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Sample records for simultaneous 31p-nmr spectroscopy

  1. Rapid assignment of solution 31P NMR spectra of large proteins by solid-state spectroscopy.

    PubMed

    Iuga, Adriana; Spoerner, Michael; Ader, Christian; Brunner, Eike; Kalbitzer, Hans Robert

    2006-07-21

    The application of the (31)P NMR spectroscopy to large proteins or protein complexes in solution is hampered by a relatively low intrinsic sensitivity coupled with large line widths. Therefore, the assignment of the phosphorus signals by two-dimensional NMR methods in solution is often extremely time consuming. In contrast, the quality of solid-state NMR spectra is not dependent on the molecular mass and the solubility of the protein. For the complex of Ras with the GTP-analogue GppCH(2)p we show solid-state (31)P NMR methods to be more sensitive by almost one order of magnitude than liquid-state NMR. Thus, solid-state NMR seems to be the method of choice for obtaining the resonance assignment of the phosphorus signals of protein complexes in solution. Experiments on Ras.GDP complexes show that the microcrystalline sample can be substituted by a precipitate of the sample and that unexpectedly the two structural states observed earlier in solution are present in crystals as well.

  2. Detoxification of organophosphorus pesticides and nerve agents through RSDL: efficacy evaluation by (31)P NMR spectroscopy.

    PubMed

    Elsinghorst, Paul W; Worek, Franz; Koller, Marianne

    2015-03-01

    Intoxication by organophosphorus compounds, especially by pesticides, poses a considerable risk to the affected individual. Countermeasures involve both medical intervention by means of antidotes as well as external decontamination to reduce the risk of dermal absorption. One of the few decontamination options available is Reactive Skin Decontamination Lotion (RSDL), which was originally developed for military use. Here, we present a (31)P NMR spectroscopy based methodology to evaluate the detoxification efficacy of RSDL with respect to a series of organophosphorus pesticides and nerve agents. Kinetic analysis of the obtained NMR data provided degradation half-lives proving that RSDL is also reasonably effective against organophosphorus pesticides. Unexpected observations of different RSDL degradation patterns are presented in view of its reported oximate-catalyzed mechanism of action.

  3. Detoxification of organophosphorus pesticides and nerve agents through RSDL: efficacy evaluation by (31)P NMR spectroscopy.

    PubMed

    Elsinghorst, Paul W; Worek, Franz; Koller, Marianne

    2015-03-01

    Intoxication by organophosphorus compounds, especially by pesticides, poses a considerable risk to the affected individual. Countermeasures involve both medical intervention by means of antidotes as well as external decontamination to reduce the risk of dermal absorption. One of the few decontamination options available is Reactive Skin Decontamination Lotion (RSDL), which was originally developed for military use. Here, we present a (31)P NMR spectroscopy based methodology to evaluate the detoxification efficacy of RSDL with respect to a series of organophosphorus pesticides and nerve agents. Kinetic analysis of the obtained NMR data provided degradation half-lives proving that RSDL is also reasonably effective against organophosphorus pesticides. Unexpected observations of different RSDL degradation patterns are presented in view of its reported oximate-catalyzed mechanism of action. PMID:25597861

  4. In vivo dephosphorylation of WR-2721 monitored by 31P NMR spectroscopy

    SciTech Connect

    Knizner, S.A.; Jacobs, A.J.; Lyon, R.C.; Swenberg, C.E.

    1986-01-01

    The in vivo dephosphorylation of the radioprotective agent S-2-(3-(aminopropylamino))ethylphosphorothioic acid (WR-2721) in male CD2F1 mice was measured by 31P NMR spectroscopy after i.p. injection. The disappearance of the WR-2721 phosphate NMR signal with time was concurrent with an increase and splitting of the inorganic phosphate NMR signal. The more acidic inorganic phosphate resonance is shown to be attributed to phosphate (inorganic phosphate) in the urine. Using regression first-order kinetic analysis of data, after i.p. injection of 600 mg/kg, the half-life of WR-2721 was determined to be 40.9 +/- 5.9 (S.D.) min (n = 10).

  5. 31P-NMR SPECTROSCOPY OF RAT LIVER DURING SIMPLE STORAGE OR CONTINUOUS HYPOTHERMIC PERFUSION1

    PubMed Central

    Rossaro, Lorenzo; Murase, Noriko; Caldwell, Cary; Farghali, Hassan; Casavilla, Adrian; Starzl, Thomas E.; Ho, Chien; Van Thiel, David H.

