

    Jiang, Jinhui; Hu, Yonghua; Tian, Zhenfeng; Chen, Kaibo; Ge, Shaolin; Xu, Yingbo; Tian, Dong; Yang, Jun

    2016-01-01

    A method was developed for rapid quantitative determination of cellulose in tobacco by utilizing (13)C cross polarization magic angle spinning NMR spectroscopy ((13)C CP/MAS NMR). Sample powder was loaded into NMR rotor, which was customized rotor containing a matched silicon tube as an intensity reference. (13)C CP/MAS NMR spectra of tobacco samples were processed with spectral deconvolution to obtain the area of the C-1 resonance at 105.5ppm and the internal standard at 0ppm. The ratio between the area of 105.5ppm and 0ppm of a set of standard cellulose samples was used to construct a calibration curve. The cellulose content of a tobacco sample was determined by comparison of the ratio between the area of 105.5ppm and 0ppm to the calibration curve. Results of this developed method showed good agreement with those obtained from chemical analysis. The proposed method has such advantages of accuracy, quickness and efficiency, and could be an alternative to chemical analyses of cellulose. PMID:26453859

  7. Conversion of propan-2-ol on zeolites LaNaY and HY investigated by gas chromatography and in situ MAS NMR spectroscopy under continuous-flow conditions

    SciTech Connect

    Hunger, M.; Horvath, T.

    1997-04-01

    The conversion of propan-2-ol on zeolites HY and LaNaY has been investigated by gas chromatography (GC) and in situ {sup 1}H and {sup 13}C MAS NMR spectroscopy under continuous-flow conditions using a new MAS NMR microreactor with cylindrical catalyst bed. At reaction temperatures of T = 373 K and T = 393 K a propan-2-ol conversion of 50 and 100%, respectively, and the formation of propene, diisopropyl. ether, and small amounts of acetone was determined by GC. Applying in situ {sup 1}H and {sup 13}C MAS NMR spectroscopy, the initial step of the reaction was found to be the physisorption of propan-2-ol on Bronsted acid sites. A formation of isopropoxy species could be excluded by {sup 13}C MAS NMR spectroscopy. {sup 1}H MAS NMR spectroscopy indicated that the Bronsted acid sites of the zeolites LaNaY and HY were hydrated by water molecules in the first part of the induction period. These water molecules were formed in result of the propan-2-ol dehydration. The strong low-field shift of the {sup 1}H MAS NMR signals of the hydrated Bronsted acid sites is due to a partial protonation of adsorbed water molecules. At T = 393 K, a significant {sup 13}C MAS NMR signal of strongly bonded acetone molecules appeared at 220 ppm in the spectra of zeolites LaNaY and HY. As demonstrated by propan-2-ol conversion on a partially dealuminated zeolite HY, this by-reaction is promoted by extra-framework aluminium species. The formation of coke precursors which caused {sup 13}C MAS NMR signals at 10-50 ppm is explained by an oligomerization of propene. In situ {sup 13}C MAS NMR experiments carried out under a continuous flow of propene showed that the above-mentioned coke precursors are also formed on partially rehydrated zeolite HY. 25 refs., 14 figs., 1 tab.

  8. Solid-state dynamics in the closo-carboranes: a (11)B MAS NMR and molecular dynamics study.

    PubMed

    Ahumada, Hernán; Kurkiewicz, Teresa; Thrippleton, Michael J; Wimperis, Stephen

    2015-03-19

    This work explores the dynamic behavior of the three closo-carborane isomers (formula C2B10H12) using modern solid-state magic angle spinning (MAS) NMR techniques and relates the experimental measurements to theoretical results obtained using molecular dynamics simulations. At high temperatures and at B0 = 9.4 T, the (11)B MAS line widths are narrow (40-90 Hz) for the three isomers. The rotational correlation times (?c) calculated by molecular dynamics are on the picosecond time scale, showing a quasi-isotropic rotation at these temperatures, typical for liquid systems. For all three isomers, the values of the (11)B spin-lattice relaxation times (T1) show discontinuities as the temperature is decreased, confirming the phase changes reported in the literature. At low temperatures, the (11)B MAS spectra of all three isomers exhibit much broader lines. The simulations showed that the molecular reorientation was anisotropic around different symmetry axes for each isomer, and this was supported by the values of the reduced quadrupolar parameter PQ(eff) derived from "dynamic shift" measurements using (11)B MQMAS NMR spectroscopy. The behavior of PQ(eff) as a function of temperature for p-carborane suggests that molecular reorientation is about the C5 symmetry axis of the molecule at low temperatures, and this was supported by the molecular dynamics simulations. PMID:25710751

  9. Determination of the structural changes by Raman and 13C CP/MAS NMR spectroscopy on native corn starch with plasticizers

    NASA Astrophysics Data System (ADS)

    Cozar, O.; Filip, C.; Cioica, N.; Coţa, C.; Tripon, C.; Nagy, E. M.

    2013-11-01

    The plasticizing - antiplasticizing effect of water and glycerol contents on native corn starch samples is investigated by FT-Raman and 13C CP/MAS NMR spectroscopy. The presence of both amorphous and crystalline structural phases was evidenced in pure native corn starch and also in the samples containing plasticizers. Among the crystalline starch structures, the A- and V- types were suggested by CP/MAS NMR spectra.

  10. Determination of the structural changes by Raman and {sup 13}C CP/MAS NMR spectroscopy on native corn starch with plasticizers

    SciTech Connect

    Cozar, O.; Filip, C.; Tripon, C.; Cioica, N.; Coţa, C.; Nagy, E. M.

    2013-11-13

    The plasticizing - antiplasticizing effect of water and glycerol contents on native corn starch samples is investigated by FT-Raman and {sup 13}C CP/MAS NMR spectroscopy. The presence of both amorphous and crystalline structural phases was evidenced in pure native corn starch and also in the samples containing plasticizers. Among the crystalline starch structures, the A- and V- types were suggested by CP/MAS NMR spectra.

  11. Slow motions in microcrystalline proteins as observed by MAS-dependent 15N rotating-frame NMR relaxation

    NASA Astrophysics Data System (ADS)

    Krushelnitsky, Alexey; Zinkevich, Tatiana; Reif, Bernd; Saalwächter, Kay

    2014-11-01

    15N NMR relaxation rate R1ρ measurements reveal that a substantial fraction of residues in the microcrystalline chicken alpha-spectrin SH3 domain protein undergoes dynamics in the μs-ms timescale range. On the basis of a comparison of 2D site-resolved with 1D integrated 15N spectral intensities, we demonstrate that the significant fraction of broad signals in the 2D spectrum exhibits the most pronounced slow mobility. We show that 15N R1ρ's in proton-diluted protein samples are practically free from the coherent spin-spin contribution even at low MAS rates, and thus can be analysed quantitatively. Moderate MAS rates (10-30 kHz) can be more advantageous in comparison with the rates >50-60 kHz when slow dynamics are to be identified and quantified by means of R1ρ experiments.

  12. Sealed Rotors for In Situ High Temperature High Pressure MAS NMR†

    PubMed Central

    Hu, Jian Zhi; Hu, Mary Y.; Zhao, Zhenchao; Xu, Suochang; Vjunov, Aleksei; Shi, Hui; Camaioni, Donald M.; Peden, Charles H. F.; Lercher, Johannes A.

    2015-01-01

    Here we present the design of reusable and perfectly-sealed all-zircornia MAS rotors. The rotors are used to study AlPO4-5 molecular sieve crystallization under hydrothermal conditions, high temperature high pressure cyclohexanol dehydration reaction, and low temperature metabolomics of intact biological tissue. PMID:26171928

  13. Study of chemically inequivalent N(CH3)4 ions in [N(CH3)4]2ZnBr4 near the phase transition temperature using 1H MAS NMR, 13C CP/MAS NMR, and 14N NMR

    NASA Astrophysics Data System (ADS)

    Lim, Ae Ran

    2016-02-01

    The temperature dependences of the chemical shifts and intensities of 1H, 13C, and 14N nuclei in tetramethylammonium tetrabromozincate, [N(CH3)4]2ZnBr4, were investigated using single-crystal nuclear magnetic resonance (NMR) and magic angle spinning (MAS) NMR spectroscopy to elucidate the structural geometry near the phase transition temperature. Based on the analysis of the 13C cross-polarization (CP)/MAS NMR and 14N NMR spectra, the two chemically inequivalent N(1) (CH3)4 and N(2) (CH3)4 ions were distinguished. Furthermore, the 14N NMR spectrum at the phase transition temperature indicated the existence of the ferroelastic characteristics of the N(CH3)4 ions.

  14. CaCl 2 -Accelerated Hydration of Tricalcium Silicate: A STXM Study Combined with 29 Si MAS NMR

    DOE PAGESBeta

    Li, Qinfei; Ge, Yong; Geng, Guoqing; Bae, Sungchul; Monteiro, Paulo J. M.

    2015-01-01

    Tmore » he effect of calcium chloride (CaCl 2 ) on tricalcium silicate (C 3 S) hydration was investigated by scanning transmission X-ray microscopy (STXM) with Near Edge X-ray Absorption Fine Structure (NEXAFS) spectra and 29 Si MAS NMR. STXM is demonstrated to be a powerful tool for studying the chemical composition of a cement-based hydration system. The Ca L 3,2 -edge NEXAFS spectra obtained by examining C 3 S hydration in the presence of CaCl 2 showed that this accelerator does not change the coordination of calcium in the calcium silicate hydrate (C-S-H), which is the primary hydration product. O K-edge NEXAFS is also very useful in distinguishing the chemical components in hydrated C 3 S. Based on the Ca L 3,2 -edge spectra and chemical component mapping, we concluded that CaCl 2 prefers to coexist with unhydrated C 3 S instead of C-S-H. In Si K-edge NEXAFS analysis, CaCl 2 increases the degree of silicate polymerization of C-S-H in agreement with the 29 Si CP/MAS NMR results, which show that the presence of CaCl 2 in hydrated C 3 S considerably accelerates the formation of middle groups ( Q 2 ) and branch sites ( Q 3 ) in the silicate chains of C-S-H gel at 1-day hydration.« less

  15. An investigation into the structure and reactivity of calcium-zinc-silicate ionomer glasses using MAS-NMR spectroscopy.

    PubMed

    Boyd, D; Towler, M R; Law, R V; Hill, R G

    2006-05-01

    The suitability of Glass Polyalkenoate Cements (GPCs) for orthopaedic applications is retarded by the presence in the glass phase of aluminium, a neurotoxin. Unfortunately, the aluminium ion plays an integral role in the setting process of GPCs and its absence is likely to hinder cement formation. However, the authors have previously shown that aluminium-free GPCs may be formulated based on calcium zinc silicate glasses and these novel materials exhibit significant potential as hard tissue biomaterials. However there is no data available on the structure of these glasses. (29)Si MAS-NMR, differential thermal analysis (DTA), X-ray diffraction (XRD), and network crosslink density (CLD) calculations were used to characterize the structure of five calcium zinc silicate glasses and relate glass structure to reactivity. The results indicate that glasses capable of forming Zn-GPCs are predominantly Q(2)/Q(3) in structure with corresponding network crosslink densities greater than 2. The correlation of CLD and MAS-NMR results indicate the primary role of zinc in these simple glass networks is as a network modifier and not an intermediate oxide; this fact will allow for more refined glass compositions, with less reactive structures, to be formulated in the future. PMID:16688578

  16. 71Ga NMR of reference GaIV, GaV, and GaVI compounds by MAS and QPASS, extension of gallium/aluminum NMR parameter correlation.

    PubMed

    Massiot, D; Vosegaard, T; Magneron, N; Trumeau, D; Montouillout, V; Berthet, P; Loiseau, T; Bujoli, B

    1999-12-01

    We report new measurements of NMR parameters for 71Ga in gallium bearing oxide reference compounds, ranging from perfectly ordered systems to disordered crystalline structures and their aluminate counterparts. Static, MAS, and QPASS spectra are obtained at magnetic fields ranging from 7.0 to 18.8 T. With these results we enhance the previously established correlation between isotropic chemical shifts of 71Ga and 27Al and propose a correlation between gallium and aluminum electric field gradients (EFG). This correlation shows that the EFG at 71Ga sites are generally three times greater than those at equivalent 27Al sites. PMID:10672940

  17. Phase Cycling Schemes for finite-pulse-RFDR MAS Solid State NMR Experiments

    PubMed Central

    Zhang, Rongchun; Nishiyama, Yusuke; Sun, Pingchuan; Ramamoorthy, Ayyalusamy

    2015-01-01

    The finite-pulse radio frequency driven dipolar recoupling (fp-RFDR) pulse sequence is used in 2D homonuclear chemical shift correlation experiments under magic angle spinning (MAS). A recent study demonstrated the advantages of using a short phase cycle, XY4, and its super-cycle, XY414, for the fp-RFDR pulse sequence employed in 2D 1H/1H single-quantum/single-quantum correlation experiments under ultrafast MAS conditions. In this study, we report a comprehensive analysis on the dipolar recoupling efficiencies of XY4, XY412, XY413, XY414, and XY814 phase cycles under different spinning speeds ranging from 10 to 100 kHz. The theoretical calculations reveal the presence of second-order terms (T10T2,±2, T1,±1T2,±1, etc.) in the recoupled homonuclear dipolar coupling Hamiltonian only when the basic XY4 phase cycle is utilized, making it advantageous for proton-proton magnetization transfer under ultrafast MAS conditions. It is also found that the recoupling efficiency of fp-RFDR is quite dependent on the duty factor (τ180/τR) as well as on the strength of homonuclear dipolar couplings. The rate of longitudinal magnetization transfer increases linearly with the duty factor of fp-RFDR for all the XY-based phase cycles investigated in this study. Examination of the performances of different phase cycles against chemical shift offset and RF field in homogeneity effects revealed that XY414 is the most tolerant phase cycle, while the shortest phase cycle XY4 suppressed the RF field inhomogeneity effects most efficiently under slow spinning speeds. Our results suggest that the difference in the fp-RFDR recoupling efficiencies decreases with the increasing MAS speed, while ultrafast (>60 kHz) spinning speed is advantageous as it recouples a large amount of homonuclear dipolar couplings and therefore enable fast magnetization exchange. The effects of higher-order terms and cross terms between various interactions in the effective Hamiltonian of fp-RFDR are also analyzed using numerical simulations for various phase cycles. Results obtained via numerical simulations are in excellent agreement with ultrafast MAS experimental results from the powder samples of glycine and L-alanine. PMID:25655451

  18. Phase cycling schemes for finite-pulse-RFDR MAS solid state NMR experiments.

    PubMed

    Zhang, Rongchun; Nishiyama, Yusuke; Sun, Pingchuan; Ramamoorthy, Ayyalusamy

    2015-03-01

    The finite-pulse radio frequency driven dipolar recoupling (fp-RFDR) pulse sequence is used in 2D homonuclear chemical shift correlation experiments under magic angle spinning (MAS). A recent study demonstrated the advantages of using a short phase cycle, XY4, and its super-cycle, XY4(1)4, for the fp-RFDR pulse sequence employed in 2D (1)H/(1)H single-quantum/single-quantum correlation experiments under ultrafast MAS conditions. In this study, we report a comprehensive analysis on the dipolar recoupling efficiencies of XY4, XY4(1)2, XY4(1)3, XY4(1)4, and XY8(1)4 phase cycles under different spinning speeds ranging from 10 to 100 kHz. The theoretical calculations reveal the presence of second-order terms (T(10)T(2,±2), T(1,±1)T(2,±1), etc.) in the recoupled homonuclear dipolar coupling Hamiltonian only when the basic XY4 phase cycle is utilized, making it advantageous for proton-proton magnetization transfer under ultrafast MAS conditions. It is also found that the recoupling efficiency of fp-RFDR is quite dependent on the duty factor (?180/?R) as well as on the strength of homonuclear dipolar couplings. The rate of longitudinal magnetization transfer increases linearly with the duty factor of fp-RFDR for all the XY-based phase cycles investigated in this study. Examination of the performances of different phase cycles against chemical shift offset and RF field inhomogeneity effects revealed that XY4(1)4 is the most tolerant phase cycle, while the shortest phase cycle XY4 suppressed the RF field inhomogeneity effects most efficiently under slow spinning speeds. Our results suggest that the difference in the fp-RFDR recoupling efficiencies decreases with the increasing MAS speed, while ultrafast (>60 kHz) spinning speed is advantageous as it recouples a large amount of homonuclear dipolar couplings and therefore enable fast magnetization exchange. The effects of higher-order terms and cross terms between various interactions in the effective Hamiltonian of fp-RFDR are also analyzed using numerical simulations for various phase cycles. Results obtained via numerical simulations are in excellent agreement with ultrafast MAS experimental results from the powder samples of glycine and l-alanine. PMID:25655451

  19. Phase cycling schemes for finite-pulse-RFDR MAS solid state NMR experiments

    NASA Astrophysics Data System (ADS)

    Zhang, Rongchun; Nishiyama, Yusuke; Sun, Pingchuan; Ramamoorthy, Ayyalusamy

    2015-03-01

    The finite-pulse radio frequency driven dipolar recoupling (fp-RFDR) pulse sequence is used in 2D homonuclear chemical shift correlation experiments under magic angle spinning (MAS). A recent study demonstrated the advantages of using a short phase cycle, XY4, and its super-cycle, XY414, for the fp-RFDR pulse sequence employed in 2D 1H/1H single-quantum/single-quantum correlation experiments under ultrafast MAS conditions. In this study, we report a comprehensive analysis on the dipolar recoupling efficiencies of XY4, XY412, XY413, XY414, and XY814 phase cycles under different spinning speeds ranging from 10 to 100 kHz. The theoretical calculations reveal the presence of second-order terms (T10T2,±2, T1,±1T2,±1, etc.) in the recoupled homonuclear dipolar coupling Hamiltonian only when the basic XY4 phase cycle is utilized, making it advantageous for proton-proton magnetization transfer under ultrafast MAS conditions. It is also found that the recoupling efficiency of fp-RFDR is quite dependent on the duty factor (?180/?R) as well as on the strength of homonuclear dipolar couplings. The rate of longitudinal magnetization transfer increases linearly with the duty factor of fp-RFDR for all the XY-based phase cycles investigated in this study. Examination of the performances of different phase cycles against chemical shift offset and RF field inhomogeneity effects revealed that XY414 is the most tolerant phase cycle, while the shortest phase cycle XY4 suppressed the RF field inhomogeneity effects most efficiently under slow spinning speeds. Our results suggest that the difference in the fp-RFDR recoupling efficiencies decreases with the increasing MAS speed, while ultrafast (>60 kHz) spinning speed is advantageous as it recouples a large amount of homonuclear dipolar couplings and therefore enable fast magnetization exchange. The effects of higher-order terms and cross terms between various interactions in the effective Hamiltonian of fp-RFDR are also analyzed using numerical simulations for various phase cycles. Results obtained via numerical simulations are in excellent agreement with ultrafast MAS experimental results from the powder samples of glycine and L-alanine.

  20. Polydisperse methyl β-cyclodextrin–epichlorohydrin polymers: variable contact time 13C CP-MAS solid-state NMR characterization

    PubMed Central

    Mallard, Isabelle; Baudelet, Davy; Castiglione, Franca; Ferro, Monica; Panzeri, Walter; Ragg, Enzio

    2015-01-01

    Summary The polymerization of partially methylated β-cyclodextrin (CRYSMEB) with epichlorohydrin was carried out in the presence of a known amount of toluene as imprinting agent. Three different preparations (D1, D2 and D3) of imprinted polymers were obtained and characterized by solid-state 13C NMR spectroscopy under cross-polarization magic angle spinning (CP-MAS) conditions. The polymers were prepared by using the same synthetic conditions but with different molar ratios of imprinting agent/monomer, leading to morphologically equivalent materials but with different absorption properties. The main purpose of the work was to find a suitable spectroscopic descriptor accounting for the different imprinting process in three homogeneous polymeric networks. The polymers were characterized by studying the kinetics of the cross-polarization process. This approach is based on variable contact time CP-MAS spectra, referred to as VCP-MAS. The analysis of the VCP-MAS spectra provided two relaxation parameters: T CH (the CP time constant) and T 1ρ (the proton spin-lattice relaxation time in the rotating frame). The results and the analysis presented in the paper pointed out that T CH is sensitive to the imprinting process, showing variations related to the toluene/cyclodextrin molar ratio used for the preparation of the materials. Conversely, the observed values of T 1ρ did not show dramatic variations with the imprinting protocol, but rather confirmed that the three polymers are morphologically similar. Thus the combined use of T CH and T 1ρ can be helpful for the characterization and fine tuning of imprinted polymeric matrices. PMID:26877800

  1. Simple and accurate determination of X-H distances under ultra-fast MAS NMR

    NASA Astrophysics Data System (ADS)

    Paluch, Piotr; Pawlak, Tomasz; Amoureux, Jean-Paul; Potrzebowski, Marek J.

    2013-08-01

    We demonstrate that a very simple experiment, Cross-Polarization with Variable Contact-time (CP-VC), is very efficient at ultra-fast MAS (?R ? 60 kHz) to measure accurately the C-H and N-H distances, and to analyze the dynamics of bio-molecules. This experiment can be performed with samples that are either 13C or 15N labeled or without any labeling. The method is very robust experimentally with respect to imperfect Hartman-Hahn setting, and presents a large scaling factor allowing a better dipolar determination, especially for long C-H or N-H distances, or for CH3 or NH3 moieties with three-site hopping. At ultra-fast MAS, it can be used quantitatively in a 2D way, because its scaling factor is then little dependent on the offsets. This robustness with respect to offset is related to the ultra-fast spinning speed, and hence to the related small rotor diameter. Indeed, these two specifications lead to efficient n = ±1 zero-quantum Hartman-Hahn CP-transfers with large RF-fields on proton and carbon or nitrogen channels, and large dipolar scaling factor.

  2. Measuring (19)F shift anisotropies and (1)H-(19)F dipolar interactions with ultrafast MAS NMR.

    PubMed

    Martini, Francesca; Miah, Habeeba K; Iuga, Dinu; Geppi, Marco; Titman, Jeremy J

    2015-10-01

    A new (19)F anisotropic-isotropic shift correlation experiment is described that operates with ultrafast MAS, resulting in good resolution of isotropic (19)F shifts in the detection dimension. The new experiment makes use of a recoupling sequence designed using symmetry principles that reintroduces the (19)F chemical shift anisotropy in the indirect dimension. The situations in which the new experiment is appropriate are discussed, and the (19)F shift anisotropy parameters in poly(difluoroethylene) (PVDF) are measured. In addition, similar recoupling sequences are shown to be effective for measuring (1)H-(19)F distances via the heteronuclear dipolar interaction. This is demonstrated by application to a recently synthesized zirconium phosphonate material that contains one-dimensional chains linked by H-F hydrogen bonds. PMID:26318626

  3. Measuring 19F shift anisotropies and 1H-19F dipolar interactions with ultrafast MAS NMR

    NASA Astrophysics Data System (ADS)

    Martini, Francesca; Miah, Habeeba K.; Iuga, Dinu; Geppi, Marco; Titman, Jeremy J.

    2015-10-01

    A new 19F anisotropic-isotropic shift correlation experiment is described that operates with ultrafast MAS, resulting in good resolution of isotropic 19F shifts in the detection dimension. The new experiment makes use of a recoupling sequence designed using symmetry principles that reintroduces the 19F chemical shift anisotropy in the indirect dimension. The situations in which the new experiment is appropriate are discussed, and the 19F shift anisotropy parameters in poly(difluoroethylene) (PVDF) are measured. In addition, similar recoupling sequences are shown to be effective for measuring 1H-19F distances via the heteronuclear dipolar interaction. This is demonstrated by application to a recently synthesized zirconium phosphonate material that contains one-dimensional chains linked by H-F hydrogen bonds.

  4. A MAS NMR study of the bacterial ABC transporter ArtMP.

    PubMed

    Lange, Vivien; Becker-Baldus, Johanna; Kunert, Britta; van Rossum, Barth-Jan; Casagrande, Fabio; Engel, Andreas; Roske, Yvette; Scheffel, Frank M; Schneider, Erwin; Oschkinat, Hartmut

    2010-03-01

    ATP-binding cassette (ABC) transport systems facilitate the translocation of substances, like amino acids, across cell membranes energised by ATP hydrolysis. This work describes first structural studies on the ABC transporter ArtMP from Geobacillus stearothermophilus in native lipid environment by magic-angle spinning NMR spectroscopy. The 2D crystals of ArtMP and 3D crystals of isolated ArtP were prepared in different nucleotide-bound or -unbound states. From selectively (13)C,(15)N-labelled ArtP, several sequence-specific assignments were obtained, most of which could be transferred to spectra of ArtMP. Residues Tyr133 and Pro134 protrude directly into the ATP-binding pocket at the interface of the ArtP subunits, and hence, are sensitive monitors for structural changes during nucleotide binding and hydrolysis. Distinct sets of NMR shifts were obtained for ArtP with different phosphorylation states of the ligand. Indications were found for an asymmetric or inhomogeneous state of the ArtP dimer bound with triphosphorylated nucleotides. With this investigation, a model system was established for screening all functional states occurring in one ABC transporter in native lipid environment. PMID:20099290

  5. Red coralline algae assessed as marine pH proxies using 11B MAS NMR

    PubMed Central

    Cusack, M.; Kamenos, N. A.; Rollion-Bard, C.; Tricot, G.

    2015-01-01

    Reconstructing pH from biogenic carbonates using boron isotopic compositions relies on the assumption that only borate, and no boric acid, is present. Red coralline algae are frequently used in palaeoenvironmental reconstruction due to their widespread distribution and regular banding frequency. Prior to undertaking pH reconstructions using red coralline algae we tested the boron composition of the red coralline alga Lithothamnion glaciale using high field NMR. In bulk analysed samples, thirty percent of boron was present as boric acid. We suggest that prior to reconstructing pH using coralline algae 1) species-specific boron compositions and 2) within-skeleton special distributions of boron are determined for multiple species. This will enable site selective boron analyses to be conducted validating coralline algae as palaeo-pH proxies based on boron isotopic compositions. PMID:25640229

  6. Red coralline algae assessed as marine pH proxies using 11B MAS NMR.

    PubMed

    Cusack, M; Kamenos, N A; Rollion-Bard, C; Tricot, G

    2015-01-01

    Reconstructing pH from biogenic carbonates using boron isotopic compositions relies on the assumption that only borate, and no boric acid, is present. Red coralline algae are frequently used in palaeoenvironmental reconstruction due to their widespread distribution and regular banding frequency. Prior to undertaking pH reconstructions using red coralline algae we tested the boron composition of the red coralline alga Lithothamnion glaciale using high field NMR. In bulk analysed samples, thirty percent of boron was present as boric acid. We suggest that prior to reconstructing pH using coralline algae 1) species-specific boron compositions and 2) within-skeleton special distributions of boron are determined for multiple species. This will enable site selective boron analyses to be conducted validating coralline algae as palaeo-pH proxies based on boron isotopic compositions. PMID:25640229

  7. Red coralline algae assessed as marine pH proxies using 11B MAS NMR

    NASA Astrophysics Data System (ADS)

    Cusack, M.; Kamenos, N. A.; Rollion-Bard, C.; Tricot, G.

    2015-02-01

    Reconstructing pH from biogenic carbonates using boron isotopic compositions relies on the assumption that only borate, and no boric acid, is present. Red coralline algae are frequently used in palaeoenvironmental reconstruction due to their widespread distribution and regular banding frequency. Prior to undertaking pH reconstructions using red coralline algae we tested the boron composition of the red coralline alga Lithothamnion glaciale using high field NMR. In bulk analysed samples, thirty percent of boron was present as boric acid. We suggest that prior to reconstructing pH using coralline algae 1) species-specific boron compositions and 2) within-skeleton special distributions of boron are determined for multiple species. This will enable site selective boron analyses to be conducted validating coralline algae as palaeo-pH proxies based on boron isotopic compositions.

  8. Imaging of the B1 distribution and background signal in a MAS NMR probehead using inhomogeneous B0 and B1 fields.

    PubMed

    Odedra, Smita; Wimperis, Stephen

    2013-06-01

    Several widely used methods for suppressing the "background" signal in (1)H magic angle spinning (MAS) NMR spectroscopy are based on the assumption of a significant difference between the B1 radiofrequency field experienced by the sample (within the MAS rotor) and that felt by static components of the probehead (where the background signal is believed to originate). In this work, a two-dimensional correlation experiment employing inhomogeneous B0 and B1 fields is used to image the B1 distribution in a MAS NMR probehead. The experiment, which can be performed on any spectrometer, allows the distribution of the B1 field to be measured and also correlated with the spatial location of the NMR signal within the probehead. The method can also readily be combined with various "depth pulse" techniques for background suppression, allowing their performances to be more rigorously evaluated. PMID:23644349

  9. Imaging of the B1 distribution and background signal in a MAS NMR probehead using inhomogeneous B0 and B1 fields

    NASA Astrophysics Data System (ADS)

    Odedra, Smita; Wimperis, Stephen

    2013-06-01

    Several widely used methods for suppressing the "background" signal in 1H magic angle spinning (MAS) NMR spectroscopy are based on the assumption of a significant difference between the B1 radiofrequency field experienced by the sample (within the MAS rotor) and that felt by static components of the probehead (where the background signal is believed to originate). In this work, a two-dimensional correlation experiment employing inhomogeneous B0 and B1 fields is used to image the B1 distribution in a MAS NMR probehead. The experiment, which can be performed on any spectrometer, allows the distribution of the B1 field to be measured and also correlated with the spatial location of the NMR signal within the probehead. The method can also readily be combined with various "depth pulse" techniques for background suppression, allowing their performances to be more rigorously evaluated.

  10. Sensitivity gains, linearity, and spectral reproducibility in nonuniformly sampled multidimensional MAS NMR spectra of high dynamic range

    PubMed Central

    Suiter, Christopher L.; Paramasivam, Sivakumar; Hou, Guangjin; Sun, Shangjin; Rice, David; Hoch, Jeffrey C.; Rovnyak, David

    2014-01-01

    Recently, we have demonstrated that considerable inherent sensitivity gains are attained in MAS NMR spectra acquired by nonuniform sampling (NUS) and introduced maximum entropy interpolation (MINT) processing that assures the linearity of transformation between the time and frequency domains. In this report, we examine the utility of the NUS/MINT approach in multidimensional datasets possessing high dynamic range, such as homonuclear 13C–13C correlation spectra. We demonstrate on model compounds and on 1–73-(U-13C, 15N)/74–108-(U-15N) E. coli thioredoxin reassembly, that with appropriately constructed 50 % NUS schedules inherent sensitivity gains of 1.7–2.1-fold are readily reached in such datasets. We show that both linearity and line width are retained under these experimental conditions throughout the entire dynamic range of the signals. Furthermore, we demonstrate that the reproducibility of the peak intensities is excellent in the NUS/MINT approach when experiments are repeated multiple times and identical experimental and processing conditions are employed. Finally, we discuss the principles for design and implementation of random exponentially biased NUS sampling schedules for homonuclear 13C–13C MAS correlation experiments that yield high-quality artifact-free datasets. PMID:24752819

  11. Non-bridging oxygens in borate glasses: characterization by 11B and 17O MAS and 3QMAS NMR.

    PubMed

    Stebbins, J F; Zhao, P; Kroeker, S

    2000-05-01

    The concentrations of non-bridging oxygens (NBO) in oxide glasses has major effects on their properties and on those of their precursor glass melts. In borate and borosilicate glasses, the presence of NBO bonded to boron has generally been inferred from 11B NMR spectra and mass balance considerations. Here we report the direct observation of such NBO using 17O MAS and 3QMAS techniques, and compare estimates of their populations with those derived from high-resolution 11B MAS spectra. For the latter, two independent methods are used, based on the ratios of trigonal to tetrahedral boron and on the concentrations of trigonal boron sites with large quadrupolar asymmetry parameters. We include data on crystalline sodium pyroborate (Na4B2O5) and sodium metaborate (NaBO2), and several sodium and barium borate glasses. 17O chemical shifts and quadrupolar coupling constants for NBO bonded to boron vary considerably depending on their coordination environment. In borosilicates, peaks for this species may be hidden by overlap with B-O-Si or Si-O-Si resonances. PMID:10811425

  12. Sensitivity Gains, Linearity, and Spectral Reproducibility in Nonuniformly Sampled Multidimensional MAS NMR Spectra of High Dynamic Range.

    SciTech Connect

    Suiter, Christopher L.; Paramasivam, Sivakumar; Hou, Guangjin; Sun, Shangjin; Rice, David M.; Hoch, Jeffrey C.; Rovnyak, David S.; Polenova, Tatyana E.

    2014-04-22

    Recently, we have demonstrated that considerable inherent sensitivity gains are attained in MAS NMR spectra acquired by nonuniform sampling (NUS) and introduced maximum entropy interpolation (MINT) processing that assures the linearity of transformation between the time and frequency domains. In this report, we examine the utility of the NUS/MINT approach in multidimensional datasets possessing high dynamic range, such as homonuclear 13C–13C correlation spectra. We demonstrate on model compounds and on 1–73-(U-13C,15N)/74–108-(U-15N) E. coli thioredoxin reassembly, that with appropriately constructed 50 % NUS schedules inherent sensitivity gains of 1.7–2.1-fold are readily reached in such datasets. We show that both linearity and line width are retained under these experimental conditions throughout the entire dynamic range of the signals. Furthermore, we demonstrate that the reproducibility of the peak intensities is excellent in the NUS/MINT approach when experiments are repeated multiple times and identical experimental and processing conditions are employed. Finally, we discuss the principles for design and implementation of random exponentially biased NUS sampling schedules for homonuclear 13C–13C MAS correlation experiments that yield high quality artifact-free datasets.

  13. A Cross-Polarization Based Rotating-Frame Separated-Local-Field NMR Experiment Under Ultrafast MAS Conditions

    PubMed Central

    Zhang, Rongchun; Damron, Joshua; Vosegaard, Thomas

    2014-01-01

    Rotating-frame separated-local-field solid-state NMR experiments measure highly resolved heteronuclear dipolar couplings which, in turn, provide valuable interatomic distances for structural and dynamic studies of molecules in the solid-state. Though many different rotating-frame SLF sequences have been put forth, recent gains in ultrafast MAS technology have considerably simplified pulse sequence requirements due to the suppression of proton-proton dipolar interactions. In this study we revisit a simple two-dimensional 1H-13C dipolar coupling/chemical shift correlation experiment using 13C detected Cross-Polarization with a Variable Contact time (CPVC) and systematically study the conditions for its optimal performance at 60 kHz MAS. In addition, we demonstrate the feasibility of a proton-detected version of the CPVC experiment. The theoretical analysis of the CPVC pulse sequence under different Hartmann-Hahn matching conditions confirms that it performs optimally under the ZQ (w1H-w1C=±wr) condition for polarization transfer. The limits of the cross polarization process are explored and precisely defined as a function of offset and Hartmann-Hahn mismatch via spin dynamics simulation and experiments on a powder sample of uniformly 13C-labeled L-isoleucine. Our results show that the performance of the CPVC sequence and subsequent determination of 1H-13C dipolar couplings are insensitive to 1H/13C frequency offset frequency when high RF fields are used on both RF channels. Conversely, the CPVC sequence is quite sensitive to the Hartmann-Hahn mismatch, particularly for systems with weak heteronuclear dipolar couplings. We demonstrate the use of the CPVC based SLF experiment as a tool to identify different carbon groups, and hope to motivate the exploration of more sophisticated 1H detected avenues for ultrafast MAS. PMID:25486635

  14. Acetylation of raw cotton for oil spill cleanup application: an FTIR and 13C MAS NMR spectroscopic investigation

    NASA Astrophysics Data System (ADS)

    Adebajo, Moses O.; Frost, Ray L.

    2004-08-01

    Fourier transform infrared (FTIR) and 13C MAS NMR spectroscopy have been used to investigate the acetylation of raw cotton samples with acetic anhydride without solvents in the presence of different amounts of 4-dimethylaminopyridine (DMAP) catalyst. This is a continuation of our previous investigation of acetylation of commercial cotton in an effort to develop hydrophobic, biodegradable, cellulosic sorbent materials for cleaning up oil spills. The FTIR data have again provided a clear evidence for successful acetylation. The NMR results further confirm the successful acetylation. The extent of acetylation was quantitatively determined using the weight percent gain (WPG) due to acetylation and by calculating the ratio R between the intensity of the acetyl C?O stretching band at 1740-1745 cm -1 and the intensity of C?O stretching vibration of the cellulose backbone at about 1020-1040 cm -1. The FTIR technique was found to be highly sensitive and reliable for the determination of the extent of acetylation. The level of acetylation of the raw cotton samples was found to be much higher than that of cotton fabrics and the previously studied commercial cotton. The variation of the R and WPG with reaction time, amount of DMAP catalyst and different samples of raw cotton is discussed.

  15. Acetylation of raw cotton for oil spill cleanup application: an FTIR and 13C MAS NMR spectroscopic investigation.

    PubMed

    Adebajo, Moses O; Frost, Ray L

    2004-08-01

    Fourier transform infrared (FTIR) and 13C MAS NMR spectroscopy have been used to investigate the acetylation of raw cotton samples with acetic anhydride without solvents in the presence of different amounts of 4-dimethylaminopyridine (DMAP) catalyst. This is a continuation of our previous investigation of acetylation of commercial cotton in an effort to develop hydrophobic, biodegradable, cellulosic sorbent materials for cleaning up oil spills. The FTIR data have again provided a clear evidence for successful acetylation. The NMR results further confirm the successful acetylation. The extent of acetylation was quantitatively determined using the weight percent gain (WPG) due to acetylation and by calculating the ratio R between the intensity of the acetyl C=O stretching band at 1740-1745 cm(-1) and the intensity of C-O stretching vibration of the cellulose backbone at about 1020-1040 cm(-1). The FTIR technique was found to be highly sensitive and reliable for the determination of the extent of acetylation. The level of acetylation of the raw cotton samples was found to be much higher than that of cotton fabrics and the previously studied commercial cotton. The variation of the R and WPG with reaction time, amount of DMAP catalyst and different samples of raw cotton is discussed. PMID:15249021

  16. MAS-NMR investigations of the crystallization behaviour of lithium aluminum silicate (LAS) glasses containing P 2O 5 and TiO 2 nucleants

    NASA Astrophysics Data System (ADS)

    Ananthanarayanan, A.; Kothiyal, G. P.; Montagne, L.; Revel, B.

    2010-06-01

    Lithium aluminum silicate (LAS) glass of composition (mol%) 20.4Li 2O-4.0Al 2O 3-68.6SiO 2-3.0K 2O-2.6B 2O 3-0.5P 2O 5-0.9TiO 2 was prepared by melt quenching. The glass was then nucleated and crystallized based on differential thermal analysis (DTA) data and was characterized by 29Si, 31P, 11B and 27Al MAS-NMR. XRD and 29Si NMR showed that lithium metasilicate (Li 2SiO 3) is the first phase to c form followed by cristobalite (SiO 2) and lithium disilicate (Li 2Si 2O 5). 29Si MAS-NMR revealed a change in the network structure already for the glasses nucleated at 550 °C. Since crystalline Li 3PO 4, as observed by 31P MAS-NMR, forms concurrently with the silicate phases, we conclude that crystalline Li 3PO 4 does not act as a nucleating agent for lithium silicate phases. Moreover, 31P NMR indicates the formation of M-PO 4 ( M=B, Al or Ti) complexes. The presence of BO 3 and BO 4 structural units in all the glass/glass-ceramic samples is revealed through 11B MAS-NMR. B remains in the residual glass and the crystallization of silicate phases causes a reduction in the number of alkali ions available for charge compensation. As a result, the number of trigonally coordinated B (BO 3) increases at the expense of tetrahedrally coordinated B (BO 4). The 27Al MAS-NMR spectra indicate the presence of tetrahedrally coordinated Al species, which are only slightly perturbed by the crystallization.

  17. Studying soil organic matter using 13C CP-MAS NMR: the effect of soil chemical pre-treatments on spectra quality and representativity.

    PubMed

    Salati, Silvia; Adani, Fabrizio; Cosentino, Cesare; Torri, Giacomo

    2008-02-01

    (13)C CP-MAS NMR spectroscopy is a technique that has proved to be useful in studying soil organic matter (SOM). Nevertheless, NMR spectra exhibit a weak signal and have very low resolution due to: the low natural abundance of (13)C (1.1% of C) in SOM, the generally low SOM content of soils, and the presence of paramagnetic impurities. This paper studies the effects of soil chemical pre-treatments on (13)CP-MAS NMR spectra quality and spectra representativity i.e. soil C mass balance. After chemical pre-treatment to increase total organic carbon (TOC) content and C/Fe ratio, eight soils characterized by different levels of organic carbon content and C/Fe ratios were studied using (13)CP-MAS NMR. Moreover, where chemical treatments were not applicable due to high carbon losses, the number of (13)CP-MAS NMR scans was increased in order to obtain satisfactory spectra. Results show that chemical pre-treatment of soils with C/Fe>1 caused high C losses. Bulk soils were therefore studied by increasing the number of (13)CP-MAS NMR scans. Acceptable spectra were obtained from 8K scans (1K=1024 transient). On the other hand, even when a large number of scan (32K) are used, soil with C/Fe<1 cannot be studied. As these soils are characterized by low C losses after HCl treatments (range of 2.9-25.4%), a pre-treatment of at least 1.39 mol l(-1) HCl removes excess Fe and at the same time increases C/Fe ratio resulting in 32K scans providing good spectra. PMID:17936330

  18. Following Solid-Acid-Catalyzed Reactions by MAS NMR Spectroscopy in Liquid Phase -Zeolite-Catalyzed Conversion of Cyclohexanol in Water

    SciTech Connect

    Vjunov, Aleksei; Hu, Mary Y.; Feng, Ju; Camaioni, Donald M.; Mei, Donghai; Hu, Jian Z.; Zhao, Chen; Lercher, Johannes A.

    2014-01-07

    The catalytic conversion of cyclohexanol on zeolite HBEA in hot liquid water leads to dehydration as well as alkylation products. A novel micro autoclave suitable for application in MAS NMR at high temperatures and pressures is developed and successfully applied to obtain new insight into the mechanistic pathway leading to an understanding of the reactions under selected experimental conditions.

  19. CHANGES IN PROTEIN AND STARCH CONFORMATION DURING VARIABLE TEMPERATURE PARBOILING OF RICE: FT-RAMAN AND 13C CP-MAS NMR SPECTROSCOPIC ASSESSMENT

    Technology Transfer Automated Retrieval System (TEKTRAN)

    FT-Raman and solid-state 13C cross polarization magic-angle spinning (CP-MAS) NMR spectroscopies were employed to assess the conformational changes to protein and starch in paddy rice under variable conditions of parboiling. Rice variety, TOX 3108 from Ghana, was parboiled by the soaking-steaming-d...

  20. FT-RAMAN AND 13C CP-MAS NMR SPECTROSCOPIC ASSESSMENT OF CONFORMATIONAL CHANGES IN PROTEIN AND STARCH UNDER VARIOUS PARABOILING CONDITIONS FOR RICE

    Technology Transfer Automated Retrieval System (TEKTRAN)

    FT-Raman and solid-state 13C CP-MAS NMR spectroscopies were employed to assess the conformational changes to protein and starch in rice under variable conditions of parboiling. TOX 3108 rice from Ghana, was parboiled by the soaking-steaming-drying method under conditions that mimicked various local...

  1. Hydration properties and phosphorous speciation in native, gelatinized and enzymatically modified potato starch analyzed by solid-state MAS NMR.

    PubMed

    Larsen, Flemming H; Kasprzak, Mirosław M; Lærke, Helle N; Knudsen, Knud Erik B; Pedersen, Sven; Jørgensen, Anne S; Blennow, Andreas

    2013-09-12

    Hydration of granular, gelatinized and molecularly modified states of potato starch in terms of molecular mobility were analyzed by (13)C and (31)P solid-state MAS NMR. Gelatinization (GEL) tremendously reduced the immobile fraction compared to native (NA) starch granules. This effect was enhanced by enzyme-assisted catalytic branching with branching enzyme (BE) or combined BE and β-amylase (BB) catalyzed exo-hydrolysis. Carbons of the glycosidic α-1,6 linkages required high hydration rates before adopting uniform chemical shifts indicating solid-state disorder and poor water accessibility. Comparative analysis of wheat and waxy maize starches demonstrated that starches were similar upon gelatinization independent of botanical origin and that the torsion angles of the glycosidic linkages were averages of the crystalline A and B type structures. In starch suspension phosphorous in immobile regions was only observed in NA starch. Moreover phosphorous was observed in a minor pH-insensitive form and as major phosphate in hydrated GEL and BE starches. PMID:23911477

  2. Line shapes and widths of MAS sidebands for 27Al satellite transitions. multinuclear MAS NMR of tugtupite Na8Al2Be2Si8O24Cl2.

    PubMed

    Skibsted, J; Norby, P; Bildsøe, H; Jakobsen, H J

    1995-12-01

    A multinuclear 9Be, 23Na, 27Al, and 29Si magic-angle spinning (MAS) NMR study has been performed for the mineral tugtupite (Na8Al2Be2Si8O24Cl2). The extremely well-resolved spectra allow observation of separate spinning sidebands (ssb's) from the inner (+/- 1/2, +/- 3/2) and outer (+/- 3/2, +/- 5/2) 27Al satellite transitions, and are utilized in a detailed analysis of the line shapes and widths of the individual ssb's from simulations. The line widths of the ssb's from the inner and outer 27Al satellite transitions are found to decrease systematically with increasing order of the ssb's across the spectrum. Accurate values for the 9Be, 23Na, and 27Al quadrupole coupling parameters and isotropic chemical shifts are obtained from simulations of the manifolds of ssb's from the satellite transitions. MAS NMR of the 9Be satellite transitions for tugtupite, BeO, and beryl(Al2Be3Si6O18) shows that these transitions are particularly useful for determination of 9Be quadrupole couplings because of the small 9Be quadrupole moment. The 29Si shielding anisotropy of delta sigma = 48 ppm in tugtupite is the largest determined so far for a framework SiO4 tetrahedron. Finally, the crystal structure of the tugtupite sample has been refined by single-crystal X-ray diffraction, and correlations between the multinuclear NMR parameters and structural data are reported. PMID:9053115

  3. Identification of Li-Ion Battery SEI Compounds through (7)Li and (13)C Solid-State MAS NMR Spectroscopy and MALDI-TOF Mass Spectrometry.

    PubMed

    Huff, Laura A; Tavassol, Hadi; Esbenshade, Jennifer L; Xing, Wenting; Chiang, Yet-Ming; Gewirth, Andrew A

    2016-01-13

    Solid-state (7)Li and (13)C MAS NMR spectra of cycled graphitic Li-ion anodes demonstrate SEI compound formation upon lithiation that is followed by changes in the SEI upon delithiation. Solid-state (13)C DPMAS NMR shows changes in peaks associated with organic solvent compounds (ethylene carbonate and dimethyl carbonate, EC/DMC) upon electrochemical cycling due to the formation of and subsequent changes in the SEI compounds. Solid-state (13)C NMR spin-lattice (T1) relaxation time measurements of lithiated Li-ion anodes and reference poly(ethylene oxide) (PEO) powders, along with MALDI-TOF mass spectrometry results, indicate that large-molecular-weight polymers are formed in the SEI layers of the discharged anodes. MALDI-TOF MS and NMR spectroscopy results additionally indicate that delithiated anodes exhibit a larger number of SEI products than is found in lithiated anodes. PMID:26653886

  4. Laser-supported high-temperature MAS NMR for time-resolved in situ studies of reaction steps in heterogeneous catalysis.

    PubMed

    Ernst, H; Freude, D; Mildner, T; Wolf, I

    1996-04-01

    The temperature of zeolite samples containing various adsorbed molecules was rapidly changed (within 15 s) from room temperature to 600 K by means of a laser beam. The location of the sealed glass ampoule in a boron nitride container decreases the temperature gradient in the sample and avoids laser-induced reactions. The technique facilitates time-dependent magic-angle-spinning (MAS) NMR spectroscopy of high-temperature reactions which take place within 60 s. The H-D exchange in the hydrogen form of zeolites loaded with fully deuterated molecules, the methanol-to-gasoline conversion and the catalytic ethylbenzene disproportionation in zeolites were monitored by 13C and 1H MAS NMR by means of a "stop and go" method. PMID:8784954

  5. Advancements in natural abundance solid-state 33S MAS NMR: characterization of transition-metal M=S bonds in ammonium tetrathiometallates.

    PubMed

    Jakobsen, Hans J; Hove, Anders R; Bildsøe, Henrik; Skibsted, Jørgen; Brorson, Michael

    2007-04-28

    We report the first (33)S chemical shift anisotropy (CSA) data as obtained from a combined determination of (33)S CSA and quadrupole coupling parameters utilizing the observation of both the (33)S (I = 3/2) central and satellite transitions in a natural abundance (33)S MAS NMR study aimed at characterizing the two important tetrathiometallates (NH4)(2)MoS(4) and (NH4)(2)WS(4). PMID:17530082

  6. Synthesis, characterization, and {sup 1}H and {sup 71}Ga MAS NMR spectroscopy of a novel Mg/Ga double layered hydroxide

    SciTech Connect

    Aramendia, M.A.; Borau, V.; Jimenez, C.

    1997-06-01

    A new brucite-like layered Mg/Ga double hydroxide (LDH) of composition [Mg{sub 0.174}Ga{sub 0.256}(OH){sub 2}](CO{sub 3}){sub 0}.134 {center_dot}mH{sub 2}O was synthesized by coprecipitation at pH 10. The hydroxide and the mixed oxides resulting from its thermal decomposition at 523, 823 and 1073K were characterized by X-ray diffraction, diffuse reflectance infrared spectroscopy, high-resolution solid-state nuclear magnetic resonance (MAS NMR), and thermogravimetric analysis. The surface properties of the solid (specific surface) and its basicity were also determined. The Mg /Ga LDH was found to be stable up to 523 K and to decompose into a mixture of periclase MgO and amorphous Ga{sub 2}O{sub 3} at 823 K. Its changes with temperature were monitored by using {sup 1}H and {sup 71}Ga MAS NMR; {sup 1}H MAS NMR spectra revealed the loss of interlayer OH groups supporting the brucite-like structure on calcination at 823 K.

  7. Sensitivity enhancement in natural-abundance solid-state 33S MAS NMR spectroscopy employing adiabatic inversion pulses to the satellite transitions.

    PubMed

    Hansen, Michael Ryan; Brorson, Michael; Bildsøe, Henrik; Skibsted, Jørgen; Jakobsen, Hans J

    2008-02-01

    The WURST (wideband uniform rate smooth truncation) and hyperbolic secant (HS) pulse elements have each been employed as pairs of inversion pulses to induce population transfer (PT) between the four energy levels in natural abundance solid-state (33)S (spin I=3/2) MAS NMR, thereby leading to a significant gain in intensity for the central transition (CT). The pair of inversion pulses are applied to the satellite transitions for a series of inorganic sulfates, the sulfate ions in the two cementitious materials ettringite and thaumasite, and the two tetrathiometallates (NH(4))(2)WS(4) and (NH(4))(2)MoS(4). These materials all exhibit (33)S quadrupole coupling constants (C(Q)) in the range 0.1-1.0 MHz, with precise C(Q) values being determined from analysis of the PT enhanced (33)S MAS NMR spectra. The enhancement factors for the WURST and HS elements are quite similar and are all in the range 1.74-2.25 for the studied samples, in excellent agreement with earlier reports on HS enhancement factors (1.6-2.4) observed for other spin I=3/2 nuclei with similar C(Q) values (0.3-1.2 MHz). Thus, a time saving in instrument time by a factor up to five has been achieved in natural abundance (33)S MAS NMR, a time saving which is extremely welcome for this important low-gamma nucleus. PMID:18082436

  8. Identification of lithium-sulfur battery discharge products through 6Li and 33S solid-state MAS and 7Li solution NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Huff, Laura A.; Rapp, Jennifer L.; Baughman, Jessi A.; Rinaldi, Peter L.; Gewirth, Andrew A.

    2015-01-01

    6Li and 33S solid-state magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy was used to identify the discharge products in lithium-sulfur (Li-S) battery cathodes. Cathodes were stopped at different potentials throughout battery discharge and measured ex-situ to obtain chemical shifts and T2 relaxation rates of the products formed. The chemical shifts in the spectra of both 6Li and 33S NMR demonstrate that long-chain, soluble lithium polysulfide species formed at the beginning of discharge are indistinguishable from each other (similar chemical shifts), while short-chain, insoluble polysulfide species that form at the end of discharge (presumably Li2S2 and Li2S) have a different chemical shift, thus distinguishing them from the soluble long-chain products. T2 relaxation measurements of discharged cathodes were also performed which resulted in two groupings of T2 rates that follow a trend and support the previous conclusions that long-chain polysulfide species are converted to shorter chain species during discharge. Through the complementary techniques of 1-D 6Li and 33S solid-state MAS NMR spectroscopy, solution 7Li and 1H NMR spectroscopy, and T2 relaxation rate measurements, structural information about the discharge products of Li-S batteries is obtained.

  9. A spectrometer designed for 6.7 and 14.1 T DNP-enhanced solid-state MAS NMR using quasi-optical microwave transmission

    NASA Astrophysics Data System (ADS)

    Pike, Kevin J.; Kemp, Thomas F.; Takahashi, Hiroki; Day, Robert; Howes, Andrew P.; Kryukov, Eugeny V.; MacDonald, James F.; Collis, Alana E. C.; Bolton, David R.; Wylde, Richard J.; Orwick, Marcella; Kosuga, Kosuke; Clark, Andrew J.; Idehara, Toshitaka; Watts, Anthony; Smith, Graham M.; Newton, Mark E.; Dupree, Ray; Smith, Mark E.

    2012-02-01

    A Dynamic Nuclear Polarisation (DNP) enhanced solid-state Magic Angle Spinning (MAS) NMR spectrometer operating at 6.7 T is described and demonstrated. The 187 GHz TE13 fundamental mode of the FU CW VII gyrotron is used as the microwave source for this magnetic field strength and 284 MHz 1H DNP-NMR. The spectrometer is designed for use with microwave frequencies up to 395 GHz (the TE16 second-harmonic mode of the gyrotron) for DNP at 14.1 T (600 MHz 1H NMR). The pulsed microwave output from the gyrotron is converted to a quasi-optical Gaussian beam using a Vlasov antenna and transmitted to the NMR probe via an optical bench, with beam splitters for monitoring and adjusting the microwave power, a ferrite rotator to isolate the gyrotron from the reflected power and a Martin-Puplett interferometer for adjusting the polarisation. The Gaussian beam is reflected by curved mirrors inside the DNP-MAS-NMR probe to be incident at the sample along the MAS rotation axis. The beam is focussed to a ˜1 mm waist at the top of the rotor and then gradually diverges to give much more efficient coupling throughout the sample than designs using direct waveguide irradiation. The probe can be used in triple channel HXY mode for 600 MHz 1H and double channel HX mode for 284 MHz 1H, with MAS sample temperatures ⩾85 K. Initial data at 6.7 T and ˜1 W pulsed microwave power are presented with 13C enhancements of 60 for a frozen urea solution (1H-13C CP), 16 for bacteriorhodopsin in purple membrane (1H-13C CP) and 22 for 15N in a frozen glycine solution (1H-15N CP) being obtained. In comparison with designs which irradiate perpendicular to the rotation axis the approach used here provides a highly efficient use of the incident microwave beam and an NMR-optimised coil design.

  10. A spectrometer designed for 6.7 and 14.1 T DNP-enhanced solid-state MAS NMR using quasi-optical microwave transmission.

    PubMed

    Pike, Kevin J; Kemp, Thomas F; Takahashi, Hiroki; Day, Robert; Howes, Andrew P; Kryukov, Eugeny V; MacDonald, James F; Collis, Alana E C; Bolton, David R; Wylde, Richard J; Orwick, Marcella; Kosuga, Kosuke; Clark, Andrew J; Idehara, Toshitaka; Watts, Anthony; Smith, Graham M; Newton, Mark E; Dupree, Ray; Smith, Mark E

    2012-02-01

    A Dynamic Nuclear Polarisation (DNP) enhanced solid-state Magic Angle Spinning (MAS) NMR spectrometer operating at 6.7 T is described and demonstrated. The 187 GHz TE(13) fundamental mode of the FU CW VII gyrotron is used as the microwave source for this magnetic field strength and 284 MHz (1)H DNP-NMR. The spectrometer is designed for use with microwave frequencies up to 395 GHz (the TE(16) second-harmonic mode of the gyrotron) for DNP at 14.1T (600 MHz (1)H NMR). The pulsed microwave output from the gyrotron is converted to a quasi-optical Gaussian beam using a Vlasov antenna and transmitted to the NMR probe via an optical bench, with beam splitters for monitoring and adjusting the microwave power, a ferrite rotator to isolate the gyrotron from the reflected power and a Martin-Puplett interferometer for adjusting the polarisation. The Gaussian beam is reflected by curved mirrors inside the DNP-MAS-NMR probe to be incident at the sample along the MAS rotation axis. The beam is focussed to a ~1 mm waist at the top of the rotor and then gradually diverges to give much more efficient coupling throughout the sample than designs using direct waveguide irradiation. The probe can be used in triple channel HXY mode for 600 MHz (1)H and double channel HX mode for 284 MHz (1)H, with MAS sample temperatures ≥85 K. Initial data at 6.7 T and ~1 W pulsed microwave power are presented with (13)C enhancements of 60 for a frozen urea solution ((1)H-(13)C CP), 16 for bacteriorhodopsin in purple membrane ((1)H-(13)C CP) and 22 for (15)N in a frozen glycine solution ((1)H-(15)N CP) being obtained. In comparison with designs which irradiate perpendicular to the rotation axis the approach used here provides a highly efficient use of the incident microwave beam and an NMR-optimised coil design. PMID:22218011

  11. Rapid quantification of starch molecular order through multivariate modelling of (13)C CP/MAS NMR spectra.

    PubMed

    Flanagan, Bernadine M; Gidley, Michael J; Warren, Frederick J

    2015-10-14

    A partial least squares model has been generated enabling the rapid assessment of ordered molecular structure in a semi-crystalline polymer, starch, directly from solid state NMR spectra. Solid state NMR spectroscopy offers many advantages over conventional analysis tools being non-destructive and functional in complex mixtures. PMID:26299429

  12. Structure determination of uniformly (13)C, (15)N labeled protein using qualitative distance restraints from MAS solid-state (13)C-NMR observed paramagnetic relaxation enhancement.

    PubMed

    Tamaki, Hajime; Egawa, Ayako; Kido, Kouki; Kameda, Tomoshi; Kamiya, Masakatsu; Kikukawa, Takashi; Aizawa, Tomoyasu; Fujiwara, Toshimichi; Demura, Makoto

    2016-01-01

    Magic angle spinning (MAS) solid-state nuclear magnetic resonance (NMR) is a powerful method for structure determination of insoluble biomolecules. However, structure determination by MAS solid-state NMR remains challenging because it is difficult to obtain a sufficient amount of distance restraints owing to spectral complexity. Collection of distance restraints from paramagnetic relaxation enhancement (PRE) is a promising approach to alleviate this barrier. However, the precision of distance restraints provided by PRE is limited in solid-state NMR because of incomplete averaged interactions and intermolecular PREs. In this report, the backbone structure of the B1 domain of streptococcal protein G (GB1) has been successfully determined by combining the CS-Rosetta protocol and qualitative PRE restraints. The derived structure has a Cα RMSD of 1.49 Å relative to the X-ray structure. It is noteworthy that our protocol can determine the correct structure from only three cysteine-EDTA-Mn(2+) mutants because this number of PRE sites is insufficient when using a conventional structure calculation method based on restrained molecular dynamics and simulated annealing. This study shows that qualitative PRE restraints can be employed effectively for protein structure determination from a limited conformational sampling space using a protein fragment library. PMID:26728076

  13. Obtaining aluminas from the thermal decomposition of their different precursors: An {sup 27}Al MAS NMR and X-ray powder diffraction studies

    SciTech Connect

    Chagas, L.H.; De Carvalho, G.S.G.; San Gil, R.A.S.; Chiaro, S.S.X.; Leitão, A.A.; Diniz, R.

    2014-01-01

    Graphical abstract: - Highlights: • We synthesized three precursors of alumina from different methods. • The calcination of the precursors generated several alumina polymorphs. • XRD and NMR were used for structural investigation of the polymorphs. • The synthesis route determines the structural and textural properties of the solids. - Abstract: A commercial sample of Boehmite was used as precursor of alumina polymorphs. For comparison, three other precursors were synthesized from different methods. Particularly, the use of excess of urea promoted a very crystalline form of basic aluminum carbonate. The characteristics of the four precursors were investigated by thermal, vibrational and X-ray powder diffraction (XRD) analysis. Additionally, the nuclear magnetic resonance, with magic angle spinning ({sup 27}Al MAS NMR), was used to verify the coordination of aluminum cations. Each precursor was calcined at various temperatures generating alumina polymorphs, which were structurally analyzed by XRD and {sup 27}Al MAS NMR. Due to interest in catalysis supports, special attention was given to the ?-Al{sub 2}O{sub 3} phase, which in addition to structural investigation was subjected to textural analysis. The results showed that, from different synthesis procedures and common route of calcination, one can obtain materials with the same composition but with different structural and textural properties, which in turn can significantly influence the performance of a supported catalyst.

  14. FTIR and 1H MAS NMR investigations on the correlation between the frequency of stretching vibration and the chemical shift of surface OH groups of solids

    NASA Astrophysics Data System (ADS)

    Brunner, Eike; Karge, H. G.; Pfeifer, H.

    1992-03-01

    The study of surface hydroxyl groups of solids, especially of zeolites, belongs to the 'classical' topics of IR spectroscopy since physico-chemical information may be derived from the wavenumber (nu) OH of the stretching vibration of the different hydroxyls. On the other hand, the last decade has seen the development of high resolution solid-state NMR spectroscopy and through the use of the so-called magic-angle-spinning technique (MAS) the signals of different hydroxyl species can be resolved in the 1H NMR spectra of solids. The chemical shift (delta) H describing the position of these lines may be used as well as (nu) OH to characterize quantitatively the strength of acidity of surface OH groups of solids. In a first comparison of (nu) OH with (delta) H for several types of surface OH groups, a linear correlation between them could be found. The aim of this paper was to prove the validity of this correlation for a wide variety of hydroxyls. The IR measurements were carried out on a Perkin-Elmer FTIR spectrometer 1800 at the Fritz Haber Institute of the Max Planck Society, Berlin, and the 1H MAS NMR spectra were recorded on a Bruker MSL- 300 at the University of Leipzig.

  15. Solid-state single and triple-quantum 93Nb MAS NMR studies of ferroelectric Pb(Mg1/3Nb2/3)O3 and a related pyrochlore.

    PubMed

    Cruz, L P; Rocha, J; Pedrosa de Jesus, J D; Savariault, J M; Galy, J

    1999-12-01

    Pb(Mg1/3Nb2/3)O3 (PMN), a well-known relaxor ferroelectric material, and a related pyrochlore phase have been studied by single- and triple-quantum 93Nb MAS NMR spectroscopy. The assignment of the NMR resonances has been attempted. PMID:10672939

  16. Action Spectroscopy on Dense Samples of Photosynthetic Reaction Centers of Rhodobacter sphaeroides WT Based on Nanosecond Laser-Flash C Photo-CIDNP MAS NMR.

    PubMed

    Daviso, Eugenio; Diller, Anna; Gast, Peter; Alia, A; Lugtenburg, Johan; Müller, Marc G; Matysik, Jörg

    2010-03-01

    Photochemically induced dynamic nuclear polarization magic-angle spinning nuclear magnetic resonance (photo-CIDNP MAS NMR) allows for the investigation of the electronic structure of the photochemical machinery of photosynthetic reaction centers (RCs) at atomic resolution. For such experiments, either continuous radiation from white xenon lamps or green laser pulses are applied to optically dense samples. In order to explore their optical properties, optically thick samples of isolated and quinone-removed RCs of the purple bacteria of Rhodobacter sphaeroides wild type are studied by nanosecond laser-flash (13)C photo-CIDNP MAS NMR using excitation wavelengths between 720 and 940 nm. Action spectra of both the transient nuclear polarization as well as the nuclear hyperpolarization, remaining in the electronic ground state at the end of the photocycle, are obtained. It is shown that the signal intensity is limited by the amount of accessible RCs and that the different mechanisms of the photo-CIDNP production rely on the same photophysical origin, which is the photocycle induced by one single photon. PMID:20208980

  17. New opportunities in acquisition and analysis of natural abundance complex solid-state 33S MAS NMR spectra: (CH3NH3)2WS4.

    PubMed

    Jakobsen, Hans J; Bildsøe, Henrik; Skibsted, Jørgen; Brorson, Michael; Srinivasan, Bikshandarkoil R; Näther, Christian; Bensch, Wolfgang

    2009-08-28

    Population transfer from the satellite transitions to the central transition in solid-state (33)S MAS NMR, employing WURST inversion pulses, has led to detection of the most complex (33)S MAS NMR spectrum observed so far. The spectrum is that of (CH(3)NH(3))(2)WS(4) and consists of three sets of overlapping resonances for the three non-equivalent S atoms, in accord with its crystal structure. It has been fully analyzed in terms of three sets of (33)S quadrupole coupling and anisotropic/isotropic chemical shift parameters along with their corresponding set of three Euler angles describing the relative orientation of the tensors for these two interactions. The three sets of spectral parameters have been assigned to the three different sulfur sites in (CH(3)NH(3))(2)WS(4) by relating the changes observed for the spectral parameters to the changes in crystal structures in a comparison with the corresponding data for the isostructural (NH(4))(2)WS(4) analog. PMID:19652832

  18. Characterization of humic and fulvic acids extracted from landfill by elemental composition, 13C CP/MAS NMR and TMAH-Py-GC/MS.

    PubMed

    Xiaoli, Chai; Shimaoka, Takayuki; Qiang, Guo; Youcai, Zhao

    2008-01-01

    Humic acid (HA) and fulvic acid (FA) extracted from landfills at different landfill ages were characterized by elemental composition, (13)C CP/MAS NMR, and TMAH-Py-GC/MS. The elemental composition analysis revealed high O/C and low H/C ratios in the FA, indicating a high proportion of O-alkyl and carboxylic acids in the FA. The analytical results of (13)C CP/MAS NMR suggested that there were more oxygenated aliphatic carbons and fewer aromatic carbons in FA than in HA. The Py-GC/MS products showed that the HA and FA extracted from the refuse in the landfill were mainly composed of various lignin-derived compounds. Oxidized aromatic acid derivatives originated from the oxidation of side-chains of lignin-like compounds, and this process played a significant role in the process of HA and FA formation in the landfill. All of the results demonstrated that the degree of humification increased with landfill age. PMID:17376666

  19. Low-power broadband homonuclear dipolar recoupling in MAS NMR by two-fold symmetry pulse schemes for magnetization transfers and double-quantum excitation.