    2010-01-01

    SUMMARY The ATP content and intracellular pH (pHi)3 of isolated rat liver before, during, and after cold preservation in either UW-lactobionate (UW, n=10) or Euro-Collins (EC, n=8) solutions were monitored using phosphorus-31 nuclear magnetic resonance (31P-NMR) spectroscopy. The 31P-NMR spectra were obtained on a 4.7-Tesla system operating at 81 MHz. Fructose metabolism, liver enzyme release, O2 consumption, and rat survival after liver transplantation were also evaluated. During simple cold storage (SCS), the ATP level declined to undetectable levels with both preservation solutions while the pHi declined to approximately 7.0. In contrast, during continuous hypothermic perfusion (CHP), hepatic ATP levels remained measurable during the 24-hour EC preservation and actually increased significantly (p>0.01) during UW preservation. After reperfusion at 37°C with Krebs-lactate, the SCS livers treated with EC differed significantly from the UW livers in terms of their ATP and pHi as well as their response to a fructose challenge. In contrast, livers undergoing CHP demonstrated similar behaviors with both solutions. These results demonstrate an increase in the hepatic ATP content during CHP which occurs with UW but is not seen with EC. On the other hand, only livers that were simply stored with UW achieved significant survival after transplant, while CHP livers were affected by vascular damage as demonstrated by fatal thrombosis after transplant. These data suggest that ATP content is not the only determinant of good liver function although a system of hypothermic perfusion might further improve liver preservation efficacy should injury to vascular endothelium be avoided. PMID:1402332

  6. Chemical Characterization and Water Content Determination of Bio-Oils Obtained from Various Biomass Species using 31P NMR Spectroscopy

    SciTech Connect

    David, K.; Ben, H.; Muzzy, J.; Feik, C.; Iisa, K.; Ragauskas, A.

    2012-03-01

    Pyrolysis is a promising approach to utilize biomass for biofuels. One of the key challenges for this conversion is how to analyze complicated components in the pyrolysis oils. Water contents of pyrolysis oils are normally analyzed by Karl Fischer titration. The use of 2-chloro-4,4,5,5,-tetramethyl-1,3,2-dioxaphospholane followed by {sup 31}P NMR analysis has been used to quantitatively analyze the structure of hydroxyl groups in lignin and whole biomass. Results: {sup 31}P NMR analysis of pyrolysis oils is a novel technique to simultaneously characterize components and analyze water contents in pyrolysis oils produced from various biomasses. The water contents of various pyrolysis oils range from 16 to 40 wt%. The pyrolysis oils obtained from Loblolly pine had higher guaiacyl content, while that from oak had a higher syringyl content. Conclusion: The comparison with Karl Fischer titration shows that {sup 31}P NMR could also reliably be used to measure the water content of pyrolysis oils. Simultaneously with analysis of water content, quantitative characterization of hydroxyl groups, including aliphatic, C-5 substituted/syringyl, guaiacyl, p-hydroxyl phenyl and carboxylic hydroxyl groups, could also be provided by {sup 31}P NMR analysis.

  7. Analysis of monoglycerides, diglycerides, sterols, and free fatty acids in coconut (Cocos nucifera L.) oil by 31P NMR spectroscopy.

    PubMed

    Dayrit, Fabian M; Buenafe, Olivia Erin M; Chainani, Edward T; de Vera, Ian Mitchelle S

    2008-07-23

    Phosphorus-31 nuclear magnetic resonance spectroscopy ( (31)P NMR) was used to differentiate virgin coconut oil (VCO) from refined, bleached, deodorized coconut oil (RCO). Monoglycerides (MGs), diglycerides (DGs), sterols, and free fatty acids (FFAs) in VCO and RCO were converted into dioxaphospholane derivatives and analyzed by (31)P NMR. On the average, 1-MG was found to be higher in VCO (0.027%) than RCO (0.019%). 2-MG was not detected in any of the samples down to a detection limit of 0.014%. On the average, total DGs were lower in VCO (1.55%) than RCO (4.10%). When plotted in terms of the ratio [1,2-DG/total DGs] versus total DGs, VCO and RCO samples grouped separately. Total sterols were higher in VCO (0.096%) compared with RCO (0.032%), and the FFA content was 8 times higher in VCO than RCO (0.127% vs 0.015%). FFA determination by (31)P NMR and titration gave comparable results. Principal components analysis shows that the 1,2-DG, 1,3-DG, and FFAs are the most important parameters for differentiating VCO from RCO.

  8. On the noninvasive measurement of intracellular free magnesium by 31P NMR spectroscopy.

    PubMed

    Gupta, R K; Gupta, P; Yushok, W D; Rose, Z B

    1983-01-01

    We previously introduced a noninvasive measurement of the concentration of free Mg2+ in intact cells and tissues using 31P NMR. To resolve a controversy in the literature concerning the affinity of Mg2+ for ATP used in our procedure, the apparent dissociation constant of MgATP under simulated intracellular conditions has been determined by three independent magnetic resonance methods, including a newly developed combination procedure for determining this value at intracellular ATP levels. The new combination method, which utilizes 31P NMR to determine the degree of Mg2+ chelation of ATP and the dye antipyrylazo III for optical determination of free Mg2+, yielded a value of (50 +/- 10) microM for this apparent dissociation constant at pH 7.2 in the presence of 0.15 M K+ and 25 degrees C. We further show that hydroxyquinolines are not satisfactory indicators for optical determination of the Mg2+-nucleotide dissociation constant. From our determinations a low value of free Mg2+ (less than 1 mM) is established for all of the tissues studied, including perfused heart muscle, contrary to a recent report in the literature. Saturating human erythrocytes with Mg2+ results in an alpha- and beta-phosphorus resonance separation for intracellular ATP that is indistinguishable from that observed in a noncellular MgATP control under similar conditions, showing that MgATP resonances in this cell are unaffected by the cellular environment.