    PubMed

    Teymoori, Gholamhasan; Pahari, Bholanath; Edén, Mattias

    2015-12-01

    We provide an experimental, numerical, and high-order average Hamiltonian evaluation of an open-ended series of homonuclear dipolar recoupling sequences, SR [Formula: see text] with p=1,2,3,…. While operating at a very low radio-frequency (rf) power, corresponding to a nutation frequency of 1/2 of the magic-angle spinning (MAS) rate (?nut=?r/2), these recursively generated double-quantum (2Q) dipolar recoupling schemes offer a progressively improved compensation to resonance offsets and rf inhomogeneity for increasing pulse-sequence order p. The excellent recoupling robustness to these experimental obstacles, as well as to CSA, is demonstrated for 2Q filtering (2QF) experiments and for driving magnetization transfers in 2D NMR correlation spectroscopy, where the sequences may provide either double or zero quantum dipolar Hamiltonians during mixing. Experimental and numerical demonstrations, which mostly target conditions of "ultra-fast" MAS (?50kHz) and high magnetic fields, are provided for recoupling of (13)C across a wide range of isotropic and anisotropic chemical shifts, as well as dipolar coupling constants, encompassing [2,3-(13)C2]alanine, [1,3-(13)C2]alanine, diammonium [1,4-(13)C2]fumarate, and [U-(13)C]tyrosine. When compared at equal power levels, a superior performance is observed for the SR [Formula: see text] sequences with p?3 relative to existing and well-established 2Q recoupling techniques. At ultra-fast MAS, proton decoupling is redundant during the homonuclear dipolar recoupling of dilute spins in organic solids, which renders the family of SR [Formula: see text] schemes the first efficient 2Q recoupling option for general applications, such as 2Q-1Q correlation NMR and high-order multiple-quantum excitation, under truly low-power rf conditions. PMID:26515279

  20. Low-power broadband homonuclear dipolar recoupling in MAS NMR by two-fold symmetry pulse schemes for magnetization transfers and double-quantum excitation

    NASA Astrophysics Data System (ADS)

    Teymoori, Gholamhasan; Pahari, Bholanath; Edén, Mattias

    2015-12-01

    We provide an experimental, numerical, and high-order average Hamiltonian evaluation of an open-ended series of homonuclear dipolar recoupling sequences, SR2 2p 1 with p = 1, 2, 3, … . While operating at a very low radio-frequency (rf) power, corresponding to a nutation frequency of 1/2 of the magic-angle spinning (MAS) rate (?nut =?r / 2), these recursively generated double-quantum (2Q) dipolar recoupling schemes offer a progressively improved compensation to resonance offsets and rf inhomogeneity for increasing pulse-sequence order p. The excellent recoupling robustness to these experimental obstacles, as well as to CSA, is demonstrated for 2Q filtering (2QF) experiments and for driving magnetization transfers in 2D NMR correlation spectroscopy, where the sequences may provide either double or zero quantum dipolar Hamiltonians during mixing. Experimental and numerical demonstrations, which mostly target conditions of "ultra-fast" MAS (?50 kHz) and high magnetic fields, are provided for recoupling of 13C across a wide range of isotropic and anisotropic chemical shifts, as well as dipolar coupling constants, encompassing [2,3-13C2 ]alanine, [1,3-13C2 ]alanine, diammonium [1,4-13C2 ]fumarate, and [U-13 C]tyrosine. When compared at equal power levels, a superior performance is observed for the SR2p 1 sequences with p ? 3 relative to existing and well-established 2Q recoupling techniques. At ultra-fast MAS, proton decoupling is redundant during the homonuclear dipolar recoupling of dilute spins in organic solids, which renders the family of SR2p 1 schemes the first efficient 2Q recoupling option for general applications, such as 2Q-1Q correlation NMR and high-order multiple-quantum excitation, under truly low-power rf conditions.

  1. Satellite-Transition MAS NMR of Spin I=3/2, 5/2, 7/2, and 9/2 Nuclei: Sensitivity, Resolution, and Practical Implementation

    NASA Astrophysics Data System (ADS)

    Ashbrook, Sharon E.; Wimperis, Stephen

    2002-06-01

    The satellite-transition MAS (STMAS) experiment offers an alternative approach to established methods such as dynamic angle spinning (DAS), double rotation (DOR), and multiple-quantum MAS (MQMAS) for obtaining high-resolution NMR spectra of half-integer quadrupolar nuclei. Unlike the multiple-quantum experiment, STMAS involves two-dimensional correlation of purely single-quantum coherences; satellite transitions in t1 (or F1) and the central transition in t2 (or F2). To date, STMAS has primarily been demonstrated for nuclei with spin quantum numbers I=3/2 and, to a lesser extent, I>5/2. However, many chemically relevant nuclei possess I>3/2, such as 17O and 27Al (both I=5/2), 59Co ( I=7/2), and 93Nb ( I=9/2). Here, we discuss the application of STMAS to nuclei with spin quantum numbers from I=3/2 to 9/2. First, we consider the practical implementation of the STMAS experiment using 87Rb ( I=3/2) NMR as an example. We then extend the discussion to include nuclei with higher spin quantum numbers, demonstrating 27Al, 45Sc ( I=7/2), 59Co, and 93Nb STMAS experiments on both crystalline and amorphous samples. We also consider the possibility of experiments involving satellite transitions other than mI=±1/2?±3/2 and, using 93Nb NMR, demonstrate the correlation of all single-quantum satellite transitions up to and including mI=±7/2?±9/2. The absolute chemical shift scaling factors in these experiments are discussed, as are the implications for isotropic resolution.

  2. Observation of 1H-13C and 1H-1H proximities in a paramagnetic solid by NMR at high magnetic field under ultra-fast MAS

    NASA Astrophysics Data System (ADS)

    Li, Shenhui; Trébosc, Julien; Lafon, Olivier; Zhou, Lei; Shen, Ming; Pourpoint, Frédérique; Amoureux, Jean-Paul; Deng, Feng

    2015-02-01

    The assignment of NMR signals in paramagnetic solids is often challenging since: (i) the large paramagnetic shifts often mask the diamagnetic shifts specific to the local chemical environment, and (ii) the hyperfine interactions with unpaired electrons broaden the NMR spectra and decrease the coherence lifetime, thus reducing the efficiency of usual homo- and hetero-nuclear NMR correlation experiments. Here we show that the assignment of 1H and 13C signals in isotopically unmodified paramagnetic compounds with moderate hyperfine interactions can be facilitated by the use of two two-dimensional (2D) experiments: (i) 1H-13C correlations with 1H detection and (ii) 1H-1H double-quantum ? single-quantum correlations. These methods are experimentally demonstrated on isotopically unmodified copper (II) complex of L-alanine at high magnetic field (18.8 T) and ultra-fast Magic Angle Spinning (MAS) frequency of 62.5 kHz. Compared to 13C detection, we show that 1H detection leads to a 3-fold enhancement in sensitivity for 1H-13C 2D correlation experiments. By combining 1H-13C and 1H-1H 2D correlation experiments with the analysis of 13C longitudinal relaxation times, we have been able to assign the 1H and 13C signals of each L-alanine ligand.

  3. {sup 13}C chemical shift anisotropies for carbonate ions in cement minerals and the use of {sup 13}C, {sup 27}Al and {sup 29}Si MAS NMR in studies of Portland cement including limestone additions

    SciTech Connect

    Sevelsted, Tine F.; Herfort, Duncan

    2013-10-15

    {sup 13}C isotropic chemical shifts and chemical shift anisotropy parameters have been determined for a number of inorganic carbonates relevant in cement chemistry from slow-speed {sup 13}C MAS or {sup 13}C({sup 1}H) CP/MAS NMR spectra (9.4 T or 14.1 T) for {sup 13}C in natural abundance. The variation in the {sup 13}C chemical shift parameters is relatively small, raising some doubts that different carbonate species in Portland cement-based materials may not be sufficiently resolved in {sup 13}C MAS NMR spectra. However, it is shown that by combining {sup 13}C MAS and {sup 13}C({sup 1}H) CP/MAS NMR carbonate anions in anhydrous and hydrated phases can be distinguished, thereby providing valuable information about the reactivity of limestone in cement blends. This is illustrated for three cement pastes prepared from an ordinary Portland cement, including 0, 16, and 25 wt.% limestone, and following the hydration for up to one year. For these blends {sup 29}Si MAS NMR reveals that the limestone filler accelerates the hydration for alite and also results in a smaller fraction of tetrahedrally coordinated Al incorporated in the C-S-H phase. The latter result is more clearly observed in {sup 27}Al MAS NMR spectra of the cement–limestone blends and suggests that dissolved aluminate species in the cement–limestone blends readily react with carbonate ions from the limestone filler, forming calcium monocarboaluminate hydrate. -- Highlights: •{sup 13}C chemical shift anisotropies for inorganic carbonates from {sup 13}C MAS NMR. •Narrow {sup 13}C NMR chemical shift range (163–171 ppm) for inorganic carbonates. •Anhydrous and hydrated carbonate species by {sup 13}C MAS and {sup 13}C({sup 1}H) CP/MAS NMR. •Limestone accelerates the hydration for alite in Portland – limestone cements. •Limestone reduces the amount of aluminium incorporated in the C-S-H phase.

  4. Correlations between 11B NMR parameters and structural characters in borate and borosilicate minerals investigated by high-resolution MAS NMR and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Zhou, Bing; Sun, Zhaohua; Yao, Yefeng; Pan, Yuanming

    2012-05-01

    Borates consisting of diverse fundamental building blocks (FBB) formed from complex polymerization of planar triangular [B?3] groups and tetrahedral [B?4] groups, where ? = O and OH, provide an excellent opportunity for investigation of correlations between the NMR parameters and local structures. However, previous studies suggested that the 11B NMR parameters in borates are insensitive to local structural environments other than the B coordination number, in contrast to those documented for 29Si, 23Na and 27Al in silicates, and no correlation between 11B chemical shifts and the sum of bond valences has been established for borate minerals with hydroxyl groups or molecular water in the structures. In this study, high-resolution NMR spectra have been acquired at the ultra high field of 21 T as well as at 14 T for selected borate and borosilicate minerals, and have been used to extract high-precision NMR parameters by using combined ab initio theoretical calculations and spectral simulations. These new NMR parameters reveal subtle correlations with various structural characters, especially the effects of the 11B chemical shifts from the bridging oxygen atom(s), site symmetry, symmetry of FBB, the sum of bond valences, as well as the next-nearest-neighbor cations and hydrogen bonding. Also, these results provide new insights into the shielding mechanism for 11B in borate and borosilicate minerals. In particular, this study demonstrates that the small variation in 11B chemical shifts can still be used to probe the local structural environments and that the established correlations can be used to investigate the structural details in borates and amorphous materials.

  5. Constant-time 2D and 3D through-bond correlation NMR spectroscopy of solids under 60 kHz MAS.

    PubMed

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2016-01-21

    Establishing connectivity and proximity of nuclei is an important step in elucidating the structure and dynamics of molecules in solids using magic angle spinning (MAS) NMR spectroscopy. Although recent studies have successfully demonstrated the feasibility of proton-detected multidimensional solid-state NMR experiments under ultrafast-MAS frequencies and obtaining high-resolution spectral lines of protons, assignment of proton resonances is a major challenge. In this study, we first re-visit and demonstrate the feasibility of 2D constant-time uniform-sign cross-peak correlation (CTUC-COSY) NMR experiment on rigid solids under ultrafast-MAS conditions, where the sensitivity of the experiment is enhanced by the reduced spin-spin relaxation rate and the use of low radio-frequency power for heteronuclear decoupling during the evolution intervals of the pulse sequence. In addition, we experimentally demonstrate the performance of a proton-detected pulse sequence to obtain a 3D (1)H/(13)C/(1)H chemical shift correlation spectrum by incorporating an additional cross-polarization period in the CTUC-COSY pulse sequence to enable proton chemical shift evolution and proton detection in the incrementable t1 and t3 periods, respectively. In addition to through-space and through-bond (13)C/(1)H and (13)C/(13)C chemical shift correlations, the 3D (1)H/(13)C/(1)H experiment also provides a COSY-type (1)H/(1)H chemical shift correlation spectrum, where only the chemical shifts of those protons, which are bonded to two neighboring carbons, are correlated. By extracting 2D F1/F3 slices ((1)H/(1)H chemical shift correlation spectrum) at different (13)C chemical shift frequencies from the 3D (1)H/(13)C/(1)H spectrum, resonances of proton atoms located close to a specific carbon atom can be identified. Overall, the through-bond and through-space homonuclear/heteronuclear proximities determined from the 3D (1)H/(13)C/(1)H experiment would be useful to study the structure and dynamics of a variety of chemical and biological solids. PMID:26801026

  6. Constant-time 2D and 3D through-bond correlation NMR spectroscopy of solids under 60 kHz MAS

    NASA Astrophysics Data System (ADS)

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2016-01-01

    Establishing connectivity and proximity of nuclei is an important step in elucidating the structure and dynamics of molecules in solids using magic angle spinning (MAS) NMR spectroscopy. Although recent studies have successfully demonstrated the feasibility of proton-detected multidimensional solid-state NMR experiments under ultrafast-MAS frequencies and obtaining high-resolution spectral lines of protons, assignment of proton resonances is a major challenge. In this study, we first re-visit and demonstrate the feasibility of 2D constant-time uniform-sign cross-peak correlation (CTUC-COSY) NMR experiment on rigid solids under ultrafast-MAS conditions, where the sensitivity of the experiment is enhanced by the reduced spin-spin relaxation rate and the use of low radio-frequency power for heteronuclear decoupling during the evolution intervals of the pulse sequence. In addition, we experimentally demonstrate the performance of a proton-detected pulse sequence to obtain a 3D 1H/13C/1H chemical shift correlation spectrum by incorporating an additional cross-polarization period in the CTUC-COSY pulse sequence to enable proton chemical shift evolution and proton detection in the incrementable t1 and t3 periods, respectively. In addition to through-space and through-bond 13C/1H and 13C/13C chemical shift correlations, the 3D 1H/13C/1H experiment also provides a COSY-type 1H/1H chemical shift correlation spectrum, where only the chemical shifts of those protons, which are bonded to two neighboring carbons, are correlated. By extracting 2D F1/F3 slices (1H/1H chemical shift correlation spectrum) at different 13C chemical shift frequencies from the 3D 1H/13C/1H spectrum, resonances of proton atoms located close to a specific carbon atom can be identified. Overall, the through-bond and through-space homonuclear/heteronuclear proximities determined from the 3D 1H/13C/1H experiment would be useful to study the structure and dynamics of a variety of chemical and biological solids.

  7. Investigation of the Use of Solid State Cp/mas NMR for Characterization of Thermoplastic Polyamides and Unique Thermally Curable Polyamides Containing the Cyclobutene Moiety.

    NASA Astrophysics Data System (ADS)

    Powell, Douglas Graham

    1990-08-01

    A series of model diamides was synthesized from mono- and disubstituted amines with the diacid chloride of cyclobutene-1,2-dicarboxylic acid. Relative rates of thermolysis (by DSC) were dependent on the number and type of substituents. Thermolysis products were Diels-Alder dimers and spontaneously formed polymers. Thermal imidization of cycloadducts was possible in some cases with concomitant oxidation to N, N^'-disubstituted aromatic bisimides. Polyamides were prepared from cyclobutene-1,2 -dicarboxylic acid using low temperature condensation reaction conditions. The unusual solubility characteristics of the diacid as well as the instability of the diacid chloride severely limited formation of high molecular weight polymers. Secondary monomers were synthesized in order to take advantage of the more predictable reactivity of the aromatic carboxyl group. Secondary monomers were polymerized with diamine comonomers using low temperature condensation methods. Solid state ^{13}C CP/MAS NMR confirmed the polymer structure. The thermalized product was found to be insoluble, although swellable, in polar aprotic solvents. Solid state ^{13 }C NMR spectra of the thermal products confirmed crosslinking by intermolecular Diels-Alder cycloaddition. Several important aliphatic polyamides were characterized using high resolution techniques with an emphasis on the ^{15}N nucleus. Chemical shifts from ^{15}N CP/MAS were found to correlate with the alpha and gamma crystal forms found in aliphatic polyamides. This chemical shift difference is rationalized as a conformationally dependent interaction of the amide nitrogen with its substituents. Evidence is presented from molecular orbital calculations which support this theory. Nylon 6 and nylon 11 were synthesized with 20% and 99% ^{15}N enrichment, respectively. ^{15}N CP/MAS of the enriched nylon 6 showed the amorphous region of the polymer for the first time. ^{15 }N relaxation times (T_1, T_1_rho) confirmed the assignment of the crystalline and amorphous regions. The two component decay of the amorphous peak is thought to result from a liquid-like amorphous region and a glassy, noncrystalline "interphase" region. ^{15 }N CP/MAS of nylon 11 was used to observe the delta and delta^ ' crystal forms found in that polymer. Chemical shift anisotropy (CSA) spectra were obtained on the ^{15}N-enriched polyamides. At temperatures above T_{ rm g}, but below the polymer melting point, a narrow peak was observed in the CSA spectra of both polymers corresponding to the mobile amorphous component. Addition of plasticizer (caprolactam) to nylon 6 contributed to this mobility resulting in further narrowing of the amorphous peak.

  8. Structural investigations of PuIII phosphate by X-ray diffraction, MAS-NMR and XANES spectroscopy

    NASA Astrophysics Data System (ADS)

    Popa, Karin; Raison, Philippe E.; Martel, Laura; Martin, Philippe M.; Prieur, Damien; Solari, Pier L.; Bouëxière, Daniel; Konings, Rudy J. M.; Somers, Joseph

    2015-10-01

    PuPO4 was prepared by a solid state reaction method and its crystal structure at room temperature was solved by powder X-ray diffraction combined with Rietveld refinement. High resolution XANES measurements confirm the +III valence state of plutonium, in agreement with valence bond derivation. The presence of the americium (as ?- decay product of plutonium) in the +III oxidation state was determined based on XANES spectroscopy. High resolution solid state 31P NMR agrees with the XANES results and the presence of a solid-solution.

  9. Resolution and measurement of heteronuclear dipolar couplings of a noncrystalline protein immobilized in a biological supramolecular assembly by proton-detected MAS solid-state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Park, Sang Ho; Yang, Chen; Opella, Stanley J.; Mueller, Leonard J.

    2013-12-01

    Two-dimensional 15N chemical shift/1H chemical shift and three-dimensional 1H-15N dipolar coupling/15N chemical shift/1H chemical shift MAS solid-state NMR correlation spectra of the filamentous bacteriophage Pf1 major coat protein show single-site resolution in noncrystalline, intact-phage preparations. The high sensitivity and resolution result from 1H detection at 600 MHz under 50 kHz magic angle spinning using ?0.5 mg of perdeuterated and uniformly 15N-labeled protein in which the exchangeable amide sites are partially or completely back-exchanged (reprotonated). Notably, the heteronuclear 1H-15N dipolar coupling frequency dimension is shown to select among 15N resonances, which will be useful in structural studies of larger proteins where the resonances exhibit a high degree of overlap in multidimensional chemical shift correlation spectra.

  10. Proton-detected MAS NMR experiments based on dipolar transfers for backbone assignment of highly deuterated proteins

    NASA Astrophysics Data System (ADS)

    Chevelkov, Veniamin; Habenstein, Birgit; Loquet, Antoine; Giller, Karin; Becker, Stefan; Lange, Adam

    2014-05-01

    Proton-detected solid-state NMR was applied to a highly deuterated insoluble, non-crystalline biological assembly, the Salmonella typhimurium type iii secretion system (T3SS) needle. Spectra of very high resolution and sensitivity were obtained at a low protonation level of 10-20% at exchangeable amide positions. We developed efficient experimental protocols for resonance assignment tailored for this system and the employed experimental conditions. Using exclusively dipolar-based interspin magnetization transfers, we recorded two sets of 3D spectra allowing for an almost complete backbone resonance assignment of the needle subunit PrgI. The additional information provided by the well-resolved proton dimension revealed the presence of two sets of resonances in the N-terminal helix of PrgI, while in previous studies employing 13C detection only a single set of resonances was observed.

  11. Dipolar Assisted Assignment Protocol (DAAP) for MAS solid-state NMR of Rotationally Aligned Membrane Proteins in Phospholipid Bilayers

    PubMed Central

    Das, Bibhuti B.; Zhang, Hua; Opella, Stanley J.

    2014-01-01

    A method for making resonance assignments in magic angle spinning solid-state NMR spectra of membrane proteins that utilizes the range of hetero-nuclear dipolar coupling frequencies in combination with conventional chemical shift based assignment methods is demonstrated. The dipolar assisted assignment protocol (DAAP) takes advantage of the rotational alignment of the membrane proteins in liquid crystalline phospholipid bilayers. Improved resolution is obtained by combining the magnetically inequivalent heteronuclear dipolar frequencies with isotropic chemical shift frequencies. Spectra with both dipolar and chemical shift frequency axes assist with resonance assignments. DAAP can be readily extended to three- and four- dimensional experiments and to include both backbone and side chain sites in proteins. PMID:24698983

  12. Composite-180° Pulse-Based Symmetry Sequences to Recouple Proton Chemical Shift Anisotropy Tensors under Ultrafast MAS Solid-State NMR Spectroscopy

    PubMed Central

    Pandey, Manoj Kumar; Malon, Michal; Ramamoorthy, Ayyalusamy; Nishiyama, Yusuke

    2015-01-01

    There is considerable interest in the measurement of proton (1H) chemical shift anisotropy (CSA) tensors to obtain deeper insights into H-bonding interactions which find numerous applications in chemical and biological systems. However, the presence of strong 1H/1H dipolar interaction makes it difficult to determine small size 1H CSAs from the homogeneously broadened NMR spectra. Previously reported pulse sequences for 1H CSA recoupling are prone to the effects of radio frequency field (B1) inhomogeneity. In the present work we have carried out a systematic study using both numerical and experimental approaches to evaluate ?-encoded radio frequency (RF) pulse sequences based on R-symmetries that recouple 1H CSA in the indirect dimension of a 2D 1H/1H anisotropic/isotropic chemical shift correlation experiment under ultrafast magic angle spinning (MAS) frequencies. The spectral resolution and sensitivity can be significantly improved in both frequency dimensions of the 2D 1H/1H correlation spectrum without decoupling 1H/1H dipolar couplings but by using ultrafast MAS rates up to 70 kHz. We successfully demonstrate that with a reasonable RF field requirement (< 200 kHz) a set of symmetry-based recoupling sequences, with a series of phase-alternating 270°0-90°180 composite-180° pulses, are more robust in combating B1 inhomogeneity effects. In addition, our results show that the new pulse sequences render remarkable 1H CSA recoupling efficiency and undistorted CSA lineshapes. Experimental results on citric acid and malonic acid comparing the efficiencies of these newly developed pulse sequences with that of previously reported CSA recoupling pulse sequences are also reported under ultrafast MAS conditions. PMID:25497846

  13. Composite-180° pulse-based symmetry sequences to recouple proton chemical shift anisotropy tensors under ultrafast MAS solid-state NMR spectroscopy.

    PubMed

    Pandey, Manoj Kumar; Malon, Michal; Ramamoorthy, Ayyalusamy; Nishiyama, Yusuke

    2015-01-01

    There is considerable interest in the measurement of proton ((1)H) chemical shift anisotropy (CSA) tensors to obtain deeper insights into H-bonding interactions which find numerous applications in chemical and biological systems. However, the presence of strong (1)H/(1)H dipolar interaction makes it difficult to determine small size (1)H CSAs from the homogeneously broadened NMR spectra. Previously reported pulse sequences for (1)H CSA recoupling are prone to the effects of radio frequency field (B1) inhomogeneity. In the present work we have carried out a systematic study using both numerical and experimental approaches to evaluate γ-encoded radio frequency (RF) pulse sequences based on R-symmetries that recouple (1)H CSA in the indirect dimension of a 2D (1)H/(1)H anisotropic/isotropic chemical shift correlation experiment under ultrafast magic angle spinning (MAS) frequencies. The spectral resolution and sensitivity can be significantly improved in both frequency dimensions of the 2D (1)H/(1)H correlation spectrum without decoupling (1)H/(1)H dipolar couplings but by using ultrafast MAS rates up to 70 kHz. We successfully demonstrate that with a reasonable RF field requirement (<200 kHz) a set of symmetry-based recoupling sequences, with a series of phase-alternating 270°0-90°180 composite-180° pulses, are more robust in combating B1 inhomogeneity effects. In addition, our results show that the new pulse sequences render remarkable (1)H CSA recoupling efficiency and undistorted CSA lineshapes. Experimental results on citric acid and malonic acid comparing the efficiencies of these newly developed pulse sequences with that of previously reported CSA recoupling pulse sequences are also reported under ultrafast MAS conditions. PMID:25497846

  14. Composite-180° pulse-based symmetry sequences to recouple proton chemical shift anisotropy tensors under ultrafast MAS solid-state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Pandey, Manoj Kumar; Malon, Michal; Ramamoorthy, Ayyalusamy; Nishiyama, Yusuke

    2015-01-01

    There is considerable interest in the measurement of proton (1H) chemical shift anisotropy (CSA) tensors to obtain deeper insights into H-bonding interactions which find numerous applications in chemical and biological systems. However, the presence of strong 1H/1H dipolar interaction makes it difficult to determine small size 1H CSAs from the homogeneously broadened NMR spectra. Previously reported pulse sequences for 1H CSA recoupling are prone to the effects of radio frequency field (B1) inhomogeneity. In the present work we have carried out a systematic study using both numerical and experimental approaches to evaluate ?-encoded radio frequency (RF) pulse sequences based on R-symmetries that recouple 1H CSA in the indirect dimension of a 2D 1H/1H anisotropic/isotropic chemical shift correlation experiment under ultrafast magic angle spinning (MAS) frequencies. The spectral resolution and sensitivity can be significantly improved in both frequency dimensions of the 2D 1H/1H correlation spectrum without decoupling 1H/1H dipolar couplings but by using ultrafast MAS rates up to 70 kHz. We successfully demonstrate that with a reasonable RF field requirement (<200 kHz) a set of symmetry-based recoupling sequences, with a series of phase-alternating 270°0-90°180 composite-180° pulses, are more robust in combating B1 inhomogeneity effects. In addition, our results show that the new pulse sequences render remarkable 1H CSA recoupling efficiency and undistorted CSA lineshapes. Experimental results on citric acid and malonic acid comparing the efficiencies of these newly developed pulse sequences with that of previously reported CSA recoupling pulse sequences are also reported under ultrafast MAS conditions.

  15. Investigation of the Structure and Active Sites of TiO2 Nanorod Supported VOx Catalysts by High-Field and Fast-Spinning 51V MAS NMR

    SciTech Connect

    Hu, Jian Z.; Xu, Suochang; Li, Weizhen; Hu, Mary Y.; Deng, Xuchu; Dixon, David A.; Vasiliu, Monica; Craciun, Raluca; Wang, Yong; Bao, Xinhe; Peden, Charles HF

    2015-07-02

    Supported VOx/TiO2-Rod catalysts were studied by 51V MAS NMR at high field using a sample spinning rate of 55 kHz. The superior spectral resolution allows for the observation of at least five vanadate species. The assignment of these vanadate species was carried out by quantum mechanical calculations of 51V NMR chemical shifts of model V-surface structures. Methanol oxidative dehydrogenation (ODH) was used to establish the correlation between the reaction rate and the various surface V-sites. It is found that monomeric V-species dominated the catalyst at low vanadium loadings with two peaks observed at about -502 and -529 ppm. V-dimers with two bridged oxygen appeare at about -555 ppm. Vanadate dimers and polyvanadates connected by one bridged oxygen atom between two adjacent V atoms resonate at about -630 ppm. A positive correlation is found between the V-dimers related to the -555 ppm peak and the ODH rate while a better correlation is obtained by including monomeric contributions. This result indicates that surface V-dimers related to the -555 ppm peak are the major active sites for ODH reaction despite mono-V species are more catalytic active but their relative ratios are decreased dramatically at high V-loadings. Furthermore, a portion of the V-species is found invisible. In particular, the level of such invisibility increases with decreased level of V-loading, suggesting the existence of paramagnetic V-species at the surface.

  16. Analysis of mercerization process based on the intensity change of deconvoluted resonances of (13)C CP/MAS NMR: Cellulose mercerized under cooling and non-cooling conditions.

    PubMed

    Miura, Kento; Nakano, Takato

    2015-08-01

    The area intensity change of C1, C4, and C6 in spectrum obtained by (13)C CP/MAS NMR and the mutual relationship between their changes were examined for cellulose samples treated with various concentrations of aqueous NaOH solutions under non-cooling and cooling conditions. The area intensity of C1-up and C6-down changed cooperatively with that of C4-down which corresponds to the crystallinity of samples: "-up" and "-down" are the up- and down- field component in a splitting peak of NMR spectrum, respectively. The intensity change of C1-up starts to decrease with decreasing in that of C4-down after that of C6-down is almost complete. These changes were more clearly observed for samples treated under cooling condition. It can be suggested that their characteristic change relates closely to the change in conformation of cellulose chains by induced decrystallization and the subsequent crystallization of cellulose II, and presumed that their changes at microscopic level relate to the macroscopic morphological changes such as contraction along the length of cellulose chains and recovery along the length. PMID:26042706

  17. Atomic structure and dehydration mechanism of amorphous silica: Insights from 29Si and 1H solid-state MAS NMR study of SiO2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Kim, Hyun Na; Lee, Sung Keun

    2013-11-01

    Detailed knowledge of the atomic structure of hydrous species on surface of amorphous silica and the effect of temperature and particle size on their atomic configurations are essential to understand the nature of fluids-amorphous silicates interactions and the dehydration processes in the amorphous oxides. Here, we report the 29Si, 1H MAS, and 1H-29Si heteronuclear correlation (HetCor) NMR spectra of 7 nm and 14 nm amorphous silica nanoparticles—a model system for natural amorphous silica—where previously unknown details of changes in their atomic structures with varying dehydration temperature and particle size are revealed. Diverse hydroxyl groups with varying atomic configurations and molecular water apparently show distinct dehydration trends. The dehydration (i.e., removal of water) of amorphous silica nanoparticles mostly results in the increase of isolated silanol by removing water molecules from hydrogen-bonded silanols associated water molecules. With further increase in dehydration temperature, the intensity of isolated silanol peak decreases above ˜873 K, suggesting that the condensation of isolated silanol may occur mainly above ˜873 K. The entire dehydration (and dehydroxylation) process completes at ˜1473 K. Both the water (i.e., physisorbed water and hydrogen-bonded water) and hydrogen-bonded silanol species show a dramatic change in the slope of intensity variation at ˜873 K, indicating that most of silanols is hydrogen-bonded to water rather than to other silanols. The fraction of hydrogen-bonded proton species is also much smaller in 14 nm amorphous silica nanoparticles than in 7 nm amorphous silica nanoparticles mainly due to the presences of larger fractions of water and hydrogen-bonded silanol species. 29Si NMR results show that with increasing dehydration temperature, the fraction of Q4 species apparently increases at the expense of Q2 and Q3 species. The fractions of Q2 and Q3 structures in 7 nm amorphous silica nanoparticles are larger than those in 14 nm amorphous silica nanoparticles. Dehydration of 7 nm amorphous silica nanoparticles occurs at a lower temperature than that of 14 nm amorphous silica nanoparticles. 29Si MAS NMR results show that a possible simultaneous dehydroxylation can also occur with removal of the hydrogen bonded silanol in the 7 nm silica nanoparticles. The energy penalty of dehydroxylation estimated from 29Si MAS NMR spectra varies with Q species and is smaller in 7 nm than in 14 nm amorphous silica nanoparticles. These results demonstrate that the particle size of nanoparticles plays an important role in controlling the hydrogen contents, and thus overall hydrogen bond strength of hydroxyl groups and atomic structure of silanols can control dehydroxylation of amorphous silica nanoparticles. The structural information and mechanistic details obtained from the current study provide insights into the structure of hydrous species and dehydration mechanisms in crystalline and amorphous silicates in diverse geological settings, highlighting usually unknown effects of particle size on the dehydration processes.

  18. In situ (1)H and (13)C MAS NMR kinetic study of the mechanism of H/D exchange for propane on zeolite H-ZSM-5.

    PubMed

    Arzumanov, Sergei S; Reshetnikov, Sergei I; Stepanov, Alexander G; Parmon, Valentin N; Freude, Dieter

    2005-10-27

    The kinetics of hydrogen (H/D) exchange between Brønsted acid sites of zeolite H-ZSM-5 and variously deuterated propanes (propane-d(8), propane-1,1,1,3,3,3-d(6), propane-2,2-d(2)) have been monitored in situ by (1)H MAS NMR spectroscopy within the temperature range of 503-556 K. The contribution of intramolecular hydrogen transfer to the H/D exchange in the adsorbed propane was estimated by monitoring the kinetics of (13)C-labeled carbon scrambling in propane-2-(13)C in situ with (13)C MAS NMR at 543-573 K. Possible mechanisms of the exchange have been verified on the basis of the analysis of the variation of protium concentration in both the methyl and the methylene groups of propane in dependence of the reaction time. The main route of the exchange consists of a direct exchange of the acidic OH groups of the zeolite with either the methyl groups or the methylene group presumably with a pentacoordinated carbonium ion intermediate. The assumption that the intramolecular H scrambling between the methyl groups and the methylene group of propane via carbenium-ion-type intermediates is the fastest process among the other possible routes does not account for the experimental kinetics of H/D exchange for propanes with different initial contents and locations of deuterium in a propane molecule. The rate constant (k(3)) for intramolecular H/D exchange between the methyl and the methylene groups is 4-5 times lower compared to those of the direct exchange of both the methyl (k(1)) and the methylene (k(2)) groups with Brønsted acid sites of the zeolite, the k(1) being ca. 1.5 times higher than k(2). At lower temperature (473 K), the exchange is slower, and the expected difference between k(1) and k(2) is more essential, k(1) = 3k(2). This accounts for earlier observed regioselectivity of the exchange for propane on H-ZSM-5 at 473 K. Faster direct exchange with the methyl groups compared to that with the methylene groups was attributed to a possible, more spatial accessibility of the methyl groups for the exchange. Similar activation energies for H and C scramblings with a 2 times more rapid rate of H scrambling was rationalization by the proceeding of these two processes through an isopropyl cation intermediate, as in classical carbenium ion chemistry. PMID:16853554

  19. Effect of organic matter application on CP-MAS-13C-NMR spectra of humic acids from a brown soil

    NASA Astrophysics Data System (ADS)

    Dou, S.

    2009-04-01

    The humified SOM or humic substances (HS) composed of humic acid (HA), fulvic acid (FA) and humin (HM) represent the most microbially recalcitrant and stable reservoir of organic carbon in soil (Piccolo et al., 2004). OM applications can influence the amount and structural characteristics of HS(Dou et al., 2008). During the past few decades, there has been much research on HS, but their chemical structure is still not fully understood (Dong, 2006).CP-MAS-13C-NMR spectroscopy was considered as an effective method to study structures of HS without dissolving problem compared with liquid 13C-NMR (Conte et al., 1997; Dou et al., 2008). It can directly measure the carbon framework and reflect the nature of HS transformation after OM application (Spaccini et al., 2000). For that reason, this method was applied in this study. The objective of this paper was to clarify the effect of long term OM application on the changes of structural characteristics in HAs, which provided new information for improving soil fertility by OM application. The experiment was carried out on a brown soil (Paleudalf in USDA Soil Taxonomy) at Shenyang Agricultural University, Liaoning province, China (N41°48'-E123°25'). The experiment included 3 treatments: zero-treatment (CKbr), and two pig manure (PM) treatments (O1 and O2) at the rates of 0.9 t ha-1 and 1.8 t ha-1 of organic carbon, respectively. The samples of the HA fraction were extracted, separated and purified according to the method described by Dou et al. (1991). Elemental composition, Differential thermal analysis (DTA), -lgK value, FT-IR and CP-MAS- 13C-NMR of HAs were performed. Effects on the contents of orgaic carbon and its composition. The contents of TOC were from 8.77 g kg-1 to 12.25 g kg-1. The relative contents in TOC for WSS, HA, and FA were 6.87%, 14.2% and 19.8%. Comparing the CKbr, the contents of WSS, HA and FA for O1 and O2 increased, but relative contents of WSS and FA decreased. The content of the HA increased after OM application, which was consistent with other studies (Wang et al., 2001). The content of the WSS increased after the OM application indicating that the increase of labile organic carbon. The C/H mole ratio of the HS could reflect the degree of condensation (Dou et al., 1995). Effects on HA chemical and optical properties. The chemical and optical properties of HA were listed. The C/H ratios decreased after OM application, from 0.830 (CKbr) to 0.754 (O2). While ?lgK increased, from 0.623 (CKbr) to 0.658 (O2). The HA structure tended to become simpler. The C/H ratio of the HA decreased after OM application. This indicates that OM application decreased the degree of condensation. The ?lgK values can be used as the index of HA molecule complexity in the soil. If ?lgK increased, the molecular structure becomes simpler. After OM application, ?lgK increased indicating that the molecular structure became simpler. Effects on HA thermal properties. It could be seen that HA had exothermic peaks in moderate and high temperature regions. After OM application, heat (H2) of exothermic peak increased in moderate temperature region, while heat (H3) of exothermic peak decreased in high temperature region. The the heat ratio of exothermic peaks in high temperature region to moderate (H3/H2) decreased. From CKbr to O2, H3/H2 decreased from 4.31 to0.86. The HA had moderate and high temperature exothermic peaks. The heat of exothermic peaks in the moderate temperature region might show that aliphatic compounds decomposed and peripheral functional groups decarboxylated. The heat of the exothermic peaks in the high temperature region might show that the HA was oxidized completely and inter-aromatic structures in the molecule decomposed. The heat ratio of the high to moderate temperature exothermic regions (H3/H2) decreased significantly after PM application, indicating that the proportion of aromatic structure decreased and the HA molecular structure simplified. Effects on CP-MAS-13C-NMR spectrum of HA. The CP-MAS- 13C-NMR spectra of the HA were quite similar to each other

  20. 31P MAS-NMR study of flux-grown rare-earth element orthophosphate (monazite/xenotime) solid solutions: Evidence of random cation distribution from paramagnetically shifted NMR resonances

    SciTech Connect

    Palke, A. C.; Stebbins, J. F.; Boatner, Lynn A

    2013-01-01

    We present 31P magic angle spinning nuclear magnetic resonance (MAS-NMR) spectra of flux-grown solid solutions of La1-xCexPO4 ( x between 0.027 and 0.32) having the monoclinic monazite structure, and of Y1-xMxPO4 (M = Vn+, Ce3+, Nd3+, x between 0.001 and 0.014) having the tetragonal zircon structure. Paramagnetically shifted NMR resonances are observed in all samples due to the presence of paramagnetic Vn+, Ce3+, and Nd3+ in the diamagnetic LaPO4 or YPO4. As a first-order observation, the number and relative intensity of these peaks is related to the symmetry and structure of the diamagnetic host phase. The presence of paramagnetic shifts allows for increased resolution between NMR resonances for distinct atomic species which leads to the observation of low intensity peaks related to PO4 species having more than one paramagnetic neighbor two or four atomic bonds away. Through careful analysis of peak areas and comparison with predictions for simple models, it was determined that solid solutions in the systems examined here are characterized by complete disorder (random distribution) of diamagnetic La3+ or Y3+ with the paramagnetic substitutional species Ce3+ and Nd3+. The increased resolution given by the paramagnetic interactions also leads to the observation of splitting of specific resonances in the 31P NMR spectra that may be caused by local, small-scale distortions from the substitution of ions having dissimilar ionic radii.

  1. I: Low Frequency NMR and NQR Using a dc SQUID. II: Variable-temperature 13C CP/MAS of Organometallics

    SciTech Connect

    Ziegeweid, M.A.

    1995-11-29

    NMR and NQR at low frequencies are difficult prospects due to small nuclear spin polarization. Furthermore, the sensitivity'of the inductive pickup circuitry of standard spectrometers is reduced as the frequency is lowered. I have used a cw-SQUID (Superconducting QUantum Interference Device) spectrometer, which has no such frequency dependence, to study the local atomic environment of {sup 14}N via the quadrupolar interaction. Because {sup 14}N has spin I = 1 and a 0-6 MHz frequency range, it is not possible to obtain well-resolved spectra in high magnetic fields. I have used a technique to observe {sup 14}N NQR resonances via their effect on neighboring protons mediated by the heteronuclear dipolar interaction to study peptides and narcotics. The sensitivity of the SQUID is not enough to measure low-frequency surface (or other low spin density) systems. The application of spin-polarized xenon has been previously used to enhance polarization in conventional NMR experiments. Because xenon only polarizes spins with which it is in contact, it is surface selective. While differences in chemical shifts between surface and bulk spins are not large, it is expected that the differences in quadrupole coupling constant should be very large due to the drastic change of the electric field gradient surrounding spins at the surface. With this in mind, I have taken preliminary steps to measure SQUID detected polarization transfer from Xe to another spin species at 4.2 K and in small magnetic fields (<50 G). In this regime, the spin-lattice relaxation of xenon is dependent on the applied magnetic field. The results of our efforts to characterize the relaxation of xenon are presented. The final section describes the solid-state variable-temperature (VT) one- and two-dimensional {sup 13}C cross polarization (CP)/magic angle spinning (MAS) NMR of Hf({eta}{sup 5}-C{sub 5}H{sub 5}){sub 2}({eta}{sup 1}-C{sub 5}H{sub 5}){sub 2}, Zr({eta}{sup 5}-C{sub 5}H{sub 5}){sub 3}({eta}{sup 1}-C{sub 5}H{sub 5}) and Sn({eta}{sup 1}-C{sub 5}H{sub 5}){sub 4}. This work was undertaken in the hope of gaining insight into the intramolecuhrr dynamics, specifically which fluxional processes exist in the solid state, by what mechanism rearrangements are occurring, and the activation energies by which these processes are governed.

  2. Solid state {sup 31}P MAS NMR spectroscopy and conductivity measurements on NbOPO{sub 4} and H{sub 3}PO{sub 4} composite materials

    SciTech Connect

    Risskov Sørensen, Daniel; Nielsen, Ulla Gro; Skou, Eivind M.

    2014-11-15

    A systematic study of composite powders of niobium oxide phosphate (NbOPO{sub 4}) and phosphoric acid (H{sub 3}PO{sub 4}) has been performed in order to characterize the material's ability to perform as an electrolyte material in medium temperature fuel cells and electrolyzers. Powders of H{sub 3}PO{sub 4} contents between 13.1 and 74.2 M% were produced and characterized with powder X-ray diffraction, {sup 31}P MAS NMR and impedance spectroscopy. NMR revealed that a significant degree of dehydration and vaporization of H{sub 3}PO{sub 4} takes place above 200 °C, and increases with temperature. At 500 °C the NbOPO{sub 4} and H{sub 3}PO{sub 4} has reacted to form niobium pyrophosphate (Nb{sub 2}P{sub 4}O{sub 15}). Impedance spectroscopy showed an increase in conductivity with increasing acid concentration, whereas the conductivity decreased slightly with increasing temperature. The highest conductivity measured was 2.5·10{sup −3} S/cm for a sample containing 74.2 M% of H{sub 3}PO{sub 4}. Lastly, it was shown that NbOPO{sub 4} has no significant conductivity of its own. - Graphical abstract: Conductivity of NbOPO{sub 4}/H{sub 3}PO{sub 4} composites as a function of equivalent P{sub 2}O{sub 5} content. The conductivity is insignificant for pure NbOPO{sub 4}. - Highlights: • Composites have been made from NbOPO{sub 4} and H{sub 3}PO{sub 4}. • The composites composition has been investigated with solid state NMR. • The composites have shown clear signs of acid dehydration upon heating. • The conductivity of the composites increases for increasing acid content. • NbOPO{sub 4} has no significant conductivity of its own.

  3. Analysis of local molecular motions of aromatic sidechains in proteins by 2D and 3D fast MAS NMR spectroscopy and quantum mechanical calculations.

    PubMed

    Paluch, Piotr; Pawlak, Tomasz; Jeziorna, Agata; Trébosc, Julien; Hou, Guangjin; Vega, Alexander J; Amoureux, Jean-Paul; Dracinsky, Martin; Polenova, Tatyana; Potrzebowski, Marek J

    2015-10-28

    We report a new multidimensional magic angle spinning NMR methodology, which provides an accurate and detailed probe of molecular motions occurring on timescales of nano- to microseconds, in sidechains of proteins. The approach is based on a 3D CPVC-RFDR correlation experiment recorded under fast MAS conditions (?R = 62 kHz), where (13)C-(1)H CPVC dipolar lineshapes are recorded in a chemical shift resolved manner. The power of the technique is demonstrated in model tripeptide Tyr-(d)Ala-Phe and two nanocrystalline proteins, GB1 and LC8. We demonstrate that, through numerical simulations of dipolar lineshapes of aromatic sidechains, their detailed dynamic profile, i.e., the motional modes, is obtained. In GB1 and LC8 the results unequivocally indicate that a number of aromatic residues are dynamic, and using quantum mechanical calculations, we correlate the molecular motions of aromatic groups to their local environment in the crystal lattice. The approach presented here is general and can be readily extended to other biological systems. PMID:26451400

  4. Simultaneous cross polarization to 13C and 15N with 1H detection at 60 kHz MAS solid-state NMR

    NASA Astrophysics Data System (ADS)

    Das, Bibhuti B.; Opella, Stanley J.

    2016-01-01

    We describe high resolution MAS solid-state NMR experiments that utilize 1H detection with 60 kHz magic angle spinning; simultaneous cross-polarization from 1H to 15N and 13C nuclei; bidirectional cross-polarization between 13C and 15N nuclei; detection of both amide nitrogen and aliphatic carbon 1H; and measurement of both 13C and 15N chemical shifts through multi-dimensional correlation experiments. Three-dimensional experiments correlate amide 1H and alpha 1H selectively with 13C or 15N nuclei in a polypeptide chain. Two separate three-dimensional spectra correlating 1H?/13C?/1HN and 1HN/15N/1H? are recorded simultaneously in a single experiment, demonstrating that a twofold savings in experimental time is potentially achievable. Spectral editing using bidirectional coherence transfer pathways enables simultaneous magnetization transfers between 15N, 13C?(i) and 13C?(i-1), facilitating intra- and inter-residue correlations for sequential resonance assignment. Non-uniform sampling is integrated into the experiments, further reducing the length of experimental time.

  5. Simultaneous cross polarization to (13)C and (15)N with (1)H detection at 60kHz MAS solid-state NMR.

    PubMed

    Das, Bibhuti B; Opella, Stanley J

    2016-01-01

    We describe high resolution MAS solid-state NMR experiments that utilize (1)H detection with 60kHz magic angle spinning; simultaneous cross-polarization from (1)H to (15)N and (13)C nuclei; bidirectional cross-polarization between (13)C and (15)N nuclei; detection of both amide nitrogen and aliphatic carbon (1)H; and measurement of both (13)C and (15)N chemical shifts through multi-dimensional correlation experiments. Three-dimensional experiments correlate amide (1)H and alpha (1)H selectively with (13)C or (15)N nuclei in a polypeptide chain. Two separate three-dimensional spectra correlating (1)H?/(13)C?/(1)H(N) and (1)H(N)/(15)N/(1)H? are recorded simultaneously in a single experiment, demonstrating that a twofold savings in experimental time is potentially achievable. Spectral editing using bidirectional coherence transfer pathways enables simultaneous magnetization transfers between (15)N, (13)C?(()(i)()) and (13)C'(()(i)(-1)), facilitating intra- and inter-residue correlations for sequential resonance assignment. Non-uniform sampling is integrated into the experiments, further reducing the length of experimental time. PMID:26705905

  6. Effects of solvent concentration and composition on protein dynamics: 13C MAS NMR studies of elastin in glycerol-water mixtures.

    PubMed

    Demuth, Dominik; Haase, Nils; Malzacher, Daniel; Vogel, Michael

    2015-08-01

    We use (13)C CP MAS NMR to investigate the dependence of elastin dynamics on the concentration and composition of the solvent at various temperatures. For elastin in pure glycerol, line-shape analysis shows that larger-scale fluctuations of the protein backbone require a minimum glycerol concentration of ~0.6 g/g at ambient temperature, while smaller-scale fluctuations are activated at lower solvation levels of ~0.2 g/g. Immersing elastin in various glycerol-water mixtures, we observe at room temperature that the protein mobility is higher for lower glycerol fractions in the solvent and, thus, lower solvent viscosity. When decreasing the temperature, the elastin spectra approach the line shape for the rigid protein at 245 K for all studied samples, indicating that the protein ceases to be mobile on the experimental time scale of ~10(-5) s. Our findings yield evidence for a strong coupling between elastin fluctuations and solvent dynamics and, hence, such interaction is not restricted to the case of protein-water mixtures. Spectral resolution of different carbon species reveals that the protein-solvent couplings can, however, be different for side chain and backbone units. We discuss these results against the background of the slaving model for protein dynamics. PMID:25917596

  7. Identifying Inter-Residue Resonances in Crowded 2D 13C-13C Chemical Shift Correlation Spectra of Membrane Proteins by Solid-State MAS NMR Difference Spectroscopy

    PubMed Central

    Miao, Yimin; Cross, Timothy A.; Fu, Riqiang

    2013-01-01

    The feasibility of using difference spectroscopy, i.e. subtraction of two correlation spectra at different mixing times, for substantially enhanced resolution in crowded two-dimensional 13C-13C chemical shift correlation spectra is presented. With the analyses of 13C-13C spin diffusion in simple spin systems, difference spectroscopy is proposed to partially separate the spin diffusion resonances of relatively short intra-residue distances from the longer inter-residue distances, leading to a better identification of the inter-residue resonances. Here solid-state magic-angle-spinning (MAS) NMR spectra of the full length M2 protein embedded in synthetic lipid bilayers have been used to illustrate the resolution enhancement in the difference spectra. The integral membrane M2 protein of Influenza A virus assembles as a tetrameric bundle to form a protonconducting channel that is activated by low pH and is essential for the viral lifecycle. Based on known amino acid resonance assignments from amino acid specific labeled samples of truncated M2 sequences or from time-consuming 3D experiments of uniformly labeled samples, some inter-residue resonances of the full length M2 protein can be identified in the difference spectra of uniformly 13C labeled protein that are consistent with the high resolution structure of the M2 (22–62) protein (Sharma et al. 2010). PMID:23708936

  8. Pseudo-symmetry, rotation- and inversion-twinning of a structure with dinuclear and trinuclear Cd complexes. CP-MAS-NMR and IR spectroscopies characterisation

    NASA Astrophysics Data System (ADS)

    Soudani, Sarra; Zeller, Matthias; Wenger, Emmanuel; Jelsch, Christian; Lefebvre, Frédéric; Nasr, Cherif Ben

    2014-10-01

    The structure of the complex [C18H30Cd3Cl6N18S12·2(C18H30Cd2Cl3N18S12)·CdCl4], or [L6Cd3Cl6·2(L6Cd2Cl3)·CdCl4], with L being 2-amino-5-(methylthio)-1,3,4-thiadiazole, C3H5N3S2, crystallizes in the trigonal polar space group R3. The crystal packing features three chemically distinct cadmium complex species with eight crystallographically independent Cd(II) ions distributed over two types of L ligand complexes with two and three Cd(II) centers, respectively, and a tetrachlorocadmate(II) ion. The coordination environment of the cadmium ions in the dinuclear and trinuclear complexes is a distorted octahedron. The tetrachlorocadmate(II) is disordered around a crystallographic threefold rotation axis, which is, in turn, inducing disorder onto the two methyl-thio groups in closest proximity to a CdCl4 anion. The crystal under investigation was found to be twinned by rotational and inversion merohedry. In the higher symmetry setting, the trinuclear complex would feature exact inversion symmetry, and the two binuclear cationic complexes would be inversion counterparts of each other. The R3bar symmetry is broken by a mismatch of less than 1 Å between one pair of ligands L between the dinuclear cations, which feature slightly different rotational angles around the Cd ion in the otherwise symmetry equivalent complexes. This compound is also investigated by FT-IR and solid-state 13CCP-MAS NMR spectroscopies.

  9. In situ variable-temperature MAS sup 13 C NMR study of the reactions of isobutylene in zeolites HY and HZSM-5

    SciTech Connect

    Lazo, N.D.; Richardson, B.R.; Schettler, P.D.; White, J.L.; Munson, E.J.; Haw, J.F. )

    1991-11-14

    The low-temperature chemistry of isobutylene in zeolites HY and HZSM-5 was probed by in situ variable-temperature {sup 13}C NMR spectroscopy with magic-angle spinning (MAS). Isobutylene interacts with Bronsted acid sites of the zeolites at a temperature of ca. 123 K to form a hydrogen-bonded species, as indicated by 2{sup 13}{Delta}{delta} value (relative to the 2-{sup 13}C resonance of isobutylene) of 12 ppm in HY and a {Delta}{delta} value of 16 ppm in HZSM-5. The greater {Delta}{delta} value observed for hydrogen-bonded isobutylene in HZSM-5 is consistent with the acid sites in HZSM-5 being more acidic than those in HY. The maximum number of hydrogen-bonded species detected did not exceed the number of Bronsted acid sites in the zeolites. As the temperature was raised from 123 K, hydrogen-bonded isobutylene was presumably converted to an unobserved symmetrical intermediate (a tert-butylcarbenium ion) that either underwent deprotonation to re-form isobutylene and the acid site or reacted with another isobutylene molecule to form a dimer. Evidence for this process included scrambling between the 1- and 3-{sup 13}C labels of isobutylene. In all of the spectra obtained by either cross polarization or single-pulse excitation, no peaks were observed that could be assigned to a surface-bound silyl ether species. However, in experiments performed on the 2-methyl-2-propanol-2-{sup 13}C/HZSM-5 system, the formation of a surface-bound tert-butyl silyl ether species was observed, as was reported earlier by another laboratory.

  10. Structural investigations of silicate-phosphate glasses containing MoO3 by FTIR, Raman and 31P MAS NMR spectroscopies.

    PubMed

    Szumera, M

    2014-09-15

    Molybdenum is a transition metal (refers to the "d" block of the periodic table) whose atom has an incomplete d sub-shell. It is known that in silicate glasses molybdenum may exist under four oxidation states: Mo6+, Mo5+, Mo4+ and Mo3+, simultaneously molybdenum cations, depending on their content in the glass network, may either be a glass forming component, or act as a modifier. The contemporary literature data show studies conducted mostly on the structure of silicate, phosphate, borate and borosilicate glasses containing molybdenum ions, but not silicate-phosphate glasses. Therefore, the author has undertaken detailed studies using FTIR, Raman and 31P MAS NMR techniques in order to examine the effect of MoO3 addition into the structure of silicate-phosphate glasses from SiO2P2O5K2OCaOMgO system. On the basis of obtained results it was concluded that molybdenum ions in the analysed glasses act as a modifier, which follows from the gradual breakage of oxygen bridges, i.e. POP, SiOSi, and SiOP, and the following formation of connections such as Mo[MoO4]OSi and/or Mo[MoO4]OP. In summary, it is concluded that the increase of MoO3 content (up to 4.4 mol.%) in the structure of glasses of SiO2P2O5K2OMgOCaO system results in weakening of the structure and gradual increase of the degree of silico-oxygen and phosphor-oxygen frameworks depolymerisation. PMID:24759778

  11. {sup 1}H and {sup 23}Na MAS NMR spectroscopy of cationic species in CO{sub 2} selective alkaline earth metal porous silicoaluminophosphates prepared via liquid and solid state ion exchange

    SciTech Connect

    Arevalo-Hidalgo, Ana G.; Dugar, Sneha; Fu, Riqiang; Hernandez-Maldonado, Arturo J.

    2012-07-15

    The location of extraframework cations in Sr{sup 2+} and Ba{sup 2+} ion-exchanged SAPO-34 was estimated by means of {sup 1}H and {sup 23}Na MAS NMR spectroscopy and spectral deconvolution. Incorporation of the alkaline earth metal cations onto the SAPO framework was achieved via liquid state ion exchange, coupled partial detemplation/solid-state ion exchange, and combination of both techniques. MAS NMR revealed that the level of ion exchange was limited by the presence of protons and sodium cations near hexagonal prisms (site SI), which are relatively difficult to exchange with the alkaline earth metal due to steric and charge repulsion criteria. In addition, the presence of ammonium cations in the supercages facilitated the exchange of otherwise tenacious hydrogen as corroborated by unit cell compositional data as well as enhanced CO{sub 2} adsorption at low partial pressures. The extraframework ammonium species were produced from partial detemplation of the structure-directing agent employed for the SAPO-34 synthesis, tetraethylammonium. - Graphical abstract: MAS NMR was used to elucidate the position the cationic species in alkaline earth metal exchanged silicoaluminophosphates. These species played a significant role during the ion exchange process and, therefore, the materials ultimate CO{sub 2} adsorption performance. Highlights: Black-Right-Pointing-Pointer Location of extraframework Sr{sup 2+} or Ba{sup 2+} cations was estimated by means of {sup 1}H and {sup 23}Na MAS NMR. Black-Right-Pointing-Pointer Level of Sr{sup 2+} or Ba{sup 2+} ion exchange was limited by the presence of protons and sodium cations. Black-Right-Pointing-Pointer Presence of ammonium cations in the supercages facilitated the exchange. Black-Right-Pointing-Pointer Sr{sup 2+} and Ba{sup 2+} ion exchanged SAPOs are outstanding CO{sub 2} adsorbents.

  12. Complete protocol for slow-spinning high-resolution magic-angle spinning NMR analysis of fragile tissues.

    PubMed

    André, Marion; Dumez, Jean-Nicolas; Rezig, Lamya; Shintu, Laetitia; Piotto, Martial; Caldarelli, Stefano

    2014-11-01

    High-resolution magic-angle spinning (HR-MAS) nuclear magnetic resonance (NMR) is an essential tool to characterize a variety of semisolid systems, including biological tissues, with virtually no sample preparation. The "non-destructive" nature of NMR is typically compromised, however, by the extreme centrifugal forces experienced under conventional HR-MAS frequencies of several kilohertz. These features limit the usefulness of current HR-MAS approaches for fragile samples. Here, we introduce a full protocol for acquiring high-quality HR-MAS NMR spectra of biological tissues at low spinning rates (down to a few hundred hertz). The protocol first consists of a carefully designed sample preparation, which yields spectra without significant spinning sidebands at low spinning frequency for several types of sample holders, including the standard disposable inserts classically used in HR-MAS NMR-based metabolomics. Suppression of broad spectral features is then achieved using a modified version of the recently introduced PROJECT experiment with added water suppression and rotor synchronization, which deposits limited power in the sample and which can be suitably rotor-synchronized at low spinning rates. The performance of the slow HR-MAS NMR procedure is demonstrated on conventional (liver tissue) and very delicate (fish eggs) samples, for which the slow-spinning conditions are shown to preserve the structural integrity and to minimize intercompartmental leaks of metabolites. Taken together, these results expand the applicability and reliability of HR-MAS NMR spectroscopy. These results have been obtained at 400 and 600 MHz and suggest that high-quality slow HR-MAS spectra can be expected at higher magnetic fields using the described protocol. PMID:25286333

  13. Deactivation of HDT catalysts by formation of silica gels from silicone oil. Characterization of spent catalysts from HDT of coker naphtha using [sup 29]Si and [sup 13]C CP/MAS NMR

    SciTech Connect

    Kellberg, L.; Jakobsen, H.J. ); Zeuthen, P. )

    1993-09-01

    Catalysts used for hydrotreating of coker naphtha are found to deactivate very quickly because of deposition of Si-containing species on their surface. These species originate from the silicone oil (polydimethylsiloxane) added to the coker unit in order to suppress foaming during the coking process. Six samples of a spent catalyst from a HDT reactor have been analyzed by [sup 29]Si MAS, [sup 29]Si CP/MAS, and [sup 13]C CP/MAS NMR spectroscopy. From these studies it is concluded that the silicone oil in the naphtha feed is transformed (oxidized) to modified silica gels, i.e., silica with a partly methylated surface, under the operating conditions of the catalyst. Physi- or chemisorption of the silica gels on the catalyst explains the fast irreversible loss of activity during HDT of coker naphtha. 23 refs., 3 figs., 2 tabs.

  14. Forensic examination of electrical tapes using high resolution magic angle spinning (1)H NMR spectroscopy.

    PubMed

    Schoenberger, Torsten; Simmross, Ulrich; Poppe, Christian

    2016-01-01

    The application of high resolution magic angle spinning (HR-MAS) (1)H NMR spectroscopy is ideally suited for the differentiation of plastics. In addition to the actual material composition, the different types of polymer architectures and tacticity provide characteristic signals in the fingerprint of the (1)H NMR spectra. The method facilitates forensic comparison, as even small amounts of insoluble but swellable plastic particles are utilized. The performance of HR-MAS NMR can be verified against other methods that were recently addressed in various articles about forensic tape comparison. In this study samples of the 90 electrical tapes already referenced by the FBI laboratory were used. The discrimination power of HR-MAS is demonstrated by the fact that more tape groups can be distinguished by NMR spectroscopy than by using the combined evaluation of several commonly used analytical techniques. An additional advantage of this robust and quick method is the very simple sample preparation. PMID:26558760

  15. Structure of framework aluminum Lewis sites and perturbed aluminum atoms in zeolites as determined by 27Al{1H} REDOR (3Q) MAS NMR spectroscopy and DFT/molecular mechanics.

    PubMed

    Brus, Jiří; Kobera, Libor; Schoefberger, Wolfgang; Urbanová, Martina; Klein, Petr; Sazama, Petr; Tabor, Edyta; Sklenak, Stepan; Fishchuk, Anna V; Dědeček, Jiří

    2015-01-01

    Zeolites are highly important heterogeneous catalysts. Besides Brønsted SiOHAl acid sites, also framework AlFR Lewis acid sites are often found in their H-forms. The formation of AlFR Lewis sites in zeolites is a key issue regarding their selectivity in acid-catalyzed reactions. The local structures of AlFR Lewis sites in dehydrated zeolites and their precursors--"perturbed" AlFR atoms in hydrated zeolites--were studied by high-resolution MAS NMR and FTIR spectroscopy and DFT/MM calculations. Perturbed framework Al atoms correspond to (SiO)3AlOH groups and are characterized by a broad (27)Al NMR resonance (δi = 59-62 ppm, CQ = 5 MHz, and η = 0.3-0.4) with a shoulder at 40 ppm in the (27)Al MAS NMR spectrum. Dehydroxylation of (SiO)3AlOH occurs at mild temperatures and leads to the formation of AlFR Lewis sites tricoordinated to the zeolite framework. Al atoms of these (SiO)3Al Lewis sites exhibit an extremely broad (27)Al NMR resonance (δi ≈ 67 ppm, CQ ≈ 20 MHz, and η ≈ 0.1). PMID:25393612

  16. Silicate-phosphate interactions in silicate glasses and melts: I. A multinuclear ( 27Al, 29Si, 31P) MAS NMR and ab initio chemical shielding ( 31P) study of phosphorous speciation in silicate glasses

    NASA Astrophysics Data System (ADS)

    Cody, George D.; Mysen, Bjorn; Sághi-Szabó, Gotthard; Tossell, John A.

    2001-07-01

    An investigation of the structure of sodium aluminum silicate glasses [composition (x)Na 2O, (1-x)Al 2O 3, 0.9SiO 2 perturbed through the addition of 2 mol.% P 2O 5] was performed using a combination of 27Al, 29Si, and 31P solid state NMR spectroscopy and ab initio chemical shielding calculations (GIAO method). Speciation within these glasses was estimated using a physically consistent method for the deconvolution of inhomogeneously broadened 31P MAS-NMR spectra by employing a combination of spinning sideband analysis with the results of ab initio shielding calculations. A minimum of 13 different phosphorus-bearing species were estimated to contribute to the spectral complexity in these glasses over the compositional range investigated. The majority of these species are oxygen-bridged to the silicate lattice. These are described as (Al,Si)Q pn species, where n corresponds to the number of bridging oxygens ( n = 1-4) and where there is variation in the Al/Si ratio of the tetrahedral nearest neighbors. In addition to the species bridging to the silicate lattice, nonlattice bridged Na-P type species, including ortho-, pyro-, and tripolyphosphates, are observed or deduced based on spectral behavior. A sharp crossover in the predominance of Na-P species relative to (Al,Si) Q pn dominant species occurs at low Al 2O 3 content. Within the group of nonbridging (Na-P) species, increased bulk aluminum content shifts the predominance from orthophosphate toward tripolyphosphate. Within the group of bridging [(Al,Si) Q pn] species, increasing bulk aluminum content shifts the predominance toward a greater number of oxygen bridges to the silicate lattice. To highlight the perturbative effect of 2 mol.% P 2O 5 addition on glass structure, 29Si MAS-NMR of P-bearing and P-absent glasses were compared. The speciation estimated from the combined 31P MAS-NMR and ab initio shielding calculations is consistent with 29Si MAS-NMR spectroscopic data. Analysis of 27Al MAS-NMR spectra for P-bearing and P-absent glasses reveals extensive Al-O-P interactions evident by systematic shifts in peak maxima to lower frequencies (greater shielding). Increases in the central transition peak half widths in the P-bearing samples reflect enhanced second-order quadrupolar interactions, also consistent with an abundance of (Al,Si) Q pn species. Analysis of the 27Al inner satellite transition sidebands reveals only a minor amount of VIAl. It is concluded that the addition of even a small amount of P 2O 5 (2 mol.%) results in a large perturbation of the structure of silicate glasses and should manifest significant effects on the physical properties of melts derived from them.

  17. Discrimination of Basal Cell Carcinoma from Normal Skin Tissue Using High-Resolution Magic Angle Spinning 1H NMR Spectroscopy.

    PubMed

    Mun, Je-Ho; Lee, Heonho; Yoon, Dahye; Kim, Byung-Soo; Kim, Moon-Bum; Kim, Shukmann

    2016-01-01

    High-resolution magic angle spinning nuclear magnetic resonance (HR-MAS NMR) spectroscopy is a useful tool for investigating the metabolism of various cancers. Basal cell carcinoma (BCC) is the most common skin cancer. However, to our knowledge, data on metabolic profiling of BCC have not been reported in the literature. The objective of the present study was to investigate the metabolic profiling of cutaneous BCC using HR-MAS 1H NMR spectroscopy. HR-MAS 1H NMR spectroscopy was used to analyze the metabolite profile and metabolite intensity of histopathologically confirmed BCC tissues and normal skin tissue (NST) samples. The metabolic intensity normalized to the total spectral intensities in BCC and NST was compared, and multivariate analysis was performed with orthogonal partial least-squares discriminant analysis (OPLS-DA). P values < 0.05 were considered statistically significant. Univariate analysis revealed 9 metabolites that showed statistically significant difference between BCC and NST. In multivariate analysis, the OPLS-DA models built with the HR-MAS NMR metabolic profiles revealed a clear separation of BCC from NST. The receiver operating characteristic curve generated from the results revealed an excellent discrimination of BCC from NST with an area under the curve (AUC) value of 0.961. The present study demonstrated that the metabolite profile and metabolite intensity differ between BCC and NST, and that HR-MAS 1H NMR spectroscopy can be a valuable tool in the diagnosis of BCC. PMID:26934749

  18. Discrimination of Basal Cell Carcinoma from Normal Skin Tissue Using High-Resolution Magic Angle Spinning 1H NMR Spectroscopy

    PubMed Central

    Mun, Je-Ho; Lee, Heonho; Yoon, Dahye; Kim, Byung-Soo; Kim, Moon-Bum; Kim, Shukmann

    2016-01-01

    High-resolution magic angle spinning nuclear magnetic resonance (HR-MAS NMR) spectroscopy is a useful tool for investigating the metabolism of various cancers. Basal cell carcinoma (BCC) is the most common skin cancer. However, to our knowledge, data on metabolic profiling of BCC have not been reported in the literature. The objective of the present study was to investigate the metabolic profiling of cutaneous BCC using HR-MAS 1H NMR spectroscopy. HR-MAS 1H NMR spectroscopy was used to analyze the metabolite profile and metabolite intensity of histopathologically confirmed BCC tissues and normal skin tissue (NST) samples. The metabolic intensity normalized to the total spectral intensities in BCC and NST was compared, and multivariate analysis was performed with orthogonal partial least-squares discriminant analysis (OPLS-DA). P values < 0.05 were considered statistically significant. Univariate analysis revealed 9 metabolites that showed statistically significant difference between BCC and NST. In multivariate analysis, the OPLS-DA models built with the HR-MAS NMR metabolic profiles revealed a clear separation of BCC from NST. The receiver operating characteristic curve generated from the results revealed an excellent discrimination of BCC from NST with an area under the curve (AUC) value of 0.961. The present study demonstrated that the metabolite profile and metabolite intensity differ between BCC and NST, and that HR-MAS 1H NMR spectroscopy can be a valuable tool in the diagnosis of BCC. PMID:26934749

  19. MAS-NMR studies of lithium aluminum silicate (LAS) glasses and glass-ceramics having different Li{sub 2}O/Al{sub 2}O{sub 3} ratio

    SciTech Connect

    Ananthanarayanan, A.; Kothiyal, G.P.; Montagne, L.; Revel, B.