  9. In vivo 31P-NMR spectroscopy of right ventricle in pigs.

    PubMed

    Schwartz, G G; Steinman, S K; Weiner, M W; Matson, G B

    1992-06-01

    The energy metabolism of the right ventricle (RV) in vivo has been largely unexplored. The goal of this study was to develop and implement techniques for in vivo 31P nuclear magnetic resonance (NMR) spectroscopy of the RV free wall. A two-turn, crossover-design elliptical surface coil was constructed to provide high sensitivity across the thin RV wall but minimal sensitivity in the blood-filled RV cavity. In 36 open-chest, anesthetized pigs, 31P spectroscopy of the RV free wall was performed with this coil at a field strength of 2 Tesla. Spectra were obtained from 800 acquisitions in 24 min with an average signal-to-noise ratio of 13.2 for phosphocreatine (PCr). The PCr-to-ATP (PCr/ATP) ratio of porcine RV was 1.42 +/- 0.05 (mean +/- SE), uncorrected for saturation at a repetition time of 1.8 s. With the use of literature values of the time constant of longitudinal relaxation (T1) to correct for partial saturation, the RV PCr/ATP was estimated to lie between 1.7 and 2.3. Decreased RV PCr/ATP was observed during RV ischemia and pressure overload. Thus in vivo 31P spectroscopy of the RV is readily accomplished with an appropriate surface coil and can provide new information about RV energy metabolism. PMID:1621852

  10. 2D exchange 31P NMR spectroscopy of bacteriophage M13 and tobacco mosaic virus.

    PubMed Central

    Magusin, P C; Hemminga, M A

    1995-01-01

    Two-dimensional (2D) exchange 31P nuclear magnetic resonance spectroscopy is used to study the slow overall motion of the rod-shaped viruses M13 and tobacco mosaic virus in concentrated gels. Even for short mixing times, observed diagonal spectra differ remarkably from projection spectra and one-dimensional spectra. Our model readily explains this to be a consequence of the T2e anisotropy caused by slow overall rotation of the viruses about their length axis. 2D exchange spectra recorded for 30% (w/w) tobacco mosaic virus with mixing times < 1 s do not show any off-diagonal broadening, indicating that its overall motion occurs in the sub-Hz frequency range. In contrast, the exchange spectra obtained for 30% M13 show significant off-diagonal intensity for mixing times of 0.01 s and higher. A log-gaussian distribution around 25 Hz of overall diffusion coefficients mainly spread between 1 and 10(3) Hz faithfully reproduces the 2D exchange spectra of 30% M13 recorded at various mixing times in a consistent way. A small but notable change in diagonal spectra at increasing mixing time is not well accounted for by our model and is probably caused by 31P spin diffusion. PMID:7756532

  11. Hetergeneous tumour response to photodynamic therapy assessed by in vivo localised 31P NMR spectroscopy.

    PubMed Central

    Ceckler, T. L.; Gibson, S. L.; Kennedy, S. D.; Hill, R.; Bryant, R. G.

    1991-01-01

    Photodynamic therapy (PDT) is efficacious in the treatment of small malignant lesions when all cells in the tumour receive sufficient drug, oxygen and light to induce a photodynamic effect capable of complete cytotoxicity. In large tumours, only partial effectiveness is observed presumably because of insufficient light penetration into the tissue. The heterogeneity of the metabolic response in mammary tumours following PDT has been followed in vivo using localised phosphorus NMR spectroscopy. Alterations in nucleoside triphosphates (NTP), inorganic phosphate (Pi) and pH within localised regions of the tumour were monitored over 24-48 h following PDT irradiation of the tumour. Reduction of NTP and increases in Pi were observed at 4-6 h after PDT irradiation in all regions of treated tumours. The uppermost regions of the tumours (those nearest the skin surface and exposed to the greatest light fluence) displayed the greatest and most prolonged reduction of NTP and concomitant increase in Pi resulting in necrosis. The metabolite concentrations in tumour regions located towards the base of the tumour returned a near pre-treatment levels by 24-48 h after irradiation. The ability to follow heterogeneous metabolic responses in situ provides one means to assess the degree of metabolic inhibition which subsequently leads to tumour necrosis. Images Figure 4 PMID:1829953

  12. 31P NMR spectroscopy of hypertrophied rat heart: effect of graded global ischemia.