    2010-01-15

    Emergence of phases in lithium aluminum silicate (LAS) glasses of composition (wt%) xLi{sub 2}O-71.7SiO{sub 2}-(17.7-x)Al{sub 2}O{sub 3}-4.9K{sub 2}O-3.2B{sub 2}O{sub 3}-2.5P{sub 2}O{sub 5} (5.1<=x<=12.6) upon heat treatment were studied. {sup 29}Si, {sup 27}Al, {sup 31}P and {sup 11}B MAS-NMR were employed for structural characterization of both LAS glasses and glass-ceramics. In glass samples, Al is found in tetrahedral coordination, while P exists mainly in the form of orthophosphate units. B exists as BO{sub 3} and BO{sub 4} units. {sup 27}Al NMR spectra show no change with crystallization, ruling out the presence of any Al containing phase. Contrary to X-ray diffraction studies carried out, {sup 11}B (high field 18.8 T) and {sup 29}Si NMR spectra clearly indicate the unexpected crystallization of a borosilicate phase (Li,K)BSi{sub 2}O{sub 6}, whose structure is similar to the aluminosilicate virgilite. Also, lithium disilicate (Li{sub 2}Si{sub 2}O{sub 5}), lithium metasilicate (Li{sub 2}SiO{sub 3}) and quartz (SiO{sub 2}) were identified in the {sup 29}Si NMR spectra of the glass-ceramics. {sup 31}P NMR spectra of the glass-ceramics revealed the presence of Li{sub 3}PO{sub 4} and a mixed phase (Li,K){sub 3}PO{sub 4} at low alkali concentrations. - Graphical Abstract: The {sup 11}B MAS-NMR spectra of lithium aluminum silicate (LAS) glass-ceramics indicating the formation of Li/KBSiO{sub 6} phase. This phase is isostructural with virgilite and cannot be distinguished in X-ray diffractograms.

  20. 2H-13C HETCOR MAS NMR for indirect detection of 2H quadrupole patterns and spin-lattice relaxation rates.

    PubMed

    Shi, Xiangyan; Yarger, Jeffery L; Holland, Gregory P

    2013-01-01

    Two-dimensional (2D) cross-polarization magic angle spinning (CP-MAS) (2)H-(13)C heteronuclear correlation (HETCOR) experiments were utilized to indirectly detect site-specific deuterium MAS powder patterns. The (2)H-(13)C cross-polarization efficiency is orientation-dependent and non-uniform for all crystallites. This leads to difficulty in extracting the correct (2)H MAS quadrupole powder patterns. In order to obtain accurate deuterium line shapes, (13)C spin lock rf field, spin lock rf ramp and CP contact time were carefully calibrated with the assistance of theoretical simulations. The extracted quadrupole patterns for U-[(2)H/(13)C/(15)N]-alanine indicate that the methyl deuterium undergoes classic, three-site jumping in the fast motion regime (10(-8)-10(-12)s) and the methine deuterium has a rigid deuterium powder pattern. For U-[(2)H/(13)C/(15)N]-phenylalanine, indirectly detected deuterium line shapes illustrate that the aromatic ring undergoes 180° flips in the fast motion regime while (2)H? and (2)H? are completely rigid. The experimental deuterium line shapes for U-[(2)H/(13)C/(15)N]-proline reflect that (2)H?, (2)H? and (2)H? are subjected to fast, two-site reorientations at an angle of (15±5)°, (30±5)° and (25±10)° respectively. In addition, an approach that combines a composite inversion pulse with (2)H-(13)C CP-MAS is applied to measure (2)H spin-lattice relaxation times in a site-specific, (13)C-detected fashion. PMID:23174312

  1. HR, Streamlined

    ERIC Educational Resources Information Center

    Ramaswami, Rama

    2008-01-01

    Human Resources (HR) administrators are finding that as software modules are installed to automate various processes, they have more time to focus on strategic objectives. And as compliance with affirmative action and other employment regulations comes under increasing scrutiny, HR staffers are finding that software can deliver and track data with…

  2. Photochemically induced dynamic nuclear polarization in the reaction center of the green sulphur bacterium Chlorobium tepidum observed by 13C MAS NMR.

    PubMed

    Roy, Esha; Alia; Gast, Peter; van Gorkom, Hans; de Groot, Huub J M; Jeschke, Gunnar; Matysik, Jörg

    2007-06-01

    Photochemically induced dynamic nuclear polarization has been observed in reaction centres of the green sulphur bacterium Chlorobium tepidum by (13)C magic-angle spinning solid-state NMR under continuous illumination with white light. An almost complete set of chemical shifts of the aromatic ring carbons of a BChl a molecule has been obtained. All light-induced (13)C NMR signals appear to be emissive, which is similar to the pattern observed in the reaction centers of plant photosystem I and purple bacterial reaction centres of Rhodobacter sphaeroides wild type. The donor in RCs of green sulfur bacteria clearly differs from the substantially asymmetric special pair of purple bacteria and appears to be similar to the more symmetric donor of photosystem I. PMID:17292850

  3. 13C and 15N—Chemical Shift Anisotropy of Ampicillin and Penicillin-V Studied by 2D-PASS and CP/MAS NMR

    NASA Astrophysics Data System (ADS)

    Antzutkin, Oleg N.; Lee, Young K.; Levitt, Malcolm H.

    1998-11-01

    The principal values of the chemical shift tensors of all13C and15N sites in two antibiotics, ampicillin and penicillin-V, were determined by 2-dimensionalphaseadjustedspinningsideband (2D-PASS) and conventional CP/MAS experiments. The13C and15N chemical shift anisotropies (CSA), and their confidence limits, were evaluated using a Mathematica program. The CSA values suggest a revised assignment of the 2-methyl13C sites in the case of ampicillin. We speculate on a relationship between the chemical shift principal values of many of the13C and15N sites and the β-lactam ring conformation.

  4. The Local Structural State of Aluminosilicate Garnet Solid Solutions: An Investigation of Grospydite Garnet from the Roberts Victor Kimberlite Using Paramagnetically Shifted 27Al and 29Si MAS NMR Resonances

    NASA Astrophysics Data System (ADS)

    Geiger, C. A.; Palke, A. C.; Stebbins, J. F.

    2014-12-01

    Most rock-forming silicates are substitutional solid solutions. Over the years extensive research has been done to determine their structural and crystal chemical properties. Here, the distribution of cations, or order-disorder behavior, is of central importance. In the case of aluminosilicate garnet solid solutions (X3Al2Si3O12 with X = Mg, Fe2+, Mn2+ and Ca) it has been shown that both synthetic and natural crystals have random long-range X-cation disorder in space group Ia-3d, as given by X-ray single-crystal diffraction measurements. However, the structural state of natural garnets at the local scale is not known. Garnet from a grospydite xenolith from the Roberts Victor kimberlite, South Africa, was studied by 27Al and 29Si MAS NMR spectroscopy. The research thrust was placed on measuring and analyzing paramagnetically shifted resonances to determine the local (short range) structural state of the X-cations in a grossular-rich ternary aluminosilicate garnet solid solution. The garnet crystals are compositionally homogeneous based on microprobe analysis, showing no measurable zoning, and have the formula Grs46.7Prp30.0Alm23.3. The garnet is cubic with the standard garnet space group Ia-3d. The 27Al MAS NMR spectrum shows a very broad asymmetric resonance located between about 100 and -50 ppm. It consists of a number of individual overlapping paramagnetically shifted resonances, which are difficult to analyze quantitatively. The 29Si MAS NMR spectrum, showing better resolution, has two observable resonances termed S0 and S4. S0 is located between about -60 ppm and -160 ppm and S4 is centered at roughly 95 ppm. Both S0 and S4 are composite resonances in nature containing many overlapping individual peaks. S0 contains information on local cation configurations whereby an isolated SiO4 group in the garnet structure does not have an edge-shared Fe2+-containing dodecahedron. S4 involves local configurations where there is one edge-shared dodecahedron containing Fe2+. The measured intensity of the resonances S0 and S4 are roughly similar to calculated intensities assuming random cation mixing. These first results do not indicate any overt short-range cation order in grossular-rich grospydite garnet.

  5. Hyperfine fields at the Li site in LiFePO(4)-type olivine materials for lithium rechargeable batteries: a (7)Li MAS NMR and SQUID study.

    PubMed

    Tucker, Michael C; Doeff, Marca M; Richardson, Thomas J; Fiñones, Rita; Cairns, Elton J; Reimer, Jeffrey A

    2002-04-17

    The (7)Li NMR isotropic shift for olivine LiMPO(4) (M = Fe, Mn, Co, Ni) is assigned to hyperfine coupling between the (7)Li nucleus and the transition metal unpaired electrons on the basis of the Curie-Weiss temperature dependence of the shift. The hyperfine shift arises from a linear combination of Li-O-M through-bond interactions wherein the unpaired A' electrons contribute a negative shift and the unpaired A' ' electrons contribute a positive shift. The hyperfine coupling constant is determined for each composition. PMID:11942811

  6. Stoichiometric compounds of magnesium dichloride with ethanol for the supported Ziegler-Natta catalysis: first recognition and multidimensional MAS NMR study.

    PubMed

    Sozzani, Piero; Bracco, Silvia; Comotti, Angiolina; Simonutti, Roberto; Camurati, Isabella

    2003-10-22

    Ethanol associates easily with MgCl(2) to form adducts of complex architecture, but until now available characterization methods have failed to identify the pure stoichiometric compounds and their structures. To remedy this, we set about applying homonuclear and heteronuclear 2D correlated solid-state NMR spectroscopy to identify the pure compounds and the ethanol-to-magnesium coordination pattern. High spinning speed and Lee-Goldburg sequences were able to reduce the hydrogen spin-diffusion and homonuclear coupling in the crystalline solid, thus achieving high resolution also in the hydrogen domain. On this basis, the pure adducts, of interest as catalyst supports for Ziegler-Natta polymerization, were isolated for the first time. Magnesium coordination sites with given numbers of ligands and their multiplicity in the crystal cells were determined in the new-found stoichiometric complexes. Variable temperature and 2D carbon-carbon exchange NMR, as well as relaxation times in the fast motion regime, revealed the disordering phenomena generated by ethanol dynamics in the crystal. Decoding the intriguing polymorphism of the precursors permits to trace the genealogy of tailored MgCl(2) titanate granules, active as highly productive catalysts for the stereospecific polymerization of olefins. PMID:14558837

  7. Elemental and structural analysis of silicon forms in herbal drugs using silicon-29 MAS NMR and WD-XRF spectroscopic methods.

    PubMed

    Pajchel, L; Nykiel, P; Kolodziejski, W

    2011-12-01

    The objective of this work was to study concentration of silicon and its structural forms present in herbal drugs. Equisetum arvense and Urtica dioica L. from teapot bags, dietary supplements (tablets and capsules) containing those herbs, dry extract obtained from a teapot bag of E. arvense, and samples of the latter herb harvested in wild habitat over four months were studied using wavelength dispersive X-ray spectroscopy (WD-XRF) and high-resolution solid-state (29)Si NMR. The highest concentration of Si, ca. 27mg/g, was found in the herbal material from the teapot bags containing E. arvense. The Si content in natural E. arvense (whole plants) increased from May to August by ca. 7mg/g, reaching value 26mg/g. Three different silicon forms were detected in the studied herbal samples: Si(OSi)4 (Q(4)), Si(OH)(OSi)3 (Q(3)) and Si(OH)2(OSi)2 (Q(2)). Those sites were populated in E. arvense in the following order: Q(4)≫Q(3)>Q(2). A dramatic, ca. 50-fold decrease of the Si concentration during the infusion process was observed. The infusion process and the subsequent drying procedure augmented population of the Q(4) sites at the cost of the Q(2) sites. The WD-XRF and (29)Si NMR methods occurred useful and complementary in the study of herbal materials. PMID:21813258

  8. Interface Induced Growth and Transformation of Polymer-Conjugated Proto-Crystalline Phases in Aluminosilicate Hybrids: A Multiple-Quantum (23)Na-(23)Na MAS NMR Correlation Spectroscopy Study.

    PubMed

    Brus, Jiri; Kobera, Libor; Urbanova, Martina; Doušová, Barbora; Lhotka, Miloslav; Koloušek, David; Kotek, Jiří; Čuba, Pavel; Czernek, Jiri; Dědeček, Jiří

    2016-03-22

    Nanostructured materials typically offer enhanced physicochemical properties because of their large interfacial area. In this contribution, we present a comprehensive structural characterization of aluminosilicate hybrids with polymer-conjugated nanosized zeolites specifically grown at the organic-inorganic interface. The inorganic amorphous Al-O-Si framework is formed by alkali-activated low-temperature transformation of metakaoline, whereas simultaneous copolymerization of organic comonomers creates a secondary epoxide network covalently bound to the aluminosilicate matrix. This secondary epoxide phase not only enhances the mechanical integrity of the resulting hybrids but also introduces additional binding sites accessible for compensating negative charge on the aluminosilicate framework. This way, the polymer network initiates growth and subsequent transformation of protocrystalline short-range ordered zeolite domains that are located at the organic-inorganic interface. By applying an experimental approach based on 2D (23)Na-(23)Na double-quantum (DQ) MAS NMR spectroscopy, we discovered multiple sodium binding sites in these protocrystalline domains, in which immobilized Na(+) ions form pairs or small clusters. It is further demonstrated that these sites, the local geometry of which allows for the pairing of sodium ions, are preferentially occupied by Pb(2+) ions during the ion exchange. The proposed synthesis protocol thus allows for the preparation of a novel type of geopolymer hybrids with polymer-conjugated zeolite phases suitable for capturing and storage of metal cations. The demonstrated (23)Na-(23)Na DQ MAS NMR combined with DFT calculations represents a suitable approach for understanding the role of Na(+) ions in aluminositicate solids and related inorganic-organic hybrids, particularly their specific arrangement and clustering at interfacial areas. PMID:26931131

  9. Magic angle Lee-Goldburg frequency offset irradiation improves the efficiency and selectivity of SPECIFIC-CP in triple-resonance MAS solid-state NMR

    PubMed Central

    Wu, C.H.; De Angelis, Anna A.; Opella, Stanley J.

    2014-01-01

    The efficiency and selectivity of SPECIFIC-CP, a widely used method for selective double cross-polarization in triple-resonance magic angle spinning solid-state NMR, is improved by performing the tangential-shaped 13C irradiation at an offset frequency that meets the Lee-Goldburg condition (LG-SPECIFIC-CP). This is demonstrated on polycrystalline samples of uniformly 13C, 15N labeled N-acetyl-leucine and N-formyl-Met-Leu-Phe-OH (MLF) at 700 MHz and 900 MHz 1H resonance frequencies, respectively. For the single 13Cα of N-acetyl-leucine, relative to conventional broad band cross-polarization, the SPECIFIC-CP signal has 47% of the intensity. Notably, the LG-SPECIFIC-CP signal has 72% of the intensity, essentially the theoretical maximum. There were no other changes in the experimental parameters. The three 13Cα signals in MLF show some variation in intensities, reflecting the relatively narrow bandwidth of a frequency-offset procedure, and pointing to future developments for this class of experiment. PMID:25051542

  10. Magic angle Lee-Goldburg frequency offset irradiation improves the efficiency and selectivity of SPECIFIC-CP in triple-resonance MAS solid-state NMR.

    PubMed

    Wu, Chin H; De Angelis, Anna A; Opella, Stanley J

    2014-09-01

    The efficiency and selectivity of SPECIFIC-CP, a widely used method for selective double cross-polarization in triple-resonance magic angle spinning solid-state NMR, is improved by performing the tangential-shaped (13)C irradiation at an offset frequency that meets the Lee-Goldburg condition (LG-SPECIFIC-CP). This is demonstrated on polycrystalline samples of uniformly (13)C, (15)N labeled N-acetyl-leucine and N-formyl-Met-Leu-Phe-OH (MLF) at 700MHz and 900MHz (1)H resonance frequencies, respectively. For the single (13)Cα of N-acetyl-leucine, relative to conventional broad band cross-polarization, the SPECIFIC-CP signal has 47% of the intensity. Notably, the LG-SPECIFIC-CP signal has 72% of the intensity, essentially the theoretical maximum. There were no other changes in the experimental parameters. The three (13)Cα signals in MLF show some variation in intensities, reflecting the relatively narrow bandwidth of a frequency-offset procedure, and pointing to future developments for this class of experiment. PMID:25051542

  11. MAS NMR Study of the Metastable Solid Solutions Found in the LiFePO4/FePO4 System

    SciTech Connect

    Cabana, Jordi; Shirakawa, Junichi; Chen, Guoying; Richardson, Thomas; Grey, Clare P.

    2009-10-09

    Li and 3IP NMR experiments were conducted on a series of single- or two-phase samples in the LiFePCvFePCM system with different overall lithium contents, and containing the two end-members and/or two metastable solid solution hases, Lio.6FeP04 or Lio.34FeP04. These experiments were carried out at different temperatures in order to search for vacancy/charge ordering and ion/electron mobility in the metastable phases. Evidence for Li+-Fe2+ interactions was bserved for both Lio.6FeP04 and Lio.34FePC>4. The strength of this interaction leads to the formation of LiFePCvlike clusters in the latter, as shown by the room temperature data. Different motional processes are proposed to exist as the temperature is increased and various scenarios are discussed. While concerted lithium-electron hopping and/or correlations explains the data below 125C, evidence for some uncorrelated motion is found at higher temperatures, together with the onset of phase mixing.

  12. High-Resolution 1H NMR Spectroscopy of Fish Muscle, Eggs and Small Whole Fish via Hadamard-Encoded Intermolecular Multiple-Quantum Coherence

    PubMed Central

    Cai, Honghao; Chen, Yushan; Cui, Xiaohong; Cai, Shuhui; Chen, Zhong

    2014-01-01

    Background and Purpose Nuclear magnetic resonance (NMR) spectroscopy has become an important technique for tissue studies. Since tissues are in semisolid-state, their high-resolution (HR) spectra cannot be obtained by conventional NMR spectroscopy. Because of this restriction, extraction and high-resolution magic angle spinning (HR MAS) are widely applied for HR NMR spectra of tissues. However, both of the methods are subject to limitations. In this study, the feasibility of HR 1H NMR spectroscopy based on intermolecular multiple-quantum coherence (iMQC) technique is explored using fish muscle, fish eggs, and a whole fish as examples. Materials and Methods Intact salmon muscle tissues, intact eggs from shishamo smelt and a whole fish (Siamese algae eater) are studied by using conventional 1D one-pulse sequence, Hadamard-encoded iMQC sequence, and HR MAS. Results When we use the conventional 1D one-pulse sequence, hardly any useful spectral information can be obtained due to the severe field inhomogeneity. By contrast, HR NMR spectra can be obtained in a short period of time by using the Hadamard-encoded iMQC method without shimming. Most signals from fatty acids and small metabolites can be observed. Compared to HR MAS, the iMQC method is non-invasive, but the resolution and the sensitivity of resulting spectra are not as high as those of HR MAS spectra. Conclusion Due to the immunity to field inhomogeneity, the iMQC technique can be a proper supplement to HR MAS, and it provides an alternative for the investigation in cases with field distortions and with samples unsuitable for spinning. The acquisition time of the proposed method is greatly reduced by introduction of the Hadamard-encoded technique, in comparison with that of conventional iMQC method. PMID:24466083

  13. The Amblygonite (LiAlPO{sub 4}F)-Montebrasite (LiAlPO{sub 4}OH) Solid Solution: A Combined powder and single-crystal neutron diffraction and solid-state {sup 6}Li MAS, CP MAS, and REDOR NMR study

    SciTech Connect

    Groat, Lee A.; Chakoumakos, Bryan C.; Brouwer, Darren H.; Hoffman, Christina M.; Fyfe, Colin A.; Morell, Heiko; Schultz, Arthur J.

    2003-01-01

    The amblygonite-montebrasite series of minerals, common constituents of granitic pegmatites and topaz-bearing granites, show complete solid solution with ideal composition LiAlPO{sub 4}(F, OH). These compounds are ideal for studying F {leftrightarrow} OH solid solution in minerals because natural members of the series generally show little deviation from the ideal composition. In this study, we used powder and single-crystal neutron diffraction and solid-state {sup 6}Li MAS, CP MAS, and REDOR NMR techniques to study the effect of F {leftrightarrow} OH substitution on the series. Lattice parameters refined from single-crystal neutron diffraction data show increasing b and decreasing a, c, and V with increasing F/(F + OH). The volume is highest for the OH end-member because of the presence of an additional atom (H). The a and c parameters decrease with increasing F/(F + OH) because the O-H vector is close to the a-c plane and the Al-OH/F vectors are approximately parallel to c. Lattice parameters refined from neutron powder diffraction patterns collected at lower T show that thermal contraction increases with F/(F + OH), presumably because the F anion takes up less space than the OH molecule. The results show that the OH/F position is always fully occupied. The H displacement ellipsoid shows little change with occupancy, which obviously corresponds negatively with increasing F/(F + OH). However, the Li displacement ellipsoid becomes extremely large and anisotropic with increasing F fraction. Most of the distortion is associated with the U{sub 3} eigenvalue, which lies between the c and c* directions. U{sub eq} values corresponding to the Li atom show a greater reduction with decreasing temperature than the other atoms. The temperature dependence of Li is the same regardless of F content. Even when extrapolated to absolute zero the Li displacement ellipsoid is very large, which implies a large static disorder.

  14. Impact of structural differences in carcinopreventive agents indole-3-carbinol and 3,3'-diindolylmethane on biological activity. An X-ray, ¹H-¹?N NQDR, ¹³C CP/MAS NMR, and periodic hybrid DFT study.

    PubMed

    Latosi?ska, Jolanta Natalia; Latosi?ska, Magdalena; Szafra?ski, Marek; Seliger, Janez; Žagar, Veselko; Burchardt, Dorota V

    2015-09-18

    Three experimental techniques (1)H-(14)N NQDR, (13)C CP/MAS NMR and X-ray and Density Functional Theory (GGA/BLYP with PBC) and Hirshfeld surfaces were applied for the structure-activity oriented studies of two phyto-antioxidants and anticarcinogens: indole-3-carbinol, I3C, and 3,3'-diindolylmethane, DIM, (its bioactive metabolite). One set of (14)N NQR frequencies for DIM (2.310, 2.200 and 0.110 MHz at 295K) and I3C (2.315, 1.985 and 0.330 MHz at 160K) was recorded. The multiplicity of NQR lines recorded at RT revealed high symmetry (chemical and physical equivalence) of both methyl indazole rings of DIM. Carbonyl (13)C CSA tensor components were calculated from the (13)C CP/MAS solid state NMR spectrum of I3C recorded under fast and slow spinning. At room temperature the crystal structure of I3C is orthorhombic: space group Pca21, Z=4, a=5.78922(16), b=15.6434(7) and c=8.4405(2)Å. The I3C molecules are aggregated into ribbons stacked along [001]. The oxygen atomsare disorderedbetween the two sites of different occupancy factors. It implies that the crystal is built of about 70% trans and 30% gauche conformers, and apart from the weak OH?O hydrogen bonds (O?O=3.106Å) the formation of alternative O'H?O bonds (O'?O=2.785Å) is possible within the 1D ribbons. The adjacent ribbons are further stabilised by O'H?O bonds (O'?O=2.951Å). The analysis of spectra and intermolecular interactions pattern by experimental techniques was supported by solid (periodic) DFT calculations. The knowledge of the topology and competition of the interactions in crystalline state shed some light on the preferred conformations of CH2OH in I3C and steric hindrance of methyl indole rings in DIM. A comparison of the local environment in gas phase and solid permitted drawing some conclusions on the nature of the interactions required for effective processes of recognition and binding of a given anticarcinogen to the protein or nucleic acid. PMID:26066413

  15. In situ solid state B-11 MAS-NMR studies of the thermal decomposition of ammonia borane: mechanistic studies of the hydrogen release pathways from a solid state hydrogen storage material

    SciTech Connect

    Stowe, Ashley C.; Shaw, Wendy J.; Linehan, John C.; Schmid, Benjamin; Autrey, Thomas

    2007-02-20

    The mechanism of hydrogen release from solid state ammonia borane (AB) has been investigated via in situ solid state 11B{1H} MAS-NMR techniques in external fields of 7.06 T and 18.8 T at a decomposition temperature of 88 oC, well below the reported melting point. The decomposition of AB is well described by an induction, nucleation and growth mechanistic pathway. During the induction period, little hydrogen is released from AB; however, a new species identified as a mobile phase of AB is observed in the 11B NMR spectra. Subsequent to induction, at reaction times when hydrogen is initially being released, three additional species are observed: the diammoniate of diborane (DADB), [(NH3)2BH2]+[BH4]-, and two BH2N2 species believed to be the linear (NH3BH2NH2BH3) and cyclic dimer (NH2BH2)2 of aminoborane. At longer reaction times the sharper features are replaced by broad, structureless peaks of a complex polymeric aminoborane (PAB) containing both BH2N2 and BHN3 species. We propose the following mechanistic model for the induction, nucleation and growth for AB decomposition leading to formation of hydrogen: (1) an induction period that yields a mobile phase of AB caused by disruption of the dihydrogen bonds, (2) nucleation that yields reactive DADB from the mobile AB and (3) growth that includes a bimolecular reaction between DADB and AB to release the stored hydrogen. Support for this work by the U.S. Department of Energy, Office of Science, Basic Energy Sciences is gratefully acknowledged. A portion of the research described in this paper was performed in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the U.S. Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.

  16. Thermal decomposition of monocalcium aluminate decahydrate (CaAl2O4.10H2O) investigated by in-situ synchrotron X-ray powder diffraction, thermal analysis and 27Al, 2H MAS NMR spectroscopy.

    PubMed

    Christensen, Axel Nørlund; Jensen, Torben R; Lebech, Bente; Hanson, Jonathan C; Jakobsen, Hans J; Skibsted, Jørgen

    2008-01-28

    The stability of monocalcium aluminate decahydrate, with the nominal composition CaAl(2)O(4).10H(2)O (CAH(10)), has a decisive role for the strength development and durability of cementitious materials based on high alumina cements. This has prompted an investigation of the thermal transformation of crystalline monocalcium aluminate decahydrate in air to an amorphous phase by in-situ synchrotron X-ray powder diffraction in the temperature range from 25 to 500 degrees C, by DTA/TGA, and (2)H, (27)Al MAS NMR spectroscopy. The decomposition includes the loss of hydrogen-bonded water molecules in the temperature range up to 175 degrees C, coupled with a reduction of the unit cell volume from 1928 A(3) at 25 degrees C, to 1674 A(3) at 185 degrees C. Furthermore, X-ray diffraction shows that CaAl(2)O(4).10H(2)O starts to transform to an amorphous phase at approximately 65 degrees C. This phase is fully developed at approximately 175 degrees C and it converts to crystalline CaAl(2)O(4) when heated to 1300 degrees C. The thermal decomposition in the temperature range from approximately 65 to approximately 175 degrees C involves both formation of an amorphous phase including AlO(4) tetrahedra and structural changes in the remaining crystalline phase. PMID:18185861

  17. Characterization of white Portland cement hydration and the C-S-H structure in the presence of sodium aluminate by {sup 27}Al and {sup 29}Si MAS NMR spectroscopy

    SciTech Connect

    Andersen, Morten Daugaard; Jakobsen, Hans J.; Skibsted, Joergen

    2004-05-01

    The effects of hydrating a white Portland cement (wPc) in 0.30 and 0.50 M solutions of sodium aluminate (NaAlO{sub 2}) at 5 and 20 deg. C are investigated by {sup 27}Al and {sup 29}Si magic-angle spinning (MAS) NMR spectroscopy. It is demonstrated that NaAlO{sub 2} accelerates the hydration of alite and belite and results in calcium-silicate-hydrate (C-S-H) phases with longer average chain lengths of SiO{sub 4}/AlO{sub 4} tetrahedra. The C-S-H phases are investigated in detail and it is shown that the Al/Si ratio for the chains of tetrahedra is quite constant during the time studied for the hydration (6 h to 2 years) but increases for higher concentration of the NaAlO{sub 2} solution. The average chain lengths of 'pure' silicate and SiO{sub 4}/AlO{sub 4} tetrahedra demonstrate that Al acts as a linker for the silicate chains, thereby producing aluminosilicate chains with longer average chain lengths. Finally, it is shown that NaAlO{sub 2} reduces the quantity of ettringite and results in larger quantities of monosulfate and a calcium aluminate hydrate phase.

  18. ?High resolution-magic-angle spinning NMR spectroscopy for metabolic phenotyping of Caenorhabditis elegans.

    PubMed

    Wong, Alan; Li, Xiaonan; Molin, Laurent; Solari, Florence; Elena-Herrmann, Bénédicte; Sakellariou, Dimitris

    2014-06-17

    Analysis of model organisms, such as the submillimeter-size Caenorhabditis elegans, plays a central role in understanding biological functions across species and in characterizing phenotypes associated with genetic mutations. In recent years, metabolic phenotyping studies of C. elegans based on (1)H high-resolution magic-angle spinning (HR-MAS) nuclear magnetic resonance (NMR) spectroscopy have relied on the observation of large populations of nematodes, requiring labor-intensive sample preparation that considerably limits high-throughput characterization of C. elegans. In this work, we open new platforms for metabolic phenotyping of C. elegans mutants. We determine rich metabolic profiles (31 metabolites identified) from samples of 12 individuals using a (1)H NMR microprobe featuring high-resolution magic-angle coil spinning (HR-MACS), a simple conversion of a standard HR-MAS probe to ?HR-MAS. In addition, we characterize the metabolic variations between two different strains of C. elegans (wild-type vs slcf-1 mutant). We also acquire a NMR spectrum of a single C. elegans worm at 23.5 T. This study represents the first example of a metabolomic investigation carried out on a small number of submillimeter-size organisms, demonstrating the potential of NMR microtechnologies for metabolomics screening of small model organisms. PMID:24897622

  19. Metabolite localization in living drosophila using High Resolution Magic Angle Spinning NMR.

    PubMed

    Sarou-Kanian, Vincent; Joudiou, Nicolas; Louat, Fanny; Yon, Maxime; Szeremeta, Frédéric; Même, Sandra; Massiot, Dominique; Decoville, Martine; Fayon, Franck; Beloeil, Jean-Claude

    2015-01-01

    We have developed new methods enabling in vivo localization and identification of metabolites through their (1)H NMR signatures, in a drosophila. Metabolic profiles in localized regions were obtained using HR-MAS Slice Localized Spectroscopy and Chemical Shift Imaging at high magnetic fields. These methods enabled measurement of metabolite contents in anatomic regions of the fly, demonstrated by a decrease in ?-alanine signals in the thorax of flies showing muscle degeneration. PMID:25892587

  20. Ultra-low temperature MAS-DNP.

    PubMed

    Lee, Daniel; Bouleau, Eric; Saint-Bonnet, Pierre; Hediger, Sabine; De Paëpe, Gaël

    2016-03-01

    Since the infancy of NMR spectroscopy, sensitivity and resolution have been the limiting factors of the technique. Regular essential developments on this front have led to the widely applicable, versatile, and powerful spectroscopy that we know today. However, the Holy Grail of ultimate sensitivity and resolution is not yet reached, and technical improvements are still ongoing. Hence, high-field dynamic nuclear polarization (DNP) making use of high-frequency, high-power microwave irradiation of electron spins has become very promising in combination with magic angle sample spinning (MAS) solid-state NMR experiments. This is because it leads to a transfer of the much larger polarization of these electron spins under suitable irradiation to surrounding nuclei, greatly increasing NMR sensitivity. Currently, this boom in MAS-DNP is mainly performed at minimum sample temperatures of about 100K, using cold nitrogen gas to pneumatically spin and cool the sample. This Perspective deals with the desire to improve further the sensitivity and resolution by providing "ultra"-low temperatures for MAS-DNP, using cryogenic helium gas. Different designs on how this technological challenge has been overcome are described. It is shown that stable and fast spinning can be attained for sample temperatures down to 30K using a large cryostat developed in our laboratory. Using this cryostat to cool a closed-loop of helium gas brings the additional advantage of sample spinning frequencies that can greatly surpass those achievable with nitrogen gas, due to the differing fluidic properties of these two gases. It is shown that using ultra-low temperatures for MAS-DNP results in substantial experimental sensitivity enhancements and according time-savings. Access to this temperature range is demonstrated to be both viable and highly pertinent. PMID:26920837

  1. Ultra-low temperature MAS-DNP

    NASA Astrophysics Data System (ADS)

    Lee, Daniel; Bouleau, Eric; Saint-Bonnet, Pierre; Hediger, Sabine; De Paëpe, Gaël

    2016-03-01

    Since the infancy of NMR spectroscopy, sensitivity and resolution have been the limiting factors of the technique. Regular essential developments on this front have led to the widely applicable, versatile, and powerful spectroscopy that we know today. However, the Holy Grail of ultimate sensitivity and resolution is not yet reached, and technical improvements are still ongoing. Hence, high-field dynamic nuclear polarization (DNP) making use of high-frequency, high-power microwave irradiation of electron spins has become very promising in combination with magic angle sample spinning (MAS) solid-state NMR experiments. This is because it leads to a transfer of the much larger polarization of these electron spins under suitable irradiation to surrounding nuclei, greatly increasing NMR sensitivity. Currently, this boom in MAS-DNP is mainly performed at minimum sample temperatures of about 100 K, using cold nitrogen gas to pneumatically spin and cool the sample. This Perspective deals with the desire to improve further the sensitivity and resolution by providing "ultra"-low temperatures for MAS-DNP, using cryogenic helium gas. Different designs on how this technological challenge has been overcome are described. It is shown that stable and fast spinning can be attained for sample temperatures down to 30 K using a large cryostat developed in our laboratory. Using this cryostat to cool a closed-loop of helium gas brings the additional advantage of sample spinning frequencies that can greatly surpass those achievable with nitrogen gas, due to the differing fluidic properties of these two gases. It is shown that using ultra-low temperatures for MAS-DNP results in substantial experimental sensitivity enhancements and according time-savings. Access to this temperature range is demonstrated to be both viable and highly pertinent.

  2. 13C, 15N NMR and CP-MAS as well as FT-IR and PM5 studies of Schiff base of gossypol with L-phenylalanine methyl ester in solution and solid

    NASA Astrophysics Data System (ADS)

    Przybylski, Piotr; Schilf, Wojciech; Brzezinski, Bogumi?

    2005-01-01

    The Schiff bases of racemic gossypol with L-phenylalanine amino acid methyl ester (GSBA) was studied by FT-IR, 13C and 15N NMR spectroscopy as well as by the PM5 semiempirical method. The spectroscopic methods have provided clear evidence that GSBA exists in the solid state and in solution as enamine-enamine tautomer. The existence of diastereoisomers is very well evidenced in the 13C NMR spectra in the solution by the double character of all carbon atoms' signals of the naphthalene rings. The structure of GSBA and the hydrogen bonds within this structure are discussed.

  3. Supramolecular self-organisation and conformational isomerism of a binuclear O,O'-dipropyl dithiophosphate gold(I) complex, [Au2{S2P(OC3H7)2}2]: Synthesis, (13)C and (31)P CP/MAS NMR spectroscopy, single-crystal X-ray diffraction study and thermal behaviour.

    PubMed

    Rodina, Tatyana A; Korneeva, Eugenia V; Antzutkin, Oleg N; Ivanov, Alexander V

    2015-10-01

    Crystalline one-dimensional polymeric catena-poly[bis(μ2-O,O'-dipropyldithiophosphato-S,S')digold(I)] (Au-Au) (1) was prepared and studied using (13)C and (31)P CP/MAS NMR spectroscopy and single-crystal X-ray diffraction. To elucidate the structural function of Dtph ligands in crystalline gold(I) O,O'-dipropyl dithiophosphate, the chemical shift anisotropy parameters (δaniso and η) were calculated from spinning sideband manifolds in (31)P MAS NMR spectra. A novel structure of the gold(I) compound comprises two isomeric, non-centrosymmetric binuclear molecules of [Au2{S2P(OC3H7)2}2] (isomers 'A' and 'B'), whose four Dtph groups display structural inequivalence. In each isomeric binuclear molecule of 1, a pair of μ2-bridging dipropyl Dtph ligands almost symmetrically links two neighbouring gold atoms, forming an extensive eight-membered metallocycle [Au2S4P2], while the intramolecular aurophilic Au⋯Au bond additionally stabilises this central cyclic moiety. At the supramolecular level of complex 1, intermolecular aurophilic Au⋯Au bonds yield almost linear infinite polymeric chains (⋯'A'⋯'B'⋯'A'⋯'B'⋯)n. The thermal behaviour of this compound was studied by the simultaneous thermal analysis (STA) technique (a combination of TG and DSC) under an argon atmosphere. PMID:26004097

  4. 14N overtone NMR under MAS: signal enhancement using symmetry-based sequences and novel simulation strategies† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4cp03994g Click here for additional data file.

    PubMed Central

    Haies, Ibraheem M.; Jarvis, James A.; Bentley, Harry; Heinmaa, Ivo; Kuprov, Ilya; Williamson, Philip T. F.

    2015-01-01

    Overtone 14N NMR spectroscopy is a promising route for the direct detection of 14N signals with good spectral resolution. Its application is currently limited, however, by the absence of efficient polarization techniques for overtone signal enhancement and the lack of efficient numerical simulation techniques to aid in both the development of new methods and the analysis and interpretation of experimental data. In this paper we report a novel method for the transfer of polarization from 1H to the 14N overtone using symmetry-based R-sequences that overcome many of the limitations of adiabatic approaches that have worked successfully on static samples. Refinement of these sequences and the analysis of the resulting spectra have been facilitated through the development of an efficient simulation strategy for 14N overtone NMR spectroscopy of spinning samples, using effective Hamiltonians on top of Floquet and Fokker–Planck equations. PMID:25662410

  5. Slow Magic Angle Sample Spinning: A Non- or Minimally Invasive Method for High- Resolution 1H Nuclear Magnetic Resonance (NMR) Metabolic Profiling

    SciTech Connect

    Hu, Jian Z.

    2011-05-01

    High resolution 1H magic angle spinning nuclear magnetic resonance (NMR), using a sample spinning rate of several kHz or more (i.e., high resolution-magic angle spinning (hr-MAS)), is a well established method for metabolic profiling in intact tissues without the need for sample extraction. The only shortcoming with hr-MAS is that it is invasive and is thus unusable for non-destructive detections. Recently, a method called slow-MAS, using the concept of two dimensional NMR spectroscopy, has emerged as an alternative method for non- or minimal invasive metabolomics in intact tissues, including live animals, due to the slow or ultra-slow-sample spinning used. Although slow-MAS is a powerful method, its applications are hindered by experimental challenges. Correctly designing the experiment and choosing the appropriate slow-MAS method both require a fundamental understanding of the operation principles, in particular the details of line narrowing due to the presence of molecular diffusion. However, these fundamental principles have not yet been fully disclosed in previous publications. The goal of this chapter is to provide an in depth evaluation of the principles associated with slow-MAS techniques by emphasizing the challenges associated with a phantom sample consisting of glass beads and H2O, where an unusually large magnetic susceptibility field gradient is obtained.

  6. Studies of Secondary Melanoma on C57BL/6J Mouse Liver Using 1H NMR Metabolomics

    SciTech Connect

    Feng, Ju; Isern, Nancy G.; Burton, Sarah D.; Hu, Jian Z.

    2013-10-31

    NMR metabolomics, consisting of solid state high resolution (hr) magic angle spinning (MAS) 1H NMR (1H hr-MAS), liquid state high resolution 1H-NMR, and principal components analysis (PCA) has been used to study secondary metastatic B16-F10 melanoma in C57BL/6J mouse liver . The melanoma group can be differentiated from its control group by PCA analysis of the absolute concentrations or by the absolute peak intensities of metabolites from either 1H hr-MAS NMR data on intact liver tissues or liquid state 1H-NMR spectra on liver tissue extracts. In particular, we found that the absolute concentrations of alanine, glutamate, creatine, creatinine, fumarate and cholesterol are elevated in the melanoma group as compared to controls, while the absolute concentrations of succinate, glycine, glucose, and the family of linear lipids including long chain fatty acids, total choline and acylglycerol are decreased. The ratio of glycerophosphocholine to phosphocholine is increased by about 1.5 fold in the melanoma group, while the absolute concentration of total choline is actually lower in melanoma mice. These results suggest the following picture in secondary melanoma metastasis: Linear lipid levels are decreased by beta oxidation in the melanoma group, which contributes to an increase in the synthesis of cholesterol, and also provides an energy source input for TCA cycle. These findings suggest a link between lipid oxidation, the TCA cycle and the hypoxia-inducible factors (HIF) signal pathway in tumor metastases. Thus this study indicates that the metabolic profile derived from NMR analysis can provide a valuable bio-signature of malignancy and cell hypoxia in metastatic melanoma.

  7. Exploring abiotic stress on asynchronous protein metabolism in single kernels of wheat studied by NMR spectroscopy and chemometrics

    PubMed Central

    Winning, H.; Viereck, N.; Wollenweber, B.; Larsen, F. H.; Jacobsen, S.; Søndergaard, I.; Engelsen, S. B.

    2009-01-01

    Extreme climate events are being recognized as important factors in the effects on crop growth and yield. Increased climatic variability leads to more frequent extreme conditions which may result in crops being exposed to more than one extreme event within a growing season. The aim of this study was to examine the implications of different drought treatments on the protein fractions in grains of winter wheat using 1H nuclear magnetic resonance spectroscopy followed by chemometric analysis. Triticum aestivum L. cv. Vinjett was studied in a semi-field experiment and subjected to drought episodes either at terminal spikelet, during grain-filling or at both stages. Principal component trajectories of the total protein content and the protein fractions of flour as well as the 1H NMR spectra of single wheat kernels, wheat flour, and wheat methanol extracts were analysed to elucidate the metabolic development during grain-filling. The results from both the 1H NMR spectra of methanol extracts and the 1H HR-MAS NMR of single kernels showed that a single drought event during the generative stage had as strong an influence on protein metabolism as two consecutive events of drought. By contrast, a drought event at the vegetative growth stage had little effect on the parameters investigated. For the first time, 1H HR-MAS NMR spectra of grains taken during grain-filling were analysed by an advanced multiway model. In addition to the results from the chemical protein analysis and the 1H HR-MAS NMR spectra of single kernels indicating that protein metabolism is influenced by multiple drought events, the 1H NMR spectra of the methanol extracts of flour from mature grains revealed that the amount of fumaric acid is particularly sensitive to water deficits. PMID:19213725

  8. Determination of relative orientation between (1)H CSA tensors from a 3D solid-state NMR experiment mediated through (1)H/(1)H RFDR mixing under ultrafast MAS.

    PubMed

    Pandey, Manoj Kumar; Nishiyama, Yusuke

    2015-09-01

    To obtain piercing insights into inter and intramolecular H-bonding, and ?-electron interactions measurement of (1)H chemical shift anisotropy (CSA) tensors is gradually becoming an obvious choice. While the magnitude of CSA tensors provides unique information about the local electronic environment surrounding the nucleus, the relative orientation between these tensors can offer further insights into the spatial arrangement of interacting nuclei in their respective three-dimensional (3D) space. In this regard, we present a 3D anisotropic/anisotropic/isotropic proton chemical shift (CSA/CSA/CS) correlation experiment mediated through (1)H/(1)H radio frequency-driven recoupling (RFDR) which enhances spin diffusion through recoupled (1)H-(1)H dipolar couplings under ultrafast magic angle spinning (MAS) frequency (70kHz). Relative orientation between two interacting 1H CSA tensors is obtained by fitting two-interacting (1)H CSA tensors by fitting two-dimensional (2D) (1)H/(1)H CSA/CSA spectral slices through extensive numerical simulations. To recouple (1)H CSAs in the indirect frequency dimensions of a 3D experiment we have employed ?-encoded radio frequency (RF) pulse sequence based on R-symmetry (R188(7)) with a series of phase-alternated 2700(°)-90180(°) composite-180° pulses on citric acid sample. Due to robustness of applied (1)H CSA recoupling sequence towards the presence of RF field inhomogeneity, we have successfully achieved an excellent (1)H/(1)H CSA/CSA cross-correlation efficiency between H-bonded sites of citric acid. PMID:26065628

  9. Carbon-13 CP-MAS nuclear magnetic resonance studies of teas.

    PubMed

    Martínez-Richa, Antonio; Joseph-Nathan, Pedro

    2003-05-01

    13C CP-MAS NMR spectra of green and black tea were obtained and assigned based on the solid-state NMR spectra of tropolone, (+)-catechin hydrate, gallic acid, caffeine and flavone derivatives. The peak shape and chemical shifts observed for carbonyl carbons in CP-MAS spectra of teas indicate the existence of different chemical species, mainly free phenollic acids and ester derivatives of flavonoids. The peak patterns allow to establish differences between both teas. PMID:12763559

  10. E/Z MAS demonstration

    SciTech Connect

    Boor, M.G.; Hurford, J.M.; Landry, R.P.; Martinez, B.J.; Solem, A.M.; Whiteson, R.; Zardecki, A.

    1998-12-31

    Los Alamos National Laboratory has developed E/Z MAS, a new generation nuclear material accountability application based on the latest technology and designed for facilities required to track nuclear materials with a simple-to-use interface. E/Z MAS is based on years of experience spent developing nuclear material accounting systems. E/Z MAS uses a modern relational database with a web server and enables users on a classified local area network to interact with the database with web browsers. The E/Z MAS Demonstration poster session demonstrates the E/Z MAS functions required by an operational nuclear facility to track material as it enters and leaves a facility and to account for the material as it moves through a process. The generation of internal facility reports and external reports for the Russian Federal system will be demonstrated. Bar-code readers will be used to demonstrate the ability of EZ MAS to automate certain functions, such as physical inventories at facilities.

  11. HR Structure and HR Knowledge Transfer between Subsidiaries in China

    ERIC Educational Resources Information Center

    Wang-Cowham, Cindy

    2008-01-01

    Purpose: This paper attempts to examine the issue concerning human resource (HR) structures and the transfer of HR knowledge to discover whether and how HR structure facilitates the transfer of HR knowledge between subsidiaries of an MNC in China. Design/methodology/approach: The investigation, being of an exploratory nature, follows the tradition…

  12. 13C CP (cross-polarization) MAS (magic angle spinning) NMR and GIAO-CHF calculations of buspirone analogues. Part 1. 3a,4,7,7a-Tetrahydro-2-[4-[4-(2-quinolinyl)-1-piperazinyl]butyl ]-4,7-ethane-1H-isoindole-1,3(2H)-dione hydrochloride and hydrobromide.

    PubMed

    Szelejewska-Wo?niakowska, A; Chilmonczyk, Z; Le?, A; Wawer, I

    1998-11-01

    13C CP (cross-polarization) MAS (magic angle spinning) solid state NMR spectra of buspirone analogue 3a,4,7,7a-tetrahydro-2-[4-[4-(2-quinolinyl)-1-piperazinyl]butyl]-4,7-eth ane-1H-isoindole-1,3(2H)-dione were recorded. In the spectra of hydrochloride and hydrobromide, two sets of signals appeared, in agreement with single crystal X-ray diffraction data indicating that in each of the salts two independent cations were present in the crystal unit. The largest shielding differences of 3.2-4.6 ppm between two sets of signals were found for quinoline aromatic carbons C3 and C2. Ab initio calculations of the carbon and nitrogen shielding constants were performed with the use of the GIAO-CHF method for structural fragments: N-butylsuccinimide, quinoline-(N-methyl) piperazine hydrochloride and hydrobromide. Linear correlations between theoretical and solid state results were obtained, thus enabling a reasonable assignment of carbon resonances of the conformations present in the solid state. Due to the fast dynamics in solution, the carbon chemical shifts corresponded to the averaged values of the forms present in the solid state. PMID:9875604

  13. FIRE_ACE_ER2_MAS

    Atmospheric Science Data Center

    2015-10-28

    ... NASA ER-2 Moderate Resolution Imaging Spectrometer (MODIS) Airborne Simulator (MAS) Data Project Title:  MAS ... Fortran include file IDL Code Flight Tracks Related Data:  MAS Additional ...

  14. HR Public meeting

    ScienceCinema

    None

    2011-10-06

    Cher(e)s collègues, En collaboration avec le Département HR, le Directeur général a le plaisir de vous convier à une réunion publique qui se tiendra le vendredi 25 juin 2010 à 9h30 dans l?Amphithéâtre principal (Bâtiment 500)*. Un café d?accueil y sera servi à partir de 9h. Cette réunion abordera les thèmes suivants : ? Valeurs de l?Organisation (Directeur général) ? Code de Conduite (Directeur général / Anne-Sylvie Catherin) ? Création du nouveau rôle d?Ombudsperson (Vincent Vuillemin) Ces présentations seront suivies d?une séance de questions-réponses. Nous espérons vous retrouver nombreux le 25 juin ! Meilleures salutations, Anne-Sylvie Catherin Chef du Département des Ressources humaines *Cette réunion sera retransmise simultanément dans l?Amphithéâtre BE de Prévessin (Bâtiment 864) et également disponible à l?adresse suivante : http://webcast.cern.ch -------------------------------------------------------- Dear colleagues, In collaboration with HR Department, the Director-General would like to invite you to an information meeting which will be held on Friday 25 June 2010 at 9:30 am in the Main Auditorium (Building 500)*. A welcome coffee will be available from 9:00 am. During this meeting, information will be given about: ? Organization?s values (Director-General) ? Code of Conduct (Director-General / Anne-Sylvie Catherin) ? New Ombudsperson role (Vincent Vuillemin) These presentations will be followed by a questions & answers session. We look forward to seeing you all on 25 June! Best regards, Anne-Sylvie Catherin Head, Human Resources Department *This meeting will be simultaneously retransmitted in BE Auditorium (Building 864) and available at the following address: http://webcast.cern.ch.

  15. Studies of Secondary Melanoma on C57BL/6J Mouse Liver Using 1H NMR Metabolomics

    PubMed Central

    Feng, Ju; Isern, Nancy G.; Burton, Sarah D.; Hu, Jian Zhi

    2013-01-01

    NMR metabolomics, consisting of solid state high resolution magic angle spinning (HR-MAS) 1H-NMR, liquid state high resolution 1H-NMR, and principal components analysis (PCA) has been used to study secondary metastatic B16-F10 melanoma in C57BL/6J mouse liver. The melanoma group can be differentiated from its control group by PCA analysis of the estimates of absolute concentrations from liquid state 1H-NMR spectra on liver tissue extracts or by the estimates of absolute peak intensities of metabolites from 1H HR-MAS-NMR data on intact liver tissues. In particular, we found that the estimates of absolute concentrations of glutamate, creatine, fumarate and cholesterol are elevated in the melanoma group as compared to controls, while the estimates of absolute concentrations of succinate, glycine, glucose, and the family of linear lipids including long chain fatty acids, total choline and acyl glycerol are decreased. The ratio of glycerophosphocholine (GPC) to phosphocholine (PCho) is increased by about 1.5 fold in the melanoma group, while the estimate of absolute concentration of total choline is actually lower in melanoma mice. These results suggest the following picture in secondary melanoma metastasis: Linear lipid levels are decreased by beta oxidation in the melanoma group, which contributes to an increase in the synthesis of cholesterol, and also provides an energy source input for TCA cycle. These findings suggest a link between lipid oxidation, the TCA cycle and the hypoxia-inducible factors (HIF) signal pathway in tumor metastases. Thus, this study indicates that the metabolic profile derived from NMR analysis can provide a valuable bio-signature of malignancy and cell hypoxia in metastatic melanoma. PMID:24958263

  16. HR Public meeting

    SciTech Connect

    2010-10-12

    Cher(e)s collègues, En collaboration avec le Département HR, le Directeur général a le plaisir de vous convier à une réunion publique qui se tiendra le vendredi 25 juin 2010 à 9h30 dans l’Amphithéâtre principal (Bâtiment 500)*. Un café d’accueil y sera servi à partir de 9h. Cette réunion abordera les thèmes suivants : • Valeurs de l’Organisation (Directeur général) • Code de Conduite (Directeur général / Anne-Sylvie Catherin) • Création du nouveau rôle d’Ombudsperson (Vincent Vuillemin) Ces présentations seront suivies d’une séance de questions-réponses. Nous espérons vous retrouver nombreux le 25 juin ! Meilleures salutations, Anne-Sylvie Catherin Chef du Département des Ressources humaines *Cette réunion sera retransmise simultanément dans l’Amphithéâtre BE de Prévessin (Bâtiment 864) et également disponible à l’adresse suivante : http://webcast.cern.ch -------------------------------------------------------- Dear colleagues, In collaboration with HR Department, the Director-General would like to invite you to an information meeting which will be held on Friday 25 June 2010 at 9:30 am in the Main Auditorium (Building 500)*. A welcome coffee will be available from 9:00 am. During this meeting, information will be given about: • Organization’s values (Director-General) • Code of Conduct (Director-General / Anne-Sylvie Catherin) • New Ombudsperson role (Vincent Vuillemin) These presentations will be followed by a questions & answers session. We look forward to seeing you all on 25 June! Best regards, Anne-Sylvie Catherin Head, Human Resources Department *This meeting will be simultaneously retransmitted in BE Auditorium (Building 864) and available at the following address: http://webcast.cern.ch.

  17. HR Public meeting

    SciTech Connect

    2010-06-25

    Cher(e)s collègues, En collaboration avec le Département HR, le Directeur général a le plaisir de vous convier à une réunion publique qui se tiendra le vendredi 25 juin 2010 à 9h30 dans l’Amphithéâtre principal (Bâtiment 500)*. Un café d’accueil y sera servi à partir de 9h. Cette réunion abordera les thèmes suivants : • Valeurs de l’Organisation (Directeur général) • Code de Conduite (Directeur général / Anne-Sylvie Catherin) • Création du nouveau rôle d’Ombudsperson (Vincent Vuillemin) Ces présentations seront suivies d’une séance de questions-réponses. Nous espérons vous retrouver nombreux le 25 juin ! Meilleures salutations, Anne-Sylvie Catherin Chef du Département des Ressources humaines *Cette réunion sera retransmise simultanément dans l’Amphithéâtre BE de Prévessin (Bâtiment 864) et également disponible à l’adresse suivante : http://webcast.cern.ch -------------------------------------------------------- Dear colleagues, In collaboration with HR Department, the Director-General would like to invite you to an information meeting which will be held on Friday 25 June 2010 at 9:30 am in the Main Auditorium (Building 500)*. A welcome coffee will be available from 9:00 am. During this meeting, information will be given about: • Organization’s values (Director-General) • Code of Conduct (Director-General / Anne-Sylvie Catherin) • New Ombudsperson role (Vincent Vuillemin) These presentations will be followed by a questions & answers session. We look forward to seeing you all on 25 June! Best regards, Anne-Sylvie Catherin Head, Human Resources Department *This meeting will be simultaneously retransmitted in BE Auditorium (Building 864) and available at the following address: http://webcast.cern.ch.

  18. HR Public meeting

    ScienceCinema

    None

    2011-10-06

    Cher(e)s collègues, En collaboration avec le Département HR, le Directeur général a le plaisir de vous convier à une réunion publique qui se tiendra le vendredi 25 juin 2010 à 9h30 dans l?Amphithéâtre principal (Bâtiment 500)*. Un café d?accueil y sera servi à partir de 9h. Cette réunion abordera les thèmes suivants : ? Valeurs de l?Organisation (Directeur général) ? Code de Conduite (Directeur général / Anne-Sylvie Catherin) ? Création du nouveau rôle d?Ombudsperson (Vincent Vuillemin) Ces présentations seront suivies d?une séance de questions-réponses. Nous espérons vous retrouver nombreux le 25 juin ! Meilleures salutations, Anne-Sylvie Catherin Chef du Département des Ressources humaines *Cette réunion sera retransmise simultanément dans l?Amphithéâtre BE de Prévessin (Bâtiment 864) et également disponible à l?adresse suivante : http://webcast.cern.ch -------------------------------------------------------- Dear colleagues, In collaboration with HR Department, the Director-General would like to invite you to an information meeting which will be held on Friday 25 June 2010 at 9:30 am in the Main Auditorium (Building 500)*. A welcome coffee will be available from 9:00 am. During this meeting, information will be given about: ? Organization?s values (Director-General) ? Code of Conduct (Director-General / Anne-Sylvie Catherin) ? New Ombudsperson role (Vincent Vuillemin) These presentations will be followed by a questions & answers session. We look forward to seeing you all on 25 June! Best regards, Anne-Sylvie Catherin Head, Human Resources Department *This meeting will be simultaneously retransmitted in BE Auditorium (Building 864) and available at the following address: http://webcast.cern.ch.

  19. FIRE_AX_ER2_MAS

    Atmospheric Science Data Center

    2015-11-24

    ... Stratocumulus Transition Experiment (ASTEX) ER-2 MODIS Airborne Simulator (MAS) Data Project Title:  MAS ... Temporal Resolution:  Each granule contains one flight track File Format:  HDF Tools:  ...

  20. HR Shared Services and the Realignment of HR.

    ERIC Educational Resources Information Center

    Reilly, P.

    This report examines how adopting the shared services model of human resources (HR) services delivery can help businesses achieve better alignment between their HR service and specific business needs. Chapter 1 provides background information on the research project underlying this report, which included the following data collection activities:…

  1. HR Shared Services and the Realignment of HR.

    ERIC Educational Resources Information Center

    Reilly, P.

    This report examines how adopting the shared services model of human resources (HR) services delivery can help businesses achieve better alignment between their HR service and specific business needs. Chapter 1 provides background information on the research project underlying this report, which included the following data collection activities:…

  2. Expression of MAS1 in breast cancer.

    PubMed

    Luo, Yi; Tanabe, Eriko; Kitayoshi, Misaho; Nishiguchi, Yukiko; Fujiwara, Rina; Matsushima, Sayako; Sasaki, Takamitsu; Sasahira, Tomonori; Chihara, Yoshitomo; Nakae, Dai; Fujii, Kiyomu; Ohmori, Hitoshi; Kuniyasu, Hiroki

    2015-09-01

    MAS1 is a receptor for angiotensin 1-7 (A1-7), which is derived from angiotensin II (A-II) by the action of angiotensin converting enzyme (ACE) 2. MAS1 induces anti-A-II phenotypes, such as vessel dilation and depression of blood pressure. Using immunohistochemistry, we examined the role of MAS1 in 132 cases of invasive ductal carcinoma (IDC) of the breast. While benign mammary tissues expressed MAS1 at high levels, MAS1 expression was attenuated in all IDC, especially in scirrhous IDC. The decrease in MAS1 expression was associated with tumor growth, lymph node metastasis, and grade. MAS1 expression was inversely associated with the proliferation index and epidermal growth factor receptor and human epidermal growth factor receptor-2 expression. Of the 132 cases, 12 (9.1%) were triple-negative breast cancer (TNBC) cases. All TNBC cases (the 12 cases and the additional 36 cases using a tissue array) expressed MAS1. Using the TNBC cell lines 4T1 and MDA-MB-468, which expresses MAS1, we found that cell growth, anti-apoptotic survival and invasion were suppressed by MAS1 activation with A1-7 treatment and enhanced by MAS1 knockdown. In contrast, synergic effect was found between tamoxifen and A1-7 in a luminal A breast cancer cell line, MCF-7. Combination treatment with cisplatin, an ACE2 activator, and an A-II type 1 receptor blocker showed synergic effects on tumor growth inhibition of 4T1 tumors in a syngeneic mouse model. These findings suggest that MAS1 might act as an inhibitory regulator of breast cancer and may be a possible molecular target for this malignancy. PMID:26080617

  3. Expression of MAS1 in breast cancer

    PubMed Central

    Luo, Yi; Tanabe, Eriko; Kitayoshi, Misaho; Nishiguchi, Yukiko; Fujiwara, Rina; Matsushima, Sayako; Sasaki, Takamitsu; Sasahira, Tomonori; Chihara, Yoshitomo; Nakae, Dai; Fujii, Kiyomu; Ohmori, Hitoshi; Kuniyasu, Hiroki

    2015-01-01

    MAS1 is a receptor for angiotensin 1-7 (A1-7), which is derived from angiotensin II (A-II) by the action of angiotensin converting enzyme (ACE) 2. MAS1 induces anti-A-II phenotypes, such as vessel dilation and depression of blood pressure. Using immunohistochemistry, we examined the role of MAS1 in 132 cases of invasive ductal carcinoma (IDC) of the breast. While benign mammary tissues expressed MAS1 at high levels, MAS1 expression was attenuated in all IDC, especially in scirrhous IDC. The decrease in MAS1 expression was associated with tumor growth, lymph node metastasis, and grade. MAS1 expression was inversely associated with the proliferation index and epidermal growth factor receptor and human epidermal growth factor receptor-2 expression. Of the 132 cases, 12 (9.1%) were triple-negative breast cancer (TNBC) cases. All TNBC cases (the 12 cases and the additional 36 cases using a tissue array) expressed MAS1. Using the TNBC cell lines 4T1 and MDA-MB-468, which expresses MAS1, we found that cell growth, anti-apoptotic survival and invasion were suppressed by MAS1 activation with A1-7 treatment and enhanced by MAS1 knockdown. In contrast, synergic effect was found between tamoxifen and A1-7 in a luminal A breast cancer cell line, MCF-7. Combination treatment with cisplatin, an ACE2 activator, and an A-II type 1 receptor blocker showed synergic effects on tumor growth inhibition of 4T1 tumors in a syngeneic mouse model. These findings suggest that MAS1 might act as an inhibitory regulator of breast cancer and may be a possible molecular target for this malignancy. PMID:26080617

  4. Observation of NMR noise from solid samples.

    PubMed

    Schlagnitweit, Judith; Dumez, Jean-Nicolas; Nausner, Martin; Jerschow, Alexej; Elena-Herrmann, Bénédicte; Müller, Norbert

    2010-11-01

    We demonstrate that proton NMR noise signals, i.e. NMR spectra without excitation by radio frequency, can be obtained from solid samples. Experimental results are shown for static and magic-angle spinning conditions. In addition, a tuning procedure based on the probes' NMR noise characteristics and similar to the one described previously for liquids probes can also be used to optimize signal-to-noise ratios in ¹H-MAS experiments. PMID:20850362

  5. Comprehensive multiphase NMR spectroscopy: Basic experimental approaches to differentiate phases in heterogeneous samples

    NASA Astrophysics Data System (ADS)

    Courtier-Murias, Denis; Farooq, Hashim; Masoom, Hussain; Botana, Adolfo; Soong, Ronald; Longstaffe, James G.; Simpson, Myrna J.; Maas, Werner E.; Fey, Michael; Andrew, Brian; Struppe, Jochem; Hutchins, Howard; Krishnamurthy, Sridevi; Kumar, Rajeev; Monette, Martine; Stronks, Henry J.; Hume, Alan; Simpson, André J.

    2012-04-01

    Heterogeneous samples, such as soils, sediments, plants, tissues, foods and organisms, often contain liquid-, gel- and solid-like phases and it is the synergism between these phases that determine their environmental and biological properties. Studying each phase separately can perturb the sample, removing important structural information such as chemical interactions at the gel-solid interface, kinetics across boundaries and conformation in the natural state. In order to overcome these limitations a Comprehensive Multiphase-Nuclear Magnetic Resonance (CMP-NMR) probe has been developed, and is introduced here, that permits all bonds in all phases to be studied and differentiated in whole unaltered natural samples. The CMP-NMR probe is built with high power circuitry, Magic Angle Spinning (MAS), is fitted with a lock channel, pulse field gradients, and is fully susceptibility matched. Consequently, this novel NMR probe has to cover all HR-MAS aspects without compromising power handling to permit the full range of solution-, gel- and solid-state experiments available today. Using this technology, both structures and interactions can be studied independently in each phase as well as transfer/interactions between phases within a heterogeneous sample. This paper outlines some basic experimental approaches using a model heterogeneous multiphase sample containing liquid-, gel- and solid-like components in water, yielding separate 1H and 13C spectra for the different phases. In addition, 19F performance is also addressed. To illustrate the capability of 19F NMR soil samples, containing two different contaminants, are used, demonstrating a preliminary, but real-world application of this technology. This novel NMR approach possesses a great potential for the in situ study of natural samples in their native state.

  6. Alloy NASA-HR-1

    NASA Technical Reports Server (NTRS)

    Chen, Po-Shou; Mitchell, Michael

    2005-01-01

    NASA-HR-1 is a high-strength Fe-Ni-base superalloy that resists high-pressure hydrogen environment embrittlement (HEE), oxidation, and corrosion. Originally derived from JBK-75, NASA-HR-1 has exceptional HEE resistance that can be attributed to its gamma-matrix and eta-free (Ni3Ti) grain boundaries. The chemistry was formulated using a design approach capable of accounting for the simultaneous effects of several alloy additions. This approach included: (1) Systematically modifying gamma-matrix compositions based on JBK-75; (2) Increasing gamma (Ni3(Al,Ti)) volume fraction and adding gamma-matrix strengthening elements to obtain higher strength; and (3) Obtaining precipitate-free grain boundaries. The most outstanding attribute of NASA-HR-1 is its ability to resist HEE while showing much improved strength. NASA-HR-1 has approximately 25% higher yield strength than JXK-75 and exhibits tensile elongation of more than 20% with no ductility loss in a hydrogen environment at 5 ksi, an achievement unparalleled by any other commercially available alloy. Its Cr and Ni contents provide exceptional resistance to environments that promote oxidation and corrosion. Microstructural stability was maintained by improved solid solubility of the gamma-matrix, along with the addition of alloying elements to retard eta (Ni3Ti) precipitation. NASA-HR-1 represents a new system that greatly extends the compositional ranges of existing HEE-resistant Fe-Ni-base superalloys.

  7. Solid-state NMR analysis of coals and shales from the Mesaverde Group, Green River Basin, Wyoming

    SciTech Connect

    Miknis, F.P.; MacGowan, D.B.

    1993-08-01

    Samples of coals and shales from the Almond Formation of the Mesaverde Group, Greater Green River Basin, Wyoming were analyzed using solid-state {sup 13}C nuclear magnetic resonance (NMR) techniques of cross polarization with magic-angle spinning (CP/MAS). The samples were taken from a present-day depth of burial ranging from {approximately}3,000 to {approximately}15,000 ft. In addition, CP/MAS {sup 13}C NMR measurements were made on residues from the hydrous pyrolysis of Almond coal. The hydrous pyrolysis experiments were conducted isothermally for 72 hr in the temperature range of 290 to 360{degree}C (554 to 680{degree}F). In general, the maturation trends observed by NMR for the naturally and artificially matured samples were in agreement with results obtained from other geochemical analyses. The NMR spectra of the naturally matured shale samples showed only a small aliphatic component at depths greater than about 12,000 ft, indicating little capacity for hydrocarbon generation at depths greater than this. Vitrinite reflectance measurements placed the oil window at between 4,500 and 14,500 ft. NMR measurements of the hydrous pyrolysis residues showed a clear loss of aliphatic carbon, relative to the aromatic carbon, with temperature. For the residue obtained from the highest study temperature (360{degree}C/680{degree}F), there was a 60% depletion of the hydrocarbon-producing aliphatic components. The trends in loss of aliphatic carbon with temperature suggested a means of defining a geochemical transformation ratio in terms of the loss of the aliphatic carbon fraction. A good correlation was found between the NMR transformation ratio and the production index determined by Rock-Eval pyrolysis measurements.

  8. Fluid flow dynamics in MAS systems

    NASA Astrophysics Data System (ADS)

    Wilhelm, Dirk; Purea, Armin; Engelke, Frank

    2015-08-01

    The turbine system and the radial bearing of a high performance magic angle spinning (MAS) probe with 1.3 mm-rotor diameter has been analyzed for spinning rates up to 67 kHz. We focused mainly on the fluid flow properties of the MAS system. Therefore, computational fluid dynamics (CFD) simulations and fluid measurements of the turbine and the radial bearings have been performed. CFD simulation and measurement results of the 1.3 mm-MAS rotor system show relatively low efficiency (about 25%) compared to standard turbo machines outside the realm of MAS. However, in particular, MAS turbines are mainly optimized for speed and stability instead of efficiency. We have compared MAS systems for rotor diameter of 1.3-7 mm converted to dimensionless values with classical turbomachinery systems showing that the operation parameters (rotor diameter, inlet mass flow, spinning rate) are in the favorable range. This dimensionless analysis also supports radial turbines for low speed MAS probes and diagonal turbines for high speed MAS probes. Consequently, a change from Pelton type MAS turbines to diagonal turbines might be worth considering for high speed applications. CFD simulations of the radial bearings have been compared with basic theoretical values proposing considerably smaller frictional loss values. The discrepancies might be due to the simple linear flow profile employed for the theoretical model. Frictional losses generated inside the radial bearings result in undesired heat-up of the rotor. The rotor surface temperature distribution computed by CFD simulations show a large temperature gradient over the rotor.

  9. Fluid flow dynamics in MAS systems.

    PubMed

    Wilhelm, Dirk; Purea, Armin; Engelke, Frank

    2015-08-01

    The turbine system and the radial bearing of a high performance magic angle spinning (MAS) probe with 1.3mm-rotor diameter has been analyzed for spinning rates up to 67kHz. We focused mainly on the fluid flow properties of the MAS system. Therefore, computational fluid dynamics (CFD) simulations and fluid measurements of the turbine and the radial bearings have been performed. CFD simulation and measurement results of the 1.3mm-MAS rotor system show relatively low efficiency (about 25%) compared to standard turbo machines outside the realm of MAS. However, in particular, MAS turbines are mainly optimized for speed and stability instead of efficiency. We have compared MAS systems for rotor diameter of 1.3-7mm converted to dimensionless values with classical turbomachinery systems showing that the operation parameters (rotor diameter, inlet mass flow, spinning rate) are in the favorable range. This dimensionless analysis also supports radial turbines for low speed MAS probes and diagonal turbines for high speed MAS probes. Consequently, a change from Pelton type MAS turbines to diagonal turbines might be worth considering for high speed applications. CFD simulations of the radial bearings have been compared with basic theoretical values proposing considerably smaller frictional loss values. The discrepancies might be due to the simple linear flow profile employed for the theoretical model. Frictional losses generated inside the radial bearings result in undesired heat-up of the rotor. The rotor surface temperature distribution computed by CFD simulations show a large temperature gradient over the rotor. PMID:26073599

  10. VizieR Online Data Catalog: HR 5341, HD 142070, HR 6967 & HR 8434 uvby phot. (Adelman, 2001)

    NASA Astrophysics Data System (ADS)

    Adelman, S. J.

    2001-01-01

    Differential Stroemgren uvby observations from the Four College Automated Photoelectric Telescope (FCAPT) are presented for the mCP stars HD 142070, HR 6967, and HR 8434 and the CP star HR 5341. The latter star is found to be constant. Improved periods were derived for HD 142070, 3.37189d, HR 6967, 3.91227d, and HR 8434, 1.43237d. Further observations of HD 142070 are needed to phase the magnetic data with the photometry, of HR 6967 to settle minor discrepancies between y and scaled Geneva V photometry, and of HR 8434 to resolve small discrepancies between two uvby photometric data sets. (5 data files).

  11. NMR Based Cerebrum Metabonomic Analysis Reveals Simultaneous Interconnected Changes during Chick Embryo Incubation

    PubMed Central

    Feng, Yue; Zhu, Hang; Zhang, Xu; Wang, Xuxia; Xu, Fuqiang; Tang, Huiru; Ye, Chaohui; Liu, Maili

    2015-01-01

    To find out if content changes of the major functional cerebrum metabolites are interconnected and formed a network during the brain development, we obtained high-resolution magic-angle-spinning (HR-MAS) 1H NMR spectra of cerebrum tissues of chick embryo aged from incubation day 10 to 20, and postnatal day 1, and analyzed the data with principal component analysis (PCA). Within the examined time window, 26 biological important molecules were identified and 12 of them changed their relative concentration significantly in a time-dependent manner. These metabolites are generally belonged to three categories, neurotransmitters, nutrition sources, and neuronal or glial markers. The relative concentration changes of the metabolites were interconnected among/between the categories, and, more interestingly, associated with the number and size of Nissl-positive neurons. These results provided valuable biochemical and neurochemical information to understand the development of the embryonic brain. PMID:26485040

  12. Mas' Making and Pedagogy: Imagined Possibilities

    ERIC Educational Resources Information Center

    Fournillier, Janice B.

    2009-01-01

    In this article I draw on an ethnographic case study that examined mas' makers' perceptions of the learning/teaching practices at work in the production of costumes for Trinidad and Tobago's annual Carnival celebrations. During the 2005 Carnival season I spent four months in the field, my country of birth, and collected data through participant…

  13. Access to side-chain carbon information in deuterated solids under fast MAS through non-rotor-synchronized mixing.

    PubMed

    Kulminskaya, Natalia; Vasa, Suresh Kumar; Giller, Karin; Becker, Stefan; Kwan, Ann; Sunde, Margaret; Linser, Rasmus

    2016-01-01

    We demonstrate the accessibility of aliphatic (13)C side chain chemical shift sets for solid-state NMR despite perdeuteration and fast MAS using isotropic, non-rotor-synchronized (13)C-(13)C mixing. Combined with amide proton detection, we unambiguously and sensitively detect whole side chain to backbone correlations for two proteins using around 1 mg of sample. PMID:26541699

  14. Magic Angle Spinning NMR Based Metabolic Profiling of Head and Neck Squamous Cell Carcinoma Tissues

    PubMed Central

    Somashekar, Bagganahalli S.; Kamarajan, Pachiyappan; Danciu, Theodora; Kapila, Yvonne L.; Chinnaiyan, Arul M.; Rajendiran, Thekkelnaycke M.; Ramamoorthy, Ayyalusamy

    2011-01-01

    High-resolution magic-angle spinning (HR-MAS) proton NMR spectroscopy is used to explore the metabolic signatures of head and neck squamous cell carcinoma (HNSCC) which included matched normal adjacent tissue (NAT) and tumor originating from tongue, lip, larynx and oral cavity, and associated lymph-node metastatic (LN-Met) tissues. A total of 43 tissues (18 NAT, 18 Tumor and 7 LN-Met) from twenty-two HNSCC patients were analyzed. Principal Component Analysis of NMR data showed a clear classification between NAT and tumor tissues, however, LN-Met tissues were classified among tumor. A partial least squares discriminant analysis model generated from NMR metabolic profiles was used to differentiate normal from tumor samples (Q2 > 0.80, Receiver Operator Characteristic area under the curve > 0. 86, using 7-fold cross validation). HNSCC and LN-Met tissues showed elevated levels of lactate, amino acids including leucine, isoleucine, valine, alanine, glutamine, glutamate, aspartate, glycine, phenylalanine and tyrosine, choline containing compounds, creatine, taurine, glutathione and decreased levels of triglycerides. These elevated metabolites were associated with highly active glycolysis, increased amino acids influx (anaplerosis) into the TCA cycle, altered energy metabolism, membrane choline phospholipid metabolism, and oxidative and osmotic defense mechanisms. Moreover, decreased levels of triglycerides may indicate lipolysis followed by ?-oxidation of fatty acids that may exist to deliver bioenergy for rapid tumor cell proliferation and growth. PMID:21961579

  15. NMR Spectroscopy of Human Eye Tissues: A New Insight into Ocular Biochemistry

    PubMed Central

    Kryczka, Tomasz; Wyl?ga?a, Edward; Dobrowolski, Dariusz; Midelfart, Anna

    2014-01-01

    Background. The human eye is a complex organ whose anatomy and functions has been described very well to date. Unfortunately, the knowledge of the biochemistry and metabolic properties of eye tissues varies. Our objective was to reveal the biochemical differences between main tissue components of human eyes. Methods. Corneas, irises, ciliary bodies, lenses, and retinas were obtained from cadaver globes 0-1/2 hours postmortem of 6 male donors (age: 44–61 years). The metabolic profile of tissues was investigated with HR MAS 1H NMR spectroscopy. Results. A total of 29 metabolites were assigned in the NMR spectra of the eye tissues. Significant differences between tissues were revealed in contents of the most distant eye-tissues, while irises and ciliary bodies showed minimal biochemical differences. ATP, acetate, choline, glutamate, lactate, myoinositol, and taurine were identified as the primary biochemical compounds responsible for differentiation of the eye tissues. Conclusions. In this study we showed for the first time the results of the analysis of the main human eye tissues with NMR spectroscopy. The biochemical contents of the selected tissues seemed to correspond to their primary anatomical and functional attributes, the way of the delivery of the nutrients, and the location of the tissues in the eye. PMID:25525621

  16. eHR: An Introduction. IES Report.

    ERIC Educational Resources Information Center

    Kettley, P.; Reilly, P.

    This document introduces the concept of electronic human resources (eHR) and its application. Chapter 1 presents a brief overview of the guide's development, purpose, and structure. Chapter 2 defines the concept of eHR as "the application of conventional, Web, and voice technologies to improve HR administration, transactions, and process…

  17. eHR: An Introduction. IES Report.

    ERIC Educational Resources Information Center

    Kettley, P.; Reilly, P.

    This document introduces the concept of electronic human resources (eHR) and its application. Chapter 1 presents a brief overview of the guide's development, purpose, and structure. Chapter 2 defines the concept of eHR as "the application of conventional, Web, and voice technologies to improve HR administration, transactions, and process…

  18. FCAPT uvby Photometry of the mCP Stars HD 86592, HR 4330, HR 6958, and HR 7786

    NASA Astrophysics Data System (ADS)

    Adelman, Saul J.

    2008-04-01

    New differential Strömgren uvby Four College Automated Photoelectric Telescope (FCAPT) observations of four magnetic CP stars HD 86592, HR 4330, HR 6958, and HR 7786 are presented. These observations are analyzed along with published FCAPT data to improve the periods and the light curves. The period of HD 86592 is that of Babel & North, 2.886669 days. The new periods of HR 4330, HR 6958, and HR 7786 are 3.152, 18.0642, and 8.5295 days, respectively, almost the same as their previous values from FCAPT data. The first three stars can be characterized as having constant light curves and periods. However, the small differences among the seasonal light curves of HR 7786 indicate it is a star whose rotational axis is precessing about its magnetic axis.

  19. Revisiting the optical interferometry observations of HR 4049

    NASA Astrophysics Data System (ADS)

    Menut, J.-L.; Chesneau, O.; Bakker, E.; Lopez, B.; Perrin, G.; Leinert, C.; Quirrenbach, A.

    2009-03-01

    Aims: We present high spatial resolution observations in the mid-infrared of the dusty core of the binary system HR 4049. Methods: We used the mid-infrared interferometer MIDI/VLTI with 40 m projected baselines. These observations provided two spectrally dispersed visibility curves at a spatial resolution of ~10 mas. Acquisition images and spectra are in addition obtained with a single telescope spatial resolution of ~250 mas. Results: The MIDI spectra show features due to emission lines (7.9, 8.6 and 11.3 micron) attributed to PAHs. The comparison between ISO and MIDI spectra and dispersed visibility curves allows us to investigate the budget of continuum and PAH emission from distant regions to the inner regions of the compact dusty structure. The flux balance between these different PAH features is different to the one seen in the large beam ISO spectrum, suggesting different contributions at varying locations from the central star for the different PAH species. These features are over-resolved (i.e. their correlated flux is close to zero), placing the bulk of their line forming region at least at 50-70 mas from the central star. The continuum extension is estimated to range between 23 and 27 mas using a Gaussian model, and is very close to the K-band sizes measured with VINCI/VLTI, implying that the emitting regions of the near and mid-IR are similar. The visibilities from the two different baselines do not allow us to constrain the shape of the continuum emitting region but noticeable differences between them suggest that the N band dusty environment is flattened in a direction that coincides with the one suggested by previous polarimetric observations. Based on observations made with the Very Large Telescope Interferometer at Paranal Observatory.

  20. Réunion publique HR

    SciTech Connect

    2010-04-30

    Chers Collègues,Je me permets de vous rappeler qu'une réunion publique organisée par le Département HR se tiendra aujourd'hui:Vendredi 30 avril 2010 à 9h30 dans l'Amphithéâtre principal (café offert dès 9h00).Durant cette réunion, des informations générales seront données sur:le CERN Admin e-guide, qui est un nouveau guide des procédures administratives du CERN ayant pour but de faciliter la recherche d'informations pratiques et d'offrir un format de lecture convivial;le régime d'Assurance Maladie de l'Organisation (présentation effectuée par Philippe Charpentier, Président du CHIS Board) et;la Caisse de Pensions (présentation effectuée par Théodore Economou, Administrateur de la Caisse de Pensions du CERN).Une transmission simultanée de cette réunion sera assurée dans l'Amphithéâtre BE de Prévessin et également disponible à l'adresse suivante: http://webcast.cern.chJe me réjouis de votre participation!Meilleures salutations,Anne-Sylvie CatherinChef du Département des Ressources humaines__________________________________________________________________________________Dear Colleagues,I should like to remind you that a plublic meeting organised by HR Department will be held today:Friday 30 April 2010 at 9:30 am in the Main Auditorium (coffee from 9:00 am).During this meeting, general information will be given about:the CERN Admin e-guide which is a new guide to the Organization's administrative procedures, drawn up to facilitate the retrieval of practical information and to offer a user-friendly format;the CERN Health Insurance System (presentation by Philippe Charpentier, President of the CHIS Board) and;the Pension Fund (presentation by Theodore Economou, Administrator of the CERN Pension Fund).A simultaneous transmission of this meeting will be broadcast in the BE Auditorium at Prévessin and will also be available at the following address. http://webcast.cern.chI look forward to your participation!Best regards,Anne-Sylvie CatherinHead, Human Resources Department

  1. Réunion publique HR

    ScienceCinema

    None

    2011-10-06

    Chers Collègues,Je me permets de vous rappeler qu'une réunion publique organisée par le Département HR se tiendra aujourd'hui:Vendredi 30 avril 2010 à 9h30 dans l'Amphithéâtre principal (café offert dès 9h00).Durant cette réunion, des informations générales seront données sur:le CERN Admin e-guide, qui est un nouveau guide des procédures administratives du CERN ayant pour but de faciliter la recherche d'informations pratiques et d'offrir un format de lecture convivial;le régime d'Assurance Maladie de l'Organisation (présentation effectuée par Philippe Charpentier, Président du CHIS Board) et;la Caisse de Pensions (présentation effectuée par Théodore Economou, Administrateur de la Caisse de Pensions du CERN).Une transmission simultanée de cette réunion sera assurée dans l'Amphithéâtre BE de Prévessin et également disponible à l'adresse suivante: http://webcast.cern.chJe me réjouis de votre participation!Meilleures salutations,Anne-Sylvie CatherinChef du Département des Ressources humaines__________________________________________________________________________________Dear Colleagues,I should like to remind you that a plublic meeting organised by HR Department will be held today:Friday 30 April 2010 at 9:30 am in the Main Auditorium (coffee from 9:00 am).During this meeting, general information will be given about:the CERN Admin e-guide which is a new guide to the Organization's administrative procedures, drawn up to facilitate the retrieval of practical information and to offer a user-friendly format;the CERN Health Insurance System (presentation by Philippe Charpentier, President of the CHIS Board) and;the Pension Fund (presentation by Theodore Economou, Administrator of the CERN Pension Fund).A simultaneous transmission of this meeting will be broadcast in the BE Auditorium at Prévessin and will also be available at the following address. http://webcast.cern.chI look forward to your participation!Best regards,Anne-Sylvie CatherinHead, Human Resources Department

  2. NMR imaging

    SciTech Connect

    Andrew, E.R.

    1983-04-01

    Since hydrogen is the most abundant element in all living organisms, proton NMR lends itself well as a method of investigation in biology and medicine. NMR imaging has some special advantages as a diagnostic tool: no ionizing radiation is used, it is noninvasive; it provides a safer means of imaging than the use of x-rays, gamma rays, positrons, or heavy ions. In contrast with ultrasound, the radiation penetrates the bony structures without attenuation. In additional to morphological information, NMR imaging provides additional diagnostic insights through relaxation parameters, which are not available from other imaging methods. In the decade since the first primitive NMR images were obtained, the quality of images now obtained approaches those from CT x-ray scanners. Prototype instruments are being constructed for clinical evaluation and the first whole-body scanners are beginning to appear on the market at costs comparable to CT scanners. Primary differences in equipment for conventional NMR and NMR imaging are the much larger aperture magnets that are required for the examination of human subjects and the addition of coils to generate field gradients and facilities for manipulating the gradients. Early results from clinical trials in many parts of the world are encouraging, and in a few years, the usefuleness of this modality of medical imaging to the medical profession in diagnosis and treatment of disease will be defined. 10 figures.

  3. Instrumentation for solid-state dynamic nuclear polarization with magic angle spinning NMR.

    PubMed

    Rosay, Melanie; Blank, Monica; Engelke, Frank

    2016-03-01

    Advances in dynamic nuclear polarization (DNP) instrumentation and methodology have been key factors in the recent growth of solid-state DNP NMR applications. We review the current state of the art of solid-state DNP NMR instrumentation primarily based on available commercial platforms. We start with a general system overview, including options for microwave sources and DNP NMR probes, and then focus on specific developments for DNP at 100K with magic angle spinning (MAS). Gyrotron microwave sources, passive components to transmit microwaves, the DNP MAS probe, a cooling device for low-temperature MAS, and sample preparation procedures including radicals for DNP are considered. PMID:26920834

  4. Instrumentation for solid-state dynamic nuclear polarization with magic angle spinning NMR

    NASA Astrophysics Data System (ADS)

    Rosay, Melanie; Blank, Monica; Engelke, Frank

    2016-03-01

    Advances in dynamic nuclear polarization (DNP) instrumentation and methodology have been key factors in the recent growth of solid-state DNP NMR applications. We review the current state of the art of solid-state DNP NMR instrumentation primarily based on available commercial platforms. We start with a general system overview, including options for microwave sources and DNP NMR probes, and then focus on specific developments for DNP at 100 K with magic angle spinning (MAS). Gyrotron microwave sources, passive components to transmit microwaves, the DNP MAS probe, a cooling device for low-temperature MAS, and sample preparation procedures including radicals for DNP are considered.

  5. Application of high-resolution magic-angle spinning NMR spectroscopy to define the cell uptake of MRI contrast agents.

    PubMed

    Calabi, Luisella; Alfieri, Goffredo; Biondi, Luca; De Miranda, Mario; Paleari, Lino; Ghelli, Stefano

    2002-06-01

    A new method, based on proton high-resolution magic-angle spinning ((1)H HR-MAS) NMR spectroscopy, has been employed to study the cell uptake of magnetic resonance imaging contrast agents (MRI-CAs). The method was tested on human red blood cells (HRBC) and white blood cells (HWBC) by using three gadolinium complexes, widely used in diagnostics, Gd-BOPTA, Gd-DTPA, and Gd-DOTA, and the analogous complexes obtained by replacing Gd(III) with Dy(III), Nd(III), and Tb(III) (i.e., complexes isostructural to the ones of gadolinium but acting as shift agents). The method is based on the evaluation of the magnetic effects, line broadening, or induced lanthanide shift (LIS) caused by these complexes on NMR signals of intra- and extracellular water. Since magnetic effects are directly linked to permeability, this method is direct. In all the tests, these magnetic effects were detected for the extracellular water signal only, providing a direct proof that these complexes are not able to cross the cell membrane. Line broadening effects (i.e., the use of gadolinium complexes) only allow qualitative evaluations. On the contrary, LIS effects can be measured with high precision and they can be related to the concentration of the paramagnetic species in the cellular compartments. This is possible because the HR-MAS technique provides the complete elimination of bulk magnetic susceptibility (BMS) shift and the differentiation of extra- and intracellular water signals. Thus with this method, the rapid quantification of the MRI-CA amount inside and outside the cells is actually feasible. PMID:12165257

  6. Application of High-Resolution Magic-Angle Spinning NMR Spectroscopy to Define the Cell Uptake of MRI Contrast Agents

    NASA Astrophysics Data System (ADS)

    Calabi, Luisella; Alfieri, Goffredo; Biondi, Luca; De Miranda, Mario; Paleari, Lino; Ghelli, Stefano

    2002-06-01

    A new method, based on proton high-resolution magic-angle spinning ( 1H HR-MAS) NMR spectroscopy, has been employed to study the cell uptake of magnetic resonance imaging contrast agents (MRI-CAs). The method was tested on human red blood cells (HRBC) and white blood cells (HWBC) by using three gadolinium complexes, widely used in diagnostics, Gd-BOPTA, Gd-DTPA, and Gd-DOTA, and the analogous complexes obtained by replacing Gd(III) with Dy(III), Nd(III), and Tb(III) (i.e., complexes isostructural to the ones of gadolinium but acting as shift agents). The method is based on the evaluation of the magnetic effects, line broadening, or induced lanthanide shift (LIS) caused by these complexes on NMR signals of intra- and extracellular water. Since magnetic effects are directly linked to permeability, this method is direct. In all the tests, these magnetic effects were detected for the extracellular water signal only, providing a direct proof that these complexes are not able to cross the cell membrane. Line broadening effects (i.e., the use of gadolinium complexes) only allow qualitative evaluations. On the contrary, LIS effects can be measured with high precision and they can be related to the concentration of the paramagnetic species in the cellular compartments. This is possible because the HR-MAS technique provides the complete elimination of bulk magnetic susceptibility (BMS) shift and the differentiation of extra- and intracellular water signals. Thus with this method, the rapid quantification of the MRI-CA amount inside and outside the cells is actually feasible.

  7. Performance of RINEPT is Amplified by Dipolar Couplings Under Ultrafast MAS Conditions

    PubMed Central

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2014-01-01

    The refocused insensitive nuclei enhanced by polarization transfer (RINEPT) technique is commonly used for heteronuclear polarization transfer in solution and solid-state NMR spectroscopy. Suppression of dipolar couplings, either by fast molecular motions in solution or by a combination of MAS and multiple pulse sequences in solids, enables the polarization transfer via scalar couplings. However, the presence of unsuppressed dipolar couplings could alter the functioning of RINEPT, particularly under fast/ultrafast MAS conditions. In this study, we demonstrate, through experiments on rigid solids complemented by numerical simulations, that the polarization transfer efficiency of RINEPT is dependent on the MAS frequency. In addition, we show that heteronuclear dipolar coupling is the dominant factor in the polarization transfer, which is strengthened by the presence of 1H-1H dipolar couplings. In fact, the simultaneous presence of homonuclear and heteronuclear dipolar couplings is the premise for the polarization transfer by RINEPT, whereas the scalar coupling plays an insignificant role under ultrafast MAS conditions on rigid solids. Our results additionally reveal that the polarization transfer efficiency decreases with the increasing duration of RF pulses used in the RINEPT sequence. PMID:24792960

  8. Moderate MAS enhances local 1H spin exchange and spin diffusion

    NASA Astrophysics Data System (ADS)

    Roos, Matthias; Micke, Peter; Saalwächter, Kay; Hempel, Günter

    2015-11-01

    Proton NMR spin-diffusion experiments are often combined with magic-angle spinning (MAS) to achieve higher spectral resolution of solid samples. Here we show that local proton spin diffusion can indeed become faster at low (<10 kHz) spinning rates as compared to static conditions. Spin diffusion under static conditions can thus be slower than the often referred value of 0.8 nm2/ms, which was determined using slow MAS (Clauss et al., 1993). The enhancement of spin diffusion by slow MAS relies on the modulation of the orientation-dependent dipolar couplings during sample rotation and goes along with transient level crossings in combination with dipolar truncation. The experimental finding and its explanation is supported by density matrix simulations, and also emphasizes the sensitivity of spin diffusion to the local coupling topology. The amplification of spin diffusion by slow MAS cannot be explained by any model based on independent spin pairs; at least three spins have to be considered.

  9. NMR use to quantify phlorotannins: the case of Cystoseira tamariscifolia, a phloroglucinol-producing brown macroalga in Brittany (France).

    PubMed

    Jégou, Camille; Kervarec, Nelly; Cérantola, Stéphane; Bihannic, Isabelle; Stiger-Pouvreau, Valérie

    2015-04-01

    Among the most renowned natural products from brown algae, phlorotannins are phloroglucinol polymers that have been extensively studied, both for their biotechnological potential and their interest in chemical ecology. The accurate quantification of these compounds is a key point to understand their role as mediators of chemical defense. In recent years, the Folin-Ciocalteu assay has remained a classic protocol for phlorotannin quantification, even though it frequently leads to over-estimations. Furthermore, the quantification of the whole pool of phlorotannins may not be relevant in ecological surveys. In this study, we propose a rapid (1)H qNMR method for the quantification of phlorotannins. We identified phloroglucinol as the main phenolic compound produced by the brown macroalga Cystoseira tamariscifolia. This monomer was detected in vivo using (1)H HR-MAS spectroscopy. We quantified this molecule through (1)H qNMR experiments using TSP as internal standard. The results are discussed by comparison with a standard Folin-Ciocalteu assay performed on purified extracts. The accuracy and simplicity of qNMR makes this method a good candidate as a standard phlorotannin assay. PMID:25640118

  10. The dust debris around HR 4796

    NASA Technical Reports Server (NTRS)

    Jura, M.

    1991-01-01

    The IRAS data strongly suggest that there is dust debris around the main-sequence A star HR 4796. The optical depth of the dust cloud around HR 4796 is probably twice that around Beta Pic, the main-sequence star in the Bright Star Catalog which was previously thought to have the most opaque dust debris cloud.

  11. NMR at low and ultralow temperatures.

    PubMed

    Tycko, Robert

    2013-09-17

    Solid state nuclear magnetic resonance (NMR) measurements at low temperatures have been common in physical sciences for many years and are becoming increasingly important in studies of biomolecular systems. This Account reviews a diverse set of projects from my laboratory, dating back to the early 1990s, that illustrate the motivations for low-temperature solid state NMR, the types of information that are available from the measurements, and likely directions for future research. These projects include NMR studies of both physical and biological systems, performed at low (cooled with nitrogen, down to 77 K) and ultralow (cooled with helium, below 77 K) temperatures, and performed with and without magic-angle spinning (MAS). NMR studies of physical systems often focus on phenomena that occur only at low temperatures. Two examples from my laboratory are studies of molecular rotation and orientational ordering in solid C60 at low temperatures and studies of unusual electronic states, called skyrmions, in two-dimensionally confined electron systems within semiconductor quantum wells. To study quantum wells, we used optical pumping of nuclear spin polarizations to enhance their NMR signals. The optical pumping phenomenon exists only at ultralow temperatures. In studies of biomolecular systems, low-temperature NMR has several motivations. In some cases, low temperatures suppress molecular tumbling, thereby permitting solid state NMR measurements on soluble proteins. Studies of AIDS-related peptide/antibody complexes illustrate this effect. In other cases, low temperatures suppress conformational exchange, thereby permitting quantitation of conformational distributions. Studies of chemically denatured states of the model protein HP35 illustrate this effect. Low temperatures and rapid freeze-quenching can also be used to trap transient intermediate states in a non-equilibrium kinetic process, as shown in studies of a transient intermediate in the rapid folding pathway of HP35. NMR sensitivity generally increases with decreasing sample temperature. Therefore, it can be useful to carry out experiments at the lowest possible temperatures, particularly in studies of biomolecular systems in frozen solutions. However, solid state NMR studies of biomolecular systems generally require rapid MAS. A novel MAS NMR probe design that uses nitrogen gas for sample spinning and cold helium only for sample cooling allows a wide variety of solid state NMR measurements to be performed on biomolecular systems at 20-25 K, where signals are enhanced by factors of 12-15 relative to measurements at room temperature. MAS NMR at ultralow temperatures also facilitates dynamic nuclear polarization (DNP), allowing sizeable additional signal enhancements and large absolute NMR signal amplitudes with relatively low microwave powers. Current research in my laboratory seeks to develop and exploit DNP-enhanced MAS NMR at ultralow temperatures, for example, in studies of transient intermediates in protein folding and aggregation processes and studies of peptide/protein complexes that can be prepared only at low concentrations. PMID:23470028

  12. Infrared and 13C MAS nuclear magnetic resonance spectroscopic study of acetylation of cotton

    NASA Astrophysics Data System (ADS)

    Adebajo, Moses O.; Frost, Ray L.

    2004-01-01

    The acetylation of commercial cotton samples with acetic anhydride without solvents in the presence of about 5% 4-dimethylaminopyridine (DMAP) catalyst was followed using Fourier transform infrared (FTIR) and 13C MAS NMR spectroscopy. This preliminary investigation was conducted in an effort to develop hydrophobic, biodegradable, cellulosic materials for subsequent application in oil spill cleanup. The FTIR results provide clear evidence for successful acetylation though the NMR results indicate that the level of acetylation is low. Nevertheless, the overall results indicate that cotton fibres are potential candidates suitable for further development via acetylation into hydrophobic sorbent materials for subsequent oil spill cleanup application. The results also indicate that de-acetylation, the reverse of the equilibrium acetylation reaction, occurred when the acetylation reaction was prolonged beyond 3 h.

  13. High-resolution NMR with resistive and hybrid magnets: deconvolution using a field-fluctuation signal.

    PubMed

    Iijima, Takahiro; Takegoshi, K; Hashi, Kenjiro; Fujito, Teruaki; Shimizu, Tadashi

    2007-02-01

    A method for compensating effect of field fluctuation is examined to attain high-resolution NMR spectra with resistive and hybrid magnets. In this method, time dependence of electromotive force induced for a pickup coil attached near a sample is measured synchronously with acquisition of NMR. Observed voltage across the pickup coil is converted to field fluctuation data, which is used to deconvolute NMR signals. The feasibility of the method is studied by (79)Br MAS NMR of KBr under a 30T magnetic field of a hybrid magnet. Twenty single-scan NMR signals were accumulated after the manipulation, resulting in a high-resolution NMR spectrum. PMID:17123849

  14. Ultra fast magic angle spinning solid - state NMR spectroscopy of intact bone.

    PubMed

    Singh, Chandan; Rai, Ratan Kumar; Kayastha, Arvind M; Sinha, Neeraj

    2016-02-01

    Ultra fast magic angle spinning (MAS) has been a potent method to significantly average out homogeneous/inhomogeneous line broadening in solid-state nuclear magnetic resonance (ssNMR) spectroscopy. It has given a new direction to ssNMR spectroscopy with its different applications. We present here the first and foremost application of ultra fast MAS (~60?kHz) for ssNMR spectroscopy of intact bone. This methodology helps to comprehend and elucidate the organic content in the intact bone matrix with resolution and sensitivity enhancement. At this MAS speed, amino protons from organic part of intact bone start to appear in (1) H NMR spectra. The experimental protocol of ultra-high speed MAS for intact bone has been entailed with an additional insight achieved at 60?kHz. Copyright © 2015 John Wiley & Sons, Ltd. PMID:26352739

  15. FIRE_AX_CMS_SOLAR_HR

    Atmospheric Science Data Center

    2015-11-24

    FIRE_AX_CMS_SOLAR_HR Project Title:  FIRE II ASTEX Discipline:  Clouds Field Campaigns Radiation Budget Aerosols Level:  L2 ... Order: Earthdata Search Parameters:  Solar Irradiance Order Data:  Search and Order: Earthdata ...

  16. New generation NMR bioreactor coupled with high-resolution NMR spectroscopy leads to novel discoveries in Moorella thermoaceticum metabolic profiles

    SciTech Connect

    Xue, Junfeng; Isern, Nancy G.; Ewing, R James; Liyu, Andrey V.; Sears, Jesse A.; Knapp, Harlan; Iversen, Jens; Sisk, Daniel R.; Ahring, Birgitte K.; Majors, Paul D.

    2014-06-20

    An in-situ nuclear magnetic resonance (NMR) bioreactor was developed and employed to monitor microbial metabolism under batch-growth conditions in real time. We selected Moorella thermoacetica ATCC 49707 as a test case. M. thermoacetica (formerly Clostridium thermoaceticum) is a strictly anaerobic, thermophilic, acetogenic, gram-positive bacterium with potential for industrial production of chemicals. The metabolic profiles of M. thermoacetica were characterized during growth in batch mode on xylose (a component of lignocellulosic biomass) using the new generation NMR bioreactor in combination with high-resolution, high sensitivity NMR (HR-NMR) spectroscopy. In-situ NMR measurements were performed using water-suppressed H-1 NMR spectroscopy at an NMR frequency of 500 MHz, and aliquots of the bioreactor contents were taken for 600 MHz HR-NMR spectroscopy at specific intervals to confirm metabolite identifications and expand metabolite coverage. M. thermoacetica demonstrated the metabolic potential to produce formate, ethanol and methanol from xylose, in addition to its known capability of producing acetic acid. Real-time monitoring of bioreactor conditions showed a temporary pH decrease, with a concomitant increase in formic acid during exponential growth. Fermentation experiments performed outside of the magnet showed that the strong magnetic field employed for NMR detection did not significantly affect cell metabolism. Use of the in-situ NMR bioreactor facilitated monitoring of the fermentation process in real time, enabling identification of intermediate and end-point metabolites and their correlation with pH and biomass produced during culture growth. Real-time monitoring of culture metabolism using the NMR bioreactor in combination with the HR-NMR spectroscopy will allow optimization of the metabolism of microorganisms producing valuable bioproducts.

  17. A comparative spectroscopic investigation of three pseudopolymorphs of testosterone using solid-state i.r. and high-resolution solid-state NMR

    NASA Astrophysics Data System (ADS)

    Fletton, Richard A.; Harris, Robin K.; Kenwright, Alan M.; Lancaster, Robert W.; Packer, Kenneth J.; Sheppard, Norman

    Three pseudopolymorphic forms of testosterone have been examined by i.r. and CP/MAS NMR spectroscopies. The transmittance i.r. data clearly distinguish the forms. The NMR work also provides clear distinctions and shows crystallographic splittings for the α form only, in accordance with the X-ray data. The NMR spectra are fully assigned. The effect of crystallisation procedure on the NMR spectra was explored. NMR can be used to quantitatively assess mixtures of the β and δ forms.

  18. Changes in the NMR Metabolic Profile of Live Human Neuron-Like SH-SY5Y Cells Exposed to Interferon-α2.

    PubMed

    Valeria, Righi; Luisa, Schenetti; Adele, Mucci; Stefania, Benatti; Fabio, Tascedda; Nicoletta, Brunello; Carmine, Pariante M; Silvia, Alboni

    2016-03-01

    Interferon (IFN)-α2 is an extensively therapeutically used pro-inflammatory cytokine. Though its efficacy in controlling viral replication and tumor cells proliferation, administration of IFN-α2 is often associated with the development of central side effects. Magnetic resonance spectroscopy studies have demonstrated that IFN-α2 administration affects brain metabolism, however the exact nature of this effect is not completely known. We hypothesized that IFN-α2 can affect metabolic activity of human neuron-like SH-SY5Y cells which possess many characteristics of neurons and represent one of the most used models for studying mechanisms involved in neurotoxicity or neuroprotection. To test our hypothesis we have characterized the metabolic signature of live SH-SY5Y, and their conditioned media, after 24 and 72 h of exposure to vehicle or IFN-α2 (100 ng/ml) by using High Resolution-Magic Angle Spinning (HR-MAS) Nuclear Magnetic Resonance (NMR) spectroscopy. Our results revealed that 1) the use of HR-MAS NMR is ideally suitable for the characterization of the metabolic profile of live cells and their conditioned media without extraction procedures; and 2) a 72 h exposure to IFN-α2 increases the level of metabolites involved in maintaining energetic (including creatine and lactate) and osmotic (such as myo-inositol, scyllo-inositol, taurine and glycerophosphorylcholine) balances in neuron-like cells and of metabolic waste products (namely lactate, ethanol and acetate), glycine and glutamine in their growth media. These results may contribute to gain more knowledge about the IFN-α2 induced effect on the brain and support the interpretation of magnetic resonance spectroscopy studies performed in humans. PMID:26541470

  19. Friedel's salt formation in sulfoaluminate cements: A combined XRD and {sup 27}Al MAS NMR study

    SciTech Connect

    Paul, G.; Boccaleri, E.; Buzzi, L.; Canonico, F.; Gastaldi, D.

    2015-01-15

    Four different binders based on calcium sulfoaluminate cements have been submitted to accelerated chlorination through ionic exchange on hydrated pastes, in order to investigate their ability to chemically bind chloride ions that might reduce chloride penetration. The composition of hydrated cements before and after the treatment was evaluated by means of an X-Ray Diffraction–{sup 27}Al Magic Angle Spinning Nuclear Magnetic Resonance Spectroscopy combined study, allowing to take into account even partially amorphous phases and to make quantitative assumption on the relative abundance of the different aluminium-containing phases. It was found that low SO{sub 3} Sulfoaluminate–Portland ternary systems are the most effective in binding chloride ions and the active role played by different members of the AFm family in chloride uptake was confirmed. Moreover, a peculiar behavior related to the formation of Friedel's salt in different pH conditions was also established for the different cements.

  20. Characterization of various magnesium oxides by XRD and {sup 1}H MAS NMR spectroscopy

    SciTech Connect

    Aramendia, M.A.; Benitez, J.A.; Borau, V.; Jimenez, C.; Marinas, J.M.; Ruiz, J.R.; Urbano, F.

    1999-04-01

    A magnesium oxide obtained by thermal decomposition of commercially available magnesium hydroxide was refluxed in water and acetone in order to improve its chemical and textural properties with the purpose of using it as a support for metals in heterogeneous catalysts. X-ray diffraction, CO{sub 2} chemisorption, and {sup 1}H magic-angle spinning nuclear magnetic resonance were used to identify crystal phases, the number of basic sites, and the nature of OH groups in the oxide, respectively.

  1. Effects of felodipine combined with puerarin on ACE2-Ang (1-7)-Mas axis in renovascular hypertensive rat.

    PubMed

    Bai, Song; Huang, Zheng-Gui; Chen, Li; Wang, Jiang-Tao; Ding, Bo-Ping

    2013-06-10

    This study aimed to investigate the effect of combination of felodipine+puerarin on ACE2-Ang (1-7)-Mas axis, and to explore the protective effect of the combination against kidney in renovascular hypertensive rats. Goldblatt rats were randomly divided into 5 groups as follows: 4 groups which were treated with felodipine (Felo), puerarin (Pue), Felo+Pue, and Felo+captopril (Cap), respectively, and a control group of animals that were administrated with distilled water. Contents of Ang II and Ang (1-7) in renal tissues were determined by ELISA kit. The mRNA expression of ACE2/Mas and ACE/AT1 in kidneys was analyzed by RT-PCR. After 8weeks of treatment, compared with Goldblatt group, Felo+Pue reduced SBP, DBP and HR (p<0.01 or p<0.05), ameliorated renal interstitial fibrosis, decreased the level of Ang II and increased that of Ang (1-7), upregulated mRNA expression of ACE2 and Mas, decreased that of ACE and AT1, and downregulated protein expression of TGF-?1 in kidneys (p<0.01). Compared with Felo group, Felo+Pue decreased DBP and HR more markedly, attenuated fibrosis, decreased Ang II levels and increased those of Ang (1-7), upregulated mRNA expression of ACE2 in bilateral kidneys and that of Mas in ischemic kidney, downregulated that of ACE in bilateral kidneys and that of AT1 in ischemic kidney, and decreased expression of TGF-?1 protein significantly. In a word, a combination of Felo+Pue has a more efficient therapeutic effect on DBP and HR, and contributes to a better protection against renal interstitial fibrosis. PMID:23523569

  2. Studies of minute quantities of natural abundance molecules using 2D heteronuclear correlation spectroscopy under 100 kHz MAS.

    PubMed

    Nishiyama, Y; Kobayashi, T; Malon, M; Singappuli-Arachchige, D; Slowing, I I; Pruski, M

    2015-01-01

    Two-dimensional (1)H{(13)C} heteronuclear correlation solid-state NMR spectra of naturally abundant solid materials are presented, acquired using the 0.75-mm magic angle spinning (MAS) probe at spinning rates up to 100 kHz. In spite of the miniscule sample volume (290 nL), high-quality HSQC-type spectra of bulk samples as well as surface-bound molecules can be obtained within hours of experimental time. The experiments are compared with those carried out at 40 kHz MAS using a 1.6-mm probe, which offered higher overall sensitivity due to a larger rotor volume. The benefits of ultrafast MAS in such experiments include superior resolution in (1)H dimension without resorting to (1)H-(1)H homonuclear RF decoupling, easy optimization, and applicability to mass-limited samples. The HMQC spectra of surface-bound species can be also acquired under 100 kHz MAS, although the dephasing of transverse magnetization has significant effect on the efficiency transfer under MAS alone. PMID:25773137

  3. Studies of minute quantities of natural abundance molecules using 2D heteronuclear correlation spectroscopy under 100kHz MAS

    DOE PAGESBeta

    Nishiyama, Y.; Kobayashi, T.; Malon, M.; Singappuli-Arachchige, D.; Slowing, I. I.; Pruski, M.

    2015-02-16

    Two-dimensional 1H{13C} heteronuclear correlation solid-state NMR spectra of naturally abundant solid materials are presented, acquired using the 0.75-mm magic angle spinning (MAS) probe at spinning rates up to 100 kHz. In spite of the miniscule sample volume (290 nL), high-quality HSQC-type spectra of bulk samples as well as surface-bound molecules can be obtained within hours of experimental time. The experiments are compared with those carried out at 40 kHz MAS using a 1.6-mm probe, which offered higher overall sensitivity due to a larger rotor volume. The benefits of ultrafast MAS in such experiments include superior resolution in 1H dimension withoutmore » resorting to 1H–1H homonuclear RF decoupling, easy optimization, and applicability to mass-limited samples. As a result, the HMQC spectra of surface-bound species can be also acquired under 100 kHz MAS, although the dephasing of transverse magnetization has significant effect on the efficiency transfer under MAS alone.« less

  4. Studies of minute quantities of natural abundance molecules using 2D heteronuclear correlation spectroscopy under 100kHz MAS

    SciTech Connect

    Nishiyama, Y.; Kobayashi, T.; Malon, M.; Singappuli-Arachchige, D.; Slowing, I. I.; Pruski, M.

    2015-02-16

    Two-dimensional 1H{13C} heteronuclear correlation solid-state NMR spectra of naturally abundant solid materials are presented, acquired using the 0.75-mm magic angle spinning (MAS) probe at spinning rates up to 100 kHz. In spite of the miniscule sample volume (290 nL), high-quality HSQC-type spectra of bulk samples as well as surface-bound molecules can be obtained within hours of experimental time. The experiments are compared with those carried out at 40 kHz MAS using a 1.6-mm probe, which offered higher overall sensitivity due to a larger rotor volume. The benefits of ultrafast MAS in such experiments include superior resolution in 1H dimension without resorting to 1H–1H homonuclear RF decoupling, easy optimization, and applicability to mass-limited samples. As a result, the HMQC spectra of surface-bound species can be also acquired under 100 kHz MAS, although the dephasing of transverse magnetization has significant effect on the efficiency transfer under MAS alone.

  5. 48 CFR 538.271 - MAS contract awards.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 48 Federal Acquisition Regulations System 4 2011-10-01 2011-10-01 false MAS contract awards. 538.271 Section 538.271 Federal Acquisition Regulations System GENERAL SERVICES ADMINISTRATION SPECIAL CATEGORIES OF CONTRACTING FEDERAL SUPPLY SCHEDULE CONTRACTING Establishing and Administering Federal Supply Schedules 538.271 MAS contract awards....

  6. 48 CFR 538.272 - MAS price reductions.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 48 Federal Acquisition Regulations System 4 2010-10-01 2010-10-01 false MAS price reductions. 538... Schedules 538.272 MAS price reductions. (a) Section 552.238-75, Price Reductions, requires the contractor to maintain during the contract period the negotiated price/discount relationship (and/or term and...

  7. 1020 MHz single-channel proton fast magic angle spinning solid-state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Pandey, Manoj Kumar; Zhang, Rongchun; Hashi, Kenjiro; Ohki, Shinobu; Nishijima, Gen; Matsumoto, Shinji; Noguchi, Takashi; Deguchi, Kenzo; Goto, Atsushi; Shimizu, Tadashi; Maeda, Hideaki; Takahashi, Masato; Yanagisawa, Yoshinori; Yamazaki, Toshio; Iguchi, Seiya; Tanaka, Ryoji; Nemoto, Takahiro; Miyamoto, Tetsuo; Suematsu, Hiroto; Saito, Kazuyoshi; Miki, Takashi; Ramamoorthy, Ayyalusamy; Nishiyama, Yusuke

    2015-12-01

    This study reports a first successful demonstration of a single channel proton 3D and 2D high-throughput ultrafast magic angle spinning (MAS) solid-state NMR techniques in an ultra-high magnetic field (1020 MHz) NMR spectrometer comprised of HTS/LTS magnet. High spectral resolution is well demonstrated.

  8. 1020MHz single-channel proton fast magic angle spinning solid-state NMR spectroscopy.

    PubMed

    Pandey, Manoj Kumar; Zhang, Rongchun; Hashi, Kenjiro; Ohki, Shinobu; Nishijima, Gen; Matsumoto, Shinji; Noguchi, Takashi; Deguchi, Kenzo; Goto, Atsushi; Shimizu, Tadashi; Maeda, Hideaki; Takahashi, Masato; Yanagisawa, Yoshinori; Yamazaki, Toshio; Iguchi, Seiya; Tanaka, Ryoji; Nemoto, Takahiro; Miyamoto, Tetsuo; Suematsu, Hiroto; Saito, Kazuyoshi; Miki, Takashi; Ramamoorthy, Ayyalusamy; Nishiyama, Yusuke

    2015-12-01

    This study reports a first successful demonstration of a single channel proton 3D and 2D high-throughput ultrafast magic angle spinning (MAS) solid-state NMR techniques in an ultra-high magnetic field (1020MHz) NMR spectrometer comprised of HTS/LTS magnet. High spectral resolution is well demonstrated. PMID:26524647

  9. Magic-angle spinning solid-state multinuclear NMR on low-field instrumentation.

    PubMed

    Sørensen, Morten K; Bakharev, Oleg; Jensen, Ole; Jakobsen, Hans J; Skibsted, Jørgen; Nielsen, Niels Chr

    2014-01-01

    Mobile and cost-effective NMR spectroscopy exploiting low-field permanent magnets is a field of tremendous development with obvious applications for arrayed large scale analysis, field work, and industrial screening. So far such demonstrations have concentrated on relaxation measurements and lately high-resolution liquid-state NMR applications. With high-resolution solid-state NMR spectroscopy being increasingly important in a broad variety of applications, we here introduce low-field magic-angle spinning (MAS) solid-state multinuclear NMR based on a commercial ACT 0.45 T 62 mm bore Halbach magnet along with a homebuilt FPGA digital NMR console, amplifiers, and a modified standard 45 mm wide MAS probe for 7 mm rotors. To illustrate the performance of the instrument and address cases where the low magnetic field may offer complementarity to high-field NMR experiments, we demonstrate applications for (23)Na MAS NMR with enhanced second-order quadrupolar coupling effects and (31)P MAS NMR where reduced influence from chemical shift anisotropy at low field may facilitate determination of heteronuclear dipole-dipole couplings. PMID:24291330

  10. Magic-angle spinning solid-state multinuclear NMR on low-field instrumentation

    NASA Astrophysics Data System (ADS)

    Sørensen, Morten K.; Bakharev, Oleg; Jensen, Ole; Jakobsen, Hans J.; Skibsted, Jørgen; Nielsen, Niels Chr.

    2014-01-01

    Mobile and cost-effective NMR spectroscopy exploiting low-field permanent magnets is a field of tremendous development with obvious applications for arrayed large scale analysis, field work, and industrial screening. So far such demonstrations have concentrated on relaxation measurements and lately high-resolution liquid-state NMR applications. With high-resolution solid-state NMR spectroscopy being increasingly important in a broad variety of applications, we here introduce low-field magic-angle spinning (MAS) solid-state multinuclear NMR based on a commercial ACT 0.45 T 62 mm bore Halbach magnet along with a homebuilt FPGA digital NMR console, amplifiers, and a modified standard 45 mm wide MAS probe for 7 mm rotors. To illustrate the performance of the instrument and address cases where the low magnetic field may offer complementarity to high-field NMR experiments, we demonstrate applications for 23Na MAS NMR with enhanced second-order quadrupolar coupling effects and 31P MAS NMR where reduced influence from chemical shift anisotropy at low field may facilitate determination of heteronuclear dipole-dipole couplings.

  11. The LEECH Exoplanet Imaging Survey. Further constraints on the planet architecture of the HR 8799 system

    NASA Astrophysics Data System (ADS)

    Maire, A.-L.; Skemer, A. J.; Hinz, P. M.; Desidera, S.; Esposito, S.; Gratton, R.; Marzari, F.; Skrutskie, M. F.; Biller, B. A.; Defrère, D.; Bailey, V. P.; Leisenring, J. M.; Apai, D.; Bonnefoy, M.; Brandner, W.; Buenzli, E.; Claudi, R. U.; Close, L. M.; Crepp, J. R.; De Rosa, R. J.; Eisner, J. A.; Fortney, J. J.; Henning, T.; Hofmann, K.-H.; Kopytova, T. G.; Males, J. R.; Mesa, D.; Morzinski, K. M.; Oza, A.; Patience, J.; Pinna, E.; Rajan, A.; Schertl, D.; Schlieder, J. E.; Su, K. Y. L.; Vaz, A.; Ward-Duong, K.; Weigelt, G.; Woodward, C. E.

    2015-04-01

    Context. Astrometric monitoring of directly imaged exoplanets allows the study of their orbital parameters and system architectures. Because most directly imaged planets have long orbital periods (>20 AU), accurate astrometry is challenging when based on data acquired on timescales of a few years and usually with different instruments. The LMIRCam camera on the Large Binocular Telescope is being used for the LBT Exozodi Exoplanet Common Hunt (LEECH) survey to search for and characterize young and adolescent exoplanets in L' band (3.8 ?m), including their system architectures. Aims: We first aim to provide a good astrometric calibration of LMIRCam. Then, we derive new astrometry, test the predictions of the orbital model of 8:4:2:1 mean motion resonance proposed for the system, and perform new orbital fitting of the HR 8799 bcde planets. We also present deep limits on a putative fifth planet inside the known planets. Methods: We use observations of HR 8799 and the ?1 Ori C field obtained during the same run in October 2013. Results: We first characterize the distortion of LMIRCam. We determine a platescale and a true north orientation for the images of 10.707 ± 0.012 mas/pix and -0.430 ± 0.076°, respectively. The errors on the platescale and true north orientation translate into astrometric accuracies at a separation of 1'' of 1.1 mas and 1.3 mas, respectively. The measurements for all planets agree within 3? with a predicted ephemeris. The orbital fitting based on the new astrometric measurements favors an architecture for the planetary system based on 8:4:2:1 mean motion resonance. The detection limits allow us to exclude a fifth planet slightly brighter or more massive than HR 8799 b at the location of the 2:1 resonance with HR 8799 e (~9.5 AU) and about twice as bright as HR 8799 cde at the location of the 3:1 resonance with HR 8799 e (~7.5 AU). The LBT is an international collaboration among institutions in the United States, Italy, and Germany. LBT Corporation partners are: The University of Arizona on behalf of the Arizona university system; Istituto Nazionale di Astrofisica, Italy; LBT Beteiligungsgesellschaft, Germany, representing the Max-Planck Society, the Astrophysical Institute Potsdam, and Heidelberg University; The Ohio State University, and The Research Corporation, on behalf of The University of Notre Dame, University of Minnesota, and University of Virginia.

  12. Yellow Hypergiants: A Comparative Study of HR 5171A, Rho Cas, and HR 8752

    NASA Astrophysics Data System (ADS)

    Lobel, A.; de Jager, C.; Nieuwenhuijzen, H.; van Genderen, A. M.; Oudmaijer, R.

    2015-12-01

    We present a comparative study of the detailed spectroscopic variability of selected Fe i absorption lines observed between 1991 and 1995 in the optical spectra of the bright yellow hypergiants HR 5171A and Rho Cas. We also compare with the high-resolution spectrum of HR 8752. The three cool hypergiants reveal broad lines with very similar shapes. The variations with time in the line shapes and depths of HR 5171A and Rho Cas are very similar. The spectroscopic variability is caused by quasi-periodic atmospheric pulsations that strongly correlates with the observed radial velocity and V-brightness changes.

  13. Endothelin-1 downregulates Mas receptor expression in human cardiomyocytes.

    PubMed

    Chen, Zhiheng; Tang, Yamei; Yang, Zuocheng; Liu, Shaojun; Liu, Yong; Li, Yan; He, Wei

    2013-09-01

    Endothelin-1 (ET-1) and the renin-angiotensin system (RAS) are involved in the pathogenesis of cardiac dysfunction. The Mas receptor is a functional binding site for angiotensin (Ang)‑(1-7), which is now considered a critical component of the RAS and exerts cardioprotective effects. To the best of our knowledge, the present study aimed to examine, for the first time, the effects of ET-1 on Mas expression in cultured human cardiomyocytes. Human cardiomyocytes were treated with ET-1 at different concentrations (1, 5, 10, 20 and 30 nM) for varied time periods (0.5, 1.5, 3, 4.5 or 6 h) with or without the transcription inhibitor actinomycin D, endothelin A (ETA) receptor blocker BQ123 and ETB receptor blocker BQ788, or different kinase inhibitors. ET-1 decreased the Mas mRNA level in a statistically significant dose- and time-dependent manner within 4.5 h, which was reflected in the dose-dependent downregulation of Mas promoter activity, Mas protein levels and Ang-(1-7) binding on the cell membrane. Actinomycin D (1 mg/ml), BQ123 (1 µM), p38 mitogen-activated protein kinase (MAPK) siRNA and inhibitor PD169316 (25 µM), completely eliminated the inhibitory effects of ET-1 on Mas expression in human cardiomyocytes. In conclusion, the present study demonstrated that ET-1 downregulates Mas expression at the transcription level in human cardiomyocytes via the ETA receptor by a p38 MAPK‑dependent mechanism. This study provides novel insights into the function of ET-1 and the Ang‑(1-7)/Mas axis in cardiac pathophysiology. PMID:23836146

  14. HR 7275 - A new variable star

    NASA Technical Reports Server (NTRS)

    Fried, R. E.; Lovell, L. P.; Krisciunas, K.; Chamblis, C. R.; Detterline, P. K.; Landis, H. J.; Louth, H.; Eaton, J. A.; Hall, D. S.; Henry, G. W.

    1982-01-01

    Three years of photometry in V and B of the UBV system are presented to confirm the suspicion of Herbst (1973) that HR 7275 is a variable star. The photometry is used to derive the photometric period, which proves to be about 3% shorter than the spectroscopically determined optical period of 28.59 d. Total variation observed during the three years was 0.22 m in the V, and the light curve was always asymmetrical.

  15. Nonthermal Radio Emission and the HR Diagram

    NASA Technical Reports Server (NTRS)

    Gibson, D. M.

    1985-01-01

    Perhaps the most reliable indicator of non-radiative heating/momentum in a stellar atmosphere is the presence of nonthermal radio emission. To date, 77 normal stellar objects have been detected and identified as nonthermal sources. These stellar objects are tabulated herein. It is apparent that non-thermal radio emission is not ubiquitous across the HR diagram. This is clearly the case for the single stars; it is not as clear for the binaries unless the radio emission is associated with their late-type components. Choosing to make this association, the single stars and the late-type components are plotted together. The following picture emerges: (1) there are four locations on the HR diagram where non-thermal radio stars are found; (2) the peak incoherent 5 GHz luminosities show a suprisingly small range for stars within each class; (3) the fraction of stellar energy that escapes as radio emission can be estimated by comparing the integrated maximum radio luminosity to the bolometric luminosity; (4) there are no apparent differences in L sub R between binaries with two cool components, binaries with one hot and one cool component, and single stars for classes C and D; and (5) The late-type stars (classes B, C, and D) are located in parts of the HR diagram where there is reason to suspect that the surfaces of the stars are being braked with respect to their interiors.

  16. Instability Regions in the Upper HR Diagram

    NASA Technical Reports Server (NTRS)

    deJager, Cornelis; Lobel, Alex; Nieuwenhuijzen, Hans; Stothers, Richard; Hansen, James E. (Technical Monitor)

    2001-01-01

    The following instability regions for blueward evolving supergiants are outlined and compared: (1) Areas in the Hertzsprung-Russell(HR) diagram where stars are dynamically unstable. (2) Areas where the effective acceleration in the upper part of the photospheres is negative, hence directed outward. (3) Areas where the sonic points of the stellar wind (Where wind velocity = sound velocity) are situated inside the photospheres, at a level deeper than tau(sub Ross) = 0.01. We compare the results with the positions of actual stars in the HR diagram and we find evidence that the recent strong contraction of the yellow hypergiant HR8752 was initiated in a period during which (g(sub eff)) is less than 0, whereupon the star became dynamically unstable. The instability and extreme shells around IRC+10420 are suggested to be related to three factors: (g(sub eff)) is less than 0; the sonic point is situated inside the photosphere; and the star is dynamically unstable.

  17. Enabling quaternion derivatives: the generalized HR calculus.

    PubMed

    Xu, Dongpo; Jahanchahi, Cyrus; Took, Clive C; Mandic, Danilo P

    2015-08-01

    Quaternion derivatives exist only for a very restricted class of analytic (regular) functions; however, in many applications, functions of interest are real-valued and hence not analytic, a typical case being the standard real mean square error objective function. The recent HR calculus is a step forward and provides a way to calculate derivatives and gradients of both analytic and non-analytic functions of quaternion variables; however, the HR calculus can become cumbersome in complex optimization problems due to the lack of rigorous product and chain rules, a consequence of the non-commutativity of quaternion algebra. To address this issue, we introduce the generalized HR (GHR) derivatives which employ quaternion rotations in a general orthogonal system and provide the left- and right-hand versions of the quaternion derivative of general functions. The GHR calculus also solves the long-standing problems of product and chain rules, mean-value theorem and Taylor's theorem in the quaternion field. At the core of the proposed GHR calculus is quaternion rotation, which makes it possible to extend the principle to other functional calculi in non-commutative settings. Examples in statistical learning theory and adaptive signal processing support the analysis. PMID:26361555

  18. Enabling quaternion derivatives: the generalized HR calculus

    PubMed Central

    Xu, Dongpo; Jahanchahi, Cyrus; Took, Clive C.; Mandic, Danilo P.

    2015-01-01

    Quaternion derivatives exist only for a very restricted class of analytic (regular) functions; however, in many applications, functions of interest are real-valued and hence not analytic, a typical case being the standard real mean square error objective function. The recent HR calculus is a step forward and provides a way to calculate derivatives and gradients of both analytic and non-analytic functions of quaternion variables; however, the HR calculus can become cumbersome in complex optimization problems due to the lack of rigorous product and chain rules, a consequence of the non-commutativity of quaternion algebra. To address this issue, we introduce the generalized HR (GHR) derivatives which employ quaternion rotations in a general orthogonal system and provide the left- and right-hand versions of the quaternion derivative of general functions. The GHR calculus also solves the long-standing problems of product and chain rules, mean-value theorem and Taylor's theorem in the quaternion field. At the core of the proposed GHR calculus is quaternion rotation, which makes it possible to extend the principle to other functional calculi in non-commutative settings. Examples in statistical learning theory and adaptive signal processing support the analysis. PMID:26361555

  19. Quantification of cholesteryl esters in human and rabbit atherosclerotic plaques by magic-angle spinning (13)C-NMR.

    PubMed

    Peng, S; Guo, W; Morrisett, J D; Johnstone, M T; Hamilton, J A

    2000-12-01

    Accumulation of cholesteryl esters (CEs) is a key event in the formation of atherosclerotic plaques. More recent work suggests a role for CEs in plaque rupture leading to thrombosis, which can result in an acute event such as myocardial infarction or stroke. In this study, we present nuclear magnetic resonance (NMR) protocols for quantification of CEs in plaques in situ. Total CEs quantified by (13)C magic-angle spinning (MAS) NMR in excised plaques from human carotid arteries and rabbit aortic arteries were in good agreement with the amounts determined by subsequent standard chemical assays. The latter analysis is disadvantageous because it requires that plaque lipids be extracted from the tissue, resulting in the loss of all phase information of CEs as well as other major plaque components. With our MAS-NMR protocol, the plaque components are preserved in their native phases. Combining MAS and off-MAS NMR, we were able to quantitatively distinguish isotropic (liquid) CEs from anisotropic (liquid-crystalline) CEs in plaque tissues. In a recent study, we applied a different (13)C MAS-NMR protocol to quantify crystalline cholesterol monohydrate in plaques. Together, these 2 studies describe a new, noninvasive MAS-NMR strategy for the identification and quantification of the major lipid components in plaques in situ. This approach will be useful for investigation of the relationship between plaque rupture and specific lipids in their biologically relevant phases. PMID:11116072

  20. NMR Studies of Cartilage Dynamics, Diffusion, Degradation

    NASA Astrophysics Data System (ADS)

    Huster, Daniel; Schiller, Jürgen; Naji, Lama; et al.

    An increasing number of people is suffering from rheumatic diseases, and, therefore, methods of early diagnosis of joint degeneration are urgently required. For their establishment, however, an improved knowledge about the molecular organisation of cartilage would be helpful. Cartilage consists of three main components: Water, collagen and chondroitin sulfate (CS) that is (together with further polysaccharides and proteins) a major constituent of the proteoglycans of cartilage. 1H and 13C MAS (magic-angle spinning) NMR (nuclear magnetic resonance) opened new perspectives for the study of the macromolecular components in cartilage. We have primarily studied the mobilities of CS and collagen in bovine nasal and pig articular cartilage (that differ significantly in their collagen/polysaccharide content) by measuring 13C NMR relaxation times as well as the corresponding 13C CP (cross polarisation) MAS NMR spectra. These data clearly indicate that the mobility of cartilage macromolecules is broadly distributed from almost completely rigid (collagen) to highly mobile (polysaccharides), which lends cartilage its mechanical strength and shock-absorbing properties.

  1. Rapid proton-detected NMR assignment for proteins with fast magic angle spinning.

    PubMed

    Barbet-Massin, Emeline; Pell, Andrew J; Retel, Joren S; Andreas, Loren B; Jaudzems, Kristaps; Franks, W Trent; Nieuwkoop, Andrew J; Hiller, Matthias; Higman, Victoria; Guerry, Paul; Bertarello, Andrea; Knight, Michael J; Felletti, Michele; Le Marchand, Tanguy; Kotelovica, Svetlana; Akopjana, Inara; Tars, Kaspars; Stoppini, Monica; Bellotti, Vittorio; Bolognesi, Martino; Ricagno, Stefano; Chou, James J; Griffin, Robert G; Oschkinat, Hartmut; Lesage, Anne; Emsley, Lyndon; Herrmann, Torsten; Pintacuda, Guido

    2014-09-01

    Using a set of six (1)H-detected triple-resonance NMR experiments, we establish a method for sequence-specific backbone resonance assignment of magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra of 5-30 kDa proteins. The approach relies on perdeuteration, amide (2)H/(1)H exchange, high magnetic fields, and high-spinning frequencies (?r/2? ? 60 kHz) and yields high-quality NMR data, enabling the use of automated analysis. The method is validated with five examples of proteins in different condensed states, including two microcrystalline proteins, a sedimented virus capsid, and two membrane-embedded systems. In comparison to contemporary (13)C/(15)N-based methods, this approach facilitates and accelerates the MAS NMR assignment process, shortening the spectral acquisition times and enabling the use of unsupervised state-of-the-art computational data analysis protocols originally developed for solution NMR. PMID:25102442

  2. Polystyrene-supported organotin dichloride as a recyclable catalyst in lactone ring-opening polymerization: assessment and catalysis monitoring by high-resolution magic-angle-spinning NMR spectroscopy.

    PubMed

    Deshayes, Gaëlle; Poelmans, Kevin; Verbruggen, Ingrid; Camacho-Camacho, Carlos; Degée, Philippe; Pinoie, Vanja; Martins, José C; Piotto, Martial; Biesemans, Monique; Willem, Rudolph; Dubois, Philippe

    2005-07-18

    Dialkyltin dichloride grafted to a cross-linked polystyrene, with the formula [P-H]((1-t))[P-(CH2)nSnBuCl2]t (P=[CH2CH(pC6H4)], t=the degree of functionalization, and n=6 or 11), is investigated as a recyclable catalyst in the ring-opening polymerization (ROP) of epsilon-caprolactone (CL). It is demonstrated that high-resolution magic-angle-spinning (HR-MAS) NMR spectroscopy is an invaluable tool to characterize completely the supported catalyst. The 2D 1H-13C HSQC HR-MAS spectrum, in particular, allowed extensive assignment of the 1H and 13C resonances, as well as accurate measurement of the (n)J((1)H-(117/119)Sn) and (n)J((13)C-(117/119)Sn) coupling constants. 1H and 119Sn HR-MAS NMR spectroscopy is presented as a monitoring tool for catalytic processes based on organotin compounds, particularly for the investigation of the extent to which polymerization residues are observable in situ in the material pores and for the assessment of the chemical integrity and recycling conditions of the grafted catalyst. From polymerization experiments with CL, initiated by n-propanol and with [P-H]((1-t))[P-(CH2)nSnBuCl2]t of various compositions as the supported catalyst, it appears that a partial 'burst' of the polystyrene support occurs when the length of the alkyl spacer is limited to n=6, as a result of polymer chains growing within the pores of the support. However, extension of the length of the aliphatic polymethylene spacer from 6 to 11 carbon atoms preserves the support integrity and allows the production of catalyst-deprived poly(epsilon-caprolactone) (PCL) oligomers. A preliminary attempt to recycle the heterogeneous catalyst has shown that very good reproducibility can be obtained, in terms of both catalyst activity and molecular-weight parameters of the as-recovered PCL polyester chains. PMID:15900548

  3. THE CHARA ARRAY ANGULAR DIAMETER OF HR 8799 FAVORS PLANETARY MASSES FOR ITS IMAGED COMPANIONS

    SciTech Connect

    Baines, Ellyn K.; White, Russel J.; Jones, Jeremy; Boyajian, Tabetha; McAlister, Harold A.; Ten Brummelaar, Theo A.; Turner, Nils H.; Sturmann, Judit; Sturmann, Laszlo; Goldfinger, P. J.; Farrington, Christopher D.; Riedel, Adric R.; Huber, Daniel; Ireland, Michael; Von Braun, Kaspar; Ridgway, Stephen T.

    2012-12-10

    HR 8799 is an hF0 mA5 {gamma} Doradus-, {lambda} Bootis-, Vega-type star best known for hosting four directly imaged candidate planetary companions. Using the CHARA Array interferometer, we measure HR 8799's limb-darkened angular diameter to be 0.342 {+-} 0.008 mas (an error of only 2%). By combining our measurement with the star's parallax and photometry from the literature, we greatly improve upon previous estimates of its fundamental parameters, including stellar radius (1.44 {+-} 0.06 R{sub Sun }), effective temperature (7193 {+-} 87 K, consistent with F0), luminosity (5.05 {+-} 0.29 L{sub Sun }), and the extent of the habitable zone (HZ; 1.62-3.32 AU). These improved stellar properties permit much more precise comparisons with stellar evolutionary models, from which a mass and age can be determined, once the metallicity of the star is known. Considering the observational properties of other {lambda} Bootis stars and the indirect evidence for youth of HR 8799, we argue that the internal abundance, and what we refer to as the effective abundance, is most likely near solar. Finally, using the Yonsei-Yale evolutionary models with uniformly scaled solar-like abundances, we estimate HR 8799's mass and age considering two possibilities: 1.516{sup +0.038}{sub -0.024} M{sub Sun} and 33{sup +7}{sub -13.2} Myr if the star is contracting toward the zero-age main sequence or 1.513{sup +0.023}{sub -0.024} M{sub Sun} and 90{sup +381}{sub -50} Myr if it is expanding from it. This improved estimate of HR 8799's age with realistic uncertainties provides the best constraints to date on the masses of its orbiting companions, and strongly suggests they are indeed planets. They nevertheless all appear to orbit well outside the HZ of this young star.