    PubMed

    Clarke, K; Sunn, N; Willis, R J

    1989-12-01

    To investigate the cause for the greater susceptibility of hypertrophied hearts to ischemic injury, we determined the interrelations of total work output, contractile function and energy metabolism in isolated, perfused normal and hypertrophied rat hearts subjected to graded global ischemia. Cardiac hypertrophy was induced by giving rats seven daily injections of either triiodothyronine (0.2 mg/kg) or isoproterenol (5 mg/kg). All hearts were perfused at an aortic pressure of 100 mmHg in the isovolumic mode in an NMR spectrometer (7.05 Tesla). Heart rate, developed pressure, and coronary flow were monitored simultaneously with changes in pH, creatine phosphate, ATP and inorganic phosphate. During pre-ischemic perfusion, the total work output (rate-pressure product) of hyperthyroid hearts was 28% higher than that of control hearts, whereas hearts from isoproterenol-treated animals showed no difference. However, when related to unit muscle mass, work was normal in hyperthyroid hearts and 26% lower after isoproterenol. Contractile function per unit myocardium (developed pressure/g wet weight) was lower in the hypertrophied hearts. ATP content was the same in all groups. Creatine phosphate decreased 41% after triiodothyronine and 25% after isoproterenol. Inorganic phosphate levels and intracellular pH were similar in control and isoproterenol-treated rat hearts, but were higher in the hyperthyroid rat hearts. The phosphorylation potential and the free energy change of ATP hydrolysis were lowered by hypertrophy, the levels correlating with the depressed contractile function. At each ischemic flow rate, both work and contractile function per unit myocardium were the same for all hearts, but the relations between flow and phosphorylation potential were different for each type of heart. Thus, at low flow rates, hypertrophied hearts perform the same amount of work and have the same contractile function as control hearts, but with abnormal changes in energy metabolism

  13. Organophosphates in agrogray soils with periodic water logging according to the data of 31P NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Kovalev, I. V.; Kovaleva, N. O.

    2011-01-01

    The composition of organic phosphorus compounds was studied using the 31P NMR spectroscopy method in agrogray soils with periodic water logging. The phosphorus content was determined by the specific difference between the hydrological and the redox regimes of these soils. The phosphorus of the organic compounds in the agrogray soils with contrasting water regimes is composed mostly of phosphoric monoesters and diesters, including nucleic and teichoic acids. The relative distribution of the monoesters and inorganic orthophosphates is shown depending on the climate and the soil's position in the relief. The area of the monoester peaks increases by two times and that of the mineral orthophosphate decreases by six times in the agro-gray soils of Bryansk opolie with an optimal regime of moistening and evaporation in comparison with the agro-gray gleyed soils of Kolomna opolie. As the degree of the soil hydromorphism in the sequence of deeply gleyed soils and gleyic soils increased, the portion of monoesters decreased. Favorable conditions for the microbial activity are formed in soils with a contrasting redox regime, and this is expressed in the accumulation of labile diesters. Inverse relationships were found between the distributions of the mono- and diesters in iron-manganic nodules and in the soils enclosing them; this was caused by the different mechanisms of the stabilization of the stable and labile phosphorus containing compounds. A high percentage of mineral orthophosphate in the nodules allows assuming the presence of chemisorbed orthophosphate ions in organomineral phosphate-metal-humus complexes. The transformation of iron-manganic nodules under the influence of drying demonstrates the more direct participation of microorganisms in the nodules' formation than the contribution of the physicochemical processes.

  14. Hydration behaviour of POPC/C(12)-Bet mixtures investigated by sorption gravimetry, (31)P NMR spectroscopy and X-ray diffraction.

    PubMed

    Pfeiffer, H; Weichert, H; Klose, G; Heremans, K

    2012-02-01

    The hydration behaviour of mixtures of the zwitterionic phospholipid 1-palmitoyl-2-oleolyl-sn-glycero-3-phosphocholine (POPC) and the zwitterionic surfactant N,N-dimethyl-N-dodecyl-betain (C(12)-Bet) was investigated by sorption gravimetry, solid-state (31)P NMR-spectroscopy and small angle X-ray diffraction (SAXD). Negative excess hydration (dehydration) was found for almost all hydration degrees investigated. This behaviour is explained by the formation of an inner salt between the dipoles of phospholipid and surfactant headgroups that show a reverse sequence of partial charges with respect to the hydrocarbon backbone. The formation of an inner-salt most probably reduces potential water binding sites. Moreover, NMR data suggest that the incorporation of the zwitterionic surfactant into the phospholipid membrane is correlated with reorientation of the phosphate axis towards the membrane director as well as with reduced lateral and wobbling diffusion. PMID:22285958

  15. Characterizing phosphorus speciation of Chesapeake Bay sediments using chemical extraction, 31P NMR, and X-ray absorption fine structure spectroscopy.

    PubMed

    Li, Wei; Joshi, Sunendra R; Hou, Guangjin; Burdige, David J; Sparks, Donald L; Jaisi, Deb P

    2015-01-01

    Nutrient contamination has been one of the lingering issues in the Chesapeake Bay because the bay restoration is complicated by temporally and seasonally variable nutrient sources and complex interaction between imported and regenerated nutrients. Differential reactivity of sedimentary phosphorus (P) pools in response to imposed biogeochemical conditions can record past sediment history and therefore a detailed sediment P speciation may provide information on P cycling particularly the stability of a P pool and the formation of one pool at the expense of another. This study examined sediment P speciation from three sites in the Chesapeake Bay: (i) a North site in the upstream bay, (ii) a middle site in the central bay dominated by seasonally hypoxic bottom water, and (iii) a South site at the bay-ocean boundary using a combination of sequential P extraction (SEDEX) and spectroscopic techniques, including (31)P NMR, P X-ray absorption near edge structure spectroscopy (XANES), and Fe extended X-ray absorption fine structure (EXAFS). Results from sequential P extraction reveal that sediment P is composed predominantly of ferric Fe-bound P and authigenic P, which was further confirmed by solid-state (31)P NMR, XANES, and EXAFS analyses. Additionally, solution (31)P NMR results show that the sediments from the middle site contain high amounts of organic P such as monoesters and diesters, compared to the other two sites, but that these compounds rapidly decrease with sediment depth indicating remineralized P could have precipitated as authigenic P. Fe EXAFS enabled to identify the changes in Fe mineral composition and P sinks in response to imposed redox condition in the middle site sediments. The presence of lepidocrocite, vermiculite, and Fe smectite in the middle site sediments indicates that some ferric Fe minerals can still be present along with pyrite and vivianite, and that ferric Fe-bound P pool can be a major P sink in anoxic sediments. These results provide