  4. MAS2-8 radar and digital control unit

    NASA Technical Reports Server (NTRS)

    Oberg, J. M.; Ulaby, F. T.

    1974-01-01

    The design of the MAS 2-8 (2 to 8 GHz microwave-active spectrometer), a ground-based sensor system, is presented. A major modification in 1974 to the MAS 2-8, that of a control subsystem to automate the data-taking operation, is the prime focus. The digital control unit automatically changes all system parameters except FM rate and records the return signal on paper tape. The overall system operation and a detailed discussion of the design and operation of the digital control unit are presented.

  5. NMR analysis of biodiesel

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Biodiesel is usually analyzed by the various methods called for in standards such as ASTM D6751 and EN 14214. Nuclear magnetic resonance (NMR) is not one of these methods. However, NMR, with 1H-NMR commonly applied, can be useful in a variety of applications related to biodiesel. These include monit...

  6. UVBY Photometry of the Magnetic Chemically Peculiar Stars HR 1297, 36 Aurigae, and HR 2722 and the Nonmagnetic Chemically Peculiar Stars HR 1576 and alpha CANCRI

    NASA Astrophysics Data System (ADS)

    Adelman, Saul J.; Brunhouse, Eric F.

    1998-11-01

    Differential Strömgren uvby photometric observations from the Four College Automated Photoelectric Telescope are presented for the magnetic CP stars HR 1297, 36 Aur, and HR 2722 and the nonmagnetic CP stars HR 1576 and alpha Cnc. Both the moderately rotating HR 1576, a mercury-manganese star, and alpha Cnc, a metallic-line star, are nonvariable. For HR 1297 we refined Winzer's period to 1.06457 days. Our period of 14.366 days for 36 Aur is an alias of Winzer's period and is in keeping with the sharp-lined nature of this star. We found a more accurate period of 2.31523 days for the low-amplitude variable HR 2722.

  7. The effect of sample freezing on proton magic-angle spinning NMR spectra of biological tissue.

    PubMed

    Middleton, D A; Bradley, D P; Connor, S C; Mullins, P G; Reid, D G

    1998-07-01

    Magic-angle spinning (MAS) has recently been shown to enhance spectral resolution in NMR examinations of intact biological tissue ex vivo. This work demonstrates that freezing certain tissue samples before examination by 1H MAS NMR can have a marked effect on their spectra. Spectra of rat kidney after freezing in liquid nitrogen, compared with spectra before freezing, showed a significant increase in signal intensities from alanine (>100%), glutamine (>40%), and glycine (>100%), and a decrease in signals assigned to lipids and other macromolecules. Some resonances--such as from leucine, valine, isoleucine, and aspartate--only became visible after freezing the tissue. These observations suggest that low temperature storage of tissue necropsies or biopsies might affect the results of a MAS NMR analysis, possibly resulting in the misinterpretation of metabolite changes to pathogen or disease effects. PMID:9660567

  8. Marker assisted selection (MAS) for breeding high oleic Tifguard

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Tifguard, a peanut cultivar released in 2007, has near immunity to root-knot nematode and high resistance to TSWV. However, its oil composition is within the normal O/L range. Pyramiding the disease resistant traits of ‘Tifguard’ and the high O/L trait using MAS is our current goal for breeding. ...

  9. ADP-MAS: A Math and Science Curriculum.

    ERIC Educational Resources Information Center

    National Council of La Raza, Washington, DC.

    This curriculum, Academia del Pueblo-Math and Science (ADP-MAS), is an outgrowth of the National Council of La Raza's Project EXCEL, a supplemental educational enrichment model for at-risk Latino students to be operated by Latino community-based organizations or public institutions, including schools with substantial Latino populations. ADP-MAS…

  10. Resolution and polarization distribution in cryogenic DNP/MAS experiments

    PubMed Central

    Barnes, Alexander B.; Corzilius, Björn; Mak-Jurkauskas, Melody L.; Andreas, Loren B.; Bajaj, Vikram S.; Matsuki, Yoh; Belenky, Marina L.; Lugtenburg, Johan; Sirigiri, Jagadishwar R.; Temkin, Richard J.; Herzfeld, Judith; Griffin, Robert G.

    2014-01-01

    This contribution addresses four potential misconceptions associated with high-resolution dynamic nuclear polarization/magic angle spinning (DNP/MAS) experiments. First, spectral resolution is not generally compromised at the cryogenic temperatures at which DNP experiments are performed. As we demonstrate at a modest field of 9 T (380 MHz 1H), 1 ppm linewidths are observed in DNP/MAS spectra of a membrane protein in its native lipid bilayer, and <0.4 ppm linewidths are reported in a crystalline peptide at 85 K. Second, we address the concerns about paramagnetic broadening in DNP/MAS spectra of proteins by demonstrating that the exogenous radical polarizing agents utilized for DNP are distributed in the sample in such a manner as to avoid paramagnetic broadening and thus maintain full spectral resolution. Third, the enhanced polarization is not localized around the polarizing agent, but rather is effectively and uniformly dispersed throughout the sample, even in the case of membrane proteins. Fourth, the distribution of polarization from the electron spins mediated via spin diffusion between 1H–1H strongly dipolar coupled spins is so rapid that shorter magnetization recovery periods between signal averaging transients can be utilized in DNP/MAS experiments than in typical experiments performed at ambient temperature. PMID:20454732

  11. VizieR Online Data Catalog: HR 8799e and HR 8799d spectra (Zurlo+, 2016)

    NASA Astrophysics Data System (ADS)

    Zurlo, A.; Vigan, A.; Galicher, R.; Maire, A.-L.; Mesa, D.; Gratton, R.; Chauvin, G.; Kasper, M.; Moutou, C.; Bonnefoy, M.; Desidera, S.; Abe, L.; Apai, D.; Baruffolo, A.; Baudoz, P.; Baudrand, J.; Beuzit, J.-L.; Blancard, P.; Boccaletti, A.; Cantalloube, F.; Carle, M.; Cascone, E.; Charton, J.; Claudi, R. U.; Costille, A.; de Caprio, V.; Dohlen, K.; Dominik, C.; Fantinel, D.; Feautrier, P.; Feldt, M.; Fusco, T.; Gigan, P.; Girard, J. H.; Gisler, D.; Gluck, L.; Gry, C.; Henning, T.; Hugot, E.; Janson, M.; Jaquet, M.; Lagrange, A.-M.; Langlois, M.; Llored, M.; Madec, F.; Magnard, Y.; Martinez, P.; Maurel, D.; Mawet, D.; Meyer, M. R.; Milli, J.; Moeller-Nilsson, O.; Mouillet, D.; Origne, A.; Pavlov, A.; Petit, C.; Puget, P.; Quanz, S. P.; Rabou, P.; Ramos, J.; Rousset, G.; Roux, A.; Salasnich, B.; Salter, G.; Sauvage, J.-F.; Schmid, H. M.; Soenke, C.; Stadler, E.; Suarez, M.; Turatto, M.; Udry, S.; Vakili, F.; Wahhaj, Z.; Wildi, F.; Antichi, J.

    2015-11-01

    The files contain the wavelength in micrometers in the first column, the flux in W/m2/mum in the second column and the corresponding error in the third. We refer to the text for more informations /Users/alice/paper_hr8799/readme.txt. Any further question can be addressed to alice.zurlo@mail.udp.cl (2 data files).

  12. Using a cross-coil to reduce RF heating by an order of magnitude in triple-resonance multinuclear MAS at high fields.

    PubMed

    Doty, F David; Kulkarni, Jatin; Turner, Christopher; Entzminger, George; Bielecki, Anthony

    2006-10-01

    Four different coil designs for use with MAS in triple-resonance multi-nuclear experiments at high fields are compared, using a combination of finite element analysis (FEA) software and NMR experiments, with respect to RF field strength per unit power and relative sample heating, as governed by mean E/B(1) within the sample region. A commercial FEA package, Microwave Studio 5.1 by Computer Simulation Technology (CST) is shown to obtain remarkably accurate agreement with the experiments in Q(L), L, B, E, and mode frequencies in all cases. A simplified treatment of RF heating in NMR MAS samples is derived and shown to agree with the NMR experimental results within about 10% for two representative stator designs. The coil types studied include: (1) a variable-pitch solenoid outside a ceramic coilform, (2) a conventional solenoid very closely spaced to the MAS rotor, (3) a scroll coil, and (4) a segmented saddle cross coil (XC) for (1)H with an additional solenoid over it for the two lower-frequency channels. The XC/solenoid is shown to offer substantial advantages in reduced decoupler heating, improved S/N, and improved compatibility with multinuclear tuning and high-power decoupling. This seems largely because the division of labor between two orthogonal coils allows them each, and their associated circuitry, to be separately optimized for their respective regimes. PMID:16860580

  13. How HR Leaders Can Add Value to an Organization

    ERIC Educational Resources Information Center

    Smallwood, Norm; Ulrich, Dave

    2006-01-01

    Generally speaking, it is safe to say that human resource leaders whole-heartedly believe that the HR function should add value to an organization. However, many wonder where to start. In this article, the authors outline three ways in which the HR function, and the HR leader, can create sustained value for an organization and its stakeholders.

  14. Multichannel astrometric photometer and photographic astrometric studies in the regions of Lalande 21185, BD 56 deg 2966, and HR 4784

    NASA Technical Reports Server (NTRS)

    Gatewood, George; Stein, John; De Jonge, Joost K.; Persinger, Timothy; Reiland, Thomas; Stephenson, Bruce

    1992-01-01

    The parallaxes of stars determined from the multichannel astrometric photometer (MAP) in the regions of Lalande 21185, BD 56 deg 2966, and from photographic plates in the region of BD 56 deg 2966 and the region of HR 4783 and HR 4784 are reported. The parallax determined for Lalande 21185, 395.1 +/-1.0 mas yields what is believed to be the most precise distance modulus (-2.984 +/-0.0055) known for a star other than the sun. The absolute magnitude of Lalande 21185 is found to be 10.474 +/-0.008. No significant evidence of unseen companions is detected. The photographic study of BD 56 deg 2966 indicates that the long-term (65 yr) motion of the star is linear to better than +/-16 mas, while the MAP study indicates that the motion is linear to better than +/-2.5 mas over a period of some 5 yr. The photographically determined parallaxes are compared with those observed with the MAP. The photographically calculated standard errors are found to be in agreement with the standard error of the differences.

  15. Solid-State NMR Examination of Alteration Layers on a Nuclear Waste Glasses

    SciTech Connect

    Murphy, Kelly A.; Washton, Nancy M.; Ryan, Joseph V.; Pantano, Carlo G.; Mueller, Karl T.

    2013-06-01

    Solid-state NMR is a powerful tool for probing the role and significance of alteration layers in determining the kinetics for the corrosion of nuclear waste glass. NMR methods are used to probe the chemical structure of the alteration layers to elucidate information about their chemical complexity, leading to increased insight into the mechanism of altered layer formation. Two glass compositions were examined in this study: a glass preliminarily designed for nuclear waste immobilization (called AFCI) and a simplified version of this AFCI glass (which we call SA1R). Powdered glasses with controlled and known particles sizes were corroded at 90 °C for periods of one and five months with a surface-area to solution-volume ratio of 100,000 m-1. 1H-29Si CP-CPMG MAS NMR, 1H-27Al CP-MAS NMR, 1H-11B CP-MAS NMR, and 1H-23Na CP-MAS NMR experiments provide isolated structural information about the alteration layers, which differ in structure from that of the pristine glass. Both glasses studied here develop alteration layers composed primarily of [IV]Si species. Aluminum is also retained in the alteration layers, perhaps facilitated by the observed increase in coordination from [IV]Al to [VI]Al, which correlates with a loss of charge balancing cations. 1H-11B CP-MAS NMR observations indicated a retention of boron in hydrated glass layers, which has not been characterized by previous work. For the AFCI glass, secondary phase formation begins during the corrosion times considered here, and these neophases are detected within the alteration layers. We identify precursor phases as crystalline sodium metasilicates. An important finding is that layer thickness depends on the length of the initial alteration stages and varies only with respect to silicon species during the residual rate regime.

  16. Proton-Detected Solid-State NMR Spectroscopy of Bone with Ultrafast Magic Angle Spinning.

    PubMed

    Mroue, Kamal H; Nishiyama, Yusuke; Kumar Pandey, Manoj; Gong, Bo; McNerny, Erin; Kohn, David H; Morris, Michael D; Ramamoorthy, Ayyalusamy

    2015-01-01

    While obtaining high-resolution structural details from bone is highly important to better understand its mechanical strength and the effects of aging and disease on bone ultrastructure, it has been a major challenge to do so with existing biophysical techniques. Though solid-state NMR spectroscopy has the potential to reveal the structural details of bone, it suffers from poor spectral resolution and sensitivity. Nonetheless, recent developments in magic angle spinning (MAS) NMR technology have made it possible to spin solid samples up to 110 kHz frequency. With such remarkable capabilities, (1)H-detected NMR experiments that have traditionally been challenging on rigid solids can now be implemented. Here, we report the first application of multidimensional (1)H-detected NMR measurements on bone under ultrafast MAS conditions to provide atomistic-level elucidation of the complex heterogeneous structure of bone. Our investigations demonstrate that two-dimensional (1)H/(1)H chemical shift correlation spectra for bone are obtainable using fp-RFDR (finite-pulse radio-frequency-driven dipolar recoupling) pulse sequence under ultrafast MAS. Our results infer that water exhibits distinct (1)H-(1)H dipolar coupling networks with the backbone and side-chain regions in collagen. These results show the promising potential of proton-detected ultrafast MAS NMR for monitoring structural and dynamic changes caused by mechanical loading and disease in bone. PMID:26153138

  17. Proton-Detected Solid-State NMR Spectroscopy of Bone with Ultrafast Magic Angle Spinning

    NASA Astrophysics Data System (ADS)

    Mroue, Kamal H.; Nishiyama, Yusuke; Kumar Pandey, Manoj; Gong, Bo; McNerny, Erin; Kohn, David H.; Morris, Michael D.; Ramamoorthy, Ayyalusamy

    2015-07-01

    While obtaining high-resolution structural details from bone is highly important to better understand its mechanical strength and the effects of aging and disease on bone ultrastructure, it has been a major challenge to do so with existing biophysical techniques. Though solid-state NMR spectroscopy has the potential to reveal the structural details of bone, it suffers from poor spectral resolution and sensitivity. Nonetheless, recent developments in magic angle spinning (MAS) NMR technology have made it possible to spin solid samples up to 110 kHz frequency. With such remarkable capabilities, 1H-detected NMR experiments that have traditionally been challenging on rigid solids can now be implemented. Here, we report the first application of multidimensional 1H-detected NMR measurements on bone under ultrafast MAS conditions to provide atomistic-level elucidation of the complex heterogeneous structure of bone. Our investigations demonstrate that two-dimensional 1H/1H chemical shift correlation spectra for bone are obtainable using fp-RFDR (finite-pulse radio-frequency-driven dipolar recoupling) pulse sequence under ultrafast MAS. Our results infer that water exhibits distinct 1H-1H dipolar coupling networks with the backbone and side-chain regions in collagen. These results show the promising potential of proton-detected ultrafast MAS NMR for monitoring structural and dynamic changes caused by mechanical loading and disease in bone.

  18. Proton-Detected Solid-State NMR Spectroscopy of Bone with Ultrafast Magic Angle Spinning

    PubMed Central

    Mroue, Kamal H.; Nishiyama, Yusuke; Kumar Pandey, Manoj; Gong, Bo; McNerny, Erin; Kohn, David H.; Morris, Michael D.; Ramamoorthy, Ayyalusamy

    2015-01-01

    While obtaining high-resolution structural details from bone is highly important to better understand its mechanical strength and the effects of aging and disease on bone ultrastructure, it has been a major challenge to do so with existing biophysical techniques. Though solid-state NMR spectroscopy has the potential to reveal the structural details of bone, it suffers from poor spectral resolution and sensitivity. Nonetheless, recent developments in magic angle spinning (MAS) NMR technology have made it possible to spin solid samples up to 110 kHz frequency. With such remarkable capabilities, 1H-detected NMR experiments that have traditionally been challenging on rigid solids can now be implemented. Here, we report the first application of multidimensional 1H-detected NMR measurements on bone under ultrafast MAS conditions to provide atomistic-level elucidation of the complex heterogeneous structure of bone. Our investigations demonstrate that two-dimensional 1H/1H chemical shift correlation spectra for bone are obtainable using fp-RFDR (finite-pulse radio-frequency-driven dipolar recoupling) pulse sequence under ultrafast MAS. Our results infer that water exhibits distinct 1H−1H dipolar coupling networks with the backbone and side-chain regions in collagen. These results show the promising potential of proton-detected ultrafast MAS NMR for monitoring structural and dynamic changes caused by mechanical loading and disease in bone. PMID:26153138

  19. Exploring electrolyte organization in supercapacitor electrodes with solid-state NMR

    NASA Astrophysics Data System (ADS)

    Deschamps, Michaël; Gilbert, Edouard; Azais, Philippe; Raymundo-Piñero, Encarnación; Ammar, Mohammed Ramzi; Simon, Patrick; Massiot, Dominique; Béguin, François

    2013-04-01

    Supercapacitors are electrochemical energy-storage devices that exploit the electrostatic interaction between high-surface-area nanoporous electrodes and electrolyte ions. Insight into the molecular mechanisms at work inside supercapacitor carbon electrodes is obtained with 13C and 11B ex situ magic-angle spinning nuclear magnetic resonance (MAS-NMR). In activated carbons soaked with an electrolyte solution, two distinct adsorption sites are detected by NMR, both undergoing chemical exchange with the free electrolyte molecules. On charging, anions are substituted by cations in the negative carbon electrode and cations by anions in the positive electrode, and their proportions in each electrode are quantified by NMR. Moreover, acetonitrile molecules are expelled from the adsorption sites at the negative electrode alone. Two nanoporous carbon materials were tested, with different nanotexture orders (using Raman and 13C MAS-NMR spectroscopies), and the more disordered carbon shows a better capacitance and a better tolerance to high voltages.

  20. The hot white-dwarf companions of HR 1608, HR 8210, and HD 15638

    NASA Technical Reports Server (NTRS)

    Landsman, Wayne; Simon, Theodore; Bergeron, P.

    1993-01-01

    We have obtained low-dispersion IUE spectra of the late-type stars HD 15638 (F3 V), HR 1608 (=63 Eridani, KO IV), and HR 8210 (A8m). Each of these stars had been detected as a strong EUV source with the Wide Field Camera aboard the ROSAT satellite. The short-wavelength IUE spectrum of each star reveals the presence of a hot white-dwarf companion. We have fit the Lyman-alpha profile and UV continuum of each white dwarf using pure hydrogen models. The excellent fit of the data to the models provides confirmation of the Finley and Koester absolute calibration of the SWP camera of IUE. The UV data alone are insufficient to constrain the model gravity, but an additional constraint is provided by the photometric distance to the late-type primary. The most interesting of the three white dwarfs is the companion to HR 8210 for which our results imply a mass of 1.15 +0.05/-0.15 solar mass. This result is in good agreement with the lower limit on the mass derived from the spectroscopic orbit (greater than 1.1 solar mass), provided that the inclination is close to 90 deg.

  1. NMR Characterization of Half-integer Quadrupolar Nuclei in Solids

    NASA Astrophysics Data System (ADS)

    Amoureux, J. P.

    1992-05-01

    This article describes a few aspects of NMR characterization of half-integer quadrupolar nuclei in powder samples which are either static or rotating around one fixed axis (M.A.S. and V.A.S. techniques). The simultaneous occurence of C.S.A. and quadrupole interactions with possible noncoincident tensors is discussed. Two experimental limitations are taken into accout: the sample spinning speed and the RF-amplifier power

  2. Commercial facility site selection simulating based on MAS

    NASA Astrophysics Data System (ADS)

    Chao, Yi; Li, Qingquan; Zheng, Guizhou

    2008-10-01

    The location of commercial facility decides the benefit of the operator to a large degree. Existing location methods can express the static relationships between site selection result and location factors, but there still are some limites when express the dynamic and uncertain relationship between them. Hence, a dynamic, stochastic and forecastable location model should be built which can introduce the customer's behavior into the model and combine the macro pattern and micro spatial interaction. So the authors proposes Geosim-LM based on MAS. Geosim-LM has 3 kinds of agents, CustAgent, SiteAgent and GovAgent. They represent the customers, commercial fercilities and government. The land type, land price and traffic are the model environment. Then Geosim-LM is applied in the bank branches site evaluation and selection in Liwan district, Guangzhou. In existing bank branches site evaluation, there are 70% consistent in score grade between result of Geosim-LM after 200 round runing and actual rebust location. It proves the model is reliable and feasible. The conclusions can be get from the paper. MAS have advantages in location choice than existed methods. The result of Geosim-LM running can powerfully proves that building location model based on MAS is feasible.

  3. Welding Metallurgy of Alloy HR-160

    SciTech Connect

    DuPont, J.N.; Michael, J.R.; Newbury, B.D.

    1999-05-28

    The solidification behavior and resultant solidification cracking susceptibility of autogenous gas tungsten arc fusion welds in alloy HR-160 was investigated by Varestraint testing, differential thermal analysis, and various microstructural characterization techniques. The alloy exhibited a liquidus temperature of 1387 {deg}C and initiated solidification by a primary L - {gamma} reaction in which Ni, Si, and Ti segregated to the interdendritic liquid and Co segregated to the {gamma} dendrite cores. Chromium exhibited no preference for segregation to the solid or liquid phase during solidification. Solidification terminated at {approx} 1162 {deg}C by a eutectic-type L - [{gamma}+ (Ni,Co){sub 16}(Ti,Cr){sub 6}Si{sub 7}] reaction. The (Ni,Co){sub 16}(Ti,Cr){sub 6}Si{sub 7} phase is found to be analogous to the G phase which forms in the Ni-Ti-Si and Co-Ti-Si ternary systems, and similarities are found to exist between the solidification behavior of this commercial multicomponent alloy and the simple Ni-Si and Ni-Ti binary systems. Reasonable agreement is obtained between the calculated and measured volume percent of the [{gamma} +(Ni,Co){sub l6}(Ti,Cr){sub 6}Si{sub 7}] eutectic-typr constituent with the Scheil equation using experimentally determined k values for Si and Ti from electron microprobe data. The alloy exhibited a very high susceptibility to solidification cracking in the Varestraint test. This is attributed to a large solidification temperature range of 225 {deg}C and the presence of 2 to 5 vol% solute rich interdendritic liquid which preferentially wets the grain boundaries and interdendritic regions.

  4. Solid State NMR Studies of the Aluminum Hydride Phases

    NASA Technical Reports Server (NTRS)

    Hwang, Son-Jong; Bowman, R. C., Jr.; Graetz, Jason; Reilly, J. J.

    2006-01-01

    Several solid state NMR techniques including magic-angle-spinning (MAS) and multiple-quantum (MQ) MAS experiments have been used to characterize various AlH3 samples. MAS-NMR spectra for the 1H and 27Al nuclei have been obtained on a variety of AlH3 samples that include the (beta)- and (gamma)- phases as well as the most stable (alpha)-phase. While the dominant components in these NMR spectra correspond to the aluminum hydride phases, other species were found that include Al metal, molecular hydrogen (H2), as well as peaks that can be assigned to Al-O species in different configurations. The occurrence and concentration of these extraneous components are dependent upon the initial AlH3 phase composition and preparation procedures. Both the (beta)-AlH3 and (gamma)-AlH3 phases were found to generate substantial amounts of Al metal when the materials were stored at room temperature while the (alpha)-phase materials do not exhibit these changes.

  5. New insights into the bonding arrangements of L- and D-glutamates from solid state 17O NMR

    NASA Astrophysics Data System (ADS)

    Lemaitre, V.; Pike, K. J.; Watts, A.; Anupold, T.; Samoson, A.; Smith, M. E.; Dupree, R.

    2003-03-01

    Magic angle spinning (MAS) from L- and D-glutamic acid-HCl at 14.1 T produces highly structured and very similar NMR spectra. Lines from all 4 oxygen sites are readily distinguished and assigned. These 17O NMR spectra are very different from the previously reported 17O spectrum of the D, L-form presumably because that was a racemic crystal. 17O NMR from L-monosodium glutamate-HCl is very different again requiring the application of double angle rotation and 3 quantum MAS NMR to provide resolution of 5 different sites. Hence high resolution 17O solid state NMR techniques offer possible new insight into biochemical bonding processes.

  6. The MicroMAS CubeSat Mission

    NASA Astrophysics Data System (ADS)

    Cahoy, K.; Blackwell, W. J.; Allen, G.; Bury, M.; Efromson, R.; Galbraith, C.; Hancock, T.; Leslie, V.; Osaretin, I.; Retherford, L.; Scarito, M.; Shields, M.; Toher, D.; Wight, K.; Miller, D.; Marinan, A.; Paek, S.; Peters, E.; Schmidt, F. H.; Alvisio, B.; Wise, E.; Masterson, R.; Franzim Miranda, D.; Crail, C.; Kingsbury, R.; Souffrant, A.; Orrego, L.; Eslinger, G.; Nicholas, A.; Pong, C.

    2012-12-01

    The recently published Midterm Assessment of NASA's Implementation of the Decadal Survey finds that, "The nation's Earth observing system is beginning a rapid decline in capability as long-running missions end and key new missions are delayed, lost, or canceled. The projected loss of observing capability could have significant adverse consequences for science and society." In this presentation, we explore low-cost, mission-flexible, and rapidly deployable spaceborne sensors that can meet stringent performance requirements pervading the NASA Earth Science measurement programs, including especially the recommended NRC Decadal Survey missions. New technologies have enabled a novel approach toward this science observational goal, and in this paper we describe recent technology develop efforts to address the challenges above through the use of CubeSat radiometers. The Micro-sized Microwave Atmospheric Satellite (MicroMAS) is a 3U cubesat (30x10x10 cm, ~4kg) hosting a passive microwave spectrometer operating near the 118.75-GHz oxygen absorption line. The focus of the first MicroMAS mission (hereafter, MicroMAS-1) is to observe convective thunderstorms, tropical cyclones, and hurricanes from a near-equatorial orbit at approximately 500-km altitude. A MicroMAS flight unit is currently being developed in anticipation of a 2014 launch to be provided by NASA. A parabolic reflector is mechanically rotated as the spacecraft orbits the earth, thus directing a cross-track scanned beam with FWHM beamwidth of 2.4-degrees, yielding an approximately 25-km diameter footprint from a nominal altitude of 500 km. Radiometric calibration is carried out using observations of cold space, the earth's limb, and an internal noise diode that is weakly coupled through the RF front-end electronics. A key technology feature is the development of an ultra-compact intermediate frequency processor module for channelization, detection, and A-to-D conversion. The antenna system and RF front-end electronics are highly integrated and miniaturized. A MicroMAS-2 mission is currently being planned using a multi-band spectrometer operating near 118 and 183 GHz in a sun-synchronous orbit of approximately 800-km altitude. A HyMAS-1 (Hyperspectral Microwave Atmospheric Satellite) mission with approximately 50 channels near 118 and 183 GHz is also being planned. In this talk, the mission concept of operations will be discussed, the radiometer payload will be described, and the spacecraft subsystems (avionics, power, communications, attitude determination and control, and mechanical structures) will be summarized. Test data from the recently completed MicroMAS Engineering Development Model (EDM) will also be presented. This work was sponsored by the National Oceanic and Atmospheric Administration under Air Force contract FA8721-05-C-0002. Opinions, interpretations, conclusions, and recommendations are those of the authors and not necessarily endorsed by the United States Government.

  7. Small NMR biomolecular sensors

    NASA Astrophysics Data System (ADS)

    Sun, Nan; Liu, Yong; Qin, Ling; Lee, Hakho; Weissleder, Ralph; Ham, Donhee

    2013-06-01

    By combining the physics of nuclear magnetic resonance (NMR) and silicon radio-frequency (RF) integrated circuits, we recently created progressively smaller NMR systems, which we originally reported in Refs. [1-4]. Our strategy for NMR system miniaturization proved effective, culminating in the smallest prototype [3,4] that weighs 0.1 kg and can be held at the palm of the hand. These small, low-cost NMR systems can be useful as biomolecular sensors in the personalized medicine setting, and we demonstrated their ability to detect proteins, compounds, and human cancer cells. The present paper, which is not a new technical contribution, reviews these developments.

  8. Import of proteins into yeast mitochondria: the nuclear MAS2 gene encodes a component of the processing protease that is homologous to the MAS1-encoded subunit.

    PubMed Central

    Jensen, R E; Yaffe, M P

    1988-01-01

    The mas2 mutant of Saccharomyces cerevisiae is temperature sensitive for import of proteins into mitochondria. To identify the lesion in this mutant, we have cloned and sequenced the wild-type MAS2 gene and determined the intracellular location of its protein product. MAS2 encodes an essential 53-kd protein that is located in the mitochondrial matrix and is homologous to the MAS1 protein, a previously identified subunit of the protease that cleaves presequences from mitochondrial precursor proteins. The activity of this enzyme is temperature sensitive in mas2 cells. Together with the results of the accompanying study these results show that MAS2 and MAS1 encode the two subunits of the processing protease. Images PMID:3061808

  9. NMR metabolomics of MTLn3E breast cancer cells identifies a role for CXCR4 in lipid and choline regulation.

    PubMed

    Vermeer, Louic S; Fruhwirth, Gilbert O; Pandya, Pahini; Ng, Tony; Mason, A James

    2012-05-01

    The alpha chemokine receptor CXCR4 is up-regulated in certain types of breast cancer. Truncation of the C-terminus of this receptor alters cell morphology and increases invasiveness and metastatic potential. Here, to better understand the effects of CXCR4 expression and truncation in breast cancer cells, we have used high resolution magic angle spinning (HR-MAS) NMR studies of rat breast carcinoma MtLn3E cells to characterize the metabolite complement of cells heterologously expressing human CXCR4 or its C-terminal truncation mutant, ?34-CXCR4. Notable reductions in choline levels were detected when either cells expressing wild-type CXCR4 or ?34-CXCR4 were compared with cells containing an empty expression vector. Cells expressing CXCR4-?34 had reduced lipid content when compared with either the wild-type CXCR4 expressing cells or those containing the empty expression vector. Taken together, our results show that distinct effects on the metabolite complement can be linked to either CXCR4 expression or CXCR4 regulation. The metabolite markers for these two effects identified in the present study can, in turn, be used to further investigate the role of CXCR4 in metastasis. PMID:22432781

  10. Sodium ion effect on silk fibroin conformation characterized by solid-state NMR and generalized 2D NMR NMR correlation

    NASA Astrophysics Data System (ADS)

    Ruan, Qing-Xia; Zhou, Ping

    2008-07-01

    In the present work, we investigated Na + ion effect on the silk fibroin (SF) conformation. Samples are Na +-involved regenerated silk fibroin films. 13C CP-MAS NMR demonstrates that as added [Na +] increases, partial silk fibroin conformation transit from helix-form to ?-form at certain Na + ion concentration which is much higher than that in Bombyx mori silkworm gland. The generalized two-dimensional NMR-NMR correlation analysis reveals that silk fibroin undergoes several intermediate states during its conformation transition process as [Na +] increase. The appearance order of the intermediates is followed as: helix and/or random coil ? helix-like ? ?-sheet-like ? ?-sheet, which is the same as that produced by pH decrease from 6.8 to 4.8 in the resultant regenerated silk fibroin films. The binding sites of Na + to silk fibroin might involve the carbonyl oxygen atom of certain amino acids sequence which could promote the formation of ?-sheet conformation. Since the Na +sbnd O bond is weak, the ability of Na + inducing the secondary structure transition is weaker than those of Ca 2+, Cu 2+ and even K +. It is maybe a reason why the sodium content is much lower than potassium in the silkworm gland.

  11. RHODOPSIN-LIPID INTERACTIONS STUDIED BY NMR

    PubMed Central

    Soubias, Olivier; Gawrisch, Klaus

    2012-01-01

    The biophysical properties of the lipid matrix are known to influence function of integral membrane proteins. We report on a sample preparation method for reconstitution of membrane proteins which uses porous anodic aluminum oxide (AAO) filters with 200 nm-wide pores of high density. The substrate permits formation of tubular, single membranes that line the inner surface of pores. One square centimeter of filter with a thickness of 60 ?m yields on the order of 500 cm2 of solid-supported single bilayer surface, sufficient for NMR studies. The tubular bilayers are free of detergent, fully hydrated and accessible for ligands from one side of the membrane. The use of AAO filters greatly improves reproducibility of the reconstitution process such that the influence of protein on lipid order parameters can be studied with high resolution. As an example, results for the G protein-coupled receptor of class A, bovine rhodopsin, are shown. By 2H NMR order parameter measurements it is detected that rhodopsin insertion elastically deforms membranes near the protein. Furthermore, by 1H saturation-transfer NMR under conditions of magic-angle spinning (MAS), we demonstrate detection of preferences in interactions of rhodopsin with particular lipid species. It is assumed that function of integral membrane proteins depends on both protein-induced elastic deformations of the lipid matrix and preferences for interaction of the protein with particular lipid species in the first layer of lipids surrounding the protein. PMID:23374188

  12. Elemental abundances of the B and A stars Gamma Geminorum, 7 Sextantis, HR 4817, and HR 5780

    NASA Technical Reports Server (NTRS)

    Adelman, Saul J.; Philip, A. G. D.

    1992-01-01

    Fine analyses of the B and A stars, Gamma Geminorum, 7 Sextantis, HR 4817, and HR 5780 are performed. Although the data cover rather limited spectral regions, still useful results were obtained. The data were mostly obtained at the KPNO coude feed telescope with CCD TI No. 3, camera 5, and grating A. The He/H ratio of HR 4817 confirms the similarity of many abundance values with those of the peculiar Mn star 53 Tauri. For the most part Gamma Gem, 7 Sex, and HR 5780 have derived abundances similar to those of other normal sharp-lined stars of similar effective temperature.

  13. Silver and Gold NMR

    PubMed Central

    Zangger, Klaus

    1999-01-01

    Silver and gold, together with copper, form the transition metal group IB elements in the periodic table and possess very different nuclear magnetic resonance (NMR) spectroscopic properties. While there is only one gold isotope (197Au), which has a spin of 3/2 and therefore a quadrupole moment, silver occurs in two isotopic forms (109Ag and 109Au), both of which have a spin 1/2 and similar NMR spectroscopic properties. The unfavorable properties of gold have prevented its NMR spectroscopic investigation thus far. On the other hand, there are several reports of silver NMR. However, the low sensitivity of silver, combined with its long relaxation times have rendered the direct detection of silver possible only with concentrations greater than a few tenth molar. Reviewed here are the general limitations of silver NMR and some techniques to partially overcome these limitations, as well as a summary of currently available chemical shift and scalar coupling data on 109Ag. PMID:18475898

  14. NMR logging apparatus

    SciTech Connect

    Walsh, David O; Turner, Peter

    2014-05-27

    Technologies including NMR logging apparatus and methods are disclosed. Example NMR logging apparatus may include surface instrumentation and one or more downhole probes configured to fit within an earth borehole. The surface instrumentation may comprise a power amplifier, which may be coupled to the downhole probes via one or more transmission lines, and a controller configured to cause the power amplifier to generate a NMR activating pulse or sequence of pulses. Impedance matching means may be configured to match an output impedance of the power amplifier through a transmission line to a load impedance of a downhole probe. Methods may include deploying the various elements of disclosed NMR logging apparatus and using the apparatus to perform NMR measurements.

  15. In situ solid-state NMR for heterogeneous catalysis: a joint experimental and theoretical approach.

    PubMed

    Zhang, Weiping; Xu, Shutao; Han, Xiuwen; Bao, Xinhe

    2012-01-01

    In situ solid-state NMR is a well-established tool for investigations of the structures of the adsorbed reactants, intermediates and products on the surface of solid catalysts. The techniques allow identifications of both the active sites such as acidic sites and reaction processes after introduction of adsorbates and reactants inside an NMR rotor under magic angle spinning (MAS). The in situ solid-state NMR studies of the reactions can be achieved in two ways, i.e. under batch-like or continuous-flow conditions. The former technique is low cost and accessible to the commercial instrument while the latter one is close to the real catalytic reactions on the solids. This critical review describes the research progress on the in situ solid-state NMR techniques and the applications in heterogeneous catalysis under batch-like and continuous-flow conditions in recent years. Some typical probe molecules are summarized here to detect the Brønsted and Lewis acidic sites by MAS NMR. The catalytic reactions discussed in this review include methane aromatization, olefin selective oxidation and olefin metathesis on the metal oxide-containing zeolites. With combining the in situ MAS NMR spectroscopy and the density functional theoretical (DFT) calculations, the intermediates on the catalyst can be identified, and the reaction mechanism is revealed. Reaction kinetic analysis in the nanospace instead of in the bulk state can also be performed by employing laser-enhanced MAS NMR techniques in the in situ flow mode (163 references). PMID:21743940

  16. Magic-angle-spinning NMR spectroscopy applied to small molecules and peptides in lipid bilayers.

    PubMed

    Ader, C; Schneider, R; Seidel, K; Etzkorn, M; Baldus, M

    2007-11-01

    ssNMR (solid-state NMR) spectroscopy provides increasing possibilities to study the structural and dynamic aspects of biological membranes. Here, we review recent ssNMR experiments that are based on MAS (magic angle spinning) and that provide insight into the structure and dynamics of membrane systems at the atomic level. Such methods can be used to study membrane architecture, domain formation or molecular complexation in a way that is highly complementary to other biophysical methods such as imaging or calorimetry. PMID:17956261

  17. Sampling Scheme and Compressed Sensing Applied to Solid-State NMR Spectroscopy

    PubMed Central

    Lin, Eugene C.; Opella, Stanley J.

    2013-01-01

    We describe the incorporation of non-uniform sampling (NUS) compressed sensing (CS) into Oriented Sample (OS) Solid-state NMR for stationary aligned samples and Magic Angle Spinning (MAS) Solid-state NMR for unoriented ‘powder’ samples Both simulated and experimental results indicate that 25% to 33% of a full linearly sampled data set is required to reconstruct two-and three-dimensional solid-state NMR spectra with high fidelity. A modest increase in signal-to-noise ratio is accompanies the reconstruction. PMID:24140622

  18. Professional Development of HR Practitioners--A Phenomenographic Study

    ERIC Educational Resources Information Center

    Bailey, Moira

    2015-01-01

    Purpose: The purpose of this paper is an investigation into the experiences of professional development of human resource (HR) practitioners in the North of Scotland, and the use of non-formal learning in that development. Design/methodology/approach: In-depth semi-structured interviews from a purposively selected sample of HR practitioners were…

  19. Outsourcing HR Services: The Role of Human Resource Intermediaries

    ERIC Educational Resources Information Center

    Kock, Henrik; Wallo, Andreas; Nilsson, Barbro; Hoglund, Cecilia

    2012-01-01

    Purpose: In this article, the area of interest is an emerging type of organisation called human resource intermediaries (HRIs), which focus on delivering human resource (HR) services to public sector organisations and private companies. The purpose of this article is, thus, to explore HRIs as deliverers of HR services. More specifically, the…

  20. Professional Development of HR Practitioners--A Phenomenographic Study

    ERIC Educational Resources Information Center

    Bailey, Moira

    2015-01-01

    Purpose: The purpose of this paper is an investigation into the experiences of professional development of human resource (HR) practitioners in the North of Scotland, and the use of non-formal learning in that development. Design/methodology/approach: In-depth semi-structured interviews from a purposively selected sample of HR practitioners were…

  1. African American Accounting Majors and the 150-hr Requirement

    ERIC Educational Resources Information Center

    Booker, Quinton; Hill, Cecil L.; Wright, Carl

    2010-01-01

    The study provides information on African American accounting majors' views regarding 150-hr issues. The authors collected data from 152 students at two schools. Students at one school supported the requirement while those at the other school did not. However, students believed that the 150-hr requirement enhances the quality of certified public…

  2. Outsourcing HR Services: The Role of Human Resource Intermediaries

    ERIC Educational Resources Information Center

    Kock, Henrik; Wallo, Andreas; Nilsson, Barbro; Hoglund, Cecilia

    2012-01-01

    Purpose: In this article, the area of interest is an emerging type of organisation called human resource intermediaries (HRIs), which focus on delivering human resource (HR) services to public sector organisations and private companies. The purpose of this article is, thus, to explore HRIs as deliverers of HR services. More specifically, the…

  3. Implementing HR Strategies: A Guide to Good Practice.

    ERIC Educational Resources Information Center

    Higher Education Funding Council for England, Bristol.

    This guide aims to help institutions of higher education in England develop and implement their human resources (HR) strategies. It provides advice and examples of good practice in key areas, in response to requests from institutions. The report supplements earlier guidance on developing HR strategies (March 2002) and presents information for…

  4. Characterization of the Red Giant HR 2582 Using the CHARA Array

    NASA Astrophysics Data System (ADS)

    Baines, Ellyn K.; McAlister, Harold A.; ten Brummelaar, Theo A.; Turner, Nils H.; Sturmann, Judit; Sturmann, Laszlo; Farrington, Christopher D.; Vargas, Norm; van Belle, Gerard T.; Ridgway, Stephen T.

    2013-07-01

    We present the fundamental parameters of HR 2582, a high-mass red giant star whose evolutionary state is a mystery. We used the CHARA Array interferometer to directly measure the star's limb-darkened angular diameter (1.006 ± 0.020 mas) and combined our measurement with parallax and photometry from the literature to calculate its physical radius (35.76 ± 5.31 R ?), luminosity (517.8 ± 17.5 L ?), bolometric flux (14.8 ± 0.5 × 10-8 erg s-1 cm-2), and effective temperature (4577 ± 60 K). We then determined the star's mass (5.6 ± 1.7 M ?) using our new values with stellar oscillation results from Baudin et al. Finally, using the Yonsei-Yale evolutionary models, we estimated HR 2582's age to be 165^{+20}_{-15} Myr. While our measurements do not provide the precision required to definitively state where the star is in its evolution, it remains an excellent test case for evaluating stellar interior models.

  5. CHARACTERIZATION OF THE RED GIANT HR 2582 USING THE CHARA ARRAY

    SciTech Connect

    Baines, Ellyn K.; McAlister, Harold A.; Ten Brummelaar, Theo A.; Turner, Nils H.; Sturmann, Judit; Sturmann, Laszlo; Farrington, Christopher D.; Vargas, Norm; Van Belle, Gerard T.; Ridgway, Stephen T.

    2013-07-20

    We present the fundamental parameters of HR 2582, a high-mass red giant star whose evolutionary state is a mystery. We used the CHARA Array interferometer to directly measure the star's limb-darkened angular diameter (1.006 {+-} 0.020 mas) and combined our measurement with parallax and photometry from the literature to calculate its physical radius (35.76 {+-} 5.31 R{sub Sun }), luminosity (517.8 {+-} 17.5 L{sub Sun }), bolometric flux (14.8 {+-} 0.5 Multiplication-Sign 10{sup -8} erg s{sup -1} cm{sup -2}), and effective temperature (4577 {+-} 60 K). We then determined the star's mass (5.6 {+-} 1.7 M{sub Sun }) using our new values with stellar oscillation results from Baudin et al. Finally, using the Yonsei-Yale evolutionary models, we estimated HR 2582's age to be 165{sup +20}{sub -15} Myr. While our measurements do not provide the precision required to definitively state where the star is in its evolution, it remains an excellent test case for evaluating stellar interior models.

  6. Solid State FT-IR and (31)P NMR Spectral Features of Phosphate Compounds

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Solid-state spectroscopic techniques, including Fourier transform infrared (FT-IR) and solid-state 31P magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopies, are powerful tools for evaluating metal speciation and transformation mechanisms of P compounds in the environment. Studie...

  7. 1H and 13C Solid-state NMR of G. barbadense (Pima) Cotton

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The interaction of water with cellulose and its influence on the nuclear spin dynamics in G. barbadense (Pima) cotton were investigated with 1H and 13C solid-state NMR techniques. 1H spin diffusion results from a Goldman-Shen experiment indicate that the water is multilayered. 1H MAS experiment...

  8. 1H and 13C Solid-state NMR of Gossypium barbadense (Pima) Cotton

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The interaction of water with cellulose and its influence on the nuclear spin dynamics in G. barbadense (Pima) cotton were investigated by 1H and 13C solid-state NMR techniques. 1H spin diffusion results from a Goldman-Shen experiment indicate that the water is multilayered. 1H MAS experiments pro...

  9. NMR study of crystallization in MgO-CaO-SiO 2-P 2O 5 glass-ceramics

    NASA Astrophysics Data System (ADS)

    Ren, Hai-Lan; Yue, Yong; Ye, Chao-Hui; Guo, Li-Ping; Lei, Jia-Heng

    1998-08-01

    29Si and 31P magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) measurements were employed to investigate crystallization in MgO-CaO-SiO 2-P 2O 5 bioglass-ceramics. The results suggest that wollastonite (β-CaSiO 3) is separated as a new crystalline phase, corresponding to the appearance of a sharp signal in the 29Si MAS NMR spectra, while oxyapatite (Ca 10(PO 4) 6O) forms in the process of the order of the phosphorus-rich phases increasing as a whole, corresponding to the gradual narrowing of 31P MAS NMR spectra. ZnO can make the glass stable and difficult to crystallize at a low temperature, while at a high temperature, ZnO can participate in the crystallization of β-CaSiO 3 and promote it.

  10. Line narrowing in H-1 MAS spectrum of mesoporous silica by removing adsorbed H2O using N-2

    SciTech Connect

    Hu, Jian Zhi; Kwak, Ja Hun; Herrera, Jose E.; Wang, Yong; Peden, Charles HF

    2005-05-01

    The peaks for silanol protons in the high resolution 1H NMR spectrum obtained on mesoporous silica materials may be broadened and shifted downfield by hydrogen bonding with absorbed water molecules. The spectrum may be further complicated by overlapping of the resonance for hydrogen-bonded silanol with the corresponding broad peak due to hydrogen-bonded water. These complications hamper a quantitative analysis of the spectra for these and similar materials. It is demonstrated in this paper that absorbed water can be removed by exposing the sample to dry N2 during magic angle spinning. This results in significantly enhanced spectral resolution for the silanol protons in the 1H MAS spectrum. The enhanced spectral resolution makes it possible to quantify the various hydroxyl groups in a complex metal-oxide catalyst. Results obtained on tungsten oxide supported on SBA-15 mesoporous silica materials are reported.

  11. Bulk magnetization and 1H NMR spectra of magnetically heterogeneous model systems

    SciTech Connect

    Levin, E. M.; Bud' ko, S. L.

    2011-04-28

    Bulk magnetization and {sup 1}H static and magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra of two magnetically heterogeneous model systems based on laponite (LAP) layered silicate or polystyrene (PS) with low and high proton concentration, respectively, and ferrimagnetic Fe{sub 2}O{sub 3} nano- or micro-particles have been studied. In LAP+Fe{sub 2}O{sub 3}, a major contribution to the NMR signal broadening is due to the dipolar coupling between the magnetic moments of protons and magnetic particles. In PS+Fe{sub 2}O{sub 3}, due to the higher proton concentration in polystyrene and stronger proton–proton dipolar coupling, an additional broadening is observed, i.e. {sup 1}H MAS NMR spectra of magnetically heterogeneous systems are sensitive to both proton–magnetic particles and proton–proton dipolar couplings. An increase of the volume magnetization by ∼1 emu/cm{sup 3} affects the {sup 1}H NMR signal width in a way that is similar to an increase of the proton concentration by ∼2×10{sup 22}/cm{sup 3}. {sup 1}H MAS NMR spectra, along with bulk magnetization measurements, allow the accurate determination of the hydrogen concentration in magnetically heterogeneous systems.

  12. Changes in surface structure of sodium aluminoborosilicate glasses during aqueous corrosion analyzed by using NMR

    NASA Astrophysics Data System (ADS)

    Ohkubo, Takahiro; Iwadate, Yasuhiko; Deguchi, Kenzo; Ohki, Shinobu; Shimizu, Tadashi

    2015-02-01

    Aqueous corrosion tests were performed for aluminoborosilicate glasses with different Na contents at 90 °C for 20 days. Multi-nuclear solid-state nuclear magnetic resonance (NMR) techniques were employed to characterize the structures of the pristine and altered glasses. 11B magic-angle spinning (MAS) NMR spectra showed the same line shape for the pristine and altered glasses, indicating that B species such as BO3 and BO4 were released into the solution congruently with the same fraction during the static dissolution experiments. The reconstruction of Si on the glass surface as hydrated phases was confirmed by the 29Si MAS and 1H ?29Si cross-polarization magic-angle spinning NMR spectra of the altered glasses. 23Na MAS and triple-quantum magic-angle spinning NMR spectra showed that part of the Na released from pristine glasses was incorporated in the hydrated phases, which can be identified by a 23Na chemical shift at ?iso = - 3.3 ppm. The availability of these structural data by employing solid-state NMR techniques can provide a better understanding of the formation of the hydrated phases and the effect of dissolution behavior on the glass composition.

  13. Phosphorus NMR of isolated perfused morris hepatomas

    SciTech Connect

    Graham, R.A.; Meyer, R.A.; Brown, T.R.; Sauer, L.A.

    1986-03-05

    The authors are developing techniques for the study of perfused solid tumors by NMR. Tissue-isolated solid hepatomas were grown to 1-2 cm diameter as described previously. The arterial supply was isolated and the tumors perfused (0.5 - 1.0 ml/min) in vitro at 25 C with a 15% suspension of red blood cells in Krebs-Henseliet solution. /sup 31/P-NMR spectra were acquired at 162 MHz in a specially-designed NMR probe using a solenoidal coil. Intracellular pH (monitored from the chemical shift of inorganic phosphate) and ATP levels were stable for up to 6 hrs during perfusion. During 30 min of global ischemia, ATP decreased by 75% and pH fell from 7.0 to 6.7. These changes were reversed by 1 hr reperfusion. In addition to ATP and phosphate, the spectra included a large resonance due to phosphomonoesters, as well as peaks consistent with glycerylphosphocholine, glyceryl-phosphoethanolamine, phosphocreatine, NAD, and UDPG. However, the most novel feature of the spectra was the presence of an unidentified peak in the phosphonate region (+ 16.9 ppm). The peak was not present in spectra of muscle, liver, brain, kidney, or fat tissues excised from the same animals. They are presently attempting to identify the compound that gives rise to this peak and to establish its metabolic origin.

  14. MODIS Airborne simulator (MAS) Final Report for CLASIC

    SciTech Connect

    Thomas Arnold; Steven Platnick

    2010-11-24

    The MAS was flown aboard the NASA ER-2 for the CLASIC field experiment, and for all data collected, provided calibrated and geolocated (Level-1B) radiance data for it’s 50 spectral bands (ranging in wavelength for 0.47 to 14.3 µm). From the Level-1B data, as directed in the Statement of Work, higher order (Level-2) data products were derived. The Level-2 products include: a) cloud optical thickness, b) cloud effective radius, c) cloud top height (temperature), d) cloud fraction, e) cloud phase products. Preliminary Level-1B and Level-2 products were provided during the field experiment (typically within one or two days of data collection). Final version data products were made available in December 2008 following considerable calibration analysis. Data collection, data processing (to Level-2), and discussion of the calibration work are summarized below.

  15. Anode consumption on a subsea X-mas tree

    SciTech Connect

    Lye, R.E.

    1998-12-31

    Anode consumption and coating breakdown on a X-mas tree installed at the Troll Field in the Norwegian North Sea was investigated after 5 years. A comparison with a spare tree and one tree being exposed for only 3--4 months was done. The epoxy coating has several blisters, in particular on stainless steel surfaces. Water inside the blisters has a pH of 13-14 indicating that the cathodic reaction occurs inside them. The anode dimensions indicate an overall anode consumption of approximately 20%, while the design allows 27% after 5 years. This indicates that the original design is quite conservative. If the design had been done according to present day design rules, the conservatism would be reduced; an overall anode consumption of 23% is then likely (still less than allowed 27%).

  16. Probing structure and dynamics of protein assemblies by magic angle spinning NMR spectroscopy.

    PubMed

    Yan, Si; Suiter, Christopher L; Hou, Guangjin; Zhang, Huilan; Polenova, Tatyana

    2013-09-17

    In living organisms, biological molecules often organize into multicomponent complexes. Such assemblies consist of various proteins and carry out essential functions, ranging from cell division, transport, and energy transduction to catalysis, signaling, and viral infectivity. To understand the biological functions of these assemblies, in both healthy and disease states, researchers need to study their three-dimensional architecture and molecular dynamics. To date, the large size, the lack of inherent long-range order, and insolubility have made atomic resolution studies of many protein assemblies challenging or impractical using traditional structural biology methods such as X-ray diffraction and solution NMR spectroscopy. In the past 10 years, we have focused our work on the development and application of magic angle spinning solid-state NMR (MAS NMR) methods to characterize large protein assemblies at atomic-level resolution. In this Account, we discuss the rapid progress in the field of MAS NMR spectroscopy, citing work from our laboratory and others on methodological developments that have facilitated the in-depth analysis of biologically important protein assemblies. We emphasize techniques that yield enhanced sensitivity and resolution, such as fast MAS (spinning frequencies of 40 kHz and above) and nonuniform sampling protocols for data acquisition and processing. We also discuss the experiments for gaining distance restraints and for recoupling anisotropic tensorial interactions under fast MAS conditions. We give an overview of sample preparation approaches when working with protein assemblies. Following the overview of contemporary MAS NMR methods, we present case studies into the structure and dynamics of two classes of biological systems under investigation in our laboratory. We will first turn our attention to cytoskeletal microtubule motor proteins including mammalian dynactin and dynein light chain 8. We will then discuss protein assemblies from the HIV-1 retrovirus. PMID:23402263

  17. Closed-cycle cold helium magic-angle spinning for sensitivity-enhanced multi-dimensional solid-state NMR

    NASA Astrophysics Data System (ADS)

    Matsuki, Yoh; Nakamura, Shinji; Fukui, Shigeo; Suematsu, Hiroto; Fujiwara, Toshimichi

    2015-10-01

    Magic-angle spinning (MAS) NMR is a powerful tool for studying molecular structure and dynamics, but suffers from its low sensitivity. Here, we developed a novel helium-cooling MAS NMR probe system adopting a closed-loop gas recirculation mechanism. In addition to the sensitivity gain due to low temperature, the present system has enabled highly stable MAS (vR = 4-12 kHz) at cryogenic temperatures (T = 35-120 K) for over a week without consuming helium at a cost for electricity of 16 kW/h. High-resolution 1D and 2D data were recorded for a crystalline tri-peptide sample at T = 40 K and B0 = 16.4 T, where an order of magnitude of sensitivity gain was demonstrated versus room temperature measurement. The low-cost and long-term stable MAS strongly promotes broader application of the brute-force sensitivity-enhanced multi-dimensional MAS NMR, as well as dynamic nuclear polarization (DNP)-enhanced NMR in a temperature range lower than 100 K.

  18. A simple method for analyzing 51V solid-state NMR spectra of complex systems.

    PubMed

    Fenn, Annika; Wächtler, Maria; Breitzke, Hergen; Buchholz, Axel; Lippold, Ines; Plass, Winfried; Buntkowsky, Gerd

    2011-09-01

    Five vanadium complexes as models for biological systems were investigated using (51)V-MAS-NMR spectroscopy. All spectra show an uncommon line shape, which can be attributed to a shorter relaxation time of the satellite transition in contrast to the central one. A method for the reliable analysis of such kind of spectra is presented for the first time and the most important NMR parameters of the investigated complexes (quadrupolar coupling constant C(Q), asymmetry of the EFG tensor ?(Q), isotropic chemical shift ?(iso), chemical shift anisotropy ?(?) and asymmetry of the CSA tensor ?(?)) are presented. These results are of particular importance with respect to the analysis of the (51)V-MAS-NMR spectra of vanadium moieties in biological matrices such as vanadium chloroperoxidase, which show hitherto unexplained low intensity of the satellite sideband pattern. PMID:21601435

  19. Functional studies using NMR

    SciTech Connect

    McCready, V.R.; Leach, M.; Ell, P.J.

    1987-01-01

    This volume is based on a series of lectures delivered at a one-day teaching symposium on functional and metabolic aspects of NMR measurements held at the Middlesex Hospital Medical School on 1st September 1985 as a part of the European Nuclear Medicine Society Congress. Currently the major emphasis in medical NMR in vivo is on its potential to image and display abnormalities in conventional radiological images, providing increased contrast between normal and abnormal tissue, improved definition of vasculature, and possibly an increased potential for differential diagnosis. Although these areas are undeniably of major importance, it is probable that NMR will continue to complement conventional measurement methods. The major potential benefits to be derived from in vivo NMR measurements are likely to arise from its use as an instrument for functional and metabolic studies in both clinical research and in the everyday management of patients. It is to this area that this volume is directed.

  20. Asynchronous through-bond homonuclear isotropic mixing: application to carbon-carbon transfer in perdeuterated proteins under MAS.

    PubMed

    Kulminskaya, Natalia; Vasa, Suresh Kumar; Giller, Karin; Becker, Stefan; Linser, Rasmus

    2015-11-01

    Multiple-bond carbon-carbon homonuclear mixing is a hurdle in extensively deuterated proteins and under fast MAS due to the absence of an effective proton dipolar-coupling network. Such conditions are now commonly employed in solid-state NMR spectroscopy. Here, we introduce an isotropic homonuclear (13)C-(13)C through-bond mixing sequence, MOCCA, for the solid state. Even though applied under MAS, this scheme performs without rotor synchronization and thus does not pose the usual hurdles in terms of power dissipation for fast spinning. We compare its performance with existing homonuclear (13)C-(13)C mixing schemes using a perdeuterated and partially proton-backexchanged protein. Based on the analysis of side chain carbon-carbon correlations, we show that particularly MOCCA with standard 180-degree pulses and delays leading to non-rotor-synchronized spacing performs exceptionally well. This method provides high magnetization transfer efficiency for multiple-bond transfer in the aliphatic region compared with other tested mixing sequences. In addition, we show that this sequence can also be tailor-made for recoupling within a selected spectral region using band-selective pulses. PMID:26319987

  1. NMR at the Picomole Level of a DNA Adduct

    PubMed Central

    Kautz, Roger; Wang, Poguang; Giese, Roger W.

    2014-01-01

    We investigate the limit of detection for obtaining NMR data of a DNA adduct using modern microscale NMR instrumentation, once the adduct has been isolated at the pmol level. Eighty nanograms (130 pmol) of a DNA adduct standard, N-(2?-deoxyguanosin-8-yl)-2-acetylaminofluorene 5?-monophosphate (AAF-dGMP), in 1.5 ?L of D2O with 10% methanol-d4, in a vial, was completely picked up as a droplet suspended in a fluorocarbon liquid, and loaded efficiently into a microcoil probe. This work demonstrates a practical manual method of droplet microfluidic sample loading, previously demonstrated using automated equipment, which provides a several-fold advantage over conventional flow injection. Eliminating dilution during injection and confining the sample into the observed volume realizes the full theoretical mass sensitivity of a microcoil, comparable to a micro-cryo probe. With 80 ng, an NMR spectrum acquired over 40 hr showed all of the resonances seen in a standard spectrum of AAF-dGMP, with a S/N of at least 10, despite broadening due to previously-noted effects of conformational exchange. Also a 2D TOCSY spectrum (total correlation spectroscopy) was acquired on 1.6 ?g in 18 hr. This work helps to define the utility of NMR in combination with other analytical methods for the structural characterization of a small amount of a DNA adduct. PMID:24028148

  2. Study of the ferroelastic phase transition in the tetraethylammonium compound [N(C2H5)4]2ZnBr4 by magic-angle spinning and static NMR

    NASA Astrophysics Data System (ADS)

    Lim, Ae Ran

    2016-03-01

    The ferroelastic phase transition of tetraethylammonium compound [N(C2H5)4]2ZnBr4 at the phase transition temperature (TC) = 283 K was characterized by magic-angle spinning (MAS) and static nuclear magnetic resonance (NMR), and confirmed by optical polarizing spectroscopy. The structural geometry near TC was studied in terms of the chemical shifts and the spin-lattice relaxation times T1ρ in the rotating frame for 1H MAS NMR and 13C cross-polarization (CP)/MAS NMR. The two inequivalent ethyl groups were distinguishable in the 13C NMR spectrum, and the T1ρ results indicate that they undergo tumbling motion above TC in a coupled manner. From the 14N NMR results, the two nitrogen nuclei in the N(C2H5)4+ ions were distinguishable above TC, and the splitting in the spectra below TC was related to the ferroelastic domains with different orientations.

  3. Multinuclear NMR studies of relaxor ferroelectrics

    NASA Astrophysics Data System (ADS)

    Zhou, Donghua

    Multinuclear NMR of 93Nb, 45Sc, and 207Pb has been carried out to study the structure, disorder, and dynamics of a series of important solid solutions: perovskite relaxor ferroelectric materials (1-x) Pb(Mg1/3Nb 2/3)O3-x Pb(Sc1/2Nb1/2)O 3 (PMN-PSN). 93Nb NMR investigations of the local structure and cation order/disorder are presented as a function of PSN concentration, x. The superb fidelity and accuracy of 3QMAS allows us to make clear and consistent assignments of spectral intensities to the 28 possible nearest B-site neighbor (nBn) configurations, (NMg, NSc, NNb), where each number ranges from 0 to 6 and their sum is 6. For most of the 28 possible nBn configurations, isotropic chemical shifts and quadrupole product constants have been extracted from the data. The seven configurations with only larger cations, Mg 2+ and Sc3+ (and no Nb5+) are assigned to the seven observed narrow peaks, whose deconvoluted intensities facilitate quantitative evaluation of, and differentiation between, different models of B-site (chemical) disorder. The "completely random" model is ruled out and the "random site" model is shown to be in qualitative agreement with the NMR experiments. To obtain quantitative agreement with observed NMR intensities, the random site model is slightly modified by including unlike-pair interaction energies. To date, 45Sc studies have not been as fruitful as 93Nb NMR because the resolution is lower in the 45Sc spectra. The lower resolution of 45Sc spectra is due to a smaller span of isotropic chemical shift (40 ppm for 45Sc vs. 82 ppm for 93Nb) and to the lack of a fortuitous mechanism that simplifies the 93Nb spectra; for 93Nb the overlap of the isotropic chemical shifts of 6-Sc and 6-Nb configurations results in the alignment of all the 28 configurations along only seven quadrupole distribution axes. Finally we present variable temperature 207Pb static, MAS, and 2D-PASS NMR studies. Strong linear correlations between isotropic and anisotropic chemical shifts show that Pb-O bonds vary from more ionic to more covalent environments. Distributions of Pb-O bond lengthes are also quantitatively described. Such distributions are used to examine two competing models of Pb displacements; the shell model and the unique direction model. Only the latter model is able to reproduce the observed Pb-O distance distribution.

  4. Hexameric Capsules Studied by Magic Angle Spinning Solid-State NMR Spectroscopy: Identifying Solvent Molecules in Pyrogallol[4]arene Capsules.

    PubMed

    Avram, Liat; Goldbourt, Amir; Cohen, Yoram

    2016-01-01

    Powders of pyrogallol[4]arene hexamers were produced by evaporation from organic solvents and were studied, for the first time, by magic angle spinning solid-state NMR (MAS ssNMR). Evaporation selectively removed non-encapsulated solvent molecules leaving stable hexameric capsules encapsulating solvent molecules. After exposure of the powder to solvent vapors, (1) H/(13) C heteronuclear correlation MAS ssNMR experiments were used to assign the signals of the external and encapsulated solvent molecules. The formed capsules were stable for months and the process of solvent encapsulation was reversible. According to the ssNMR experiments, the encapsulated solvent molecules occupy different sites and those sites differ in their mobility. The presented approach paves the way for studying guest exchange, guest affinity, and gas storage in hexamers of this type in the solid state. PMID:26634640

  5. Dual-band selective double cross polarization for heteronuclear polarization transfer between dilute spins in solid-state MAS NMR

    PubMed Central

    Zhang, Zhengfeng; Miao, Yimin; Liu, Xiaoli; Yang, Jun; Li, Conggang; Deng, Feng; Fu, Riqiang

    2012-01-01

    A sinusoidal modulation scheme is described for selective heteronuclear polarization transfer between two dilute spins in double cross polarization magic-angle-spinning nuclear magnetic resonance spectroscopy. During the second N ? C cross polarization, the 13C RF amplitude is modulated sinusoidally while the 15N RF amplitude is tangent. This modulation induces an effective spin-lock field in two selective frequency bands in either side of the 13C RF carrier frequency, allowing for simultaneous polarization transfers from 15N to 13C in those two selective frequency bands. It is shown by experiments and simulations that this sinusoidal modulation allows one to selectively polarize from 15N to its covalently bonded 13C? and 13C? carbons in neighboring peptide planes simultaneously, which is useful for establishing the back-bone connectivity between two sequential residues in protein structural elucidation. The selectivity and efficiency were experimentally demonstrated on a uniformly 13C,15N-labeled ?1 immunoglobulin binding domain of protein G (GB1). PMID:22445831

  6. CHARACTERIZATION OF THE WOUND INDUCED MATERIAL IN CITRUS FRUIT PEEL BY CARBON-13 CP-MAS SOLID STATE NMR SPECTROSCOPY

    Technology Transfer Automated Retrieval System (TEKTRAN)

    There are conflicting views regarding the chemical composition of the induced, phloroglucinol-HCl (PG-HCl) reacting, material accumulating in injured citrus peel tissues. Grapefruit, Citrus paradisi, were injured, inoculated with Peicillium digitatum and incubated under contitions favorable to the a...

  7. High Resolution Magic Angle Spinning 1H-NMR Metabolic Profiling of Nanoliter Biological Tissues at High Magnetic Field

    SciTech Connect

    Feng, Ju; Hu, Jian Z.; Burton, Sarah D.; Hoyt, David W.

    2013-03-05

    It is demonstrated that a high resolution magic angle spinning 1H-NMR spectrum of biological tissue samples with volumes as small as 150 nanoliters, or 0.15 mg in weight, can be acquired in a few minutes at 21.1 T magnetic field using a commercial 1.6 mm fast-MAS probe with minor modification of the MAS rotor. The strategies of sealing the samples inside the MAS rotor to avoid fluid leakage as well as the ways of optimizing the signal to noise are discussed.

  8. Perspectives for sensitivity enhancement in proton-detected solid-state NMR of highly deuterated proteins by preserving water magnetization.

    PubMed

    Chevelkov, Veniamin; Xiang, ShengQi; Giller, Karin; Becker, Stefan; Lange, Adam; Reif, Bernd

    2015-02-01

    In this work, we show how the water flip-back approach that is widely employed in solution-state NMR can be adapted to proton-detected MAS solid-state NMR of highly deuterated proteins. The scheme allows to enhance the sensitivity of the experiment by decreasing the recovery time of the proton longitudinal magnetization. The method relies on polarization transfer from non-saturated water to the protein during the inter-scan delay. PMID:25634300

  9. Fast automated protein NMR data collection and assignment by ADAPT-NMR on Bruker spectrometers.

    PubMed

    Lee, Woonghee; Hu, Kaifeng; Tonelli, Marco; Bahrami, Arash; Neuhardt, Elizabeth; Glass, Karen C; Markley, John L

    2013-11-01

    ADAPT-NMR (Assignment-directed Data collection Algorithm utilizing a Probabilistic Toolkit in NMR) supports automated NMR data collection and backbone and side chain assignment for [U-(13)C, U-(15)N]-labeled proteins. Given the sequence of the protein and data for the orthogonal 2D (1)H-(15)N and (1)H-(13)C planes, the algorithm automatically directs the collection of tilted plane data from a variety of triple-resonance experiments so as to follow an efficient pathway toward the probabilistic assignment of (1)H, (13)C, and (15)N signals to specific atoms in the covalent structure of the protein. Data collection and assignment calculations continue until the addition of new data no longer improves the assignment score. ADAPT-NMR was first implemented on Varian (Agilent) spectrometers [A. Bahrami, M. Tonelli, S.C. Sahu, K.K. Singarapu, H.R. Eghbalnia, J.L. Markley, PLoS One 7 (2012) e33173]. Because of broader interest in the approach, we present here a version of ADAPT-NMR for Bruker spectrometers. We have developed two AU console programs (ADAPT_ORTHO_run and ADAPT_NMR_run) that run under TOPSPIN Versions 3.0 and higher. To illustrate the performance of the algorithm on a Bruker spectrometer, we tested one protein, chlorella ubiquitin (76 amino acid residues), that had been used with the Varian version: the Bruker and Varian versions achieved the same level of assignment completeness (98% in 20 h). As a more rigorous evaluation of the Bruker version, we tested a larger protein, BRPF1 bromodomain (114 amino acid residues), which yielded an automated assignment completeness of 86% in 55 h. Both experiments were carried out on a 500 MHz Bruker AVANCE III spectrometer equipped with a z-gradient 5 mm TCI probe. ADAPT-NMR is available at http://pine.nmrfam.wisc.edu/ADAPT-NMR in the form of pulse programs, the two AU programs, and instructions for installation and use. PMID:24091140

  10. Fast automated protein NMR data collection and assignment by ADAPT-NMR on Bruker spectrometers

    NASA Astrophysics Data System (ADS)

    Lee, Woonghee; Hu, Kaifeng; Tonelli, Marco; Bahrami, Arash; Neuhardt, Elizabeth; Glass, Karen C.; Markley, John L.

    2013-11-01

    ADAPT-NMR (Assignment-directed Data collection Algorithm utilizing a Probabilistic Toolkit in NMR) supports automated NMR data collection and backbone and side chain assignment for [U-13C, U-15N]-labeled proteins. Given the sequence of the protein and data for the orthogonal 2D 1H-15N and 1H-13C planes, the algorithm automatically directs the collection of tilted plane data from a variety of triple-resonance experiments so as to follow an efficient pathway toward the probabilistic assignment of 1H, 13C, and 15N signals to specific atoms in the covalent structure of the protein. Data collection and assignment calculations continue until the addition of new data no longer improves the assignment score. ADAPT-NMR was first implemented on Varian (Agilent) spectrometers [A. Bahrami, M. Tonelli, S.C. Sahu, K.K. Singarapu, H.R. Eghbalnia, J.L. Markley, PLoS One 7 (2012) e33173]. Because of broader interest in the approach, we present here a version of ADAPT-NMR for Bruker spectrometers. We have developed two AU console programs (ADAPT_ORTHO_run and ADAPT_NMR_run) that run under TOPSPIN Versions 3.0 and higher. To illustrate the performance of the algorithm on a Bruker spectrometer, we tested one protein, chlorella ubiquitin (76 amino acid residues), that had been used with the Varian version: the Bruker and Varian versions achieved the same level of assignment completeness (98% in 20 h). As a more rigorous evaluation of the Bruker version, we tested a larger protein, BRPF1 bromodomain (114 amino acid residues), which yielded an automated assignment completeness of 86% in 55 h. Both experiments were carried out on a 500 MHz Bruker AVANCE III spectrometer equipped with a z-gradient 5 mm TCI probe. ADAPT-NMR is available at http://pine.nmrfam.wisc.edu/ADAPT-NMR in the form of pulse programs, the two AU programs, and instructions for installation and use.

  11. MAS C-Terminal Tail Interacting Proteins Identified by Mass Spectrometry- Based Proteomic Approach

    PubMed Central

    Tirupula, Kalyan C.; Zhang, Dongmei; Osbourne, Appledene; Chatterjee, Arunachal; Desnoyer, Russ; Willard, Belinda; Karnik, Sadashiva S.

    2015-01-01

    Propagation of signals from G protein-coupled receptors (GPCRs) in cells is primarily mediated by protein-protein interactions. MAS is a GPCR that was initially discovered as an oncogene and is now known to play an important role in cardiovascular physiology. Current literature suggests that MAS interacts with common heterotrimeric G-proteins, but MAS interaction with proteins which might mediate G protein-independent or atypical signaling is unknown. In this study we hypothesized that MAS C-terminal tail (Ct) is a major determinant of receptor-scaffold protein interactions mediating MAS signaling. Mass-spectrometry based proteomic analysis was used to comprehensively identify the proteins that interact with MAS Ct comprising the PDZ-binding motif (PDZ-BM). We identified both PDZ and non-PDZ proteins from human embryonic kidney cell line, mouse atrial cardiomyocyte cell line and human heart tissue to interact specifically with MAS Ct. For the first time our study provides a panel of PDZ and other proteins that potentially interact with MAS with high significance. A ‘cardiac-specific finger print’ of MAS interacting PDZ proteins was identified which includes DLG1, MAGI1 and SNTA. Cell based experiments with wild-type and mutant MAS lacking the PDZ-BM validated MAS interaction with PDZ proteins DLG1 and TJP2. Bioinformatics analysis suggested well-known multi-protein scaffold complexes involved in nitric oxide signaling (NOS), cell-cell signaling of neuromuscular junctions, synapses and epithelial cells. Majority of these protein hits were predicted to be part of disease categories comprising cancers and malignant tumors. We propose a ‘MAS-signalosome’ model to stimulate further research in understanding the molecular mechanism of MAS function. Identifying hierarchy of interactions of ‘signalosome’ components with MAS will be a necessary step in future to fully understand the physiological and pathological functions of this enigmatic receptor. PMID:26484771

  12. Elemental abundances of the B and A stars. 2: Gamma Geminorum, HD 60825, 7 Sextantis, HR 4817, and HR 5780

    NASA Technical Reports Server (NTRS)

    Adelman, Saul J.; Philip, A. G. Davis

    1994-01-01

    We extend fine analyses of the B and A stars, gamma Geminorum, 7 Sextantis, HR 4817, and HR 5780 using additional spectroscopic data from the Kitt Peak National Observatory (KPNO) coude feed telescope with a TI CCD, camera 5, and grating A, and ATLAS9 model atmospheres. In addition we study HD 60825, which had colors similar to the FHB A stars, but was found to be a Population I star. HD 60825, as is gamma Gem, is a sharp-lined early-A star with nearly solar derived abundances. HR 5780 and 7 Sex are also examples of stars which for the most part have solar abundances. The newly derived abundances for HR 4817 reveal important differences with respect to 53 Tau, a somewhat similar HgMn star.

  13. 6/7Li NMR study of the Li1-zNi1+zO2 phases.

    PubMed

    Chazel, Cédric; Ménétrier, Michel; Croguennec, Laurence; Delmas, Claude

    2005-10-01

    A series of Li1-zNi1+zO2 materials have been synthesised by the coprecipitation route. An X-ray diffraction study was carried out on these materials using the Rietveld method to determine the departure from the ideal stoichiometry z, which ranges from 0 to 0.138. The actual Li/Ni ratio was also checked by chemical analyses using inductively coupled plasma (ICP) for each sample. The stoichiometric sample (z approximately 0) was obtained using a 15% Li excess. (6/7)Li NMR results from LiNiO2 (z approximately 0) show that the asymmetric shape of the NMR signal is due to anisotropy. Calculations give evidence that the paramagnetic dipolar interaction from the electron spins carried by Ni is anisotropic but does not completely explain the experimental anisotropy. (6)Li MAS NMR (magic angle spinning NMR) experiments and temperature standardisation NMR measurements unambiguously assign the isotropic position at +726 ppm. The static-echo NMR spectra of the non-stoichiometric Li1-zNi1+zO2 phases also exhibit an asymmetric shape whose width increases with the departure from the ideal stoichiometry z. (6/7)Li static and MAS NMR show that the 2zNi(2+) ions thus formed modify the dipolar interaction within the materials and also affect the Fermi contact interaction, since a distribution of Li environments is observed using (6)Li NMR for non-stoichiometric samples. PMID:16041774

  14. Decentralized method for complex task allocation in massive MAS

    NASA Astrophysics Data System (ADS)

    Brahmi, Zaki; Gammoudi, M. M.

    2008-06-01

    Task allocation is still a fundamental problem in Multi-Agents System (MAS). It allows the formation a coalition of agents to cooperate together in order to carry out a complex task. Generally, the process of task allocation requires calculating the value of all the possible allocations, then determining which optimal. In the context of Massive Multi-Agent Systems (MMAS), one agent generates all the possible coalitions and then calculates the value of each, is inefficient. Moreover, the traditional approaches based on the negotiation between agents, are impractical because of the complexity of communications between agents. In this paper we propose a decentralized method, based on grouping agents using the Formal Concepts Analysis (FCA) approach for the task allocation in MMAS. In our model, agents are fully cooperative and each task is composed of several subtasks. The proposed solution is based on two steps: i) computing groups of agents having similar characteristics in the objective to distribute the task allocation process among agents and minimize the communication between agents. ii) Finding the optimal allocation by sharing the task allocation process among groups of agents.

  15. Distributed Cooperation Solution Method of Complex System Based on MAS

    NASA Astrophysics Data System (ADS)

    Weijin, Jiang; Yuhui, Xu

    To adapt the model in reconfiguring fault diagnosing to dynamic environment and the needs of solving the tasks of complex system fully, the paper introduced multi-Agent and related technology to the complicated fault diagnosis, an integrated intelligent control system is studied in this paper. Based on the thought of the structure of diagnostic decision and hierarchy in modeling, based on multi-layer decomposition strategy of diagnosis task, a multi-agent synchronous diagnosis federation integrated different knowledge expression modes and inference mechanisms are presented, the functions of management agent, diagnosis agent and decision agent are analyzed, the organization and evolution of agents in the system are proposed, and the corresponding conflict resolution algorithm in given, Layered structure of abstract agent with public attributes is build. System architecture is realized based on MAS distributed layered blackboard. The real world application shows that the proposed control structure successfully solves the fault diagnose problem of the complex plant, and the special advantage in the distributed domain.

  16. NMR imaging microscopy

    SciTech Connect

    Not Available

    1986-10-01

    In the past several years, proton nuclear magnetic resonance (NMR) imaging has become an established technique in diagnostic medicine and biomedical research. Although much of the work in this field has been directed toward development of whole-body imagers, James Aguayo, Stephen Blackband, and Joseph Schoeninger of the Johns Hopkins University School of Medicine working with Markus Hintermann and Mark Mattingly of Bruker Medical Instruments, recently developed a small-bore NMR microscope with sufficient resolution to image a single African clawed toad cell (Nature 1986, 322, 190-91). This improved resolution should lead to increased use of NMR imaging for chemical, as well as biological or physiological, applications. The future of NMR microscopy, like that of many other newly emerging techniques, is ripe with possibilities. Because of its high cost, however, it is likely to remain primarily a research tool for some time. ''It's like having a camera,'' says Smith. ''You've got a way to look at things at very fine levels, and people are going to find lots of uses for it. But it is a very expensive technique - it costs $100,000 to add imaging capability once you have a high-resolution NMR, which itself is at least a $300,000 instrument. If it can answer even a few questions that can't be answered any other way, though, it may be well worth the cost.''

  17. Solid-state NMR characterization of Mowry Formation shales

    SciTech Connect

    Miknis, F.P.

    1992-04-01

    Solid-state [sup 13]C and [sup 29]Si NMR measurements were carried out on a series of petroleum source rocks from the Mowry Formation of the Powder River Basin in Wyoming. The objectives of this study wereto use CP/MAS [sup 13]C NMR measurements to monitor changes in the carbon structure of the kerogen that result from depth of burial, and to examine the feasibility of [sup 29]Si NMR for studying the thermal alteration of clay minerals during diagenesis. Carbon and silicon NMR measurements were made on a suite of samples covering a present-day depth interval of 3,000 to 11,500 ft.In general, the NMR results endorsed other geochemical analyses that were performed on the source rocks as part of another study to examine pressure compartmentalization in the Mowry Formation. The carbon aromaticity of the kerogen increased with depth of burial, and at depths greater that approximately 10,000 ft the kerogen showed little capacity to generate additional oil because of the small fraction of residual aliphatic carbon. By combining NMR and Rock-Eval measurements, an estimate of the hydrogen budget was obtained. The calculations indicated that approximately 20% of the kerogen was converted to hydrocarbons, and that sufficient hydrogen was liberated from aromatization and condensation reactions to stabilize the generated products. The [sup 29]Si NMR spectra were characterized by a relatively sharp quartz resonance and a broad resonance from the clay minerals. With increasing depth of burial, the clay resonance became broader and shifted slightly downfield. These changes qualitatively support X-ray analysis that shows progressive alteration of illite to smectite with depth of burial.

  18. Solid-state NMR characterization of Mowry Formation shales

    SciTech Connect

    Miknis, F.P.

    1992-04-01

    Solid-state {sup 13}C and {sup 29}Si NMR measurements were carried out on a series of petroleum source rocks from the Mowry Formation of the Powder River Basin in Wyoming. The objectives of this study wereto use CP/MAS {sup 13}C NMR measurements to monitor changes in the carbon structure of the kerogen that result from depth of burial, and to examine the feasibility of {sup 29}Si NMR for studying the thermal alteration of clay minerals during diagenesis. Carbon and silicon NMR measurements were made on a suite of samples covering a present-day depth interval of 3,000 to 11,500 ft.In general, the NMR results endorsed other geochemical analyses that were performed on the source rocks as part of another study to examine pressure compartmentalization in the Mowry Formation. The carbon aromaticity of the kerogen increased with depth of burial, and at depths greater that approximately 10,000 ft the kerogen showed little capacity to generate additional oil because of the small fraction of residual aliphatic carbon. By combining NMR and Rock-Eval measurements, an estimate of the hydrogen budget was obtained. The calculations indicated that approximately 20% of the kerogen was converted to hydrocarbons, and that sufficient hydrogen was liberated from aromatization and condensation reactions to stabilize the generated products. The {sup 29}Si NMR spectra were characterized by a relatively sharp quartz resonance and a broad resonance from the clay minerals. With increasing depth of burial, the clay resonance became broader and shifted slightly downfield. These changes qualitatively support X-ray analysis that shows progressive alteration of illite to smectite with depth of burial.

  19. HR-1 Mice: A New Inflammatory Acne Mouse Model

    PubMed Central

    Jang, Yong Hyun; Lee, Kyou Chae; Lee, Seok-Jong; Kim, Do Won

    2015-01-01

    Background There is no appropriate in vivo animal model that reflects the inflammatory response of human acne. Objective This study investigated the effect of Propionibacterium acnes on the development of inflammatory acne-like lesions in four mouse strains with different degrees of immune response for the development of an optimal mouse model of inflammatory acne. Methods Human P. acnes suspensions (108 and 109 colony forming unit [CFU]/µl) were injected into the backs of HR-1, BALB/c, vitamin D receptor-knockout (VDR k/o), and severe combined immunodeficiency disease mice. Inflammation levels were evaluated two weeks after injection of P. acnes suspensions. In addition, histopathological examination and immunohistochemical staining of the expressions of inflammatory biomarkers (i.e., CD4+/CD8+ T lymphocytes, neutrophils, myeloperoxidase, interleukin-1β, matrix metalloprotease (MMP)-2, MMP-3, MMP-9, toll-like receptor (TLR)-2, LL-37, and integrin α6) were performed on tissue specimens. Results The HR-1 mouse strain exhibited the most remarkable inflammatory reaction with epithelial proliferation and microcomedone-like cyst formation. HR-1 mice also demonstrated aberrant integrin expression in the epidermis around both inflamed lesions and newly formed microcomedones. These findings were more prominent in the group receiving 109 CFU/µl P. acnes than 108 CFU/µl. MMP-9 expression in HR-1 mice was also upregulated around the microcomedone-like cysts. Finally, expression levels of TLR-2 and LL-37 were higher in HR-1 and BALB/c mice than the VDR k/o and SCID mice strains. Conclusion P. acnes induces acneiform inflammation with small microcomedones in HR-1 mice. Therefore, the HR-1 mouse strain represents a good candidate for the development of a new inflammatory acne mouse model. PMID:26082581

  20. NMR crystallography: the use of chemical shifts

    NASA Astrophysics Data System (ADS)

    Harris, Robin K.

    2004-10-01

    Measurements of chemical shifts obtained from magic-angle spinning NMR spectra (together with quantum mechanical computations of shielding) can provide valuable information on crystallography. Examples are given of the determination of crystallographic asymmetric units, of molecular symmetry in the solid-state environment, and of crystallographic space group assignment. Measurements of full tensor components for 199Hg have given additional coordination information. The nature of intermolecular hydrogen bonding in cortisone acetate polymorphs and solvates is obtained from chemical shift information, also involving measurement of the full tensor parameters. The resulting data have been used as restraints, built into the computation algorithm, in the analysis of powder diffraction patterns to give full crystal structures. A combination of quantum mechanical computation of shielding and measurement of proton chemical shifts (obtained by high-speed MAS) leads to the determination of the position of a proton in an intermolecular hydrogen bond. A recently-developed computer program specifically based on crystallographic repetition has been shown to give acceptable results. Moreover, NMR chemical shifts can distinguish between static and dynamic disorder in crystalline materials and can be used to determine modes and rates of molecular exchange motion.

  1. Biomolecular solid state NMR with magic-angle spinning at 25 K

    PubMed Central

    Thurber, Kent R.; Tycko, Robert

    2009-01-01

    A magic-angle spinning (MAS) probe has been constructed which allows the sample to be cooled with helium, while the MAS bearing and drive gases are nitrogen. The sample can be cooled to 25 K using roughly 3 liters/hour of liquid helium, while the 4 mm diameter rotor spins at 6.7 kHz with good stability (±5 Hz) for many hours. Proton decoupling fields up to at least 130 kHz can be applied. This helium-cooled MAS probe enables a variety of one-dimensional and two-dimensional NMR experiments on biomolecular solids and other materials at low temperatures, with signal-to-noise proportional to 1/T. We show examples of low-temperature 13C NMR data for two biomolecular samples, namely the peptide A?14–23 in the form of amyloid fibrils and the protein HP35 in frozen glycerol/water solution. Issues related to temperature calibration, spin-lattice relaxation at low temperatures, paramagnetic doping of frozen solutions, and 13C MAS NMR linewidths are discussed. PMID:18922715

  2. 119Sn magic angle spinning NMR of nanocrystalline SnO2.

    PubMed

    Sabarinathan, V; Vinod Chandran, C; Ramasamy, S; Ganapathy, S

    2008-01-01

    Nanocrystalline SnO2 samples of different grain sizes, prepared by inert gas condensation technique (IGCT) and chemical precipitation method and conforming to the tetragonal phase, have been studied by variable speed (3-10 kHz) 119Sn MAS NMR at 11.74 Tesla field. 119Sn solid-state NMR results show that the IGCT prepared samples have good crystallinity and phase purity compared to the samples prepared by the chemical method. The determination of 119Sn chemical shielding parameters (delta iso, delta delta and eta) from slow MAS spectra shows that the 119Sn isotropic chemical shift (delta iso) is strongly influenced at smaller grain sizes, attributable to the change in the O2- local symmetry for the surface 119Sn ions at smaller grain sizes. The observed line widths in MAS spectra are significantly larger than the life-time broadening due to spin-lattice (T1) and spin-spin (T2) relaxation. The 119Sn MAS NMR spectra are thus inhomogeneously broadened by a distribution of isotropic chemical shifts, the line broadening increasing with decrease in grain size. PMID:18468077

  3. IN SITU MAGIC ANGLE SPINNING NMR FOR STUDYING GEOLOGICAL CO(2) SEQUESTRATION

    SciTech Connect

    Hoyt, David W.; Turcu, Romulus VF; Sears, Jesse A.; Rosso, Kevin M.; Burton, Sarah D.; Kwak, Ja Hun; Felmy, Andrew R.; Hu, Jian Z.

    2011-03-27

    Geological carbon sequestration (GCS) is one of the most promising ways of mitigating atmospheric greenhouse gases (1-3). Mineral carbonation reactions are potentially important to the long-term sealing effectiveness of caprock but remain poorly predictable, particularly in low-water supercritical CO2 (scCO2)-dominated environments where the chemistry has not been adequately explored. In situ probes that provide molecular-level information is desirable for investigating mechanisms and rates of GCS mineral carbonation reactions. MAS-NMR is a powerful tool for obtaining detailed molecular structure and dynamics information of a system regardless whether the system is in a solid, a liquid, a gaseous, or a supercritical state, or a mixture thereof (4,5). However, MAS NMR under scCO2 conditions has never been realized due to the tremendous technical difficulties of achieving and maintaining high pressure within a fast spinning MAS rotor (6,7), where non-metal materials must be used. In this work, we report development of a unique high pressure MAS NMR capability, and its application to mineral carbonation chemistry in scCO2 under geologically relevant temperatures and pressures.

  4. MAS receptors mediate vasoprotective and atheroprotective effects of candesartan upon the recovery of vascular angiotensin-converting enzyme 2-angiotensin-(1-7)-MAS axis functionality.

    PubMed

    Pernomian, Larissa; do Prado, Alejandro F; Gomes, Mayara S; Pernomian, Laena; da Silva, Carlos H T P; Gerlach, Raquel F; de Oliveira, Ana M

    2015-10-01

    AT1 antagonists effectively prevent atherosclerosis since AT1 upregulation and angiotensin II-induced proinflammatory actions are critical to atherogenesis. Despite the classic mechanisms underlying the vasoprotective and atheroprotective actions of AT1 antagonists, the cross-talk between angiotensin-converting enzyme-angiotensin II-AT1 and angiotensin-converting enzyme 2-angiotensin-(1-7)-MAS axes suggests other mechanisms beyond AT1 blockage in such effects. For instance, angiotensin-converting enzyme 2 activity is inhibited by reactive oxygen species derived from AT1-mediated proinflammatory signaling. Since angiotensin-(1-7) promotes antiatherogenic effects, we hypothesized that the vasoprotective and atheroprotective effects of AT1 antagonists could result from their inhibitory effects on the AT1-mediated negative modulation of vascular angiotensin-converting enzyme 2-angiotensin-(1-7)-MAS axis functionality. Interestingly, our results showed that early atherosclerosis triggered in thoracic aorta from high cholesterol fed-Apolipoprotein E-deficient mice impairs angiotensin-converting enzyme 2-angiotensin-(1-7)-MAS axis functionality by a proinflammatory-redox AT1-mediated pathway. In such mechanism, AT1 activation leads to the aortic release of tumor necrosis factor-?, which stimulates NAD(P)H oxidase/Nox1-driven generation of superoxide and hydrogen peroxide. While hydrogen peroxide inhibits angiotensin-converting enzyme 2 activity, superoxide impairs MAS functionality. Candesartan treatment restored the functionality of angiotensin-converting enzyme 2-angiotensin-(1-7)-MAS axis by inhibiting the proinflammatory-redox AT1-mediated mechanism. Candesartan also promoted vasoprotective and atheroprotective effects that were mediated by MAS since A779 (MAS antagonist) co-treatment inhibited them. The role of MAS receptors as the final mediators of the vasoprotective and atheroprotective effects of candesartan was supported by the vascular actions of angiotensin-(1-7) upon the recovery of the functionality of vascular angiotensin-converting enzyme 2-angiotensin-(1-7)-MAS axis. PMID:26144375

  5. Angiotensin-(1-7)/Mas axis modulates fear memory and extinction in mice.

    PubMed

    Lazaroni, Thiago Luiz do Nascimento; Bastos, Cristiane Perácio; Moraes, Márcio Flávio Dutra; Santos, Robson Souza; Pereira, Grace Schenatto

    2016-01-01

    Inappropriate defense-alerting reaction to fear is a common feature of neuropsychiatric diseases. Therefore, impairments in brain circuits, as well as in molecular pathways underlying the neurovegetative adjustments to fear may play an essential role on developing neuropsychiatric disorders. Here we tested the hypothesis that interfering with angiotensin-(1-7) [Ang-(1-7)]/Mas receptor axis homeostasis, which appears to be essential to arterial pressure control, would affect fear memory and extinction. Mas knockout (MasKO) mice, in FVB/N background, showed normal cued fear memory and extinction, but increased freezing in response to context. Next, as FVB/N has poor performance in contextual fear memory, we tested MasKO in mixed 129xC57BL/6 background. MasKO mice behaved similarly to wild-type (WT), but memory extinction was slower in contextual fear conditioning to a weak protocol (1CS/US). In addition, delayed extinction in MasKO mice was even more pronounced after a stronger protocol (3CS/US). We showed previously that Angiotensin II receptor AT1 antagonist, losantan, rescued object recognition memory deficit in MasKO mice. Here, losartan was also effective. Memory extinction was accelerated in MasKO mice after treatment with losartan. In conclusion, we showed for the first time that Ang-(1-7)/Mas axis may modulate fear memory extinction. Furthermore, we suggest MasKO mice as an animal model to study post-traumatic stress disorder (PTSD). PMID:26642920

  6. Quantitative solid-state 13C NMR with signal enhancement by multiple cross polarization

    NASA Astrophysics Data System (ADS)

    Johnson, Robert L.; Schmidt-Rohr, Klaus

    2014-02-01

    A simple new method is presented that yields quantitative solid-state magic-angle spinning (MAS) 13C NMR spectra of organic materials with good signal-to-noise ratios. It achieves long (>10 ms) cross polarization (CP) from 1H without significant magnetization losses due to relaxation and with a moderate duty cycle of the radio-frequency irradiation, by multiple 1-ms CP periods alternating with 1H spin-lattice relaxation periods that repolarize the protons. The new method incorporates previous techniques that yield less distorted CP/MAS spectra, such as a linear variation (“ramp”) of the radio-frequency field strength, and it overcomes their main limitation, which is T1? relaxation of the spin-locked 1H magnetization. The ramp of the radio-frequency field strength and the asymptotic limit of cross polarization makes the spectral intensity quite insensitive to the exact field strengths used. The new multiCP pulse sequence is a “drop-in” replacement for previous CP methods and produces no additional data-processing burden. Compared to the only reliable quantitative 13C NMR method for unlabeled solids previously available, namely direct-polarization NMR, the measuring time is reduced by more than a factor of 50, enabling higher-throughput quantitative NMR studies. The new multiCP technique is validated with 14-kHz MAS on amino-acid derivatives, plant matter, a highly aromatic humic acid, and carbon materials made by low-temperature pyrolysis.

  7. Quantitative solid-state 13C NMR with signal enhancement by multiple cross polarization.

    PubMed

    Johnson, Robert L; Schmidt-Rohr, Klaus

    2014-02-01

    A simple new method is presented that yields quantitative solid-state magic-angle spinning (MAS) (13)C NMR spectra of organic materials with good signal-to-noise ratios. It achieves long (>10ms) cross polarization (CP) from (1)H without significant magnetization losses due to relaxation and with a moderate duty cycle of the radio-frequency irradiation, by multiple 1-ms CP periods alternating with (1)H spin-lattice relaxation periods that repolarize the protons. The new method incorporates previous techniques that yield less distorted CP/MAS spectra, such as a linear variation ("ramp") of the radio-frequency field strength, and it overcomes their main limitation, which is T1? relaxation of the spin-locked (1)H magnetization. The ramp of the radio-frequency field strength and the asymptotic limit of cross polarization makes the spectral intensity quite insensitive to the exact field strengths used. The new multiCP pulse sequence is a "drop-in" replacement for previous CP methods and produces no additional data-processing burden. Compared to the only reliable quantitative (13)C NMR method for unlabeled solids previously available, namely direct-polarization NMR, the measuring time is reduced by more than a factor of 50, enabling higher-throughput quantitative NMR studies. The new multiCP technique is validated with 14-kHz MAS on amino-acid derivatives, plant matter, a highly aromatic humic acid, and carbon materials made by low-temperature pyrolysis. PMID:24374751

  8. Quantitative identification of metastable magnesium carbonate minerals by solid-state 13C NMR spectroscopy.

    PubMed

    Moore, Jeremy K; Surface, J Andrew; Brenner, Allison; Wang, Louis S; Skemer, Philip; Conradi, Mark S; Hayes, Sophia E

    2015-01-01

    In the conversion of CO2 to mineral carbonates for the permanent geosequestration of CO2, there are multiple magnesium carbonate phases that are potential reaction products. Solid-state (13)C NMR is demonstrated as an effective tool for distinguishing magnesium carbonate phases and quantitatively characterizing magnesium carbonate mixtures. Several of these mineral phases include magnesite, hydromagnesite, dypingite, and nesquehonite, which differ in composition by the number of waters of hydration or the number of crystallographic hydroxyl groups. These carbonates often form in mixtures with nearly overlapping (13)C NMR resonances which makes their identification and analysis difficult. In this study, these phases have been investigated with solid-state (13)C NMR spectroscopy, including both static and magic-angle spinning (MAS) experiments. Static spectra yield chemical shift anisotropy (CSA) lineshapes that are indicative of the site-symmetry variations of the carbon environments. MAS spectra yield isotropic chemical shifts for each crystallographically inequivalent carbon and spin-lattice relaxation times, T1, yield characteristic information that assist in species discrimination. These detailed parameters, and the combination of static and MAS analyses, can aid investigations of mixed carbonates by (13)C NMR. PMID:25437754

  9. Isotropic diffusion weighting in PGSE NMR by magic-angle spinning of the q-vector

    NASA Astrophysics Data System (ADS)

    Eriksson, Stefanie; Lasic, Samo; Topgaard, Daniel

    2013-01-01

    When PGSE NMR is applied to water in microheterogeneous materials such as liquid crystals, foodstuffs, porous rocks, and biological tissues, the signal attenuation is often multi-exponential, indicating the presence of pores having a range of sizes or anisotropic domains having a spread of orientations. Here we modify the standard PGSE experiment by introducing low-amplitude harmonically modulated gradients, which effectively make the q-vector perform magic-angle spinning (MAS) about an axis fixed in the laboratory frame. With this new technique, denoted q-MAS PGSE, the signal attenuation depends on the isotropic average of the local diffusion tensor. The capability of q-MAS PGSE to distinguish between pore size and domain orientation dispersion is demonstrated by experiments on a yeast cell suspension and a polydomain anisotropic liquid crystal. In the latter case, the broad distribution of apparent diffusivities observed with PGSE is narrowed to its isotropic average with q-MAS PGSE in a manner that is analogous to the narrowing of chemical shift anisotropy powder patterns using magic-angle sample spinning in solid-state NMR. The new q-MAS PGSE technique could be useful for resolving size/orientation ambiguities in the interpretation of PGSE data from, e.g., water confined within the axons of human brain tissue.

  10. Water speciation in sodium silicate glasses (quenched melts): A comprehensive NMR study

    NASA Astrophysics Data System (ADS)

    Xue, X.; Kanzaki, M.; Eguchi, J.

    2012-12-01

    Dissolution mechanism of water is an important factor governing how the dissolved water affects the physical and thermodynamic properties of silicate melts and glasses. Our previous studies have demonstrated that 1H MAS NMR in combination with 29Si-1H and 27Al-1H double-resonance NMR experiments is an effective approach for unambiguously differentiating and quantifying different water species in quenched silicate melts (glasses). Several contrasting dissolution mechanisms have been revealed depending on the melt composition: for relatively polymerized melts, the formation of SiOH/AlOH species (plus molecular H2O) and depolymerization of the network structure dominate; whereas for depolymerized Ca-Mg silicate melts, free OH (e.g. MgOH) become increasingly important (cf. [1]). The proportion of free OH species has been shown to decrease with both increasing melt polymerization (silica content) and decreasing field strength of the network modifying cations (from Mg to Ca). Our previous 1H and 29Si MAS NMR results for hydrous Na silicate glasses of limited compositions (Na2Si4O9 and Na2Si2O5) were consistent with negligible free OH (NaOH) species and depolymerizing effect of water dissolution [2]. On the other hand, there were also other studies that proposed the presence of significant NaOH species in hydrous glasses near the Na2Si2O5 composition. The purpose of this study is apply the approach of combined 1H MAS NMR and double-resonance (29Si-1H and 23Na-1H) NMR to gain unambiguous evidence for the OH speciation in Na silicate glasses (melts) as a function of composition. Hydrous Na silicate glasses containing mostly ? 1 wt% H2O for a range of Na/Si ratios from 0.33 to 1.33 have been synthesized by rapidly quenching melts either at 0.2 GPa using an internally heated gas pressure vessel or at 1 GPa using a piston cylinder high-pressure apparatus. NMR spectra have been acquired using a 9.4 T Varian Unity-Inova spectrometer. The 29Si and 1H chemical shifts are reported relative to TMS. The 1H MAS NMR spectra show broad peaks covering a chemical shift range of 1 to 17 ppm, with peak maxima near 4 and 15 ppm for more Si-rich compositions and near 12 ppm for less Si-rich compositions. The 1H-29Si-1H and 23Na-1H cross-polarization (CP) MAS NMR spectra for all the hydrous Na silicate glasses suggest negligible NaOH species, which, if present, should show enhanced relative intensity with 23Na-1H CP and the opposite with 1H-29Si-1H CP. All the observed 1H NMR intensities can be attributed to SiOH species of a range of hydrogen-bonding distances, plus a small amount of molecular H2O for higher water-content samples that contribute to intensities around 6 ppm. In conclusion, our combined 1H MAS NMR and double-resonance (1H-29Si-1H and 23Na-1H CP) MAS NMR study on Na silicate glasses of a range of Na/Si ratios has confirmed that water dissolves predominantly as SiOH and molecular H2O species in Na silicate melts (glasses), consistent with the trend predicted from studies on the Ca-Mg silicate system [1,2]. References:[1] Xue, X. Y.; Kanzaki, M. J. Am. Ceram. Soc. 2009, 92, 2803-2830. [2] Xue, X. Y.; Kanzaki, M. Geochim. Cosmochim. Acta 2004, 68, 5027-5057.

  11. 31P Solid-state NMR based monitoring of permeation of cell penetrating peptides into skin

    PubMed Central

    Desai, Pinaki R.; Cormier, Ashley R.; Shah, Punit P.; Patlolla, Ram R.; Paravastu, Anant K.; Singh, Mandip

    2013-01-01

    The main objective of the current study was to investigate penetration of cell penetrating peptides (CPPs: TAT, R8, R11 and YKA) through skin intercellular lipids using 31P magic angle spinning (MAS) solid-state NMR. In vitro skin permeation studies were performed on rat skin, sections (0–60, 61–120 and 121–180 µm) were collected and analyzed for 31P NMR signal. The concentration dependent shift of 0, 25, 50, 100 and 200 mg/ml of TAT on skin layers, diffusion of TAT, R8, R11 and YKA in the skin and time dependent permeation of R11 was measured on various skin sections using 31P solid-state NMR. Further, CPPs and CPP-tagged fluorescent dye encapsulate liposomes (FLip) in skin layers were tagged using confocal microscopy. The change in 31P NMR chemical shift was found to depend monotonically on the amount of CPP applied on skin, with saturation behavior above 100 mg/ml CPP concentration. R11 and TAT caused more shift in solid-state NMR peaks compared to other peptides. Furthermore, NMR spectra showed R11 penetration up to 180 µm within 30 min. The results of the solid-state NMR study were in agreement with confocal microscopy studies. Thus, 31P solid-state NMR can be used to track CPP penetration into different skin layers. PMID:23702274

  12. HR 7355 - another rapidly braking He-strong CP star?

    NASA Astrophysics Data System (ADS)

    Mikulášek, Z.; Krti?ka, J.; Henry, G. W.; de Villiers, S. N.; Paunzen, E.; Zejda, M.

    2010-02-01

    Context. Strong meridional mixing induced by rapid rotation is one reason why all hot main-sequence stars are not chemically peculiar. However, the finding that the He-strong CP star HR 7355 is a rapid rotator complicates this concept. Aims: Our goal is to explain the observed behaviour of HR 7355 based on period analysis of all available photometry. Methods: Over two years, we acquired 114 new BV observations of HR 7355 at observatories in Arizona, U.S.A and Cape Town, South Africa. We performed period analyses of the new observations along with new analyses of 732 archival measurements from the Hipparcos and ASAS projects. Results: We find that the light curves of HR 7355gt; in various filters are quite similar, with amplitudes 0.035(4), 0.036(4), and 0.038(3) mag in B, Hp, and V, respectively. The light curves are double-peaked, with unevenly deep minima. We substantially refine the rotational period to be P = 0.5214410(4)d, indicating that HR 7355gt; is the most rapidly rotating CP star known. Our period analyses reveal a possible lengthening of the rotational period with dot{P}/P = 2.4(8)×10-6 yr-1. Conclusions: We conclude that the shape and amplitude of HR 7355gt; light curves are typical of magnetic He-strong CP stars, for which light variations are the result of photospheric spots on the surface of a rotating star. We hypothesise that the light variations are caused mainly by an uneven distribution of overabundant helium on the star's surface. We briefly describe and discuss the cause of the rapid rotational braking of the star. Photometric data are only available in electronic form at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsweb.u-strasbg.fr/cgi-bin/qcat?J/A+A/511/L7

  13. Screening proteins for NMR suitability

    PubMed Central

    Yee, Adelinda A.; Semesi, Anthony; Garcia, Maite; Arrowsmith, Cheryl H.

    2014-01-01

    Summary NMR spectroscopy is an invaluable tool in structural genomics. Identification of protein samples that are amenable to structure determination by NMR spectroscopy requires efficient screening. Here, we describe how we prepare multiple samples in parallel and screen by NMR. The method described here is applicable to large structural genomics projects but can easily be scaled down for application to small structural biology projects since all the equipments used are those commonly found in any NMR structural biology laboratory. PMID:24590717

  14. Identification and analysis of drugs in the solid state by 13C CPMAS NMR: suxamethonium chloride and hydrocortisonum (Corhydron).

    PubMed

    Paradowska, Katarzyna; Wolniak, Micha?; Fija?ek, Zbigniew; Wawer, Iwona

    2008-01-01

    Cross-polarization (CP) magic angle spinning (MAS) 13C NMR spectroscopy has become a routine tool in pharmacy, employed to identify and characterize drugs in the solid phase. 13C CPMAS NMR spectra were recorded for solid hydrocortisone 21-hemisuccinate and suxamethonium chloride. White crystalline substances, such as these two drugs, can be easily distinguished; and solid-state 13NMR spectra of remarkably good quality are obtained in less than half an hour. 13C CPMAS chemical shifts for solid suxamethonium chloride and hydrocortisone sodium hemisuccinate are given, as well as cross-polarization kinetic parameters for suxamethonium chloride. PMID:18646548

  15. 13C and 15N CP/MAS, 1H-15N SCT CP/MAS and FTIR spectroscopy as tools for qualitative detection of the presence of zwitterionic and non-ionic forms of ansa-macrolide 3-formylrifamycin SV and its derivatives in solid state.

    PubMed

    Przybylski, Piotr; Pyta, Krystian; Klich, Katarzyna; Schilf, Wojciech; Kamie?ski, Bohdan

    2014-01-01

    (13)C, (15)N CP/MAS, including (1)H-(13)C and (1)H-(15)N short contact time CP/MAS experiments, and FTIR methods were applied for detailed structural characterization of ansa-macrolides as 3-formylrifamycin SV (1) and its derivatives (2-6) in crystal and in powder forms. Although HPLC chromatograms for 2/CH3 OH and 2/CH3 CCl3 were the same for rifampicin crystals dissolved in respective solvents, the UV-vis data recorded for them were different in 300-375?nm region. Detailed solid state (13)C and (15)N CP/MAS NMR and FTIR studies revealed that rifampicin (2), in contrast to 3-formylrifamycin SV (1) and its amino derivatives (3-6), can occur in pure non-ionic or zwitterionic forms in crystal and in pure these forms or a mixture of them in a powder. Multinuclear CP/MAS and FTIR studies demonstrated also that 3-6 derivatives were present exclusively in pure zwitterionic forms, both in powder and in crystal. On the basis of the solid state NMR and FTIR studies, two conformers of 3-formylrifamycin SV were detected in powder form due to the different orientations of carbonyl group of amide moiety. The PM6 molecular modeling at the semi-empirical level of theory, allowed visualization the most energetically favorable non-ionic and zwitterionic forms of 1-6 antibiotics, strongly stabilized via intramolecular H-bonds. FTIR studies indicated that the originally adopted forms of these type antibiotics in crystal or in powder are stable in standard laboratory conditions in time. The results presented point to the fact that because of a possible presence of two forms of rifampicin (compound 2), quantification of the content of this antibiotic in relevant pharmaceuticals needs caution. PMID:24347399

  16. The fate of the solid matter orbiting HR 4796A

    NASA Technical Reports Server (NTRS)

    Jura, M.; Ghez, A. M.; White, Russell J.; Mccarthy, D. W.; Smith, R. C.; Martin, P. G.

    1995-01-01

    We have obtained optical spectra, 2 micrometers speckle images, and an upper limit to the 800 micrometers flux for HR 4796A, and optical spectra for its physical companion separated by 7.7 arcsecs, HR 4796B. We detect H-beta, H-gamma, and the calcium H and K lines in emission from HR 4796B; these data are consistent with the hypothesis that it is later than spectral type M2 and lies substantially above the main-sequence. From the location of HR 4796B on the H-R diagram, the estimated age of this star is 3 x 10(exp 6) yr, and assuming this age for the entire system, we find from our 2 micrometers speckle data that there is no close stellar companion to HR 4796A (M greater than 0.125 solar mass) between 11 and 120 AU from the star. From the IRAS and ground-based photometry, it seems that there is a hole in the dust distribution around HR 4796A with an inner radius of between approximately 40 and approximately 200 AU. The observed circumstellar dust grains, which lie at D greater than 40 AU from the star, are likely to be at least 3 micrometers in radius in order to be gravitationally bound to HR 4796A, if the circumstellar dust cloud is optically thin. Since they are larger than almost all interstellar grains, the circumstellar dust grains probably grew by coalescence. Because the existing grains at D greater than 40 AU have undergone measurable coalescence, it is possible that particles that presumably once existed at D less than 40 AU, where the collision times were shorter than at D greater than 40 AU, grew into macroscopic objects. A likely explanation for the dust hole is that there is a companion located at about half the inner radius of the dust hole, or between 20 and 100 AU from the star. If such a companion exists, it must have a mass less than 0.125 solar mass. Since grain coalescence has occurred, this putative companion possibly could be a planet.

  17. Mas-Mediated Antioxidant Effects Restore the Functionality of Angiotensin Converting Enzyme 2-Angiotensin-(1–7)-Mas Axis in Diabetic Rat Carotid

    PubMed Central

    Gomes, Mayara Santos; Restini, Carolina Baraldi Araujo

    2014-01-01

    We hypothesized that endothelial AT1-activated NAD(P)H oxidase-driven generation of reactive oxygen species during type I-diabetes impairs carotid ACE2-angiotensin-(1–7)-Mas axis functionality, which accounts for the impaired carotid flow in diabetic rats. We also hypothesized that angiotensin-(1–7) chronic treatment of diabetic rats restores carotid ACE2-angiotensin-(1–7)-Mas axis functionality and carotid flow. Relaxant curves for angiotensin II or angiotensin-(1–7) were obtained in carotid from streptozotocin-induced diabetic rats. Superoxide or hydrogen peroxide levels were measured by flow cytometry in carotid endothelial cells. Carotid flow was also determined. We found that endothelial AT1-activated NAD(P)H oxidase-driven generation of superoxide and hydrogen peroxide in diabetic rat carotid impairs ACE2-angiotensin-(1–7)-Mas axis functionality, which reduces carotid flow. In this mechanism, hydrogen peroxide derived from superoxide dismutation inhibits ACE2 activity in generating angiotensin-(1–7) seemingly by activating ICl,SWELL, while superoxide inhibits the nitrergic Mas-mediated vasorelaxation evoked by angiotensin-(1–7). Angiotensin-(1–7) treatment of diabetic rats restored carotid ACE2-angiotensin-(1–7)-Mas axis functionality by triggering a positive feedback played by endothelial Mas receptors, that blunts endothelial AT1-activated NAD(P)H oxidase-driven generation of reactive oxygen species. Mas-mediated antioxidant effects also restored diabetic rat carotid flow, pointing to the contribution of ACE2-angiotensin-(1–7)-Mas axis in maintaining carotid flow. PMID:24877125

  18. A combined deuterium NMR and quantum chemical investigation of inequivalent hydrogen bonds in organic solids.

    PubMed

    Webber, Renee; Penner, Glenn H

    2012-01-01

    Deuterium magic angle spinning (MAS) NMR spectroscopy and quantum chemical calculations are used to investigate organic solids in which inequivalent hydrogen bonds are present. The use of (2)H MAS allows one to measure the chemical shift, ?, quadrupolar coupling constant, C(Q), and asymmetry in the quadrupolar interaction, ?(Q), for each type of hydrogen bond present in the system. Quantum chemical calculations of the magnetic shielding (?, which can be related to ?) and the electric field gradient (EFG, which can be related to C(Q)) are compared to the experimental results and are discussed with respect to the relative strengths of the hydrogen bonds within each system. PMID:22883448

  19. Modern NMR Spectroscopy.

    ERIC Educational Resources Information Center

    Jelinski, Lynn W.

    1984-01-01

    Discusses direct chemical information that can be obtained from modern nuclear magnetic resonance (NMR) methods, concentrating on the types of problems that can be solved. Shows how selected methods provide information about polymers, bipolymers, biochemistry, small organic molecules, inorganic compounds, and compounds oriented in a magnetic…

  20. NMR Studies of Heat-Induced Transitions in Structure and Cation Binding Environments of a Strontium-Saturated Swelling Mica

    SciTech Connect

    Bowers, Geoffrey M.; Davis, Michael C.; Ravella, Ramesh; Komarneni, S.; Mueller, Karl T.

    2007-12-03

    In this work we combined Al, Si, F, and Na magic-angle spinning (MAS) nuclear magnetic resonance (NMR) to characterize the structure and interlayer cation environments in a strontium-saturated member of the swelling mica family before and after a heat induced collapse of the interlayer space.

  1. Multiple wavelength microwave observations of the RS Canum Venaticorum stars UX Arietis, HR 1099, HR 5110, and II Pegasi

    NASA Technical Reports Server (NTRS)

    Willson, Robert F.; Lang, Kenneth R.

    1987-01-01

    The variabilities, core size and magnetic field of the RS CVn star UX Arietis was measured with the VLA at pairs of frequencies near 1415 MHz and 4835 MHz on June 10, 1985. Data were also gathered on HR 1099, HR 5110 and II Peg. UX Arietis exhibited variability on time scales ranging from 30 sec to 1 hr at 4835 MHz, but no detectable variations at 1415 MHz. An upper limit of 900 billion cm was placed on the size of the core emitting region, which is estimated to have a magnetic field strength of 15 G. The 30 sec variations are attributed to absorption by thermal plasma between the G5 and K1 companions of the UX Arietis system.

  2. Bumping HR: Giving Principals More Say over Staffing

    ERIC Educational Resources Information Center

    National Council on Teacher Quality, 2010

    2010-01-01

    In what may come as a surprise to many, principals have remarkably little control over who teaches in their schools. For the most part, the human resources (HR) department in a district's central office, not individual school principals, makes the final call about when to hire teachers, whom to hire and in which schools they are placed.…

  3. Learning Culture, Line Manager and HR Professional Practice

    ERIC Educational Resources Information Center

    Harrison, Patricia

    2011-01-01

    Purpose: This paper aims to focus on the role of line management and learning culture in the development of professional practice for the human resource (HR) practitioner. Design/methodology/approach: Three-year longitudinal, matched-pair study involving five participants and their line managers. Findings: Two of the five participants experienced…

  4. Discovery of a Low-mass Companion Around HR 3549

    NASA Astrophysics Data System (ADS)

    Mawet, D.; David, T.; Bottom, M.; Hinkley, S.; Stapelfeldt, K.; Padgett, D.; Mennesson, B.; Serabyn, E.; Morales, F.; Kuhn, J.

    2015-10-01

    We report the discovery of a low-mass companion to HR 3549, an A0V star surrounded by a debris disk with a warm excess detected by WISE at 22 ?m (10? significance). We imaged HR 3549 B in the L band with NAOS-CONICA, the adaptive optics infrared camera of the Very Large Telescope, in January 2013 and confirmed its common proper motion in 2015 January. The companion is at a projected separation of ?80 AU and position angle of ?157°, so it is orbiting well beyond the warm disk inner edge of r > 10 AU. Our age estimate for this system corresponds to a companion mass in the range 15-80 MJ, spanning the brown dwarf regime, and so HR 3549 B is another recent addition to the growing list of brown dwarf desert objects with extreme mass ratios. The simultaneous presence of a warm disk and a brown dwarf around HR 3549 provides interesting empirical constraints on models of the formation of substellar companions.

  5. HR as Partner: Building Strategic Partnerships on Campus

    ERIC Educational Resources Information Center

    Connally, Sam; Neuman, Dawn

    2006-01-01

    Human resources is in an excellent position in many institutions to initiate collaboration and cooperation with other campus departments. In this article, the leaders of the departments of HR and academic resources at the University of Nevada, Las Vegas, share their insights on the importance of partnership-building on campus and describe how a…

  6. Are gaint planets forming around HR 4796A?

    NASA Technical Reports Server (NTRS)

    Chen, C. H.; Kamp, I.

    2004-01-01

    We have obtained Far Ultraviolet Spectroscopic Explorer and Hubble Space Telescope STIS spectra of HR 4796A, a nearby 8 Myr old main-sequence star that possesses a dusty circumstellar disk whose inclination has been constrained from high-resolution near-infrared observations to be 17 degrees from edge-on.

  7. An Ounce of Prevention: The Benefits of an HR Audit

    ERIC Educational Resources Information Center

    Seals, Brenda

    2011-01-01

    During her 13 years leading a school district human resources office, the author came to recognize that managing human capital is much more than recruiting, hiring, managing personnel records, and handling performance issues. In addition to implementing initiatives to increase the efficiency with which HR officers and staff perform those tasks,…

  8. Massive Stars in Transition: Spectroscopic Analysis of HR Carinae

    NASA Astrophysics Data System (ADS)

    Machado, M.; Araújo, F. X.; Pereira, C. B.

    2003-01-01

    We analysed the high-resolution data of the LBV (or S Dor variable) HR Carinae, taken with the FEROS spectrograph in the wavelength range 3900 to 8200 Å . We performed a spectral analysis of the Balmer lines with a non-LTE expanding atmosphere code in order to derive its stellar parameters and to infer its evolutive status.

  9. An Ounce of Prevention: The Benefits of an HR Audit

    ERIC Educational Resources Information Center

    Seals, Brenda

    2011-01-01

    During her 13 years leading a school district human resources office, the author came to recognize that managing human capital is much more than recruiting, hiring, managing personnel records, and handling performance issues. In addition to implementing initiatives to increase the efficiency with which HR officers and staff perform those tasks,…

  10. HR Manager Leadership in Quality Improvement in a College Environment

    ERIC Educational Resources Information Center

    Sharabi, Moshe

    2010-01-01

    Purpose: The purpose of this paper is to present the influence of the human resource (HR) manager on the quality of service in an academic college, and the human resource management (HRM) outcomes of the process. Design/methodology/approach: The paper relates to a customer satisfaction survey. More than 120 questionnaires were completed by the…

  11. HR as Partner: Building Strategic Partnerships on Campus

    ERIC Educational Resources Information Center

    Connally, Sam; Neuman, Dawn

    2006-01-01

    Human resources is in an excellent position in many institutions to initiate collaboration and cooperation with other campus departments. In this article, the leaders of the departments of HR and academic resources at the University of Nevada, Las Vegas, share their insights on the importance of partnership-building on campus and describe how a…

  12. HR Manager Leadership in Quality Improvement in a College Environment

    ERIC Educational Resources Information Center

    Sharabi, Moshe

    2010-01-01

    Purpose: The purpose of this paper is to present the influence of the human resource (HR) manager on the quality of service in an academic college, and the human resource management (HRM) outcomes of the process. Design/methodology/approach: The paper relates to a customer satisfaction survey. More than 120 questionnaires were completed by the…

  13. NMR in rotating magnetic fields: Magic angle field spinning

    SciTech Connect

    Sakellariou, D.; Meriles, C.; Martin, R.; Pines, A.

    2004-09-10

    Magic angle sample spinning has been one of the cornerstones in high-resolution solid state NMR. Spinning frequencies nowadays have increased by at least one order of magnitude over the ones used in the first experiments and the technique has gained tremendous popularity. It is currently a routine procedure in solid-state NMR, high-resolution liquid-state NMR and solid-state MRI. The technique enhances the spectral resolution by averaging away rank 2 anisotropic spin interactions thereby producing isotropic-like spectra with resolved chemical shifts and scalar couplings. Andrew proposed that it should be possible to induce similar effects in a static sample if the direction of the magnetic field is varied, e.g., magic-angle rotation of the B0 field (B0-MAS) and this has been recently demonstrated using electromagnetic field rotation. Here we discuss on the possibilities to perform field rotation using alternative hardware, together with spectroscopic methods to recover isotropic resolution even in cases where the field is not rotating at the magic angle. Extension to higher magnetic fields would be beneficial in situations where the physical manipulation of the sample is inconvenient or impossible. Such situations occur often in materials or biomedical samples where ''ex-situ'' NMR spectroscopy and imaging analysis is needed.

  14. OBSERVATIONS AND ORBITAL ANALYSIS OF THE GIANT WHITE DWARF BINARY SYSTEM HR 5692

    SciTech Connect

    Stefanik, Robert P.; Torres, Guillermo; Latham, David W.; Landsman, Wayne; Craig, Nathaniel; Murrett, James

    2011-05-15

    We report spectroscopic observations of the red giant star HR 5692, previously known to be a binary system both from other spectroscopic work and from deviations in the astrometric motion detected by the Hipparcos satellite. Earlier International Ultraviolet Explorer (IUE) observations had shown the presence of a hot white dwarf companion to the giant primary. We have combined our radial velocity observations with other existing measurements and with the Hipparcos intermediate astrometric data to determine a complete astrometric-spectroscopic orbital solution, providing the inclination angle for the first time. We also determine an improved parallax for the system of 10.12 {+-} 0.67 mas. We derive the physical properties of the primary, and with an estimate of its mass from stellar evolution models (1.84 {+-} 0.40 M{sub sun}), we infer the mass of the white dwarf companion to be M{sub WD} = 0.59 {+-} 0.12 M{sub sun}. An analysis of an IUE white dwarf spectrum, using our parallax, yields T{sub eff} = 30, 400 {+-} 780 K, log g = 8.25 {+-} 0.15, and a mass M{sub WD} = 0.79 {+-} 0.09 M{sub sun}, in marginal agreement with the dynamical mass.

  15. Why doesn't this HR department get any respect?

    PubMed

    Galford, R

    1998-01-01

    Since becoming managing partner of human resources at Loft Securities more than a year ago, Luke Robinson has tried everything he can think of to change his department's reputation as an administrative backwater. But he's swimming against the tide. Ever since the retirement of a charismatic CEO in 1995, the firm has suffered a slow bleed of good people. The new CEO doesn't have a flair for attracting and retaining talented people, and the HR department hasn't been able to pick up the slack. Robinson has done his best to turn things around. He's met with just about everyone, from senior executives to administrative assistants to external contacts. And, when he found out that recruiting wasn't Loft's only problem, he took a variety of concrete steps. Among other things, he established internal service standards and performance guarantees for his department. He created "listening posts" and implemented and "HR ambassador" program. And he drafted plans for a program to help educate all the company's employees about the role of HR--specifically, how it can contribute to creating and upholding the firm's strategy for success. But Robinson has run over some major speed bumps. Just before he joined the company, HR sullied its reputation by mishandling the investigation of a discrimination charge. And while on Robinson's watch, HR botched the issuance of year-end bonus checks for the managing directors and vice presidents. The frustrations are piling up, leading Robinson to entertain thoughts of bailing out. Five commentators on this fictional case study explain why he should avoid quitting and how he can help his department earn new respect. PMID:10177864

  16. Community Schools: Hearing before the General Subcommittee on Education of the Committee on Education and Labor, House of Representatives, Ninety-Third Congress, First Session on H.R. 972, H.R. 6697, and H.R. 10049.

    ERIC Educational Resources Information Center

    Congress of the U.S., Washington, DC. House Committee on Education and Labor.

    This report contains hearings before the 93rd Congress on the Community School Center Development Act, contained in bills H.R. 972, H.R. 6697, and H.R. 10049. The purpose of the act is to provide recreational, educational, and a variety of other community and social services through the establishment of community schools. The report contains the…

  17. {sup 29}Si and {sup 27}Al NMR study of alkali-activated slag

    SciTech Connect

    Wang, S.-D.; Scrivener, Karen L

    2003-05-01

    This paper presents the results of the investigation of the hydration of alkali-activated slag (AAS) by nuclear magnetic resonance spectroscopy (NMR). The cross-polarization (CP) technique was used in combination with magic-angle spinning (MAS). This research was part of a systematic study of alkaline activation of slag by several different techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with X-ray microanalysis of energy dispersive spectra (EDS), differential thermal analysis (DTA) and calorimetry. This NMR study provides information on the polymerization of silicates, the role of aluminates in cement hydration and the nanostructure of C-S-H gel.

  18. Psychometric Comparison of the Motivation Assessment Scale (MAS) and the Questions about Behavioral Function (QABF)

    ERIC Educational Resources Information Center

    Koritsas, S.; Iacono, T.

    2013-01-01

    Background: The Motivation Assessment Scale (MAS) and the Questions About Behavioral Function (QABF) are frequently used to assess the learned function of challenging behaviour in people with intellectual disability (ID). The aim was to explore and compare the psychometric properties of the MAS and the QABF. Method: Seventy adults with ID and…

  19. E/Z MAS: An easy-to-use computerized materials control and accountability system

    SciTech Connect

    Anderson, L.K.; Boor, M.G.; Hurford, J.M.; Landry, R.P.; Martinez, B.J.; Solem, A.M.; Whiteson, R.; Zardecki, A.

    1998-12-31

    Nuclear facilities that handle and process nuclear materials are required to track their nuclear holdings and to keep adequate records that manage and control the inventory of those holdings. The complexity of a system that does this job is directly proportional to the complexity of the facility`s operations. This paper describes an approach to computerized materials protection, control, and accountability (MPC and A) that was introduced by Los Alamos National Laboratory (LANL) in the fall of 1997. This new system, E/Z MAS, is the latest addition to the LANL suite of computerized MPC and A tools, which also includes the CoreMAS system. E/Z MAS was initially designed to address the needs of those facilities that have small to modest MPC and A needs but has been expanded to provide full functionality for any facility. The system name, E/Z MAS, reflects the system`s easy-to-use characteristics, which include ease of installation and ease of software maintenance. Both CoreMAS and E/Z MAS have been provided to facilities in the Former Soviet Union to assist them in implementing a computerized MPC and A system that meets their needs. In this paper the authors will address the functionality of CoreMAS and E/Z MAS, and an argument in favor of intranet-based material control and accountability will be advanced.

  20. Effect of magnetic particles on NMR spectra of Murchison meteorite organic matter and a polymer-based model system.

    PubMed

    Levin, E M; Bud'ko, S L; Mao, J D; Huang, Y; Schmidt-Rohr, K

    2007-04-01

    Organic matter from the Murchison meteorite shows pronounced spinning sidebands of the (1)H MAS NMR spectrum and exhibits a large bulk magnetization of 0.75emicro/g extrapolated to 94kOe at 300K. By comparison with data of diamagnetic polystyrene and laponite clay mixed with ferrimagnetic gamma-Fe(2)O(3) nano-particles, we show that the spinning sidebands arise from a combination of dipolar couplings of a given (1)H to magnetic particles, seen in a backscattered-electron image, and to other protons. Signal loss and significant broadening of protonated-carbon peaks in (13)C MAS NMR spectra of polystyrene with Fe(2)O(3) nano-particles is demonstrated, and implications for (13)C NMR spectroscopy of Murchison meteorite are discussed. PMID:17324558

  1. Coherent NMR Stark spectroscopy.

    PubMed

    Tarasek, Matthew R; Goldfarb, David J; Kempf, James G

    2012-01-01

    We demonstrate phase-coherent Stark effects from a radiofrequency E field at twice the NMR frequency (2?(0)) of (69)Ga in GaAs. The 2?(0) phase (?(E)) selects component responses from the nuclear quadrupole Hamiltonian (H(Q)). This is possible by synchronizing few-?s 2?(0) pulses with an NMR line-narrowing sequence, which averages the Stark interaction to dominate spectra on a background with 10(3)× enhanced resolution. Spectra vs ?(E) reveal relative sizes of tensorial factors in H(Q). Comparative modeling and numerical simulations evaluate spectral features unexplained by average Hamiltonian theory, and suggest improvements for quantitative calibration of individual response components. Application of this approach to bulk samples is of value to define Stark responses that may later be used to interrogate the internal electrostatics of structured samples. PMID:22197485

  2. 224} studied by NMR

    SciTech Connect

    Furukawa, Y; Fang, X; Kögerler, P

    2014-05-14

    7Li nuclear magnetic resonance (NMR) studies have been performed to investigate magnetic properties and spin dynamics of Mn3+ (S = 2) spins in the giant polyoxometalate molecule {Mn40W224}. The 7Li-NMR line width is proportional to the external magnetic field H as expected in a paramagnetic state above 3 K. Below this temperature the line width shows a sudden increase and is almost independent of H, which indicates freezing of the local Mn3+ spins. The temperature dependence of T1 for both 1H and 7Li reveals slow spin dynamics at low temperatures, consistent with spin freezing. The slow spin dynamics is also evidenced by the observation of a peak of 1/T2 around 3 K, where the fluctuation frequency of spins is of the order of ~200 kHz. An explicit form of the temperature dependence of the fluctuation frequency of Mn3+ spins is derived from the nuclear relaxation data.

  3. A generic, computerized nuclear materials accountability system (NucMAS) and its layered products

    SciTech Connect

    Davis, Jr, J M

    1989-01-01

    NucMAS provides a material balance area with a computerized data management system for nuclear materials accountability. NucMAS is a generic application. It handles the data management and reporting functions for different processing facilities by storing all process-specific information as data rather than procedure. A NucMAS application is configured for each facility it supports. NucMAS and its layered products are compatible with three types of data clients. Core NucMAS has a screen-oriented user interface to support the accountability clerk as a client. Accountability clerks enter data from operating logs and laboratory analyses one to three days after actual processing. Layered products support process operators and automated systems as near-real-time and real-time data clients. The core and layered products use a data-driven approach which results in software that is configurable and maintainable. 3 refs., 5 figs.

  4. The NMR phased array.

    PubMed

    Roemer, P B; Edelstein, W A; Hayes, C E; Souza, S P; Mueller, O M

    1990-11-01

    We describe methods for simultaneously acquiring and subsequently combining data from a multitude of closely positioned NMR receiving coils. The approach is conceptually similar to phased array radar and ultrasound and hence we call our techniques the "NMR phased array." The NMR phased array offers the signal-to-noise ratio (SNR) and resolution of a small surface coil over fields-of-view (FOV) normally associated with body imaging with no increase in imaging time. The NMR phased array can be applied to both imaging and spectroscopy for all pulse sequences. The problematic interactions among nearby surface coils is eliminated (a) by overlapping adjacent coils to give zero mutual inductance, hence zero interaction, and (b) by attaching low input impedance preamplifiers to all coils, thus eliminating interference among next nearest and more distant neighbors. We derive an algorithm for combining the data from the phased array elements to yield an image with optimum SNR. Other techniques which are easier to implement at the cost of lower SNR are explored. Phased array imaging is demonstrated with high resolution (512 x 512, 48-cm FOV, and 32-cm FOV) spin-echo images of the thoracic and lumbar spine. Data were acquired from four-element linear spine arrays, the first made of 12-cm square coils and the second made of 8-cm square coils. When compared with images from a single 15 x 30-cm rectangular coil and identical imaging parameters, the phased array yields a 2X and 3X higher SNR at the depth of the spine (approximately 7 cm). PMID:2266841

  5. NMR Studies of Peroxidases.

    NASA Astrophysics Data System (ADS)

    Veitch, Nigel Charles

    Available from UMI in association with The British Library. Requires signed TDF. Peroxidases are a haem-containing group of enzymes with a wide diversity of function within biological systems. While a common characteristic is the ability to catalyse the conversion of hydrogen peroxide to water, it is the accompanying processes of hormone synthesis and degradation which have generated such a high level of interest. However, information at the molecular level is limited to a single well-resolved crystal structure, that of yeast cytochrome c peroxidase. This thesis presents a strategy for the investigation of peroxidase structure and function based on proton nuclear magnetic resonance spectroscopy, a technique which has the ability to address aspects of both protein structure and protein dynamics in solution. The application of one- and two-dimensional NMR techniques has been developed in the context of plant peroxidases, notably the isoenzyme HRP-C derived from the horseradish root. Characterisation of the proton NMR spectra of HRP -C in resting and ligated states provided new information enabling the structure of the binding site for aromatic donor molecules, such as indole-3-propionic, ferulic and benzhydroxamic acids, to be resolved. In order to overcome difficulties encountered with a protein of the complexity of peroxidase, additional information was obtained from chemical shift parameters and the use of peroxidase variants produced by site-directed mutagenesis. A comparative study using NMR spectroscopy was undertaken for wild-type recombinant HRP-C expressed in Escherichia coli, and two protein variants with substitutions made to residues located on the distal side of the haem pocket, Phe41 to Val and Arg38 to Lys. NMR analyses of a plant peroxidase from barley grains and the fungal peroxidase from Coprinus cinereus were also successful using methods conceived with HRP-C. Examination of three specifically constructed recombinant protein variants of C. cinereus peroxidase was essential in confirming the identity of residues participating in the aromatic donor molecule binding site of peroxidases.

  6. NMR imaging of materials

    SciTech Connect

    Vinegar, H.J.; Rothwell, W.P.

    1988-03-01

    A method for obtaining at least one petrophysical property of a porous material containing therein at least one preselected fluid, is described, comprising: NMR imaging the material to generate signals dependent upon both M(0) and T/sub 1/ and M(0) and T/sub 2/, generating separate M(0), T/sub 1/ and T/sub 2/ images from the signals, and determining at least one petrophysical property from at least one of the images.

  7. Magic-angle-spinning NMR studies of acid sites in zeolite H-ZSM-5

    SciTech Connect

    Brunner, E.; Ernst, H.; Freude, D.; Froehlich, T.; Hunger, M.; Pfeifer, H. )

    1991-01-01

    {sup 1}H, {sup 13}C, {sup 27}Al, and {sup 29}Si magic-angle-spinning (MAS) NMR was used to elucidate the nature of the catalytic activity of zeolite H-ZSM-5. {sup 1}H MAS NMR of sealed samples after mild hydrothermal dealumination shows that the enhanced activity for n-hexane cracking is not due to an enhanced Bronstead acidity. The concentrations of the various OH groups and aluminous species suggest that the reason for the enhanced catalytic activity is the interaction of the n-hexane molecule with a bridging hydroxyl group and with extra-framework aluminium species, which give rise to the enhanced activity, cannot be easily removed from their positions, and are therefore immobilized by the zeolitic framework.

  8. NMR characterization and sorption behavior of agricultural and forest soil humic substances

    NASA Astrophysics Data System (ADS)

    Li, Chengliang; Berns, Anne E.; Séquaris, Jean-Marie; Klumpp, Erwin

    2010-05-01

    Humic substances are the predominant components of the organic matter in the terrestrial system, which are not only important for the physicochemical properties of soil but are also dominant factors for controlling the environmental behaviors and fates of some organic contaminants, such as hydrophobic compounds. Nonylphenol [4-(1-ethyl-1, 3 dimethylpentyl) phenol] (NP), a ubiquitous hydrophobic pollutant, has recently focused the attention owing to its endocrine disruptors property. Sorption behavior of NP on humic substances, which were isolated from agricultural and forest soils, was investigated by using the dialysis technique at room temperature. 14C-labeled NP was used to quantify the partitioning behavior. Humic substances were characterized by 13C Cross-Polarization/Magic-Angle-Spinning Nuclear Magnetic Resonance (CP/MAS NMR). The results showed that the partition parameters of NP on various humic acids were slightly different. Relationships between partition coefficients and the functional groups of humic substances identified by CP/MAS NMR were analyzed.