  16. Characterizing phosphorus speciation of Chesapeake Bay sediments using chemical extraction, 31P NMR, and X-ray absorption fine structure spectroscopy.

    PubMed

    Li, Wei; Joshi, Sunendra R; Hou, Guangjin; Burdige, David J; Sparks, Donald L; Jaisi, Deb P

    2015-01-01

    Nutrient contamination has been one of the lingering issues in the Chesapeake Bay because the bay restoration is complicated by temporally and seasonally variable nutrient sources and complex interaction between imported and regenerated nutrients. Differential reactivity of sedimentary phosphorus (P) pools in response to imposed biogeochemical conditions can record past sediment history and therefore a detailed sediment P speciation may provide information on P cycling particularly the stability of a P pool and the formation of one pool at the expense of another. This study examined sediment P speciation from three sites in the Chesapeake Bay: (i) a North site in the upstream bay, (ii) a middle site in the central bay dominated by seasonally hypoxic bottom water, and (iii) a South site at the bay-ocean boundary using a combination of sequential P extraction (SEDEX) and spectroscopic techniques, including (31)P NMR, P X-ray absorption near edge structure spectroscopy (XANES), and Fe extended X-ray absorption fine structure (EXAFS). Results from sequential P extraction reveal that sediment P is composed predominantly of ferric Fe-bound P and authigenic P, which was further confirmed by solid-state (31)P NMR, XANES, and EXAFS analyses. Additionally, solution (31)P NMR results show that the sediments from the middle site contain high amounts of organic P such as monoesters and diesters, compared to the other two sites, but that these compounds rapidly decrease with sediment depth indicating remineralized P could have precipitated as authigenic P. Fe EXAFS enabled to identify the changes in Fe mineral composition and P sinks in response to imposed redox condition in the middle site sediments. The presence of lepidocrocite, vermiculite, and Fe smectite in the middle site sediments indicates that some ferric Fe minerals can still be present along with pyrite and vivianite, and that ferric Fe-bound P pool can be a major P sink in anoxic sediments. These results provide

  17. Coal liquefaction process streams characterization and evaluation: Estimation of total phenol concentrations in coal liquefaction resids by {sup 31}P NMR spectroscopy

    SciTech Connect

    Mohan, J.T.; Verkade, J.G.

    1992-11-01

    In this study, Iowa State University researchers used {sub 31}P-tagged reagents to derivatize the labile hydrogen functional groups in the THF-soluble portion of 850{degrees}F{sup +} distillation resid materials and the THF-soluble portion of process oils derived from direct coal liquefaction.{sup 31}P-NMR was used to analyze the derivatized samples. NMR peak assignments can be made by comparison to model compounds similarly derivatized. Species can be quantified by integration of the NMR signals. Different {sup 31}P-NMR tagged reagents can be used to produce different degrees of peak resolution in the NMR spectrum. This, in turn, partially dictates the degree of speciation and/or quantification of species, or classes of compounds, that can be accomplished. Iowa State chose a {sup 31}P-tagged reagent (ClPOCMe{sub 2}CMe{sub 2}O) which was shown previously to be particularly useful in the derivatization of phenols. The derivatized samples all exhibited a small group of peaks attributed to amines and a broad group of peaks in the phenol region. The presence of paramagnetic species in the samples caused the NMR signals to broaden. Electron paramagnetic resonance (EPR) spectra confirmed the presence of paramagnetic organic free radicals in selected samples. Various methods were employed to process the NMR data. The complexity and broadness of the phenol peak, however, made speciation of the phenols impractical.

  18. Coal liquefaction process streams characterization and evaluation: Estimation of total phenol concentrations in coal liquefaction resids by [sup 31]P NMR spectroscopy

    SciTech Connect

    Mohan, J.T.; Verkade, J.G. )

    1992-11-01

    In this study, Iowa State University researchers used [sub 31]P-tagged reagents to derivatize the labile hydrogen functional groups in the THF-soluble portion of 850[degrees]F[sup +] distillation resid materials and the THF-soluble portion of process oils derived from direct coal liquefaction.[sup 31]P-NMR was used to analyze the derivatized samples. NMR peak assignments can be made by comparison to model compounds similarly derivatized. Species can be quantified by integration of the NMR signals. Different [sup 31]P-NMR tagged reagents can be used to produce different degrees of peak resolution in the NMR spectrum. This, in turn, partially dictates the degree of speciation and/or quantification of species, or classes of compounds, that can be accomplished. Iowa State chose a [sup 31]P-tagged reagent (ClPOCMe[sub 2]CMe[sub 2]O) which was shown previously to be particularly useful in the derivatization of phenols. The derivatized samples all exhibited a small group of peaks attributed to amines and a broad group of peaks in the phenol region. The presence of paramagnetic species in the samples caused the NMR signals to broaden. Electron paramagnetic resonance (EPR) spectra confirmed the presence of paramagnetic organic free radicals in selected samples. Various methods were employed to process the NMR data. The complexity and broadness of the phenol peak, however, made speciation of the phenols impractical.