  9. High resolution triple resonance micro magic angle spinning NMR spectroscopy of nanoliter sample volumes.

    PubMed

    Brauckmann, J Ole; Janssen, J W G Hans; Kentgens, Arno P M

    2016-02-01

    To be able to study mass-limited samples and small single crystals, a triple resonance micro-magic angle spinning (?MAS) probehead for the application of high-resolution solid-state NMR of nanoliter samples was developed. Due to its excellent rf performance this allows us to explore the limits of proton NMR resolution in strongly coupled solids. Using homonuclear decoupling we obtain unprecedented (1)H linewidths for a single crystal of glycine (??(CH2) = 0.14 ppm) at high field (20 T) in a directly detected spectrum. The triple channel design allowed the recording of high-resolution ?MAS (13)C-(15)N correlations of [U-(13)C-(15)N] arginine HCl and shows that the superior (1)H resolution opens the way for high-sensitivity inverse detection of heteronuclei even at moderate spinning speeds and rf-fields. Efficient decoupling leads to long coherence times which can be exploited in many correlation experiments. PMID:26806199

  10. Synthesis and solid state NMR characterization of novel peptide/silica hybrid materials.

    PubMed

    Werner, Mayke; Heil, Andreas; Rothermel, Niels; Breitzke, Hergen; Groszewicz, Pedro Braga; Thankamony, Aany Sofia; Gutmann, Torsten; Buntkowsky, Gerd

    2015-11-01

    The successful synthesis and solid state NMR characterization of silica-based organic-inorganic hybrid materials is presented. For this, collagen-like peptides are immobilized on carboxylate functionalized mesoporous silica (COOH/SiOx) materials. A pre-activation of the silica material with TSTU (O-(N-Succinimidyl)-N,N,N',N'-tetramethyluronium tetrafluoroborate) is performed to enable a covalent binding of the peptides to the linker. The success of the covalent immobilization is indicated by the decrease of the (13)C CP-MAS NMR signal of the TSTU moiety. A qualitative distinction between covalently bound and adsorbed peptide is feasible by (15)N CP-MAS Dynamic Nuclear Polarization (DNP). The low-field shift of the (15)N signal of the peptide's N-terminus clearly identifies it as the binding site. The DNP enhancement allows the probing of natural abundance (15)N nuclei, rendering expensive labeling of peptides unnecessary. PMID:26411982

  11. Coal liquefaction process streams characterization and evaluation. Solid-state NMR characterization of coal liquefaction products

    SciTech Connect

    Miknis, F.P.

    1991-11-01

    This study clearly demonstrated the usefulness of liquid- and solid-state {sup 13}C- and {sup 1}H-NMR for the examination of process-derived materials from direct coal liquefaction. The techniques can provide data not directly obtainable by other methods to examine the saturation of aromatic rings and to determine the modes of hydrogen utilization during coal liquefaction. In addition, these methods can be used to infer the extent of condensation and retrograde reactions occurring in the direct coal liquefaction process. Five NMR techniques were employed. Solid-state {sup 13}C-NMR measurements were made using the Cross Polarization Magic Angle Spinning (CP/MAS) and Single Pulse (SP) techniques. Solid-state {sup 1}H-NMR measurements were made using the technique of Combined Rotation and Multiple-Pulse spectroscopy (CRAMPS). Conventional liquid-state {sup 12}C- and {sup 1}H-NMR techniques were employed as appropriate. Interpretation of the NMR data, once obtained, is relatively straightforward. Combined with other information, such as elemental analyses and process conversion data, the NMR data prove to be a powerful tool for the examination of direct coal liquefaction process-derived material. Further development and more wide-spread application of this analytical method as a process development tool is justified on the basis of these results.

  12. An alternative solution for computer controlled tuning and matching of existing NMR probes

    NASA Astrophysics Data System (ADS)

    Koczor, Bálint; Sedyó, Inez; Rohonczy, János

    2015-10-01

    Tuning and matching of NMR probes is necessary for many fields of NMR application including temperature dependent NMR, thermoporometry and cryoporometry, or when significantly different types of samples are measured in automation using sample changers. Mismatch of the probe is an especially critical issue in the case of high magnetic fields, polar or ionic solvents, or extreme thermal conditions. Careful tuning is particularly important for quantitative NMR measurements. Manual tuning and matching of the NMR probe is not possible in the case of automated or remotely controlled measurements. Spectrometer manufacturers offer modern probes equipped with automatic tuning/matching mechanics, like Bruker ATM™, suitable for these experiments. The disadvantages of probes with built-in ATM™ are the significantly higher price, and the non-detachable and non-portable construction. Computer controlled tuning and matching is highly desirrable in solid state NMR since no industrial solution has been developed yet for MAS NMR probes. We present an alternative solution for computer controlled tuning and matching of existing Bruker probes. Building costs are significantly lower, since only commercially available components and ICs are used.

  13. An alternative solution for computer controlled tuning and matching of existing NMR probes.

    PubMed

    Koczor, Bálint; Sedyó, Inez; Rohonczy, János

    2015-10-01

    Tuning and matching of NMR probes is necessary for many fields of NMR application including temperature dependent NMR, thermoporometry and cryoporometry, or when significantly different types of samples are measured in automation using sample changers. Mismatch of the probe is an especially critical issue in the case of high magnetic fields, polar or ionic solvents, or extreme thermal conditions. Careful tuning is particularly important for quantitative NMR measurements. Manual tuning and matching of the NMR probe is not possible in the case of automated or remotely controlled measurements. Spectrometer manufacturers offer modern probes equipped with automatic tuning/matching mechanics, like Bruker ATM™, suitable for these experiments. The disadvantages of probes with built-in ATM™ are the significantly higher price, and the non-detachable and non-portable construction. Computer controlled tuning and matching is highly desirrable in solid state NMR since no industrial solution has been developed yet for MAS NMR probes. We present an alternative solution for computer controlled tuning and matching of existing Bruker probes. Building costs are significantly lower, since only commercially available components and ICs are used. PMID:26363581

  14. Investigation of Li in Clay Interlayers at Different Temperatures by NMR

    NASA Astrophysics Data System (ADS)

    Kim, Y.; Lee, J.

    2007-12-01

    We used 6Li and 7Li MAS NMR to investigate the environmental changes of Li in the interlayer of clay minerals at room and high (250°C) temperatures. We also checked the usefulness 6Li NMR in studying Li in interlayer. Hectorite, Wyoming-montmorillonite, beidellite, and lepidollite were used for our study. 6Li NMR spectra show narrower peaks than those of 7Li NMR, but S/N ratio is low and there are no noticeable chemical shift changes, which makes it difficult to apply 6Li NMR to get information on Li environment in clay interlayers. 7Li NMR spectra, however, show changes in the peak width and quadrupole pattern, providing information on the Li environment in the interlayer, even though the change in chemical shift is not observed. In montmorillonite, two different environments of Li are observed, one having narrow peak with typical quadrupole pattern, and another having broad peak without that pattern. At high temperature, the broad peak becomes relatively, narrow which was also obserbed in the 7Li NMR spectra obtained from beidellite, but not hectorite. This changes are attributed to the coordination changes in the water molecules around Li which is tightly bonded on the basal oxygen of Si tetrahedra as inner-sphere complexes. The narrow peak in montmorillnoite can be assigned to the Li bonded as outer-sphere complexes.

  15. Bayesian reconstruction of projection reconstruction NMR (PR-NMR).

    PubMed

    Yoon, Ji Won

    2014-11-01

    Projection reconstruction nuclear magnetic resonance (PR-NMR) is a technique for generating multidimensional NMR spectra. A small number of projections from lower-dimensional NMR spectra are used to reconstruct the multidimensional NMR spectra. In our previous work, it was shown that multidimensional NMR spectra are efficiently reconstructed using peak-by-peak based reversible jump Markov chain Monte Carlo (RJMCMC) algorithm. We propose an extended and generalized RJMCMC algorithm replacing a simple linear model with a linear mixed model to reconstruct close NMR spectra into true spectra. This statistical method generates samples in a Bayesian scheme. Our proposed algorithm is tested on a set of six projections derived from the three-dimensional 700 MHz HNCO spectrum of a protein HasA. PMID:25218584

  16. Possible functional co-operation of palindromes hr3 and hr4 in the genome of Cydia pomonella granulovirus affects viral replication capacity.

    PubMed

    Elmenofy, Wael H; Jehle, Johannes A

    2015-09-01

    After previous studies had shown that natural transposon insertion between the two homologous regions hr3 and hr4 of the genome of the Mexican (M) strain of Cydia pomonella granulovirus (CpGV-M) resulted in a loss of viral competitiveness, the function of these homologous regions was investigated. A CpGV-based bacmid (CpBAC) was constructed and mutants with deleted hr3 and hr4 palindromes (CpBAChr3/hr4KO) and a construct (CpBAChr3-kan-hr4) with physically separated hr3 and hr4 repeats were generated to investigate their involvement in in vivo replication. Based on median lethal concentration (LC50) and median survival time (ST50) of the mutant viruses vCpBAChr3/hr4KO and vCpBAChr3-kan-hr4 it was found that the infectivity of both mutants for codling moth Cydia pomonella L. (Lep.: Tortricidae) larvae was not influenced compared with the parental virus vCpBAC. Co-infection experiments with vCpBAChr3-kan-hr4 and vCpBAC using different virus ratios revealed that vCpBAChr3-kan-hr4 was efficiently out-competed by vCpBAC during in vivo replication. These findings suggested that the separation of hr3 and hr4 resulted in a replication disadvantage of the mutant similar to the observation made in previous co-infection experiments using the transposon-carrying mutant CpGV-MCp5 and WT CpGV-M. It was concluded that the palindromes hr3 and hr4 may play a non-essential but co-functional role in the replication of CpGV-M. PMID:26002301

  17. Solid State Multinuclear NMR Studies of Relaxor Ferroelectrics

    NASA Astrophysics Data System (ADS)

    Hoatson, Gina; Zhou, Donghua; Fayon, Franck; Massiot, Dominique; Gan, Zhehong; Vold, Robert

    2002-03-01

    Multinuclear (207Pb, 45Sc, 93Nb) NMR has been used to investigate the local structure and cation disorder in solid solutions of (1-x) Pb(Mg1/3Nb2/3)O3: x Pb(Sc1/2Nb1/2)O3, as a function of concentration. The relaxor ferroelectrics have been well characterized by X-ray and dielectric response measurements(1). MAS, and 3QMAS spectra are presented for 93Nb at 14.0 and 19.6 Tesla. The 93Nb MAS lineshapes have been assigned to species with different arrangements of the nearest B-cation neighbors. It is necessary to include distributions of the electric field gradient parameters and dispersions in isotropic chemical shifts; these have been estimated from the data. The relative intensities of each spectral component are analyzed and the data strongly supports the modified Random Site model. To explain NMR intensities and to validate the model, Monte Carlo simulations will be presented. (1) P. K., Davies, L. Farber, M. Valant, and M. A. Akabas, AIP Conf. Proc. 535 (2000) 38-46.

  18. Investigations of adsorption sites on oxide surfaces using solid-state NMR and TPD-IGC

    NASA Astrophysics Data System (ADS)

    Golombeck, Rebecca A.

    The number and chemical identity of reactive sites on surfaces of glass affects the processing, reliability, and lifetime of a number of important commercial products. Surface site densities, distributions, and structural identities are closely tied to the formation and processing of the glass surface, and exert a direct influence on strength and coating performance. The surface of a glass sample may vary markedly from the composition and chemistry of the bulk glass. We are taking a physicochemical approach to understanding adsorption sites on pristine multicomponent glass fibers surfaces, directly addressing the effect of processing on surface reactivity. This project aimed to understand the energy distributions of surface adsorption sites, the chemical/structural identity of those sites, and the relationship of these glasses to glass composition, thermal history, and in future work, surface coatings. We have studied the bulk and surface structure as well as the surface reactivity of the glass fibers with solid-state nuclear magnetic resonance (NMR) spectroscopy, inverse gas chromatography (IGC), and computational chemistry methods. These methods, solid-state NMR and IGC, typically require high surface area materials; however, by using probe molecules for NMR experiments or packing a column at high density for IGC measurements, lower surface area materials, such as glass fibers, can be investigated. The glasses used within this study were chosen as representative specimens of fibers with potentially different reactive sites on their surfaces. The two glass compositions were centered around a nominal E-glass, which contains very little alkali cations and mainly alkaline earth cations, and wool glass, which contains an abundance of alkali cations. The concentration of boron was varied from 0 to 8 mole % in both fiber compositions. Fibers were drawn from each composition at a variety of temperatures and draw speeds to provide a range of glass samples with varying diameters and thermal histories. The bulk structural features in both compositions of glass fibers were identified using high-resolution 29Si, 27Al, and 11B magic-angle spinning (MAS) NMR spectroscopic measurements. In multi-component glasses, the determination of silicon, aluminum, and boron distributions becomes difficult due to the competitive nature of the network-modifying oxides among the network-forming oxides. In pure silicates, 29Si MAS NMR can often resolve resonances arising from silicate tetrahedron having varying numbers of bridging oxygens. In aluminoborosilicate glasses, aluminum is present in four-, five-, and six- coordination with oxygen as neighbors. The speciation of the aluminum can be determined using 27Al MAS NMR. The fraction of tetrahedral boron species in the glass fibers were measured using 11B MAS NMR, which is typically used to study the short-range structure of borate containing glasses such as alkali borate, borosilicate, and aluminoborosilicate glasses. While solid-state NMR is a powerful tool for elucidating bonding environments and coordination changes in the glass structure, it cannot quantitatively probe low to moderate surface area samples due to insufficient spins. Chemical probes either physisorbed or chemisorbed to the fiber's surface can increase the surface selectivity of NMR for analysis of samples with low surface areas and provide information about the local molecular structure of the reactive surface site. Common chemical probe molecules contain NMR active nuclei such as 19F or may be enriched with 13C. A silyating agent, (3,3,3-trifluoropropyl)dimethylchlorosilane (TFS), reacts with reactive surface hydroxyls, which can be quantified by utilizing the NMR active nucleus (19F) contained in the probe molecule. The observed 19F MAS NMR peak area is integrated and compared against a standard of known fluorine spins (concentration), allowing the number of reactive hydroxyl sites to be quantified. IGC is a method used to study the surface properties of a material by examining the retention behavior of a probe molecule. The I

  19. Soils, Pores, and NMR

    NASA Astrophysics Data System (ADS)

    Pohlmeier, Andreas; Haber-Pohlmeier, Sabina; Haber, Agnes; Sucre, Oscar; Stingaciu, Laura; Stapf, Siegfried; Blümich, Bernhard

    2010-05-01

    Within Cluster A, Partial Project A1, the pore space exploration by means of Nuclear Magnetic Resonance (NMR) plays a central role. NMR is especially convenient since it probes directly the state and dynamics of the substance of interest: water. First, NMR is applied as relaxometry, where the degree of saturation but also the pore geometry controls the NMR signature of natural porous systems. Examples are presented where soil samples from the Selhausen, Merzenhausen (silt loams), and Kaldenkirchen (sandy loam) test sites are investigated by means of Fast Field Cycling Relaxometry at different degrees of saturation. From the change of the relaxation time distributions with decreasing water content and by comparison with conventional water retention curves we conclude that the fraction of immobile water is characterized by T1 < 5 ms. Moreover, the dependence of the relaxation rate on magnetic field strength allows the identification of 2D diffusion at the interfaces as the mechanism which governs the relaxation process (Pohlmeier et al. 2009). T2 relaxation curves are frequently measured for the rapid characterization of soils by means of the CPMG echo train. Basically, they contain the same information about the pore systems like T1 curves, since mostly the overall relaxation is dominated by surface relaxivity and the surface/volume ratio of the pores. However, one must be aware that T2 relaxation is additionally affected by diffusion in internal gradients, and this can be overcome by using sufficiently short echo times and low magnetic fields (Stingaciu et al. 2009). Second, the logic continuation of conventional relaxation measurements is the 2-dimensional experiment, where prior to the final detection of the CPMG echo train an encoding period is applied. This can be T1-encoding by an inversion pulse, or T2 encoding by a sequence of 90 and 180° pulses. During the following evolution time the separately encoded signals can mix and this reveals information about the connectivity of the pore system. Examples are given for T1-T2 correlation of some soil samples (Haber-Pohlmeier et al. 2010). Third, relaxometric information forms the basis of understanding magnetic resonance imaging (MRI) results. The general difficulty of imaging in soils are the inherent fast T2 relaxation times due to i) the small pore sizes, ii) presence of paramagnetic ions in the solid matrix, and iii) diffusion in internal gradients. The last point is important, since echo times can not set shorter than about 1ms for imaging purposes. The way out is either the usage of low fields for imaging in soils or special ultra-short pulse sequences, which do not create echoes. In this presentation we will give examples on conventional imaging of macropore fluxes in soil cores (Haber-Pohlmeier et al. 2010), and the combination with relaxometric imaging, as well as the advantages and drawbacks of low-field and ultra-fast pulse imaging. Also first results on the imaging of soil columns measured by SIP in Project A3 are given. Haber-Pohlmeier, S., S. Stapf, et al. (2010). "Waterflow Monitored by Tracer Transport in Natural Porous Media Using MRI." Vadose Zone J.: submitted. Haber-Pohlmeier, S., S. Stapf, et al. (2010). "Relaxation in a Natural soil: Comparison of Relaxometric Imaging, T1 - T2 Correlation and Fast-Field Cycling NMR." The Open Magnetic Resonance Journal: in print. Pohlmeier, A., S. Haber-Pohlmeier, et al. (2009). "A Fast Field Cycling NMR Relaxometry Study of Natural Soils." Vadose Zone J. 8: 735-742. Stingaciu, L. R., A. Pohlmeier, et al. (2009). "Characterization of unsaturated porous media by high-field and low-field NMR relaxometry." Water Resources Research 45: W08412

  20. Resolving the Planetesimal Belt of HR 8799 with ALMA

    NASA Astrophysics Data System (ADS)

    Booth, Mark; Jordan, Andres; Hales, Antonio; Casassus, Simon; Dent, Bill; Faramaz, Virginie; Matrà, Luca

    2015-12-01

    HR 8799 is well known for being the only star to host multiple planets discovered through direct imaging. HR 8799 also hosts a debris disc first discovered by IRAS. This disc was one of the few resolved by Spitzer showing that dust is present out to a few thousand AU. The Spitzer data also showed that there must be multiple components to the dust both inside and outside the orbits of the planets. Naturally, this system has been a prime target for observations from various telescopes in recent years. We have observed the system with ALMA in band 6 (1340µm), detecting the disc at high resolution. For the first time we resolve the inner edge of the cold planetesimal belt and can determine its inclination at much higher precision than previous observations. I will discuss how these results compare to the previous observations and what these new results can tell us about the planets in the system.

  1. Ultraviolet, optical, infrared, and microwave observations of HR 5110

    NASA Technical Reports Server (NTRS)

    Little-Marenin, I. R.; Simon, T.; Ayres, T. R.; Cohen, N. L.; Feldman, P. A.

    1986-01-01

    Near-IR JHKLM photometric data and VLBI and IUE radio burst data collected on the short-period spectroscopic binary HR 5110 are analyzed to classify the object. The observed broadband colors were indicative of an F2 IV primary and a spotted K0 IV secondary. The system is being viewed pole-on, so is observable in the UV since the K companion has filled its Roche lobe. In comparisons of such features of Algol and RS VCn stars as the mass ratio, orbital inclination, presence or absence of evidence for mass streams, accretion disks, and active regions, spectral signatures, etc., sufficient similarities are found to classify HR 5110 as an Algol system.

  2. A high-resolution sup 13 C solid-state NMR study of meso-tetraphenylporphyrin and its zinc(II) complex

    SciTech Connect

    Rocha, J.; Kolodziejski, W.; Klinowski, J. ); Cavaleiro, J.A.S. )

    1992-01-01

    High-resolution {sup 13}C solid-state NMR spectra of meso-tetraphenylporphyrin (TPP) and its zinc(II) complex (ZnTPP) are assigned by reference to low-temperature solution NMR results and using {sup 1}H- {sup 13}C cross-polarization magic-angle-spinning (CP/MAS). The splittings of the signals from pyrrole carbons in TPP are attributed to kinetic solid-state states involved in the migration of the central hydrogen atom.

  3. Structural Characterization of MAO and Related Aluminum Complexes. 1. Solid-State 27 Al NMR with Comparison to EFG Tensors from ab Initio Molecular Orbital Calculations

    SciTech Connect

    Bryant, Pamela L.; Harwell, Chris; Mrse, Anthony A.; Emery, Earl F.; Gan, Zhedong; Caldwell, Tod; Reyes, Arneil P.; Kuhns, Philip; Hoyt, David W.; Simeral, Larry S.; Hall, Randall W.; Butler, Leslie G.

    2001-11-07

    Aminato and propanolato aluminum clusters with 3-, 4-, and 6-coordinate aluminum sites are studied with three 27Al NMR techniques optimized for large 27Al Quadrupole coupling constants: field-swept, frequency-stepped, and high-field MAS NMR. The 27Al quadrupole coupling constants and asymmetry parameters of molecular species, both experimental and derived from ab initio molecular orbital calculations, are correlated with structure.

  4. The Dynamical Structure of HR 8799's Inner Debris Disk

    NASA Astrophysics Data System (ADS)

    Contro, B.; Wittenmyer, Robert A.; Horner, J.; Marshall, Jonathan P.

    2015-06-01

    The HR 8799 system, with its four giant planets and two debris belts, has an architecture closely mirroring that of our Solar system where the inner, warm asteroid belt and outer, cool Edgeworth-Kuiper belt bracket the giant planets. As such, it is a valuable laboratory for examining exoplanetary dynamics and debris disk-exoplanet interactions. Whilst the outer debris belt of HR 8799 has been well resolved by previous observations, the spatial extent of the inner disk remains unknown. This leaves a significant question mark over both the location of the planetesimals responsible for producing the belt's visible dust and the physical properties of those grains. We have performed the most extensive simulations to date of the inner, unresolved debris belt around HR 8799, using UNSW Australia's Katana supercomputing facility to follow the dynamical evolution of a model inner disk comprising 300,298 particles for a period of 60 Ma. These simulations have enabled the characterisation of the extent and structure of the inner disk in detail, and will in future allow us to provide a first estimate of the small-body impact rate and water delivery prospects for possible (as-yet undetected) terrestrial planet (s) in the inner system.

  5. New SPHERE results on the planetary system around HR8799

    NASA Astrophysics Data System (ADS)

    Zurlo, Alice; Bonnefoy, Mickaël

    2015-12-01

    Since its discovery in 2008, the multi-planetary system around HR8799 has become a unique testbed for planet formation theories at large orbital radii and the study of non-irradiated planetary atmospheres. We present new SPHERE/IRDIS data in J, H, and K band, for the four planets HR8799bcde with SPHERE/IRDIS and YH-band spectra for planets d and e with SPHERE/IFS. We detect the closest planet HR8799e in J band for the first time. The astrometry gathered for three epochs of observation set new constraints on a hypothetical planet f. We combine the SPHERE photometry and spectra to demonstrate that the 1-5 µm spectral-energy distribution (SED) of the planets e and d can be represented by those of dusty -and young - L7 dwarfs. We show that the two outermost planet SEDs are well reproduced by the spectra of peculiar early-T dwarfs reddened by refractory grain opacities. This demonstrates that the planet peculiar photometric properties are dominated by the effect of dust, and suggests that the planets c, and then b, are less massive that the two innermost ones.

  6. The Dynamical Structure of HR 8799's Inner Debris Disk.

    PubMed

    Contro, B; Wittenmyer, Robert A; Horner, J; Marshall, Jonathan P

    2015-06-01

    The HR 8799 system, with its four giant planets and two debris belts, has an architecture closely mirroring that of our Solar system where the inner, warm asteroid belt and outer, cool Edgeworth-Kuiper belt bracket the giant planets. As such, it is a valuable laboratory for examining exoplanetary dynamics and debris disk-exoplanet interactions. Whilst the outer debris belt of HR 8799 has been well resolved by previous observations, the spatial extent of the inner disk remains unknown. This leaves a significant question mark over both the location of the planetesimals responsible for producing the belt's visible dust and the physical properties of those grains. We have performed the most extensive simulations to date of the inner, unresolved debris belt around HR 8799, using UNSW Australia's Katana supercomputing facility to follow the dynamical evolution of a model inner disk comprising 300,298 particles for a period of 60 Ma. These simulations have enabled the characterisation of the extent and structure of the inner disk in detail, and will in future allow us to provide a first estimate of the small-body impact rate and water delivery prospects for possible (as-yet undetected) terrestrial planet (s) in the inner system. PMID:25862330

  7. Mg/Al Ordering in Layered Double Hydroxides Revealed by Multinuclear NMR Spectroscopy

    SciTech Connect

    Sideris, Paul J.; Nielsen, Ulla G.; Gan, Zhehong; Grey, Clare P.

    2008-07-04

    The anion-exchange ability of layered double hydroxides (LDHs) has been exploited to create materials for use in catalysis, drug delivery, and environmental remediation. The specific cation arrangements in the hydroxide layers of hydrotalcite-like LDHs, of general formula Mg2+1–xAl3+xOH2(Anionn– x/n)·yH2O, have, however, remained elusive, and their elucidation could enhance the functional optimization of these materials. We applied rapid (60 kilohertz) magic angle spinning (MAS) to obtain high-resolution hydrogen-1 nuclear magnetic resonance (1H NMR) spectra and characterize the magnesium and aluminum distribution. These data, in combination with 1H-27Al double-resonance and 25Mg triple-quantum MAS NMR data, show that the cations are fully ordered for magnesium:aluminum ratios of 2:1 and that at lower aluminum content, a nonrandom distribution of cations persists, with no Al3+-Al3+ close contacts. The application of rapid MAS NMR methods to investigate proton distributions in a wide range of materials is readily envisaged.

  8. Chronic nerve injury-induced Mas receptor expression in dorsal root ganglion neurons alleviates neuropathic pain

    PubMed Central

    ZHAO, YUANTING; QIN, YUE; LIU, TUANJIANG; HAO, DINGJUN

    2015-01-01

    Neuropathic pain, which is characterized by hyperalgesia, allodynia and spontaneous pain, is one of the most painful symptoms that can be experienced in the clinic. It often occurs as a result of injury to the peripheral nerves, dorsal root ganglion (DRG), spinal cord or brain. The renin-angiotensin system (RAS) plays an important role in nociception. As an essential component of the RAS, the angiotensin (Ang)-(1–7)/Mas axis may be involved in antinociception. The aim of the present study was to explore the expression pattern of Mas in DRG neurons following chronic nerve injury and examine the effects of Mas inhibition and activation on neuropathic pain in a chronic constriction injury (CCI) rat model. The results showed, that compared with the sham group, CCI caused a time-dependent induction of Mas expression at both the mRNA and the protein levels in DRG neurons. Consistent with the results, isolated DRG neurons showed a time-dependent increase in Ang-(1–7) binding on the cell membrane following the CCI surgery, but not the sham surgery. Compared with the sham control groups, CCI significantly decreased the paw withdrawal latency and threshold, and this was markedly improved and aggravated by intrathecal injection of the selective Mas agonist Ang-(1–7) and the selective Mas inhibitor D-Pro7-Ang-(1–7), respectively. In conclusion, this study has provided the first evidence, to the best of our knowledge, that the Mas expression in DRG neurons is time-dependently induced by chronic nerve injury and that the intrathecal activation and inhibition of Mas can improve and aggravate CCI-induced neuropathic pain, respectively. This study has provided novel insights into the pathophysiological process of neuropathic pain and suggests that the Ang-(1–7)/Mas axis could be an effective therapeutic target for neuropathic pain, warranting further study. PMID:26668645

  9. Ultraviolet spectroscopy of F and G supergiants with IUE. II - The hot companions of HR 2786 and HR 2859

    NASA Technical Reports Server (NTRS)

    Parsons, S. B.

    1982-01-01

    Hot companion stars in two binary systems are analyzed by means of IUE low-dispersion spectra. HR 2859B is found to be a B2 IV or V star, and analysis of ultraviolet to near-infrared photometry indicates the primary to be an early G star only one magnitude brighter in V with a magnitude of -4.0. A third star probably associated with this system was classified B9p Hg a probable visual absolute magnitude of about -1.6 is obtained for it. HR 2786 is now confirmed to have a hot secondary, for which a spectral class of B9-9.5 is obtained. With an assumed luminosity for this component, the G2 Ib primary then has a magnitude of -3.8.

  10. NEW PRECISION ORBITS OF BRIGHT DOUBLE-LINED SPECTROSCOPIC BINARIES. IV. 66 ANDROMEDAE, HR 6979, AND HR 9059

    SciTech Connect

    Fekel, Francis C.; Williamson, Michael H.; Tomkin, Jocelyn E-mail: jt@alexis.as.utexas.edu

    2010-04-15

    We have determined improved spectroscopic orbits for three double-lined binaries, 66 And (F4 V), HR 6979 (Am), and HR 9059 (F5 IV) using radial velocities from the 2.1 m telescope at McDonald Observatory, the coude feed telescope at Kitt Peak National Observatory, and 2 m telescope at Fairborn Observatory. The orbital periods range from 11.0 to 14.3 days, and all three systems have eccentric orbits. The new orbital dimensions (a {sub 1} sin i and a {sub 2} sin i) and minimum masses (m {sub 1} sin{sup 3} i and m {sub 2} sin{sup 3} i) have accuracies of 0.2% or better. All six components of the three binary systems are rotating more slowly than their predicted pseudosynchronous rotational velocities. Hipparcos photometry of HR 9059 shows that this system has partial eclipses. Its components are nearly identical in mass and are at the very end of their main-sequence lifetimes or perhaps have just begun to traverse the Hertsprung gap.

  11. Phosphorus-31 NMR study of the effects of UV on squirrel lenses.

    PubMed

    Thomas, D M; Papadopoulou, O; Mahendroo, P P; Zigman, S

    1993-07-01

    In a series of 31P NMR experiments the effects of near-UV radiation on the phosphorus metabolites in pigmented lenses from grey squirrels were studied; UV radiation ranged from 300 to 400 nm, peaking at 365 nm. Squirrels were killed, intact lenses removed, exposed to UV, put in an NMR perfusion cell, and 31P NMR spectra were recorded. In vitro exposure of squirrel lenses for periods ranging from 4 to 22 hr were made. ATP levels, as measured by NMR, decreased as the radiation dose increased. For a 22-hr exposure (121 J cm-2) ATP levels decreased by 67% relative to control values. At lower dose levels there was a correspondingly smaller decrease in ATP levels. Histological examination showed UV-irradiated lenses had disrupted epithelium, loss of attachment to cortical fiber cells and fluid accumulation under the capsule. It is clear that lenticular exposure to near-UV, predominantly at 365 nm (UV-A), does cause metabolic deterioration through degradation of normal ATP energy levels. The grey squirrel pigmented lens strongly absorbs near-UV radiation which enhances the observed metabolic changes and observed opacities. The results demonstrate the utility of using 31P NMR to evaluate metabolic changes associated with near-UV irradiation. PMID:8405173

  12. Intercomparison of MAS, AVIRIS, and HIS data from FIRE cirrus 2

    NASA Technical Reports Server (NTRS)

    Gumley, Liam E.; King, Michael D.; Tsay, Si-Chee; Gao, Bo-Cai; Arnold, G. Thomas

    1993-01-01

    The NASA ER-2 flight on 5 Dec. 1991 is unique among the FIRE Cirrus 2 missions in that data were acquired simultaneously by the MODIS Airborne Simulator (MAS), the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS), and the High Resolution Interferometer Sounder (HIS). These data represent a unique source of information about the spatial and spectral properties of cirrus clouds. The MAS is a new instrument which will aid in defining algorithms and building an understanding of the ability of the Moderate Resolution Imaging Spectroradiometer (MODIS) to remotely sense atmospheric conditions for assessing global change. In order to establish confidence in the absolute calibration accuracy of the MAS radiances, an inter-comparison of MAS radiances with AVIRIS and HIS has been undertaken.

  13. BOREAS Level-1B MAS Imagery At-sensor Radiance, Relative X and Y Coordinates

    NASA Technical Reports Server (NTRS)

    Strub, Richard; Strub, Richard; Newcomer, Jeffrey A.; Ungar, Stephen

    2000-01-01

    For BOReal Ecosystem-Atmosphere Study (BOREAS), the MODIS Airborne Simulator (MAS) images, along with the other remotely sensed data, were collected to provide spatially extensive information over the primary study areas. This information includes detailed land cover and biophysical parameter maps such as fraction of Photosynthetically Active Radiation (fPAR) and Leaf Area Index (LAI). Collection of the MAS images occurred over the study areas during the 1994 field campaigns. The level-1b MAS data cover the dates of 21-Jul-1994, 24-Jul-1994, 04-Aug-1994, and 08-Aug-1994. The data are not geographically/geometrically corrected; however, files of relative X and Y coordinates for each image pixel were derived by using the C-130 INS data in a MAS scan model. The data are provided in binary image format files.

  14. BOREAS Level-2 MAS Surface Reflectance and Temperature Images in BSQ Format

    NASA Technical Reports Server (NTRS)

    Hall, Forrest G. (Editor); Newcomer, Jeffrey (Editor); Lobitz, Brad; Spanner, Michael; Strub, Richard; Lobitz, Brad

    2000-01-01

    The BOReal Ecosystem-Atmosphere Study (BOREAS) Staff Science Aircraft Data Acquisition Program focused on providing the research teams with the remotely sensed aircraft data products they needed to compare and spatially extend point results. The MODIS Airborne Simulator (MAS) images, along with other remotely sensed data, were collected to provide spatially extensive information over the primary study areas. This information includes biophysical parameter maps such as surface reflectance and temperature. Collection of the MAS images occurred over the study areas during the 1994 field campaigns. The level-2 MAS data cover the dates of 21-Jul-1994, 24-Jul-1994, 04-Aug-1994, and 08-Aug-1994. The data are not geographically/geometrically corrected; however, files of relative X and Y coordinates for each image pixel were derived by using the C130 navigation data in a MAS scan model. The data are provided in binary image format files.

  15. Cassini's Maneuver Automation Software (MAS) Process: How to Successfully Command 200 Navigation Maneuvers

    NASA Technical Reports Server (NTRS)

    Yang, Genevie Velarde; Mohr, David; Kirby, Charles E.

    2008-01-01

    To keep Cassini on its complex trajectory, more than 200 orbit trim maneuvers (OTMs) have been planned from July 2004 to July 2010. With only a few days between many of these OTMs, the operations process of planning and executing the necessary commands had to be automated. The resulting Maneuver Automation Software (MAS) process minimizes the workforce required for, and maximizes the efficiency of, the maneuver design and uplink activities. The MAS process is a well-organized and logically constructed interface between Cassini's Navigation (NAV), Spacecraft Operations (SCO), and Ground Software teams. Upon delivery of an orbit determination (OD) from NAV, the MAS process can generate a maneuver design and all related uplink and verification products within 30 minutes. To date, all 112 OTMs executed by the Cassini spacecraft have been successful. MAS was even used to successfully design and execute a maneuver while the spacecraft was in safe mode.

  16. Comparative genomic analysis of eutherian Mas-related G protein-coupled receptor genes.

    PubMed

    Premzl, Marko

    2014-04-25

    The present study made attempts to update comprehensive eutherian Mas-related G protein-coupled receptor gene data sets, using public eutherian genomic sequence data sets and new genomics and molecular evolution tests. Among 254 potential coding sequences, the most comprehensive gene data set of eutherian Mas-related G protein-coupled receptor genes included 119 complete coding sequences that described eight major gene clusters. The present analysis integrated gene annotations, phylogenetic analysis and protein molecular evolution analysis and first explained differential gene expansion patterns of eutherian Mas-related G protein-coupled receptor genes. The updated classification and nomenclature of eutherian Mas-related G protein-coupled receptor genes were proposed as new framework of future experiments. PMID:24583173

  17. Expression and cellular localization of the Mas receptor in the adult and developing mouse retina

    PubMed Central

    Prasad, Tuhina; Verma, Amrisha

    2014-01-01

    Purpose Recent studies have provided evidence that a local renin-angiotensin system (RAS) exists in the retina and plays an important role in retinal neurovascular function. We have recently shown that increased expression of ACE2 and angiotensin (1-7) [Ang (1-7)], two components of the protective axis of the RAS, in the retina via adeno-associated virus (AAV)-mediated gene delivery, conferred protection against diabetes-induced retinopathy. We hypothesized that the protective molecular and cellular mechanisms of Ang (1-7) are mediated by its receptor, Mas, and the expression level and cellular localization dictate the response to Ang (1-7) and activation of subsequent protective signaling pathways. We tested this hypothesis by examining the expression and cellular localization of the Mas receptor in adult and developing mouse retinas. Methods The cellular localization of the Mas receptor protein was determined with immunofluorescence of the eyes of adult and postnatal day 1 (P1), P5, P7, P15, and P21 mice using the Mas receptor-specific antibody, and mRNA was detected with in situ hybridization of paraffin-embedded sections. Western blotting and real-time reverse-transcription (RT)–PCR analysis were performed to determine the relative levels of the Mas protein and mRNA in adult and developing retinas, as well as in cultured retinal Müller glial and RPE cells. Results In the adult eye, the Mas receptor protein was abundantly present in retinal ganglion cells (RGCs) and photoreceptor cells; a lower level of expression was observed in endothelial cells, Müller glial cells, and other neurons in the inner nuclear layer of the retina. In the developing retina, Mas receptor mRNA and protein expression was detected in the inner retina at P1, and the expression levels increased with age to reach the adult level and pattern by P15. In the adult mouse retina, Mas receptor mRNA was expressed at a much higher level when compared to angiotensin II (Ang II) type I (AT1R) and type II (AT2R) receptor mRNA. Conclusions The Mas receptor is expressed in developing and adult mouse retinas, and is more abundant in retinal neurons than in endothelial and Müller glial cells. These observations suggest that Mas receptor-mediated signaling may play important roles that extend beyond mediating the vascular effects of Ang (1-7) in developing and adult retinas. In addition, the relatively high expression of the Mas receptor when compared to AT1R suggests that they may play a more important role in maintaining normal retinal physiology than previously considered. PMID:25352750

  18. The unusual interacting S star binary HR 1105

    NASA Technical Reports Server (NTRS)

    Ake, Thomas B., III; Johnson, Hollis R.; Bopp, Bernard W.

    1994-01-01

    IUE observations of HR 1105 over its 596-day orbit show strong orbital modulation of both continuum and emission lines. These are most intense just before both conjunctions and nearly disappear near quadratures, the most intense phase being just before the hot component passes in front of the S star. High dispersion observations exhibit a blue-shifted absorption feature in Mg II, representing an outflow of material of about 55 km/s. These observations are consistent with the UV source being an optically thin gas stream between the components of the system, which is partially eclipsed when the S star is in front.

  19. Detection of a magnetic region on HR 1099

    NASA Technical Reports Server (NTRS)

    Donati, J.-F.; Semel, M.; Rees, D. E.; Taylor, K.; Robinson, R. D.

    1990-01-01

    The paper reports results of a magnetic field measuring campaign on the active K component of the RS CVn system HR 1099, using Zeeman-Doppler imaging. A localized magnetic field is detected near quadrature (phase 0.85). Assuming this magnetic region has a circular shape, its longitude and latitude are, respectively, estimated to be 86 + or - 4 deg and 5 + or - 5 deg. This equatorial region is largely monopolar, has a mean field strength of 985 + or - 270 G, covers 18 + or - 3 percent of the total stellar surface and may be colocalized with a bright photospheric spot.

  20. 10 MMBt/Hr AFBC Commercial Demonstration Cedar Lane Farms

    SciTech Connect

    Harold M. Keener; Mary H. Wicks; Tom Machamer; Dave Hoecke; Don Bonk; Bob Brown

    2005-10-31

    The objective of this project was to demonstrate and promote the commercialization of coal-fired atmospheric fluidized bed combustion (AFBC) systems, with limestone addition for SO2 emissions control and a baghouse for particulate emissions control. This AFBC system was targeted for small scale industrial-commercial-institutional space and process heat applications in the 4-40 MMBtu/hr size range. A cost effective and environmentally acceptable AFBC technology in this size range could displace a considerable amount of heating gas and oil with coal, while resulting in significant total cost savings to the owner/operators.

  1. Origins of linewidth in 1H magic-angle spinning NMR.

    PubMed

    Zorin, Vadim E; Brown, Steven P; Hodgkinson, Paul

    2006-10-14

    A detailed study of the factors determining the linewidth (and hence resolution) in 1H solid-state magic-angle spinning NMR is described. Although it has been known from the early days of magic-angle spinning (MAS) that resolution of spectra from abundant nuclear spins, such as 1H, increases approximately linearly with increasing sample rotation rate, the difficulty of describing the dynamics of extended networks of coupled spins has made it difficult to predict a priori the resolution expected for a given sample. Using recently developed, highly efficient methods of numerical simulation, together with experimental measurements on a variety of test systems, we propose a comprehensive picture of 1H resolution under MAS. The "homogeneous" component of the linewidth is shown to depend primarily on the ratio between an effective local coupling strength and the spin rate, modified by geometrical factors which loosely correspond to the "dimensionality" of the coupling network. The remaining "inhomogeneous" component of the natural linewidth is confirmed to have the same properties as in dilute-spin NMR. Variations in the NMR frequency due to chemical shift effects are shown to have minimal impact on 1H resolution. The implications of these results for solid-state NMR experiments involving 1H and other abundant-spin nuclei are discussed. PMID:17042610

  2. A Novel ?/?-Hydrolase Gene IbMas Enhances Salt Tolerance in Transgenic Sweetpotato

    PubMed Central

    Song, Xuejin; He, Shaozhen; Liu, Qingchang

    2014-01-01

    Salt stress is one of the major environmental stresses in agriculture worldwide and affects crop productivity and quality. The development of crops with elevated levels of salt tolerance is therefore highly desirable. In the present study, a novel maspardin gene, named IbMas, was isolated from salt-tolerant sweetpotato (Ipomoea batatas (L.) Lam.) line ND98. IbMas contains maspardin domain and belongs to ?/?-hydrolase superfamily. Expression of IbMas was up-regulated in sweetpotato under salt stress and ABA treatment. The IbMas-overexpressing sweetpotato (cv. Shangshu 19) plants exhibited significantly higher salt tolerance compared with the wild-type. Proline content was significantly increased, whereas malonaldehyde content was significantly decreased in the transgenic plants. The activities of superoxide dismutase (SOD) and photosynthesis were significantly enhanced in the transgenic plants. H2O2 was also found to be significantly less accumulated in the transgenic plants than in the wild-type. Overexpression of IbMas up-regulated the salt stress responsive genes, including pyrroline-5-carboxylate synthase, pyrroline-5-carboxylate reductase, SOD, psbA and phosphoribulokinase genes, under salt stress. These findings suggest that overexpression of IbMas enhances salt tolerance of the transgenic sweetpotato plants by regulating osmotic balance, protecting membrane integrity and photosynthesis and increasing reactive oxygen species scavenging capacity. PMID:25501819

  3. Comparing the Effects of Lovastatin and Cornus Mas Fruit on Fibrinogen Level in Hypercholesterolemic Rabbits

    PubMed Central

    Asgary, Sedigheh; Rafieian-Kopaei, Mahmoud; Adelnia, Azadeh; Kazemi, Somayeh; Shamsi, Fatemeh

    2010-01-01

    BACKGROUND Atherosclerosis, which is a result of gradual deposition of lipids in the lower part of blood vessel endothelium, is the leading cause of mortality and morbidity around the world. It has been proved that some inflammatory blood markers such as fibrinogen can predict the risk for cardiovascular disease conditions, not only in cardiovascular patients, but also in those who do not have any manifestations of the atherosclerotic development. In this study, the effect of cornus mas l. was evaluated on fibrinogen of hypercholesterolemic rabbits and it was also compared with lovastatin drug. METHODS In this study, 25 New Zealand adult male rabbits were randomly divided into five groups of five. They were treated for 60 days by 5 different diets, namely basic, high cholesterol, regular plus 1 g/kgBW cornus mas L. powder, high cholesterol plus 1 g/kgBW cornus mas L. powder, and high cholesterol plus 10 mg/kgBW lovastatin. At the beginning and at the end of this period, blood samples were collected from the rabbits and their serum fibrinogen levels were measured. RESULTS Cornus mas L. powder and lovastatin significantly decreased fibrinogen levels in comparison with high cholesterol group (P < 0.05). Furthermore cornus mas L. powder could reduce the fibrinogen level more than lovastatin (P < 0.05). CONCLUSION The results indicated that consumption of cornus mas L. might be beneficial in atherosclerotic patients due to its reducing effects on fibrinogen. PMID:22577405

  4. THz Dynamic Nuclear Polarization NMR

    PubMed Central

    Nanni, Emilio A.; Barnes, Alexander B.; Griffin, Robert G.; Temkin, Richard J.

    2013-01-01

    Dynamic nuclear polarization (DNP) increases the sensitivity of nuclear magnetic resonance (NMR) spectroscopy by using high frequency microwaves to transfer the polarization of the electrons to the nuclear spins. The enhancement in NMR sensitivity can amount to a factor of well above 100, enabling faster data acquisition and greatly improved NMR measurements. With the increasing magnetic fields (up to 23 T) used in NMR research, the required frequency for DNP falls into the THz band (140–600 GHz). Gyrotrons have been developed to meet the demanding specifications for DNP NMR, including power levels of tens of watts; frequency stability of a few megahertz; and power stability of 1% over runs that last for several days to weeks. Continuous gyrotron frequency tuning of over 1 GHz has also been demonstrated. The complete DNP NMR system must include a low loss transmission line; an optimized antenna; and a holder for efficient coupling of the THz radiation to the sample. This paper describes the DNP NMR process and illustrates the THz systems needed for this demanding spectroscopic application. THz DNP NMR is a rapidly developing, exciting area of THz science and technology. PMID:24639915

  5. Achievement of 1020MHz NMR.

    PubMed

    Hashi, Kenjiro; Ohki, Shinobu; Matsumoto, Shinji; Nishijima, Gen; Goto, Atsushi; Deguchi, Kenzo; Yamada, Kazuhiko; Noguchi, Takashi; Sakai, Shuji; Takahashi, Masato; Yanagisawa, Yoshinori; Iguchi, Seiya; Yamazaki, Toshio; Maeda, Hideaki; Tanaka, Ryoji; Nemoto, Takahiro; Suematsu, Hiroto; Miki, Takashi; Saito, Kazuyoshi; Shimizu, Tadashi

    2015-07-01

    We have successfully developed a 1020MHz (24.0T) NMR magnet, establishing the world's highest magnetic field in high resolution NMR superconducting magnets. The magnet is a series connection of LTS (low-Tc superconductors NbTi and Nb3Sn) outer coils and an HTS (high-Tc superconductor, Bi-2223) innermost coil, being operated at superfluid liquid helium temperature such as around 1.8K and in a driven-mode by an external DC power supply. The drift of the magnetic field was initially ±0.8ppm/10h without the (2)H lock operation; it was then stabilized to be less than 1ppb/10h by using an NMR internal lock operation. The full-width at half maximum of a (1)H spectrum taken for 1% CHCl3 in acetone-d6 was as low as 0.7Hz (0.7ppb), which was sufficient for solution NMR. On the contrary, the temporal field stability under the external lock operation for solid-state NMR was 170ppb/10h, sufficient for NMR measurements for quadrupolar nuclei such as (17)O; a (17)O NMR measurement for labeled tri-peptide clearly demonstrated the effect of high magnetic field on solid-state NMR spectra. PMID:25978708

  6. Genetic algorithm optimized triply compensated pulses in NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Manu, V. S.; Veglia, Gianluigi

    2015-11-01

    Sensitivity and resolution in NMR experiments are affected by magnetic field inhomogeneities (of both external and RF), errors in pulse calibration, and offset effects due to finite length of RF pulses. To remedy these problems, built-in compensation mechanisms for these experimental imperfections are often necessary. Here, we propose a new family of phase-modulated constant-amplitude broadband pulses with high compensation for RF inhomogeneity and heteronuclear coupling evolution. These pulses were optimized using a genetic algorithm (GA), which consists in a global optimization method inspired by Nature's evolutionary processes. The newly designed ? and ? / 2 pulses belong to the 'type A' (or general rotors) symmetric composite pulses. These GA-optimized pulses are relatively short compared to other general rotors and can be used for excitation and inversion, as well as refocusing pulses in spin-echo experiments. The performance of the GA-optimized pulses was assessed in Magic Angle Spinning (MAS) solid-state NMR experiments using a crystalline U-13C, 15N NAVL peptide as well as U-13C, 15N microcrystalline ubiquitin. GA optimization of NMR pulse sequences opens a window for improving current experiments and designing new robust pulse sequences.

  7. Multinuclear NMR approach to coal fly ash characterization

    SciTech Connect

    Netzel, D.A.

    1991-09-01

    This report describes the application of various nuclear magnetic resonance (NMR) techniques to study the hydration kinetics and mechanisms, the structural properties, and the adsorption characteristics of coal fly ash. Coal fly ash samples were obtained from the Dave Johnston and Laramie River electric power generating plants in Wyoming. Hydrogen NMR relaxation times were measured as a function of time to observe the kinetics of hydration for the two coal fly ashes at different temperatures and water-to-cement ration. The kinetic data for the hydrated coal fly ashes were compared to the hydration of portland cement. The mechanism used to describe the kinetic data for the hydration of portland cement was applied, with reservation, to describe the hydration of the coal fly ashes. The results showed that the coal fly ashes differ kinetically from that of portland cement and from each other. Consequently, both coal fly ashes were judged to be poorer cementitious materials than portland cement. Carbon-13 NMR CP/MAS spectra were obtained for the anhydrous coal fly ashes in an effort to determine the type of organic species that may be present, either adsorbed on the surface or entrained.

  8. 27Al NMR study in ZrNiAl.

    PubMed

    Nowak, B; Hayashi, S

    2000-01-01

    We have studied the microscopic properties of the hexagonal ZrNiAl, a model compound for a wide family of intermetallic compounds crystallizing in this type of structure, by using 27Al NMR spectroscopy. We have investigated the lineshape of static and MAS NMR spectra as a function of magnetic field strength (4.7-9.4 T) and temperature (5-300 K). Our data indicate that the 27Al NMR spectra result from a combined effect of quadrupole and anisotropic shift interactions. The 27Al nuclei are in an environment characterized by the quadrupole coupling constant e2qQ/h of 3.3 MHz, asymmetry parameter etaQ of 0.42, isotropic shift delta(iso) of 393 ppm, shift anisotropy delta(anis) = delta(zz) - (delta(xx) + delta(yy))/2 of 150 ppm, and asymmetry factor etaS of 0.5. They are found to be temperature independent. The spin-lattice relaxation rate measured at 7.05 T is proportional to the temperature with T1T = 135 s K. The mechanisms responsible for observed values of delta(iso), delta(anis), T1T, and the enhanced Korringa constant are discussed. PMID:11270742

  9. 93Nb NMR chemical shift scale for niobia systems.

    PubMed

    Lapina, Olga B; Khabibulin, Dzhalil F; Romanenko, Konstantin V; Gan, Zhehong; Zuev, Mikhail G; Krasil'nikov, Vladimir N; Fedorov, Vladimir E

    2005-09-01

    93Nb solid-state NMR spectra of a series of inorganic niobates with Nb in different oxygen coordination environments were measured. For all studied compounds the chemical shielding and quadrupole tensor parameters were determined using conventional and ultrahigh field NMR facilities, ultrahigh speed MAS, DQ STMAS, solid-echo and computer modeling. It has been demonstrated that the 93Nb isotropic chemical shift is sensitive to the coordination number of Nb sites. For the first time the 93Nb NMR chemical shift scale for NbOx polyhedra in solid materials has been proposed: for four-coordinated Nb sites, the isotropic shifts occur from -650 to -950 ppm; five-coordinated Nb sites have the isotropic shifts in the range of -900 to -980 ppm; for six-coordinated Nb sites the isotropic shifts vary from -900 to -1360 ppm; the shifts from -1200 to -1600 ppm are typical for seven-coordinated Nb sites; for eight-coordinated Nb sites the shifts are higher than -1400 ppm. The possible correlation between the value of the isotropic chemical shift and the ionic character of the NbOx-MOy polyhedra association has been suggested. The magnitude of the 93Nb quadrupole coupling constant depends on the local symmetry of Nb sites and may vary from hundreds of kHz to hundreds of MHz. PMID:16216475

  10. Two-dimensional NMR spectroscopy

    SciTech Connect

    Croasmun, W.R.; Carlson, R.M.K.

    1987-01-01

    Written for chemists and biochemists who are not NMR spectroscopists, but who wish to use the new techniques of two-dimensional NMR spectroscopy, this book brings together for the first time much of the practical and experimental data needed. It also serves as information source for industrial, academic, and graduate student researchers who already use NMR spectroscopy, but not yet in two dimensions. The authors describe the use of 2-D NMR in a wide variety of chemical and biochemical fields, among them peptides, steroids, oligo- and poly-saccharides, nucleic acids, natural products (including terpenoids, alkaloids, and coal-derived heterocyclics), and organic synthetic intermediates. They consider throughout the book both the advantages and limitations of using 2-D NMR.

  11. Impact of the HIV-1 env Genetic Context outside HR1–HR2 on Resistance to the Fusion Inhibitor Enfuvirtide and Viral Infectivity in Clinical Isolates

    PubMed Central

    Baatz, Franky; Nijhuis, Monique; Lemaire, Morgane; Riedijk, Martiene; Wensing, Annemarie M. J.; Servais, Jean-Yves; van Ham, Petra M.; Hoepelman, Andy I. M.; Koopmans, Peter P.; Sprenger, Herman G.; Devaux, Carole; Schmit, Jean-Claude; Perez Bercoff, Danielle

    2011-01-01

    Resistance mutations to the HIV-1 fusion inhibitor enfuvirtide emerge mainly within the drug's target region, HR1, and compensatory mutations have been described within HR2. The surrounding envelope (env) genetic context might also contribute to resistance, although to what extent and through which determinants remains elusive. To quantify the direct role of the env context in resistance to enfuvirtide and in viral infectivity, we compared enfuvirtide susceptibility and infectivity of recombinant viral pairs harboring the HR1–HR2 region or the full Env ectodomain of longitudinal env clones from 5 heavily treated patients failing enfuvirtide therapy. Prior to enfuvirtide treatment onset, no env carried known resistance mutations and full Env viruses were on average less susceptible than HR1–HR2 recombinants. All escape clones carried at least one of G36D, V38A, N42D and/or N43D/S in HR1, and accordingly, resistance increased 11- to 2800-fold relative to baseline. Resistance of full Env recombinant viruses was similar to resistance of their HR1–HR2 counterpart, indicating that HR1 and HR2 are the main contributors to resistance. Strictly X4 viruses were more resistant than strictly R5 viruses, while dual-tropic Envs featured similar resistance levels irrespective of the coreceptor expressed by the cell line used. Full Env recombinants from all patients gained infectivity under prolonged drug pressure; for HR1–HR2 viruses, infectivity remained steady for 3/5 patients, while for 2/5 patients, gains in infectivity paralleled those of the corresponding full Env recombinants, indicating that the env genetic context accounts mainly for infectivity adjustments. Phylogenetic analyses revealed that quasispecies selection is a step-wise process where selection of enfuvirtide resistance is a dominant factor early during therapy, while increased infectivity is the prominent driver under prolonged therapy. PMID:21760896

  12. Vanadium-51 NMR, characterization of V-contaminated aluminas and aluminosilicate gels

    SciTech Connect

    Iyer, P.S.; Occelli, M.L. ); Eckert, H. ); Stencel, J.M. )

    1990-08-01

    Solid state (wideline and magic angle spinning (MAS)) V-51 NMR has been used to study the speciation and typical components (the gel, clay, and zeolite) of a fluid cracking catalyst (FCC) resulting from systematic variation in vanadium loading. Formation of V{sub 2}O{sub 5} is seen at high vanadium concentrations and is observed to be dependent on the vanadium precursor and/or the conditions used in its preparation. In addition, at least three other species with different bonding environments can be distinguished based on differences in chemical shift and relaxation times. The relative proportions of these are observed to change as a function of vanadium concentration. The corresponding spectra are not only sensitive to the NMR experimental conditions but also to the presence of water coordination. Structural inferences are discussed in context with V-51 NMR studies of model compounds and previous laser Raman, ESR and X-ray investigations of these materials.

  13. Characterization of Two Distinct Amorphous Forms of Valsartan by Solid-State NMR.

    PubMed

    Skotnicki, Marcin; Apperley, David C; Aguilar, Juan A; Milanowski, Bartłomiej; Pyda, Marek; Hodgkinson, Paul

    2016-01-01

    Valsartan (VAL) is an antihypertensive drug marketed in an amorphous form. Amorphous materials can have different physicochemical properties depending on preparation method, thermal history, etc., but the nature of such materials is difficult to study by diffraction techniques. This study characterizes two different amorphous forms of valsartan (AR and AM) using solid-state NMR (SSNMR) as a primary investigation tool, supported by solution-state NMR, FT-IR, TMDSC, and dissolution tests. The two forms are found to be clearly distinct, with a significantly higher level of structural arrangement in the AR form, as observed in (13)C, (15)N, and (1)H SSNMR. (13)C and (15)N NMR indicates that the fully amorphous material (AM) contains an approximately equal ratio of cis-trans conformers about the amide bond, whereas the AR form exists mainly as one conformer, with minor conformational "defects". (1)H ultrafast MAS NMR shows significant differences in the hydrogen bonding involving the tetrazole and acid hydrogens between the two materials, while (15)N NMR shows that both forms exist as a 1,2,3,4-tetrazole tautomer. NMR relaxation times show subtle differences in local and bulk molecular mobility, which can be connected with the glass transition, the stability of the glassy material, and its response to aging. Counterintuitively the fully amorphous material is found to have a significantly lower dissolution rate than the apparently more ordered AR material. PMID:26602457

  14. Is the HR8799 extrasolar system destined for planetary scattering?

    NASA Astrophysics Data System (ADS)

    Go?dziewski, Krzysztof; Migaszewski, Cezary

    2009-07-01

    The recent discovery of a three-planet extrasolar system of HR8799 by Marois et al. is a breakthrough in the field of the direct imaging. This great achievement raises questions on the formation and dynamical stability of the system, because Keplerian fits to astrometric data disrupt during ~0.2Myr. We search for stable, self-consistent N-body orbits with the so-called GAMP (genetic algorithm with MEGNO penalty) method that incorporates stability constraints into the optimization algorithm. Our searches reveal only small regions of stable motions in the phase space of three-planet, coplanar configurations. Most likely, if the planetary masses are in 10MJ range, they may be stable only if the planets are involved in two- or three-body mean motion resonances (MMRs). We found that 80 per cent systems found by GAMP that survived 30Myr backwards integrations, eventually become unstable after 100Myr. It could mean that the HR8799 system undergo a phase of planet-planet scattering. We test a hypothesis that the less certain detection of the innermost object is due to a blending effect. In such a case, two-planet best-fitting systems are mostly stable, on quasi-circular orbits and close to the 5:2 MMR, resembling the Jupiter-Saturn pair.

  15. Restoration Technique for Pleiades-Hr Panchromatic Images

    NASA Astrophysics Data System (ADS)

    Latry, C.; Fourest, S.; Thiebaut, C.

    2012-07-01

    17th of December 2011 from Kourou Space Centre, French Guyana. Like others high resolution optical satellites, it acquires both panchromatic images, with 70cm spatial resolution, and lower resolution multispectral images with 2.8m spatial resolution. Pleiades-HR is an optimized system, which means that the Modulation Transfer Function has a low value at Nyquist frequency, in order to reduce both the telescope diameter and aliasing effects. Shannon sampling condition is thus met at first order, which also makes classical ground processing, such as image matching or resampling, more justified for a mathematical point of view. Raw images are thus blurry which implies a deconvolution stage that restores sharpness but also increases the noise level in the high frequency domain. A denoising step, based upon wavelet packet coefficients thresholding/shrinkage technique, allows controlling the final noise level. Each of these methods includes numerous parameters that have to be assessed during the inflight commissioning period: deconvolution filter that depends on MTF assessment, instrumental noise model, noise level target for denoised images, wavelet packet decomposition level. This paper aims to precisely describe the deconvolution/denoising algorithms and how their main parameters have been set up during the inflight commissioning stage. Special attention will be given to structured noise induced by Pleiades-HR on board wavelet-based compression algorithm

  16. Far Infrared and Sub-millimtre Imaging of HR 8799

    NASA Astrophysics Data System (ADS)

    Booth, M.

    2014-09-01

    HR 8799 is well known for being the only star to host multiple planets discovered through direct imaging. HR 8799 also hosts a debris disc first discovered by IRAS. This disc was one of the few resolved by Spitzer showing that dust is present out to a few thousand AU. The Spitzer data also showed that there must be multiple components to the dust both inside and outside the orbits of the planets. Naturally, this system has been a prime target for observations from various telescopes in recent years. I will focus on the results of imaging with Herschel, ALMA cycle 0 and JCMT/SCUBA-2. The disc is found to be resolved at 70, 100, 160, 250 and 850 ?m. The resolution of the Herschel data has allowed us to determine the inclination of the disc for the first time, showing it to be coplanar with the planets and star. Both Herschel and ALMA observations do not detect any clumpiness that might be expected due to interactions between the planets and the disc, implying that the eccentricity of the outermost planet is < 0.1. Combined analysis of the spectral energy distribution and the resolved images presents new questions since the dust is seen to be distributed over a wide range of radii and yet only a narrow range of temperatures is seen.

  17. Dynamical simulations of the HR8799 planetary system

    NASA Astrophysics Data System (ADS)

    Marshall, J.; Horner, J.; Carter, A.

    2010-10-01

    HR8799 is a young (20-160 Myr) A-dwarf main sequence star with a debris disc detected by IRAS (InfraRed Astronomical Satellite). In 2008, it was one of two stars around which exoplanets were directly imaged for the first time. The presence of three Jupiter-mass planets around HR8799 provoked much interest in modelling the dynamical stability of the system. Initial simulations indicated that the observed planetary architecture was unstable on timescales much shorter than the lifetime of the star (~105 yr). Subsequent models suggested that the system could be stable if the planets were locked in a 1:2:4 mutual mean motion resonance (MMR). In this work, we have examined the influence of varying orbital eccentricity and the semi-major axis on the stability of the three-planet system, through dynamical simulations using the MERCURY n-body integrator. We find that, in agreement with previous work on this system, the 1:2:4 MMR is the most stable planetary configuration, and that the system stability is dominated by the interaction between the inner pair of planets. In contrast to previous results, we find that with small eccentricities, the three-planet system can be stable for timescales comparable to the system lifetime and, potentially, much longer.

  18. Modeling the Asteroseismic Surface Term across the HR Diagram

    NASA Astrophysics Data System (ADS)

    Schmitt, Joseph R.; Basu, Sarbani

    2015-08-01

    Asteroseismology is a powerful tool that can precisely characterize the mass, radius, and other properties of field stars. However, our inability to properly model the near-surface layers of stars creates a frequency-dependent frequency difference between the observed and the modeled frequencies, usually referred to as the “surface term.” This surface term can add significant errors to the derived stellar properties unless removed properly. In this paper, we simulate surface terms across a significant portion of the HR diagram, exploring four different masses (M=0.8,1.0,1.2, and 1.5 {M}⊙ ) at five metallicities ([{Fe}/{{H}}]=0.5,0.0,-0.5,-1.0, and -1.5) from the main sequence to red giants for stars with {T}{eff}\\lt 6500 K and explore how well the most common ways of fitting and removing the surface term actually perform. We find that the two-term model proposed by Ball & Gizon works much better than other models across a large portion of the HR diagram, including the red giants, leading us to recommend its use for future asteroseismic analyses.

  19. Classification of ischaemic episodes with ST/HR diagrams.

    PubMed

    Faganeli Pucer, Jana; Demšar, Janez; Kukar, Matjaž

    2012-01-01

    Coronary artery disease is the developed world's premier cause of mortality and the most probable cause of myocardial ischaemia. More advanced diagnostic tests aside, in electrocardiogram (ECG) analysis it manifests itself as a ST segment deviation, targeted by both exercise ECG and ambulatory ECG. In ambulatory ECG, besides ischaemic ST segment deviation episodes there are also non-ischaemic heart rate related episodes which aggravate real ischaemia detection. We present methods to transform the features developed for the heart rate adjustment of ST segment depression in exercise ECG for use in ambulatory ECG. We use annotations provided by the Long-Term ST Database to plot the ST/HR diagrams and then estimate the overall and maximal slopes of the diagrams in the exercise and recovery phase for each ST segment deviation episode. We also estimate the angle at the extrema of the ST/HR diagrams. Statistical analysis shows that ischaemic ST segment deviation episodes have significantly steeper overall and maximal slopes than heart rate related episodes, which indicates the explored features' utility for distinguishing between the two types of episodes. This makes the proposed features very useful in automated ECG analysis. PMID:22874369

  20. Acute hyperhydration reduces athlete biological passport OFF-hr score.

    PubMed

    Bejder, J; Hoffmann, M F; Ashenden, M; Nordsborg, N B; Karstoft, K; Mørkeberg, J

    2016-03-01

    Anecdotal evidence suggests that athletes hyperhydrate to mask prohibited substances in urine and potentially counteract suspicious fluctuations in blood parameters in the athlete biological passport (ABP). It is examined if acute hyperhydration changes parameters included in the ABP. Twenty subjects received recombinant human erythropoietin (rhEPO) for 3 weeks. After 10 days of rhEPO washout, 10 subjects ingested normal amount of water (??270?mL), whereas the remaining 10 ingested a 1000?mL bolus of water. Blood variables were measured 20, 40, 60, and 80?min after ingestion. Three days later, the subjects were crossed-over with regard to water ingestion and the procedure was repeated. OFF-hr was reduced by ??4%,???3%, and ??2% at 40, 60, and 80?min, respectively, after drinking 1000?mL of water, compared with normal water ingestion (P?hr and reduces ABP sensitivity. PMID:25773052

  1. Images of a fourth planet orbiting HR 8799.

    PubMed

    Marois, Christian; Zuckerman, B; Konopacky, Quinn M; Macintosh, Bruce; Barman, Travis

    2010-12-23

    High-contrast near-infrared imaging of the nearby star HR 8799 has shown three giant planets. Such images were possible because of the wide orbits (>25?astronomical units, where 1?au is the Earth-Sun distance) and youth (<100?Myr) of the imaged planets, which are still hot and bright as they radiate away gravitational energy acquired during their formation. An important area of contention in the exoplanet community is whether outer planets (>10?au) more massive than Jupiter form by way of one-step gravitational instabilities or, rather, through a two-step process involving accretion of a core followed by accumulation of a massive outer envelope composed primarily of hydrogen and helium. Here we report the presence of a fourth planet, interior to and of about the same mass as the other three. The system, with this additional planet, represents a challenge for current planet formation models as none of them can explain the in situ formation of all four planets. With its four young giant planets and known cold/warm debris belts, the HR 8799 planetary system is a unique laboratory in which to study the formation and evolution of giant planets at wide (>10?au) separations. PMID:21150902

  2. The crystallization of hectorite clays as monitored by small angle X-ray scattering and NMR

    SciTech Connect

    Carrado, K. A.; Xu, L.; Seifert, S.; Gregory, D.; Song, K.; Botto, R. E.