  19. A 31P NMR spectroscopy study of Xenopus laevis heart perfused in vitro with creatinol-O-phosphate, phosphocreatine, adenosine triphosphate, fructose diphosphate and ouabain.

    PubMed

    Olsen, J I; Rossini, P; Schweizer, M P; Bernardi, M; Moretti, V; Re, L; Rossini, L

    1993-09-01

    Xenopus laevis heart was studied by 31P NMR using a 200 MHz proton spectrometer; hearts were perfused, at pH 7.35 and room temperature, with normal oxygenated or K(+)-enriched Ringer. Solution was later added with creatinol-O-phosphate (COP), phosphocreatine (PCr), adenosine triphosphate (ATP), fructose-1,6-diphosphate (FDP) and ouabain. NMR spectra of the heart show organic phosphomono- and phosphodi-esters, inorganic phosphate, PCr, overlapping alpha-ATP/ADP and gamma-ATP/beta-ADP, and beta-ATP signals. Their chemical shift positions and areas showed no significant changes in the course of 1.5 h perfusions with either solution, except in a few preparations, whether the heart was beating or reversibly arrested. While COP reduced the signals in beating hearts, the same spectra exhibited no consistent, substantial changes under PCr, ATP and FDP 1 to 10 mM, pH 7.35 perfusion with either solution, nor when ouabain mumol was added. The spectra are briefly discussed in comparison with those observed in the perfused heart of mammals (mostly rat), and particularly with those obtained in the frog (Rana temporaria) heart, both by analysing the bioenergetic equilibria on the basis of total tissue substrate levels measured in extracts of freeze-clamped tissue, and by evaluating cytochrome-b, flavin and pyridine nucleotide in vitro oxido-reduction read-outs in separate, similar experimental settings.

  20. Quantitative 31P NMR for Simultaneous Trace Analysis of Organophosphorus Pesticides in Aqueous Media Using the Stir Bar Sorptive Extraction Method

    NASA Astrophysics Data System (ADS)

    Ansari, S.; Talebpour, Z.; Molaabasi, F.; Bijanzadeh, H. R.; Khazaeli, S.

    2016-09-01

    The analysis of pesticides in water samples is of primary concern for quality control laboratories due to the toxicity of these compounds and their associated public health risk. A novel analytical method based on stir bar sorptive extraction (SBSE), followed by 31P quantitative nuclear magnetic resonance (31P QNMR), has been developed for simultaneously monitoring and determining four organophosphorus pesticides (OPPs) in aqueous media. The effects of factors on the extraction efficiency of OPPs were investigated using a Draper-Lin small composite design. An optimal sample volume of 4.2 mL, extraction time of 96 min, extraction temperature of 42°C, and desorption time of 11 min were obtained. The results showed reasonable linearity ranges for all pesticides with correlation coefficients greater than 0.9920. The limit of quantification (LOQ) ranged from 0.1 to 2.60 mg/L, and the recoveries of spiked river water samples were from 82 to 94% with relative standard deviation (RSD) values less than 4%. The results show that this method is simple, selective, rapid, and can be applied to other sample matrices.

  1. Catalytic mechanism of α-phosphate attack in dUTPase is revealed by X-ray crystallographic snapshots of distinct intermediates, 31P-NMR spectroscopy and reaction path modelling.

    PubMed

    Barabás, Orsolya; Németh, Veronika; Bodor, Andrea; Perczel, András; Rosta, Edina; Kele, Zoltán; Zagyva, Imre; Szabadka, Zoltán; Grolmusz, Vince I; Wilmanns, Matthias; Vértessy, Beáta G

    2013-12-01

    Enzymatic synthesis and hydrolysis of nucleoside phosphate compounds play a key role in various biological pathways, like signal transduction, DNA synthesis and metabolism. Although these processes have been studied extensively, numerous key issues regarding the chemical pathway and atomic movements remain open for many enzymatic reactions. Here, using the Mason-Pfizer monkey retrovirus dUTPase, we study the dUTPase-catalyzed hydrolysis of dUTP, an incorrect DNA building block, to elaborate the mechanistic details at high resolution. Combining mass spectrometry analysis of the dUTPase-catalyzed reaction carried out in and quantum mechanics/molecular mechanics (QM/MM) simulation, we show that the nucleophilic attack occurs at the α-phosphate site. Phosphorus-31 NMR spectroscopy ((31)P-NMR) analysis confirms the site of attack and shows the capability of dUTPase to cleave the dUTP analogue α,β-imido-dUTP, containing the imido linkage usually regarded to be non-hydrolyzable. We present numerous X-ray crystal structures of distinct dUTPase and nucleoside phosphate complexes, which report on the progress of the chemical reaction along the reaction coordinate. The presently used combination of diverse structural methods reveals details of the nucleophilic attack and identifies a novel enzyme-product complex structure. PMID:23982515

  2. Measurement of carbon flux through the MEP pathway for isoprenoid synthesis by (31)P-NMR spectroscopy after specific inhibition of 2-C-methyl-d-erythritol 2,4-cyclodiphosphate reductase. Effect of light and temperature.

    PubMed

    Mongélard, Gaëlle; Seemann, Myriam; Boisson, Anne-Marie; Rohmer, Michel; Bligny, Richard; Rivasseau, Corinne

    2011-08-01

    The methylerythritol 4-phosphate (MEP) and the mevalonate pathways are the unique synthesis routes for the precursors of all isoprenoids. An original mean to measure the carbon flux through the MEP pathway in plants is proposed by using cadmium as a total short-term inhibitor of 2-C-methyl-d-erythritol 2,4-cyclodiphosphate (MEcDP) reductase (GcpE) and measuring the accumulation rate of its substrate MEcDP by (31) P-NMR spectroscopy. The MEP pathway metabolic flux was determined in spinach (Spinacia oleracea), pea (Pisum sativum), Oregon grape (Mahonia aquifolium) and boxwood (Buxus sempervirens) leaves. In spinach, flux values were compared with the synthesis rate of major isoprenoids. The flux increases with light intensity (fourfold in the 200-1200 µmol m(-2) s(-1) PPFR range) and temperature (sevenfold in the 25-37 °C range). The relationship with the light and the temperature dependency of isoprenoid production downstream of the MEP pathway is discussed.

  3. Catalytic mechanism of α-phosphate attack in dUTPase is revealed by X-ray crystallographic snapshots of distinct intermediates, 31P-NMR spectroscopy and reaction path modelling

    PubMed Central

    Barabás, Orsolya; Németh, Veronika; Bodor, Andrea; Perczel, András; Rosta, Edina; Kele, Zoltán; Zagyva, Imre; Szabadka, Zoltán; Grolmusz, Vince I.; Wilmanns, Matthias; Vértessy, Beáta G.

    2013-01-01

    Enzymatic synthesis and hydrolysis of nucleoside phosphate compounds play a key role in various biological pathways, like signal transduction, DNA synthesis and metabolism. Although these processes have been studied extensively, numerous key issues regarding the chemical pathway and atomic movements remain open for many enzymatic reactions. Here, using the Mason–Pfizer monkey retrovirus dUTPase, we study the dUTPase-catalyzed hydrolysis of dUTP, an incorrect DNA building block, to elaborate the mechanistic details at high resolution. Combining mass spectrometry analysis of the dUTPase-catalyzed reaction carried out in and quantum mechanics/molecular mechanics (QM/MM) simulation, we show that the nucleophilic attack occurs at the α-phosphate site. Phosphorus-31 NMR spectroscopy (31P-NMR) analysis confirms the site of attack and shows the capability of dUTPase to cleave the dUTP analogue α,β-imido-dUTP, containing the imido linkage usually regarded to be non-hydrolyzable. We present numerous X-ray crystal structures of distinct dUTPase and nucleoside phosphate complexes, which report on the progress of the chemical reaction along the reaction coordinate. The presently used combination of diverse structural methods reveals details of the nucleophilic attack and identifies a novel enzyme–product complex structure. PMID:23982515

  4. Hepatic lipid profiling of deer mice fed ethanol using {sup 1}H and {sup 31}P NMR spectroscopy: A dose-dependent subchronic study

    SciTech Connect

    Fernando, Harshica; Bhopale, Kamlesh K.; Boor, Paul J.; Ansari, G.A. Shakeel; Kaphalia, Bhupendra S.

    2012-11-01

    Chronic alcohol abuse is a 2nd major cause of liver disease resulting in significant morbidity and mortality. Alcoholic liver disease (ALD) is characterized by a wide spectrum of pathologies starting from fat accumulation (steatosis) in early reversible stage to inflammation with or without fibrosis and cirrhosis in later irreversible stages. Previously, we reported significant steatosis in the livers of hepatic alcohol dehydrogenase (ADH)-deficient (ADH{sup −}) vs. hepatic ADH-normal (ADH{sup +}) deer mice fed 4% ethanol daily for 2 months [Bhopale et al., 2006, Alcohol 39, 179–188]. However, ADH{sup −} deer mice fed 4% ethanol also showed a significant mortality. Therefore, a dose-dependent study was conducted to understand the mechanism and identify lipid(s) involved in the development of ethanol-induced fatty liver. ADH{sup −} and ADH{sup +} deer mice fed 1, 2 or 3.5% ethanol daily for 2 months and fatty infiltration in the livers were evaluated by histology and by measuring dry weights of extracted lipids. Lipid metabolomic changes in extracted lipids were determined by proton ({sup 1}H) and {sup 31}phosphorus ({sup 31}P) nuclear magnetic resonance (NMR) spectroscopy. The NMR data was analyzed by hierarchical clustering (HC) and principle component analysis (PCA) for pattern recognition. Extensive vacuolization by histology and significantly increased dry weights of total lipids found only in the livers of ADH{sup −} deer mice fed 3.5% ethanol vs. pair-fed controls suggest a dose-dependent formation of fatty liver in ADH{sup −} deer mouse model. Analysis of NMR data of ADH{sup −} deer mice fed 3.5% ethanol vs. pair-fed controls shows increases for total cholesterol, esterified cholesterol, fatty acid methyl esters (FAMEs), triacylglycerides and unsaturation, and decreases for free cholesterol, phospholipids and allylic and diallylic protons. Certain classes of neutral lipids (cholesterol esters, fatty acyl chain (-COCH{sub 2}-) and FAMEs) were