    1999-12-13

    The authors have probed the 48-hr crystallization of a magnesium silicate clay called hectorite. Small angle X-ray scattering (SAXS) at the Advanced Photon Source using aliquots ex situ has revealed that data is consistent with ex situ XRD, TGA, AFM, and IR data in that all these techniques see clay crystallite beginning to form in the first few hours of reaction. Tetraethylammonium (TEA) ions are used to aid crystallization and become incorporated as the exchange cations within the interlayers. {sup 13}C NMR shows that 80% of the final TEA loading is accomplished in the first 10 hrs. {sup 29}Si NMR displays a visible clay silicate peak after just 1 hr. In addition, the first in situ study of clay crystallization of any kind was performed by in situ SAXS. Results are consistent with the ex situ data as well as showing the sensitivity of SAXS to sol gel reactions occurring on the order of minutes.

  3. Time Series Analysis of the A0 Supergiant HR 1040

    NASA Astrophysics Data System (ADS)

    Corliss, David J.

    A time series analysis of spectroscopic and photometric observables of the A0Ia supergiant HR 1040 has been performed. The data, obtained from 1993 through 2007, include 152 spectroscopic observations from the Ritter Observatory and 269 Stromgren photometric observations from the Four College Automated Photoelectric Telescope (FCAPT). A number of spectroscopic and photometric features have been analyzed and compared, including Wlambda, radial velocities and Stromgren photometric indices. Typical of late B- and early A-type supergiants, HR 1040 has a highly variable stellar wind including High Velocity Absorption (HVA) events. The star was found to have an active phase with large variation in the physical characteristics of the wind and with the potential for HVAs. During the active phase, correlation between the H-alpha absorption equivalent width and blue-edge radial velocity was observed. If an HVA was present, the active phase was found to begin before the onset of the HVA and continue after the end of the event by as much as several weeks. This active phase alternated with a more common quiescent phase marked by little variability and equivalent width - radial velocity correlation and no HVAs. The active phase and HVAs were found to exhibit important connections to photospheric activity. Increases in H-alpha absorption and blue-edge radial velocity at the onset of HVAs was preceded by correlated increases in Si II Wlambda and second moment, with the atmospheric changes indicated by the H-alpha line lagging the photospheric changes seen in Si II by an interval of 13 to 23 days. The observed HVAs were found to be preceded by Si II radial velocity oscillations by an interval of 19 to 42 days. The equivalent width and second moment of the photospheric Si II lambdalambda6347, 6371 lines were found to be highly variable and strongly correlated throughout the two active phases when an HVA is observed but not during the quiescent phase or in the one active phase where no HVA was seen. The Si II Wlambda and second moment showed a short-lived increase during the first few weeks of an HVA and then quickly dropped back to quiescent phase levels. Time series cluster analysis of the two HVAs observed on HR 1040, in addition to three HVAs in alpha Orionis, identified four distinct stages in the development of these events. Possible factors contributing to HVA are discussed, including gas ejection and microturbulence at the photosphere, as well as co-rotation interaction regions (CIR) in the wind. HR 1040 exhibits a broad emission feature near Halpha commonly found in late B- and early A-type supergiants. The broad emission in HR 1040 was found to be variable and not correlated to photospheric or wind observables associated with the active phase. Some indication was found that this feature is limited to a wavelength range of 6532 A to 6597 A. While the wavelength range extends roughly the same amount to either side of H-alpha line center, an asymmetry in the flux of the broad emission is observed, with a local maximum in the flux varying between 6555 A to 6564 A. If this asymmetry is real and not an instrumental effect, it argues against a photospheric origin for this broad emission feature as it would require radial velocities up to -300 km/s, well in excess of the terminal wind speed.

  4. Determination of the Average Aromatic Cluster Size of Fossil Fuels by Solid-State NMR at High Magnetic Field

    SciTech Connect

    Mao, Kanmi; Kennedy, Gordon J.; Althaus, Stacey M.; Pruski, Marek

    2013-01-07

    We show that the average aromatic cluster size in complex carbonaceous materials can be accurately determined using fast magic-angle spinning (MAS) NMR at a high magnetic field. To accurately quantify the nonprotonated aromatic carbon, we edited the 13C spectra using the recently reported MAS-synchronized spin–echo, which alleviated the problem of rotational recoupling of 1H-13C dipolar interactions associated with traditional dipolar dephasing experiments. The dependability of this approach was demonstrated on selected Argonne Premium coal standards, for which full sets of basic structural parameters were determined with high accuracy.

  5. First Satellite NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    McDowell, A. F.; Conradi, Mark S.; Haase, J.

    1996-03-01

    A new NMR spectroscopic method that detects only the /pm 3/2 to /pm 1/2 transitions (i.e., first satellites) of half-integer quadrupolar spins is presented. The technique is based on a central transition signal enhancement method that makes use of adiabatic radiofrequency sweeps. A plot of the enhanced central transition signal versus the stop frequency of the sweep is an integrated version of the first satellite spectrum. To find the quadrupole parameters one can fit this integrated spectrum directly, or differentiate the data to reveal the traditional spectrum (of the first satellites). We demonstrate the technique for ^27Al in Al_2O3 and ^93Nb in LiNbO_3. The advantages of this new spectroscopy are discussed.

  6. The Stoichiometry of Synthetic Alunite as a Function of Hydrothermal Aging Investigated by Solid-State NMR Spectroscopy, Powder X-ray Diffraction and Infrared Spectroscopy

    SciTech Connect

    Grube, Elisabeth; Nielsen, Ulla Gro

    2015-05-01

    The stoichiometry of a series of synthetic alunite [nominally KAl3(SO4)2(OH)6] samples prepared by hydrothermal methods as a function of reaction time (1–31 days) has been investigated by powder X-ray diffraction, Fourier transform infrared spectroscopy as well as solid-state 1H and 27Al magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The 1H MAS NMR spectra recorded at high magnetic field (21.1 T, 900 MHz) allowed for a clear separation of the different proton environments and for quantitative determination of the aluminum vacancy concentration as a function of time. The concentration of structural defects determined from, i.e., aluminum vacancies was reduced from 4 to 1 %, as the reaction time was extended from one to 31 days based on 1H MAS NMR. This was further supported by an increase of the unit cell parameter c, which is indicative of the relative concentration of potassium defects present, from 17.261(1) to 17.324(5) Å. Solid-state 27Al MAS NMR revealed a decrease in the defect concentration as a function of time and showed the presence of 7–10 % impurities in the samples.

  7. Study the Effects of Mechanical Activation on Li-N-H Systems With 1H and 6Li Solid-State NMR

    SciTech Connect

    Lu, Chun; Hu, Jian Zhi; Kwak, Ja Hun; Yang, Z Gary; Ren, Ruiming; Markmaitree, Tippawan; Shaw, Leonard D.

    2007-07-10

    To gain insight into the effects of mechanical activation (MA) on the hydrogen desorption of the lithium amide (LiNH2) and lithium hydride (LiH) mixture, LiNH2 and LiH+LiNH2 were mechanically activated by high-energy ball milling. The formed products were studied with in situ 1H and 6Li nuclear magic angle spinning (MAS) magnetic resonance (NMR) spectroscopy from ambient temperature to 180 degrees C. Up-field chemical shift was observed in 6Li MAS NMR spectra with increased milling time, indicating that average local electronic structure around Li nuclei was modified during MA. 1H MAS NMR was used to dynamically probe ammonia release from the activated LiNH2 at temperature as low as 50 degrees C. In the case of activated LiH+LiNH2 mixtures, the 1H MAS NMR results implied that MA enhanced the dehydrogenation reaction of LiNH2+LiH=Li2NH+H2 and suppressed ammonia generation as well.

  8. NEW PRECISION ORBITS OF BRIGHT DOUBLE-LINED SPECTROSCOPIC BINARIES. VIII. HR 1528, HR 6993, 2 SAGITTAE, AND 18 VULPECULAE

    SciTech Connect

    Fekel, Francis C.; Williamson, Michael H.; Tomkin, Jocelyn E-mail: michael.h.williamson@gmail.com

    2013-11-01

    Improved orbital elements for four A-star double-lined spectroscopic binaries have been determined with numerous new radial velocities. Three of the four systems, HR 1528, 2 Sge, and 18 Vul, have moderately short orbital periods of 7.05, 7.39, and 9.31 days, respectively, and also have circular or nearly circular orbits. Only HR 6993 with a period of 14.68 days has a significantly eccentric orbit. The close visual companion of 2 Sge has been detected spectroscopically, and its velocity measured. The orbital dimensions (a {sub 1} sin i and a {sub 2} sin i) and minimum masses (m {sub 1} sin{sup 3} i and m {sub 2} sin{sup 3} i) of the short-period binary components all have accuracies of 0.5% or better. We determine basic properties of the individual stars and compare them with solar-abundance evolutionary tracks to estimate their masses. Half of the eight components may be synchronously or pseudosynchronously rotating.

  9. New constraints on the dust surrounding HR 4796A

    NASA Astrophysics Data System (ADS)

    Milli, J.; Mawet, D.; Pinte, C.; Lagrange, A.-M.; Mouillet, D.; Girard, J. H.; Augereau, J.-C.; De Boer, J.; Pueyo, L.; Choquet, É.

    2015-05-01

    Context. HR 4796A is surrounded by a well-structured and very bright circumstellar disc shaped like an annulus with many interesting features: very sharp inner and outer edges, brightness asymmetries, centre offset, and suspected distortions in the ring. Aims: We aim to constrain the properties of the dust surrounding the star HR 4796A, in particular the grain size and composition. We also want to confirm and refine the morphological parameters derived from previous scattered light observations, and reveal the dust spatial extent in regions unexplored so far due to their proximity to the star. Methods: We have obtained new images in polarised light of the binary system HR 4796A and B in the Ks and L' band with the NaCo instrument at the Very Large Telescope (VLT). In addition, we revisit two archival data sets obtained in the L' band with that same instrument and at 2.2 ?m with the NICMOS instrument on the Hubble Space Telescope. We analyse these observations with simulations using the radiative transfer code MCFOST to investigate the dust properties. We explore a grid of models with various dust compositions and sizes in a Bayesian approach. Results: We detect the disc in polarised light in the Ks band and reveal for the first time the innermost regions down to 0.3? along the semi-minor axis. We measure a polarised fraction of 29% ± 8% in the two disc ansae, with a maximum occurring more than 13° westwards from the ansae. A very pronounced brightness asymmetry between the north-west and south-east side is detected. This contradicts the asymmetry previously reported in all images of the disc in unpolarised light at wavelengths smaller than or equal to 2.2 ?m and is inconsistent with the predicted scattered light from spherical grains using the Mie theory. Our modelling suggests the north-west side is most likely inclined towards the Earth, contrary to previous conclusions. It shows that the dust is composed of porous aggregates larger than 1 ?m.

  10. NMR measurement of pore structure

    SciTech Connect

    Earl, W.L.; Kim, Yong-Wah |; Smith, D.M.

    1993-05-31

    An attempt was made to pursue {sup 129}Xe NMR as a pore measurement technique. Samples studied were synthetic imogolite (tubular aluminosilicate with gibbsite structure), sodium Y-zeolite, and an aerogel and a xerogel. Gases used were normal Xe, {sup 13}CO{sub 2}, and {sup 15}N{sub 2}. Although a completely general NMR technique for measuring pore size distributions may not be possible, information about molecular motion and interactions can be obtained, because NMR is sensitive to short range interactions (1 nm or less) and to molecular dynamics in the range 10{sup {minus}2} to 10{sup {minus}6}s.

  11. NMR measurement of pore structure

    SciTech Connect

    Earl, W.L. ); Kim, Yong-Wah New Mexico Univ., Albuquerque, NM . Center for Microengineered Ceramics); Smith, D.M. . Center for Microengineered Ceramics)

    1993-05-31

    An attempt was made to pursue [sup 129]Xe NMR as a pore measurement technique. Samples studied were synthetic imogolite (tubular aluminosilicate with gibbsite structure), sodium Y-zeolite, and an aerogel and a xerogel. Gases used were normal Xe, [sup 13]CO[sub 2], and [sup 15]N[sub 2]. Although a completely general NMR technique for measuring pore size distributions may not be possible, information about molecular motion and interactions can be obtained, because NMR is sensitive to short range interactions (1 nm or less) and to molecular dynamics in the range 10[sup [minus]2] to 10[sup [minus]6]s.

  12. The use of a selective saturation pulse to suppress t1 noise in two-dimensional (1)H fast magic angle spinning solid-state NMR spectroscopy.

    PubMed

    Robertson, Aiden J; Pandey, Manoj Kumar; Marsh, Andrew; Nishiyama, Yusuke; Brown, Steven P

    2015-11-01

    A selective saturation pulse at fast magic angle spinning (MAS) frequencies (60+kHz) suppresses t1 noise in the indirect dimension of two-dimensional (1)H MAS NMR spectra. The method is applied to a synthetic nucleoside with an intense methyl (1)H signal due to triisopropylsilyl (TIPS) protecting groups. Enhanced performance in terms of suppressing the methyl signal while minimising the loss of signal intensity of nearby resonances of interest relies on reducing spin diffusion - this is quantified by comparing two-dimensional (1)H NOESY-like spin diffusion spectra recorded at 30-70kHz MAS. For a saturation pulse centred at the methyl resonance, the effect of changing the nutation frequency at different MAS frequencies as well as the effect of changing the pulse duration is investigated. By applying a pulse of duration 30ms and nutation frequency 725Hz at 70kHz MAS, a good compromise of significant suppression of the methyl resonance combined with the signal intensity of resonances greater than 5ppm away from the methyl resonance being largely unaffected is achieved. The effectiveness of using a selective saturation pulse is demonstrated for both homonuclear (1)H-(1)H double quantum (DQ)/single quantum (SQ) MAS and (14)N-(1)H heteronuclear multiple quantum coherence (HMQC) two-dimensional solid-state NMR experiments. PMID:26432398

  13. The use of a selective saturation pulse to suppress t1 noise in two-dimensional 1H fast magic angle spinning solid-state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Robertson, Aiden J.; Pandey, Manoj Kumar; Marsh, Andrew; Nishiyama, Yusuke; Brown, Steven P.

    2015-11-01

    A selective saturation pulse at fast magic angle spinning (MAS) frequencies (60+ kHz) suppresses t1 noise in the indirect dimension of two-dimensional 1H MAS NMR spectra. The method is applied to a synthetic nucleoside with an intense methyl 1H signal due to triisopropylsilyl (TIPS) protecting groups. Enhanced performance in terms of suppressing the methyl signal while minimising the loss of signal intensity of nearby resonances of interest relies on reducing spin diffusion - this is quantified by comparing two-dimensional 1H NOESY-like spin diffusion spectra recorded at 30-70 kHz MAS. For a saturation pulse centred at the methyl resonance, the effect of changing the nutation frequency at different MAS frequencies as well as the effect of changing the pulse duration is investigated. By applying a pulse of duration 30 ms and nutation frequency 725 Hz at 70 kHz MAS, a good compromise of significant suppression of the methyl resonance combined with the signal intensity of resonances greater than 5 ppm away from the methyl resonance being largely unaffected is achieved. The effectiveness of using a selective saturation pulse is demonstrated for both homonuclear 1H-1H double quantum (DQ)/single quantum (SQ) MAS and 14N-1H heteronuclear multiple quantum coherence (HMQC) two-dimensional solid-state NMR experiments.

  14. Photospheric imaging of the RS CVn system HR 1099

    NASA Technical Reports Server (NTRS)

    Donati, J.-F.; Brown, S. F.; Semel, M.; Rees, D. E.; Dempsey, R. C.; Matthews, J. M.; Henry, G. W.; Hall, D. S.

    1992-01-01

    Spectropolarimetric, spectroscopic, and photometric observations of the RS CVn binary system HR 1099 = V711 Tau (K1IV+G5V) were made from Oct. 1988 to Jan. 1991. From Doppler imaging of the unpolarized spectra and the corresponding data, two maximum entropy images of the temperature distribution of the active K1 subgiant at epochs 1988.9 and 1990.9 were derived. Zeeman-Doppler imaging of the circularly polarized spectra has led to the first magnetic maps of a star other than the sun. The fragmentary observations made at epoch 1989.6 suggest that the star's magnetic field lines were emerging radially and/or poloidally from an equatorial warm region at that time, quite likely one of these reconstructed in the 1988.9 temperature image.

  15. HR-TEM study of atomic defects in carbon nanostructures

    SciTech Connect

    Urita, K.; Sato, Y.; Suenaga, K.; Iijima, S.

    2005-09-27

    Direct observation of the defect formation in carbon nanostructures during electron irradiation is carried out by high-resolution transmission electron microscopy (HR-TEM) on the double-wall carbon nanotubes (DWNT) and carbon nanopeapods. The irradiation damage due to the knock-on collision with high energy electron beam are found to be dependent on the curvature of the constituent graphen layers. The formation of knock-on defects is more abundant at an inner tube than an outer tube in DWNT, and at a fullerene than a carbon nanotube in carbon nanopeapods. These results definitely indicate that the effects of electron irradiation in nanocarbon materials are quite more prominent on higher surface curvature, such as fullerene.

  16. Direct imaging of multiple planets orbiting the star HR 8799

    SciTech Connect

    Marois, C; Macintosh, B; Barman, T; Zuckerman, B; Song, I; Patience, J; Lafreniere, D; Doyon, R

    2008-10-14

    Direct imaging of exoplanetary systems is a powerful technique that can reveal Jupiter-like planets in wide orbits, can enable detailed characterization of planetary atmospheres, and is a key step towards imaging Earth-like planets. Imaging detections are challenging due to the combined effect of small angular separation and large luminosity contrast between a planet and its host star. High-contrast observations with the Keck and Gemini telescopes have revealed three planets orbiting the star HR 8799, with projected separations of 24, 38, and 68 astronomical units. Multi-epoch data show counter-clockwise orbital motion for all three imaged planets. The low luminosity of the companions and the estimated age of the system imply planetary masses between 5 and 13 times that of Jupiter. This system resembles a scaled-up version of the outer portion of our Solar System.

  17. Near infrared spectrophotometry of the chromospherically active binary HR 1099

    NASA Astrophysics Data System (ADS)

    Zhai, Di-sheng; Zhang, Xiao-yu; Wang, Jun-jie

    1995-02-01

    This paper presents the results of near infrared spectrophotometry of the chromospherically strongly active binary HR 1099 before and after the extra energetic white-light flare of December 1989. Low-dispersion, CVF spectra between 2.3-4.2 ?m for this star are given here for the first time. The effects of starspots at the time of the observation are calculated and an approximate blackbody spectrum is given. Comparison with multi-wavelength photometry and the IRAS measurements revealed strong emission band at 2.3 ?m and absorption band at 3.1 ?m by circumstellar matter. A preliminary discussion is made on the probable composition and distribution of the circumstellar matter.

  18. Radio Astrometry of the Close Active Binary HR5110

    NASA Astrophysics Data System (ADS)

    Abbuhl, E.; Mutel, R. L.; Lynch, C.; Güedel, M.

    2015-09-01

    The close active binary HR 5110 was observed at six epochs over 26 days using a global very long baseline interferometry array at 15.4 GHz. We used phase referencing to determine the position of the radio centroid at each epoch with an uncertainty significantly smaller than the component separation. After correcting for proper motion and parallax, we find that the centroid locations of all six epochs have barycenter separations consistent with an emission source located on the KIV secondary, and not in an interaction region between the stars or on the F primary. We used a homogeneous power-law gyrosynchrotron emission model to reproduce the observed flux densities and fractional circular polarization. The resulting ranges of mean magnetic field strength and relativistic electron densities are of the order of 10 G and 105 cm-3, respectively, in the source region.

  19. Ultraviolet and radio flares from UX Arietis and HR 1099

    NASA Technical Reports Server (NTRS)

    Lang, Kenneth R.; Willson, Robert F.

    1988-01-01

    Simultaneous observations of the RS CVn systems UX Ari and HR 1099 with the IUE satellite and the VLA are presented. Flaring activity is observed at ultraviolet wavelengths with the IUE when none is detected at radio wavelengths with the VLA. Radio flares with no detectable ultraviolet activity have also been observed. Thus, flares in the two spectral regions are either uncorrelated or weakly correlated. The flaring emission probably originates in different regions at the two wavelengths. Radio flares from RS CVn stars may originate in sources that are larger than, or comparable to, a star in size. This is in sharp contrast to compact, coherent radio flares from dwarf M stars. The ultraviolet flares from RS CVn stars probably originate in sources that are smaller than a component star.

  20. Time-Dependent Coupling of Lfm-Helio and MAS Models for CME Propagation

    NASA Astrophysics Data System (ADS)

    Lyon, J.; Merkin, V. G.; Lionello, R.; Linker, J.; Raouafi, N. E.

    2014-12-01

    We present initial results of coupling of the heliospheric adaptation of the Lyon-Fedder-Mobarry (LFM) magnetohydrodynamic (MHD) model — LFM-helio — with the MAS model of the solar corona. Up to now, LFM-helio has been limited to steady-state solutions dominated by corotating structures. We have developed a generalized interface for specification of time-dependent coronal boundary conditions and ingestion of MAS simulation data into the LFM model. The coupling is done by overlapping the LFM inner boundary buffer region with the outer portion of the MAS coronal grid. LFM-helio operates in the inertial rest frame, but our coupling code is sufficiently flexible that MAS solutions performed in either rotating or inertial frames can be ingested. We present results of a number of idealized coupled MAS/LFM-helio simulations — ranging from simply symmetric solar wind background to realistic including high and slow speed streams — intended to test the interface for seamless propagation of transients from the corona into the inner heliosphere domain. The transients are then tracked to larger heliocentric distances — to Earth and beyond. We specifically investigate the magnetic structure of the CMEs as they propagate through the interplanetary medium including rotation and erosion, and consider how the simulation resolution affects the results. We also developed codes for creation of synthetic white-light heliographic images which are used to help track CMEs kinematics through J-maps and put the simulations into a realistic observational context.

  1. ACE2/ANG-(1–7)/Mas pathway in the brain: the axis of good

    PubMed Central

    Xu, Ping; Sriramula, Srinivas

    2011-01-01

    The last decade has seen the discovery of several new components of the renin-angiotensin system (RAS). Among them, angiotensin converting enzyme-2 (ACE2) and the Mas receptor have forced a reevaluation of the original cascade and led to the emergence of a new arm of the RAS: the ACE2/ANG-(1–7)/Mas axis. Accordingly, the new system is now seen as a balance between a provasoconstrictor, profibrotic, progrowth axis (ACE/ANG-II/AT1 receptor) and a provasodilatory, antifibrotic, antigrowth arm (ACE2/ANG-(1–7)/Mas receptor). Already, this simplistic vision is evolving and new components are branching out upstream [ANG-(1–12) and (pro)renin receptor] and downstream (angiotensin-IV and other angiotensin peptides) of the classical cascade. In this review, we will summarize the role of the ACE2/ANG-(1–7)/Mas receptor, focusing on the central nervous system with respect to cardiovascular diseases such as hypertension, chronic heart failure, and stroke, as well as neurological diseases. In addition, we will discuss the new pharmacological (antagonists, agonists, activators) and genomic (knockout and transgenic animals) tools that are currently available. Finally, we will review the latest data regarding the various signaling pathways downstream of the Mas receptor. PMID:21178125

  2. MASSES, RADII, AND CLOUD PROPERTIES OF THE HR 8799 PLANETS

    SciTech Connect

    Marley, Mark S.; Saumon, Didier; Cushing, Michael; Ackerman, Andrew S.; Fortney, Jonathan J.; Freedman, Richard E-mail: dsaumon@lanl.gov E-mail: andrew.ackerman@nasa.gov E-mail: freedman@darkstar.arc.nasa.gov

    2012-08-01

    The near-infrared colors of the planets directly imaged around the A star HR 8799 are much redder than most field brown dwarfs of the same effective temperature. Previous theoretical studies of these objects have concluded that the atmospheres of planets b, c, and d are unusually cloudy or have unusual cloud properties. Some studies have also found that the inferred radii of some or all of the planets disagree with expectations of standard giant planet evolution models. Here, we compare the available data to the predictions of our own set of atmospheric and evolution models that have been extensively tested against observations of field L and T dwarfs, including the reddest L dwarfs. Unlike some previous studies, we require mutually consistent choices for effective temperature, gravity, cloud properties, and planetary radius. This procedure thus yields plausible values for the masses, effective temperatures, and cloud properties of all three planets. We find that the cloud properties of the HR 8799 planets are not unusual but rather follow previously recognized trends, including a gravity dependence on the temperature of the L to T spectral transition-some reasons for which we discuss. We find that the inferred mass of planet b is highly sensitive to whether or not we include the H- and the K-band spectrum in our analysis. Solutions for planets c and d are consistent with the generally accepted constraints on the age of the primary star and orbital dynamics. We also confirm that, like in L and T dwarfs and solar system giant planets, non-equilibrium chemistry driven by atmospheric mixing is also important for these objects. Given the preponderance of data suggesting that the L to T spectral type transition is gravity dependent, we present an exploratory evolution calculation that accounts for this effect. Finally we recompute the bolometric luminosity of all three planets.

  3. Global Precipitation Analyses at Monthly to 3-HR Time Scales

    NASA Technical Reports Server (NTRS)

    Adler, Robert F.; Huffman, George; Curtis, Scott; Bolvin, David; Nelkin, Eric

    2002-01-01

    Global precipitation analysis covering the last few decades and the impact of the new TRMM precipitation observations are discussed. The 20+ year, monthly, globally complete precipitation analysis of the World Climate Research Program's (WCRP/GEWEX) Global Precipitation Climatology Project (GPCP) is used to explore global and regional variations and trends and is compared to the much shorter TRMM(Tropica1 Rainfall Measuring Mission) tropical data set. A trend pattern that is a combination of both El Nino and La Nina precipitation features is evident in the 20-year data set. This pattern is related to an increase with time in the number of combined months of El Nino and La Nina during the 20 year period. Monthly anomalies of precipitation are related to ENSO variations with clear signals extending into middle and high latitudes of both hemispheres. The GPCP daily, 1deg latitude-longitude analysis, which is available from January 1997 to the present is described and the evolution of precipitation patterns on this time scale related to El Nino and La Nina is described. Finally, a TRMM-based 3-hr analysis is described that uses TRMM to calibrate polar-orbit microwave observations from SSM/I and geosynchronous IR observations and merges the various calibrated observations into a final, 3-hr resolution map. This TRMM standard product will soon be available for the entire TRMM period (January 1998- present). A real-time version of this merged product is being produced and is available at 0.25deg latitude-longitude resolution over the latitude range from 50degN-50degS. Images from this data set can be seen at the U.S. TRMM web site (trmm.gsfc.nasa.gov). Examples will be shown, including its use in monitoring flood conditions and relating weather-scale events to climate variations.

  4. [Evaluation of +Gz tolerance following simulation of 8-hr flight].

    PubMed

    Khomenko, M N; Bukhtiiarov, I V; Malashchuk, L S

    2005-01-01

    Tolerance of +Gz (head-pelvis) centrifugation of pilots was evaluated following simulation of a long flight on single-seat fighter. The experiment involved 5 test-subjects who were exposed to +Gz before and after simulated 8-hr flight with a growth gradient of 0.1 u/s without anti-g suits and muscles relaxed; in addition, limiting tolerance of intricate profile +Gz loads of 2.0 to 9.0 units with a growth gradient of 1.0 u/s of test-subjects in anti-g suits (AGS) with a change-over pressure valve in the peak mode using muscle straining and breathing maneuvers. To counteract the negative effects of extended flight, various seat configurations: with a back inclination at 30 degrees to the +Gz vector and changeable geometry with a back inclination at 55 degrees to the vector. The other counter-measures applied were cool air shower, suit ventilation, physical exercises, lower body massage with AGS, electrostimulation of the back and lumber region, profiling of the supporting and soft parts of the seat, and 30-s exposure to +5 Gz. Hemodynamic and respiration parameters as well as body temperature were measured in the course of 8 hrs of flight and during and shortly after centrifugation. According to the results of the investigation, seat inclination at 55 degrees to the +Gz vector and tested system of countermeasures prevent degradation of tolerance of large (9 u.) loads following 8-hr flight simulation with the use of the modern anti-g gear, PMID:16353624

  5. Employee Returns: Linking HR Performance Indicators to Business Strategy. IES Report 365.

    ERIC Educational Resources Information Center

    Carter, Alison; Robinson, Dilys

    This document is a practical guide that demonstrates how human resource (HR) professionals can use performance measurement to link HR to organizational strategy and business objectives, and thereby raise the profile of HR within their organization. The following are among the topics examined: (1) the strategic context of measurement (the role…

  6. Employee Returns: Linking HR Performance Indicators to Business Strategy. IES Report 365.

    ERIC Educational Resources Information Center

    Carter, Alison; Robinson, Dilys

    This document is a practical guide that demonstrates how human resource (HR) professionals can use performance measurement to link HR to organizational strategy and business objectives, and thereby raise the profile of HR within their organization. The following are among the topics examined: (1) the strategic context of measurement (the role…

  7. Morphology and molecular dynamics of hard ?-keratin under pressure by 1H and 13C solid-state NMR

    NASA Astrophysics Data System (ADS)

    Demco, Dan E.; Utiu, Lavinia; Tillmann, Walter; Blümich, Bernhard; Popescu, Crisan

    2011-06-01

    The effect of uniaxial pressure on phase composition, aminoacid side-chain and backbone dynamics, as well as rigid domain sizes of hard ?-keratin from human fingernail clippings was investigated by 1H solid-state and 13C cross-polarization MAS NMR spectroscopy. Proton spin-diffusion NMR experiments revealed that the rigid-domain sizes increased upon compression. The 13C carbonyl resonance components were shown to be very sensitive to the transition of ?-helices to ?-sheets induced by uniaxial compression. Carbon-13 longitudinal relaxation in the rotating frame showed dynamic heterogeneity of aminoacid residues especially during the ?-helix to ?-sheet transition.

  8. Chemical structures of pyridine extracts and residues of coals as indicated by solid state 13C NMR.

    NASA Astrophysics Data System (ADS)

    Erbatur, G.; Erbatur, O.; Davis, M. F.; Maciel, G. E.

    1984-03-01

    The pyridine extracts and the residues of four Turkish coals were investigated in the solid state by CP/MAS C-13 NMR. No systematic correlation was observed between the ranks of the coals and the aromaticities of the pyridine extracts. There were pronounced structural differences between the pyridine extracts and the corresponding parent fuels and these differences were most prominent in the lower rank coals. In general, the C-13 NMR spectra of the residues were quite similar to those of the corresponding parent fuels.

  9. Study of order and dynamics in liquid crystalline materials by carbon-13 and deuterium NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Xu, Jiadi

    This dissertation investigates the phase structures, molecular structures and diffusion motions in some recently discovered liquid crystals using 1D and 2D carbon-13 and deuterium NMR spectroscopy. Two classes of liquid crystals are involved: chiral rod-like liquid crystals and banana mesogens. Our investigations of these new materials were divided into five main sections. The ordering and structures of banana liquid crystals and chiral rod-like mesogens were extracted from solid-state 13C NMR experiments including Separated-Local-Field study based on Lee-Goldberg Cross-Polarization (LGCP-SLF) and temperature dependent chemical shifts. The principal values of CSA tensor were measured using Separation of Undistorted CSA Powder patterns by Effortless Recoupling (SUPER) experiment. Some ID and 2D pulse experiments were performed for the assignment of carbon peaks, such as Cross-Polarization Polarization-Inversion (CPPI), HECTOR and so on. The soliton-like distortion of the helicoidal structure in the chiral smectic C phase (SmC*) of 8BEF5 liquid crystal was observed by the angular dependent DNMR patterns, and quantitatively interpreted based on Landau theory. The distortion was induced by the NMR magnetic field. The phase structure and interlayer diffusion in anticlinic Sm C* phases (Sm C*A , Sm C*Fi1 and Sm C*Fi2 ) of 10B1M7 liquid crystal were measured using angular dependent DNMR lineshapes and echo intensities. This work represents the first study of ferrielectric smectic phases by means of NMR. Measurements of the interlayer diffusion in synclinic and anticlinic SmC* phases (SmC*, Sm C*Fi1 and Sm C*Fi2 ) of 10B1M7 were carried out using 2H NMR exchange experiments. The phase structures of anticlinic SmC* phases were also determined using the same technique. A 'deformed clock model' was found to be appropriate for these phases. Molecular structures and dynamics were investigated in an exotic B 2 phase of a banana liquid crystal Pbis11BB by means of CP-MAS 13C NMR, MAS 2D 13C NMR exchange and LGCP-SLF (with MAS) experiments. These experiments showed that the molecules have asymmetric conformation in the solid state and carry on much slower motions in solid and liquid states compared to banana molecules in the same homologous series.

  10. The mitochondrial outer membrane protein Mas22p is essential for protein import and viability of yeast.

    PubMed Central

    Lithgow, T; Junne, T; Suda, K; Gratzer, S; Schatz, G

    1994-01-01

    We have cloned the gene encoding the protein Mas22p, which spans the outer membrane of yeast mitochondria. Cells that completely lack Mas22p are inviable. The plasmid-borne MAS22 gene suppresses several defects resulting from the deletion of one or more of the mitochondrial protein import receptors. Defects of Mas20p-deficient cells are explained by the reduced level of Mas22p in these mutants. Mas22p has one acidic domain in the cytosol and a second acidic domain in the mitochondrial intermembrane space. We suggest that these domains of Mas22p on either side of the outer membrane function as a relay system for transferring the basic targeting sequences of precursor proteins into the mitochondria. Images PMID:7991567

  11. Technology Enhanced Learning for People with Intellectual Disabilities and Cerebral Paralysis: The MAS Platform

    NASA Astrophysics Data System (ADS)

    Colomo-Palacios, Ricardo; Paniagua-Martín, Fernando; García-Crespo, Ángel; Ruiz-Mezcua, Belén

    Education for students with disabilities now takes place in a wide range of settings, thus, including a wider range of assistive tools. As a result of this, one of the most interesting application domains of technology enhanced learning is related to the adoption of learning technologies and designs for people with disabilities. Following this unstoppable trend, this paper presents MAS, a software platform aimed to help people with severe intellectual disabilities and cerebral paralysis in their learning processes. MAS, as a technology enhanced learning platform, provides several tools that supports learning and monitoring for people with special needs, including adaptative games, data processing and monitoring tools. Installed in a special needs education institution in Madrid, Spain, MAS provides special educators with a tool that improved students education processes.

  12. Compact orthogonal NMR field sensor

    SciTech Connect

    Gerald, II, Rex E.; Rathke, Jerome W.

    2009-02-03

    A Compact Orthogonal Field Sensor for emitting two orthogonal electro-magnetic fields in a common space. More particularly, a replacement inductor for existing NMR (Nuclear Magnetic Resonance) sensors to allow for NMR imaging. The Compact Orthogonal Field Sensor has a conductive coil and a central conductor electrically connected in series. The central conductor is at least partially surrounded by the coil. The coil and central conductor are electrically or electro-magnetically connected to a device having a means for producing or inducing a current through the coil and central conductor. The Compact Orthogonal Field Sensor can be used in NMR imaging applications to determine the position and the associated NMR spectrum of a sample within the electro-magnetic field of the central conductor.

  13. Essential NMR for Scientists and Engineers

    NASA Astrophysics Data System (ADS)

    Blömich, Bernhard

    ESSENTIAL NMR is a set of lecture notes for scientists and engineers who want to brush up on their knowledge of NMR. This book is also a compendium for graduate and postgraduate students of physics and chemistry as well as for their teachers, covering all fields of NMR, i.e. NMR methodology and hardware, chemical analysis, 2D-spectroscopy, NMR imaging, flow NMR, and quality control NMR. The material, selected and organized for a one-semester course, is presented with pairs of pages addressing particular topics.

  14. Polarization transfer NMR imaging

    DOEpatents

    Sillerud, Laurel O.; van Hulsteyn, David B.

    1990-01-01

    A nuclear magnetic resonance (NMR) image is obtained with spatial information modulated by chemical information. The modulation is obtained through polarization transfer from a first element representing the desired chemical, or functional, information, which is covalently bonded and spin-spin coupled with a second element effective to provide the imaging data. First and second rf pulses are provided at first and second frequencies for exciting the imaging and functional elements, with imaging gradients applied therebetween to spatially separate the nuclei response for imaging. The second rf pulse is applied at a time after the first pulse which is the inverse of the spin coupling constant to select the transfer element nuclei which are spin coupled to the functional element nuclei for imaging. In a particular application, compounds such as glucose, lactate, or lactose, can be labeled with .sup.13 C and metabolic processes involving the compounds can be imaged with the sensitivity of .sup.1 H and the selectivity of .sup.13 C.

  15. "Decoupled" Proton NMR Spectra

    NASA Astrophysics Data System (ADS)

    Woodley, M.; Freeman, R.

    High-resolution proton NMR spectra are recorded in a new form where all resonances are singlets at the chemical-shift frequencies, with no spin-spin splittings. These "decoupled" proton spectra are derived from two-dimensional J spectra after real Fourier transformation (without frequency discrimination in F1) so that each spin multiplet lies along both the 45° and the 135° diagonal, forming a pattern similar to St. Andrew's cross, with C 4 symmetry. The chemical shifts are located by searching for these centers of symmetry with a postacquisition data-processing algorithm. This is designed to facilitate the separation of overlapping and interpenetrating spin multiplets. The method is illustrated with applications to the 400 MHz high-resolution proton spectra of dehydrotestosterone and 4-androsten-3,17-dione. It is also possible to separate the spectra of components in a mixture and this is illustrated by breaking down the spectrum of an aqueous solution of D-glucose into subspectra from the α and β anomers, in order to follow the time evolution of the mutarotation.

  16. Multispectral Analysis of NMR Imagery

    NASA Technical Reports Server (NTRS)

    Butterfield, R. L.; Vannier, M. W. And Associates; Jordan, D.

    1985-01-01

    Conference paper discusses initial efforts to adapt multispectral satellite-image analysis to nuclear magnetic resonance (NMR) scans of human body. Flexibility of these techniques makes it possible to present NMR data in variety of formats, including pseudocolor composite images of pathological internal features. Techniques do not have to be greatly modified from form in which used to produce satellite maps of such Earth features as water, rock, or foliage.

  17. NMR characterization of thin films

    SciTech Connect

    Gerald II, Rex E.; Klingler, Robert J.; Rathke, Jerome W.; Diaz, Rocio; Vukovic, Lela

    2010-06-15

    A method, apparatus, and system for characterizing thin film materials. The method, apparatus, and system includes a container for receiving a starting material, applying a gravitational force, a magnetic force, and an electric force or combinations thereof to at least the starting material, forming a thin film material, sensing an NMR signal from the thin film material and analyzing the NMR signal to characterize the thin film of material.

  18. NMR characterization of thin films

    SciTech Connect

    Gerald, II, Rex E.; Klingler, Robert J.; Rathke, Jerome W.; Diaz, Rocio; Vukovic, Lela

    2008-11-25

    A method, apparatus, and system for characterizing thin film materials. The method, apparatus, and system includes a container for receiving a starting material, applying a gravitational force, a magnetic force, and an electric force or combinations thereof to at least the starting material, forming a thin film material, sensing an NMR signal from the thin film material and analyzing the NMR signal to characterize the thin film of material.

  19. Optical pumping and xenon NMR

    SciTech Connect

    Raftery, M.D.

    1991-11-01

    Nuclear Magnetic Resonance (NMR) spectroscopy of xenon has become an important tool for investigating a wide variety of materials, especially those with high surface area. The sensitivity of its chemical shift to environment, and its chemical inertness and adsorption properties make xenon a particularly useful NMR probe. This work discusses the application of optical pumping to enhance the sensitivity of xenon NMR experiments, thereby allowing them to be used in the study of systems with lower surface area. A novel method of optically-pumping {sup 129}Xe in low magnetic field below an NMR spectrometer and subsequent transfer of the gas to high magnetic field is described. NMR studies of the highly polarized gas adsorbed onto powdered samples with low to moderate surface areas are now possible. For instance, NMR studies of optically-pumped xenon adsorbed onto polyacrylic acid show that xenon has a large interaction with the surface. By modeling the low temperature data in terms of a sticking probability and the gas phase xenon-xenon interaction, the diffusion coefficient for xenon at the surface of the polymer is determined. The sensitivity enhancement afforded by optical pumping also allows the NMR observation of xenon thin films frozen onto the inner surfaces of different sample cells. The geometry of the thin films results in interesting line shapes that are due to the bulk magnetic susceptibility of xenon. Experiments are also described that combine optical pumping with optical detection for high sensitivity in low magnetic field to observe the quadrupoler evolution of 131 Xe spins at the surface of the pumping cells. In cells with macroscopic asymmetry, a residual quadrupolar interaction causes a splitting in the {sup 131}Xe NMR frequencies in bare Pyrex glass cells and cells with added hydrogen.

  20. Optical pumping and xenon NMR

    SciTech Connect

    Raftery, M.D.

    1991-11-01

    Nuclear Magnetic Resonance (NMR) spectroscopy of xenon has become an important tool for investigating a wide variety of materials, especially those with high surface area. The sensitivity of its chemical shift to environment, and its chemical inertness and adsorption properties make xenon a particularly useful NMR probe. This work discusses the application of optical pumping to enhance the sensitivity of xenon NMR experiments, thereby allowing them to be used in the study of systems with lower surface area. A novel method of optically-pumping [sup 129]Xe in low magnetic field below an NMR spectrometer and subsequent transfer of the gas to high magnetic field is described. NMR studies of the highly polarized gas adsorbed onto powdered samples with low to moderate surface areas are now possible. For instance, NMR studies of optically-pumped xenon adsorbed onto polyacrylic acid show that xenon has a large interaction with the surface. By modeling the low temperature data in terms of a sticking probability and the gas phase xenon-xenon interaction, the diffusion coefficient for xenon at the surface of the polymer is determined. The sensitivity enhancement afforded by optical pumping also allows the NMR observation of xenon thin films frozen onto the inner surfaces of different sample cells. The geometry of the thin films results in interesting line shapes that are due to the bulk magnetic susceptibility of xenon. Experiments are also described that combine optical pumping with optical detection for high sensitivity in low magnetic field to observe the quadrupoler evolution of 131 Xe spins at the surface of the pumping cells. In cells with macroscopic asymmetry, a residual quadrupolar interaction causes a splitting in the [sup 131]Xe NMR frequencies in bare Pyrex glass cells and cells with added hydrogen.

  1. Gene expression profile of the skin in the 'hairpoor' (HrHp) mice by microarray analysis

    PubMed Central

    2010-01-01

    Background The transcriptional cofactor, Hairless (HR), acts as one of the key regulators of hair follicle cycling; the loss of function mutations is the cause of the expression of the hairless phenotype in humans and mice. Recently, we reported a new Hr mutant mouse called 'Hairpoor' (HrHp). These mutants harbor a gain of the function mutation, T403A, in the Hr gene. This confers the overexpression of HR and HrHp is an animal model of Marie Unna hereditary hypotrichosis in humans. In the present study, the expression profile of HrHp/HrHp skin was investigated using microarray analysis to identify genes whose expression was affected by the overexpression of HR. Results From 45,282 mouse probes, differential expressions in 43 (>2-fold), 306 (>1.5-fold), and 1861 genes (>1.2-fold) in skin from HrHp/HrHp mice were discovered and compared with skin from wild-type mice. Among the 1861 genes with a > 1.2-fold increase in expression, further analysis showed that the expression of eight genes known to have a close relationship with hair follicle development, ascertained by conducting real-time PCR on skin RNA produced during hair follicle morphogenesis (P0-P14), indicated that four genes, Wif1, Casp14, Krt71, and Sfrp1, showed a consistent expression pattern with respect to HR overexpression in vivo. Conclusion Wif1 and Casp14 were found to be upregulated, whereas Krt71 and Sfrp1 were downregulated in cells overexpressing HR in transient transfection experiments on keratinocytes, suggesting that HR may transcriptionally regulate these genes. Further studies are required to understand the mechanism of this regulation by the HR cofactor. PMID:21083932

  2. Using solution state NMR spectroscopy to probe NMR invisible gelators.

    PubMed

    Wallace, Matthew; Iggo, Jonathan A; Adams, Dave J

    2015-10-21

    Supramolecular hydrogels are formed via the self-assembly of gelator molecules upon application of a suitable trigger. The exact nature of this self-assembly process has been widely investigated as a practical understanding is vital for the informed design of these materials. Solution-state NMR spectroscopy is an excellent non-invasive tool to follow the self-assembly of supramolecular hydrogels. However, in most cases the self-assembled aggregates are silent by conventional (1)H NMR spectroscopy due to the low mobility of the constituent molecules, limiting NMR spectroscopy to following only the initial assembly step(s). Here, we present a new solution-state NMR spectroscopic method which allows the entire self-assembly process of a dipeptide gelator to be followed. This gelator forms transparent hydrogels by a multi-stage assembly process when the pH of an initially alkaline solution is lowered via the hydrolysis of glucono-?-lactone (GdL). Changes in the charge, hydrophobicity and relative arrangement of the supramolecular aggregates can be followed throughout the assembly process by measuring the residual quadrupolar couplings (RQCs) of various molecular probes (here, (14)NH4(+) and isopropanol-d8), along with the NMR relaxation rates of (23)Na(+). The initially-formed aggregates comprise negatively charged fibrils which gradually lose their charge and become increasingly hydrophobic as the pH falls, eventually resulting in a macroscopic contraction of the hydrogel. We also demonstrate that the in situ measurement of pH by NMR spectroscopy is both convenient and accurate, representing a useful tool for the characterisation of self-assembly processes by NMR. PMID:26313637

  3. Structural Analysis of Nanoscale Self-Assembled Discoidal Lipid Bilayers by Solid-State NMR Spectroscopy

    PubMed Central

    Li, Ying; Kijac, Aleksandra Z.; Sligar, Stephen G.; Rienstra, Chad M.

    2006-01-01

    Nanodiscs are an example of discoidal nanoscale self-assembled lipid/protein particles similar to nascent high-density lipoproteins, which reduce the risk of coronary artery disease. The major protein component of high-density lipoproteins is human apolipoprotein A-I, and the corresponding protein component of Nanodiscs is membrane scaffold protein 1 (MSP1), a 200-residue lipid-binding domain of human apolipoprotein A-I. Here we present magic-angle spinning (MAS) solid-state NMR studies of uniformly 13C,15N-labeled MSP1 in polyethylene glycol precipitated Nanodiscs. Two-dimensional MAS 13C-13C correlation spectra show excellent microscopic order of MSP1 in precipitated Nanodiscs. Secondary isotropic chemical shifts throughout the protein are consistent with a predominantly helical structure. Moreover, the backbone conformations of prolines derived from their 13C chemical shifts are consistent with the molecular belt model but not the picket fence model of lipid-bound MSP1. Overall comparison of experimental spectra and 13C chemical shifts predicted from several structural models also favors the belt model. Our study thus supports the belt model of Nanodisc structure and demonstrates the utility of MAS NMR to study the structure of high molecular weight lipid-protein complexes. PMID:16905610

  4. Masses, Radii, and Cloud Properties of the HR 8799 Planets

    NASA Technical Reports Server (NTRS)

    Marley, Mark S.; Saumon, Didier; Cushing, Michael; Ackerman, Andrew S.; Fortney, Jonathan J.; Freedman, Richard

    2012-01-01

    The near-infrared colors of the planets directly imaged around the A star HR 8799 are much redder than most field brown dwarfs of the same effective temperature. Previous theoretical studies of these objects have compared the photometric and limited spectral data of the planets to the predictions of various atmosphere and evolution models and concluded that the atmospheres of planets b, c, and d are unusually cloudy or have unusual cloud properties. Most studies have also found that the inferred radii of some or all of the planets disagree with expectations of standard giant planet evolution models. Here we compare the available data to the predictions of our own set of atmospheric and evolution models that have been extensively tested against field L and T dwarfs, including the reddest L dwarfs. Unlike almost all previous studies we specify mutually self-consistent choices for effective temperature, gravity, cloud properties, and planetary radius. This procedure yields plausible and self-consistent values for the masses, effective temperatures, and cloud properties of all three planets. We find that the cloud properties of the HR 8799 planets are in fact not unusual but rather follow previously recognized trends including a gravity dependence on the temperature of the L to T spectral transition, some reasons for which we discuss. We find that the inferred mass of planet b is highly sensitive to the H and K band spectrum. Solutions for planets c and particularly d are less certain but are consistent with the generally accepted constraints on the age of the primary star and orbital dynamics. We also confirm that as for L and T dwarfs and solar system giant planets, non-equilibrium chemistry driven by atmospheric mixing is also important for these objects. Given the preponderance of data suggesting that the L to T spectral type transition is gravity dependent, we present a new evolution calculation that predicts cooling tracks on the near-infrared color-magnitude diagram. Finally we argue that the range of uncertainty conventionally quoted for the bolometric luminosity of all three planets is too small.

  5. Solid-State NMR Characterization of Aluminum Oxide Nanofibers

    SciTech Connect

    Cross, Jennifer L.; Tuttle, Ricky W.; Ramsier, Rex D.; Espe, Mathew

    2006-07-24

    Aluminum oxide nanofibers have been generated by an electrospinning process, creating fibers with diameters on the nanometer scale and aspect ratios greater than a thousand. These nanofibers have the potential of providing enhanced catalytic properties, due to their large surface area and controllable compositions. Solid-state NMR is being used to investigate both the bulk and surface properties of these materials. 27Al NMR has shown that no chemistry occurs during the electrospinning process, even though potentials in excess of 20 kV are applied to the sample. Thermal treatment of the fibers to convert them to alumina results in the formation of different phases, with the phases identified by the relative populations of 4-, 5-, and 6-coordinate alumina sites. Heating to 525°C or 1200°C produces a species similar to the catalytically active gamma-phase or conversion of the nanofibers into the thermodynamically stable ?-alumina phase, respectively. 1H-27Al CP/MAS has shown that the ?-alumina phase has a low population of surface hydroxyls, whereas the “gamma-alumina” form has a much higher fraction of 5-coordinate sites, compared to materials synthesized by traditional techniques. Organophosphates are being used as molecular probes in the characterization of the nanofiber surfaces. 31P CP/MAS data has revealed the presence of mono-, bi- and tri-denate bound phosphate groups on the surface, with the onset of surface alumina dissolution with sample heating. The application of 1H-31P HETCOR shows that the three different types of bound organophosphates are intermixed, rather than there being separate domains for each type. 31P-27Al CP is also being used to distinguish the types of surface alumina sites bound to the phosphate species.

  6. Efficient design of multituned transmission line NMR probes: the electrical engineering approach.

    PubMed

    Frydel, J A; Krzystyniak, M; Pienkowski, D; Pietrzak, M; de Sousa Amadeu, N; Ratajczyk, T; Idzik, K; Gutmann, T; Tietze, D; Voigt, S; Fenn, A; Limbach, H H; Buntkowsky, G

    2011-01-01

    Transmission line-based multi-channel solid state NMR probes have many advantages regarding the cost of construction, number of RF-channels, and achievable RF-power levels. Nevertheless, these probes are only rarely employed in solid state-NMR-labs, mainly owing to the difficult experimental determination of the necessary RF-parameters. Here, the efficient design of multi-channel solid state MAS-NMR probes employing transmission line theory and modern techniques of electrical engineering is presented. As technical realization a five-channel ((1)H, (31)P, (13)C, (2)H and (15)N) probe for operation at 7 Tesla is described. This very cost efficient design goal is a multi port single coil transmission line probe based on the design developed by Schaefer and McKay. The electrical performance of the probe is determined by measuring of Scattering matrix parameters (S-parameters) in particular input/output ports. These parameters are compared to the calculated parameters of the design employing the S-matrix formalism. It is shown that the S-matrix formalism provides an excellent tool for examination of transmission line probes and thus the tool for a rational design of these probes. On the other hand, the resulting design provides excellent electrical performance. From a point of view of Nuclear Magnetic Resonance (NMR), calibration spectra of particular ports (channels) are of great importance. The estimation of the π/2 pulses length for all five NMR channels is presented. PMID:21316931

  7. The ABC exporter MsbA probed by solid state NMR – challenges and opportunities.

    PubMed

    Kaur, Hundeep; Lakatos, Andrea; Spadaccini, Roberta; Vogel, Ramona; Hoffmann, Christian; Becker-Baldus, Johanna; Ouari, Olivier; Tordo, Paul; Mchaourab, Hassane; Glaubitz, Clemens

    2015-09-01

    ATP binding cassette (ABC) transporters form a superfamily of integral membrane proteins involved in translocation of substrates across the membrane driven by ATP hydrolysis. Despite available crystal structures and extensive biochemical data, many open questions regarding their transport mechanisms remain. Therefore, there is a need to explore spectroscopic techniques such as solid state NMR in order to bridge the gap between structural and mechanistic data. In this study, we investigate the feasibility of using Escherichia coli MsbA as a model ABC transporter for solid state NMR studies. We show that optimised solubilisation and reconstitution procedures enable preparing stable and homogenous protein samples. Depending on the duration of solubilisation, MsbA can be obtained in either an apo- or in a native lipid A bound form. Building onto these optimisations, the first promising MAS-NMR spectra with narrow lines have been recorded. However, further sensitivity improvements are required so that complex NMR experiments can be recorded within a reasonable amount of time. We therefore demonstrate the usability of paramagnetic doping for rapid data acquisition and explore dynamic nuclear polarisation as a method for general signal enhancement. Our results demonstrate that solid state NMR provides an opportunity to address important biological questions related to complex mechanisms of ABC transporters. PMID:25849794

  8. A "special perspectives" issue: Recent achievements and new directions in biomolecular solid state NMR

    NASA Astrophysics Data System (ADS)

    Tycko, Robert

    2015-04-01

    Twenty years ago, applications of solid state nuclear magnetic resonance (NMR) methods to real problems involving biological systems or biological materials were few and far between. Starting in the 1980s, a small number of research groups had begun to explore the possibility of obtaining structural and dynamical information about peptides, proteins, and other biopolymers from solid state NMR spectra. Progress was initially slow due to the relatively primitive state of solid state NMR probes, spectrometers, sample preparation methods, and pulse sequence techniques, coupled with the small number of people contributing to this research area. By the early 1990s, with the advent of new ideas about pulse sequence techniques such as dipolar recoupling, improvements in techniques for orienting membrane proteins and in technology for magic-angle spinning (MAS), improvements in the capabilities of commercial NMR spectrometers, and general developments in multidimensional spectroscopy, it began to appear that biomolecular solid state NMR might have a viable future. It was not until 1993 that the annual number of publications in this area crept above twenty.

  9. Dynamic Nuclear Polarization enhanced NMR at 187 GHz/284 MHz using an Extended Interaction Klystron amplifier

    NASA Astrophysics Data System (ADS)

    Kemp, Thomas F.; Dannatt, Hugh R. W.; Barrow, Nathan S.; Watts, Anthony; Brown, Steven P.; Newton, Mark E.; Dupree, Ray

    2016-04-01

    A Dynamic Nuclear Polarisation (DNP) enhanced solid-state Magic Angle Spinning (MAS) NMR spectrometer which uses a 187 GHz (corresponding to 1H NMR frequency of 284 MHz) Extended Interaction Klystron (EIK) amplifier as the microwave source is briefly described. Its performance is demonstrated for a biomolecule (bacteriorhodopsin), a pharmaceutical, and surface functionalised silica. The EIK is very compact and easily incorporated into an existing spectrometer. The bandwidth of the amplifier is sufficient that it obviates the need for a sweepable magnetic field, once set, for all commonly used radicals. The variable power (CW or pulsed) output from the EIK is transmitted to the DNP-NMR probe using a quasi-optic system with a high power isolator and a corrugated waveguide which feeds the microwaves into the DNP-NMR probe. Curved mirrors inside the probe project the microwaves down the axis of the MAS rotor, giving a very efficient system such that maximum DNP enhancement is achieved with less than 3 W output from the microwave source. The DNP-NMR probe operates with a sample temperature down to 90 K whilst spinning at 8 kHz. Significant enhancements, in excess of 100 for bacteriorhodopsin in purple membrane (bR in PM), are shown along with spectra which are enhanced by ≈25 with respect to room temperature, for both the pharmaceutical furosemide and surface functionalised silica. These enhancements allow hitherto prohibitively time consuming experiments to be undertaken. The power at which the DNP enhancement in bR in PM saturates does not change significantly between 90 K and 170 K even though the enhancement drops by a factor of ≈11. As the DNP build up time decreases by a factor 3 over this temperature range, the reduction in T1n is presumably a significant contribution to the drop in enhancement.

  10. 93Nb NMR and DFT investigation of the polymorphs of NaNbO3.

    PubMed

    Johnston, Karen E; Griffin, John M; Walton, Richard I; Dawson, Daniel M; Lightfoot, Philip; Ashbrook, Sharon E

    2011-04-28

    Sodium niobate (NaNbO(3)) has a particularly complex phase diagram, with a series of phase transitions as a function of temperature and pressure, and even at room temperature a number of different structural variations have been suggested. Recent work has demonstrated that bulk powders of NaNbO(3), prepared using a variety of synthetic approaches, contain a mixture of perovskite phases; the commonly reported Pbcm phase and a second, polar phase tentatively identified as belonging to space group P2(1)ma. The two phases exhibit very similar (23)Na MAS NMR spectra, although high-resolution MQMAS spectra were able to distinguish between them. Here, we investigate whether different perovskite polymorphs can be distinguished and/or identified using a variety of (93)Nb NMR methods, including MAS, MQMAS and wideline experiments. We compare the experimental results obtained for these more common perovskite materials to those for the metastable ilmenite polymorph of NaNbO(3). Our experimental results are supported by first-principles calculations of NMR parameters using a planewave pseudopotential approach. The calculated NMR parameters appear very different for each of the phases investigated, but high forces on the atoms indicate many of the structural models derived from diffraction require optimisation of the atomic coordinates. After geometry optimisation, most of these perovskite phases exhibit very similar NMR parameters, in contrast to recent work where it was suggested that (93)Nb provides a useful tool for distinguishing NaNbO(3) polymorphs. Finally, we consider the origin of the quadrupolar coupling in these materials, and its dependence on the deviation from ideality of the NbO(6) octahedra. PMID:21423997

  11. An efficient method and device for transfer of semisolid materials into solid-state NMR spectroscopy rotors

    NASA Astrophysics Data System (ADS)

    Hisao, Grant S.; Harland, Michael A.; Brown, Robert A.; Berthold, Deborah A.; Wilson, Thomas E.; Rienstra, Chad M.

    2016-04-01

    The study of mass-limited biological samples by magic angle spinning (MAS) solid-state NMR spectroscopy critically relies upon the high-yield transfer of material from a biological preparation into the MAS rotor. This issue is particularly important for maintaining biological activity and hydration of semi-solid samples such as membrane proteins in lipid bilayers, pharmaceutical formulations, microcrystalline proteins and protein fibrils. Here we present protocols and designs for rotor-packing devices specifically suited for packing hydrated samples into Pencil-style 1.6 mm, 3.2 mm standard, and 3.2 mm limited speed MAS rotors. The devices are modular and therefore readily adaptable to other rotor and/or ultracentrifugation tube geometries.

  12. jsNMR: an embedded platform-independent NMR spectrum viewer.

    PubMed

    Vosegaard, Thomas

    2015-04-01

    jsNMR is a lightweight NMR spectrum viewer written in JavaScript/HyperText Markup Language (HTML), which provides a cross-platform spectrum visualizer that runs on all computer architectures including mobile devices. Experimental (and simulated) datasets are easily opened in jsNMR by (i) drag and drop on a jsNMR browser window, (ii) by preparing a jsNMR file from the jsNMR web site, or (iii) by mailing the raw data to the jsNMR web portal. jsNMR embeds the original data in the HTML file, so a jsNMR file is a self-transforming dataset that may be exported to various formats, e.g. comma-separated values. The main applications of jsNMR are to provide easy access to NMR data without the need for dedicated software installed and to provide the possibility to visualize NMR spectra on web sites. PMID:25641013

  13. Medical applications of NMR imaging and NMR spectroscopy with stable isotopes. Summary

    SciTech Connect

    Matwiyoff, N.A.

    1983-01-01

    The current status of NMR imaging and NMR spectroscopy are summarized. For the most part examples from the March 1983 Puerto Rico symposium are used to illustrate the utility of NMR in medicine. 18 refs., 5 figs.

  14. Resolving the Planetesimal Belt of HR 8799 with ALMA

    NASA Astrophysics Data System (ADS)

    Booth, Mark; Jordán, Andrés; Casassus, Simon; Hales, Antonio S.; Dent, William R. F.; Faramaz, Virginie; Matrà, Luca; Barkats, Denis; Brahm, Rafael; Cuadra, Jorge

    2016-03-01

    The star HR 8799 hosts one of the largest known debris discs and at least four giant planets. Previous observations have found evidence for a warm belt within the orbits of the planets, a cold planetesimal belt beyond their orbits and a halo of small grains. With the infrared data, it is hard to distinguish the planetesimal belt emission from that of the grains in the halo. With this in mind, the system has been observed with ALMA in band 6 (1.34 mm) using a compact array format. These observations allow the inner edge of the planetesimal belt to be resolved for the first time. A radial distribution of dust grains is fitted to the data using an MCMC method. The disc is best fit by a broad ring between 145^{+12}_{-12} AU and 429^{+37}_{-32} AU at an inclination of 40^{+5}_{-6}° and a position angle of 51^{+8}_{-8}°. A disc edge at ˜145 AU is too far out to be explained simply by interactions with planet b, requiring either a more complicated dynamical history or an extra planet beyond the orbit of planet b.

  15. HR 1362 - A test case for stellar dynamo theories

    NASA Technical Reports Server (NTRS)

    Strassmeier, Klaus G.; Hall, Douglas S.; Barksdale, William S.; Jusick, Anthony T.; Henry, Gregory W.

    1990-01-01

    An analysis of 11 yr of photometry of HR 1362 = EK Eri has shown a well-established photometric period of 335 days. This confirms an earlier period determination of about 310 days from 3 yr of APT data and is consistent with a new v sin i determination of 2 + or - 2 km/s. Recent Ca II H and K observations show moderately strong H and K emission lines at a flux level of log F prime (K) of about 6.5 ergs sq m/s. If the photometric period is interpreted as the rotation period, this surface flux is more than one order of magnitude larger than what can be expected from empirical activity versus rotation relationships. The spectrum and the U-B and B-V colors are consistent with a single G8 III-IV spectral classification, while the V-R and V-I values indicate a small color excess, typical of chromospherically active stars.

  16. Aquifer test plan for the 100-HR-3 Operable Unit

    SciTech Connect

    Swanson, L.C.; Hartman, M.J.

    1994-03-28

    This test plan directs hydrologic testing activities planned at three existing Comprehensive Environmental Response, Compensation, and Liability Act of 1980 (CERCLA) wells in the 100-HR-3 Operable Unit of the Hanford Site. Three additional wells will be installed near these existing wells and used as additional testing arid observation points during the field activities. Figure 1 shows the locations of the three test sites. A primary objective of the testing program is to provide more detailed hydraulic characterization information for the unconfined aquifer and targeted test sites than provided by the initial reconnaissance-level slug testing of Vukelich. A second objective is to evaluate the applicability of slug interference and dipole flow tests for detailed hydraulic characterization in an unconfined aquifer. This aquifer testing program will also be useful for substantiating hydraulic conductivities reported from previous slug tests and evaluating the effects of filter pack volume/configuration on slug test data. Vukelich recommended additional testing to address the latter two issues.

  17. Solid State Multinuclear NMR Studies of Relaxor Ferroelectrics

    NASA Astrophysics Data System (ADS)

    Zhou, Donghua; Hoatson, Gina; Fayon, Franck; Massiot, Dominique; Vold, Robert; Gan, Zhehong

    2001-11-01

    Multinuclear NMR has been used to investigate the local structure and cation disorder in solid solutions of (1-x) Pb(Mg1/3Nb2/3)O3: x Pb(Sc1/2Nb1/2)O3, as a function of concentration. Static, MAS, and 3QMAS spectra are presented for 93Nb and 45Sc at 7.0, 9.4, 14.0 and 19.6 Tesla. The 14 and 19.6 T 93Nb MAS lineshapes have been assigned to species with different numbers of Sc next nearest neighbours. It is necessary to include distributions of the electric field gradient parameters and dispersions in isotropic chemical shifts; these have been estimated from the data. The relative intensities of each spectral component are interpreted in terms of distributions of next nearest neighbor cations and the data strongly supports the Random Layer model. 7 T 207Pb 2D-PASS experiments show residual isotropic chemical shift dispersion reflecting the cation disorder. The anisotropic chemical shielding tensor elements are correlated with the isotropic chemical shifts: this is ascribed to more disordered PbO12 sites with increased covalency character of the PbO bond.

  18. Coherent and stochastic averaging in solid-state NMR

    NASA Astrophysics Data System (ADS)

    Nevzorov, Alexander A.

    2014-12-01

    A new approach for calculating solid-state NMR lineshapes of uniaxially rotating membrane proteins under the magic-angle spinning conditions is presented. The use of stochastic Liouville equation (SLE) allows one to account for both coherent sample rotation and stochastic motional averaging of the spherical dipolar powder patterns by uniaxial diffusion of the spin-bearing molecules. The method is illustrated via simulations of the dipolar powder patterns of rigid samples under the MAS conditions, as well as the recent method of rotational alignment in the presence of both MAS and rotational diffusion under the conditions of dipolar recoupling. It has been found that it is computationally more advantageous to employ direct integration over a spherical grid rather than to use a full angular basis set for the SLE solution. Accuracy estimates for the bond angles measured from the recoupled amide 1H-15N dipolar powder patterns have been obtained at various rotational diffusion coefficients. It has been shown that the rotational alignment method is applicable to membrane proteins approximated as cylinders with radii of approximately 20 Å, for which uniaxial rotational diffusion within the bilayer is sufficiently fast and exceeds the rate 2 × 105 s-1.

  19. NMR Imaging: Instrumentation and Techniques

    NASA Astrophysics Data System (ADS)

    Tingle, Jeremy Mark

    Available from UMI in association with The British Library. This thesis presents three original contributions to the field of Nuclear Magnetic Resonance (NMR): the experimental framework and analysis for the measurement of a new imaging parameter to describe perfusion; the measurement and analysis of magnetic field inhomogeneity and a practical correction system for their reduction; a novel system for the synchronous control of NMR experiments based on the microprogrammed concept. The thesis begins with an introduction to the theory of NMR. The application of NMR to imaging is also introduced with emphasis on the techniques which developed into those in common use today. Inaccurate determination of the traditional NMR parameters (T_1 and T_2 and the molecular diffusion coefficient) can be caused by non-diffusive fluid movement within the sample. The experimental basis for determining a new imaging parameter --the Perfusion coefficient--is presented. This provides a measure of forced isotropic fluid motion through an organ or tissue. The instrumentation required for conducting NMR experiments is described in order to introduce the contribution made in this area during this research: A sequence controller. The controller is based on the concept of microprogramming and enables completely synchronous output of 128 bits of data. The software for the generation and storage of control data and the regulation of the data to provide experimental control is microcomputer based. It affords precise and accurate regulation of the magnetic field gradients, the rf synthesizer and the spectrometer for spectroscopic and imaging applications. Fundamental to the science of NMR is the presence of a magnetic field. A detailed study of the analysis of magnetic field inhomogeneity in terms of spherical harmonics is presented. The field of a whole body imaging system with poor inhomogeneity was measured and analyzed to determine and describe the components of the inhomogeneity. Finally a description is given of the design and application of practical methods for reducing the dominant inhomogeneities.

  20. An Analysis of the Rise and Fall of the AA-MAS Policy

    ERIC Educational Resources Information Center

    Lazarus, Sheryl S.; Thurlow, Martha L.; Ysseldyke, James E.; Edwards, Lynn M.

    2015-01-01

    In 2005, to address concerns about students who might fall in the "gap" between the regular assessment and the alternate assessment based on alternate achievement standards (AA-AAS), the U.S. Department of Education announced that states could develop alternate assessments based on modified achievement standards (AA-MAS). This article…