  5. Identification by stopped-exchange solution /sup 31/P NMR spectroscopy of the stepwise formation of (AgL/sub n/)PF/sub 6/ (n = 1-4). Comparison of metal-phosphorus coupling constants for triphenylphosphine and 5-phenyldibenzophosphole

    SciTech Connect

    Alyea, E.C.; Malito, J.; Nelson, J.H.

    1987-12-16

    The coordination properties of 5-phenyldibenzophosphate (PhDBP) have been studied extensively. The stepwise formation of (L/sub n/Ag)/sup +/PF/sub 6//sup -/ (n = 1-4) for L = PhDBP and PhP/sub 3/ observed in situ by stopped-exchange solution /sup 31/P NMR spectroscopy is reported herein. The relative coordinating properties of PhDBP and PhP/sub 3/ are compared. 21 references, 1 figure, 2 tables.

  6. Comparison of phosphorus forms in three extracts of dairy feces by solution 31P NMR analysis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Using solution 31P NMR spectroscopy, we compared three extractants, deionized water, sodium acetate buffer (pH 5.0) with fresh sodium dithionite (NaAc-SD), and 0.25 M NaOH-0.05 M EDTA (NaOH-EDTA), for the profile of P compounds in two dairy fecal samples. Phosphorus extracted was 35% for water, and...

  7. Paramagnetic interactions in 31P NMR spectroscopy as a probe for short-range order/disorder of flux-grown rare earth element orthophosphate (monazite/xenotime) solid solutions

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

    Many models of inorganic solid solutions relevant to earth scientists start with the assumption of a completely random distribution of substitutional species. This is, in large part, due to the difficulty of obtaining robust experimental confirmation of short-range order/disorder using standard diffraction techniques that provide information about long-range order. Solid-state Nuclear Magnetic Resonance (NMR) spectroscopy has long been used in this capacity, as the technique is characteristically sensitive to variations in local atomic structure around specific NMR-active nuclei. NMR studies of geologically important inorganic materials have historically concentrated on diamagnetic systems in which the complicating effects of unpaired electrons from paramagnetic species (most ions of the transition metals or rare-earth elements) can be ignored. In these diamagnetic materials, variations in small-scale atomic structure in the solid state typically cause shifts in the frequencies of NMR peaks of up to a few tens of ppm. However, NMR spectroscopy is increasingly being applied to inorganic solid solutions in which one of the end members is paramagnetic. In many cases, this leads to the observation of parmagnetically-shifted peaks. Paramagnetic interactions can be much stronger than in ordinary diamagnetic materials and these peaks are typically shifted from tens to thousands of ppm. In this study we present the results of a 31P NMR investigation of a series 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 resonances were observed in the spectra of all samples shifted by up to -204 ppm due to the presence of paramagnetic Vn+, Ce3+, or Nd3+ in the diamagnetic host phase - either LaPO4 or YPO4. Analysis of the spectra and comparison to the crystal structures leads to the

  8. Phosphorus speciation by (31)P NMR spectroscopy in bracken (Pteridium aquilinum (L.) Kuhn) and bluebell (Hyacinthoides non-scripta (L.) Chouard ex Rothm.) dominated semi-natural upland soil.

    PubMed

    Ebuele, Victor O; Santoro, Anna; Thoss, Vera

    2016-10-01

    Access to P species is a driver for plant community composition based on nutrient acquisition. Here we investigated the distribution and accumulation of soil inorganic P (Pi) and organic P (Po) forms in a bracken and bluebell dominated upland soil for the period between bluebell above ground dominance until biomass is formed from half bluebells and half bracken. Chemical characterisation and (31)P Nuclear Magnetic Resonance spectroscopy was used to determine the organic and inorganic P species. Total P concentration in soils was 0.87gkg(-1), while in plants (above- and below-ground parts) total P ranged between 0.84-4.0gkg(-1) and 0.14-2.0gkg(-1) for bluebell and bracken, respectively. The P speciation in the plant samples was reflected in the surrounding soil. The main forms of inorganic P detected in the NaOH-EDTA soil extracts were orthophosphate (20.0-31.5%), pyrophosphate (0.6-2.5%) and polyphosphate (0.4-7.0%). Phytate (myo-IP6) was the most dominant organic P form (23.6-40.0%). Other major peaks were scyllo-IP6 and α- and β- glycerophosphate (glyP). In bluebells and bracken the main P form detected was orthophosphate ranging from (21.7-80.4%) and 68.5-81.1%, in above-ground and below-ground biomass, respectively. Other detected forms include α-glyP (4.5-14.4%) and β-glyP (0.9-7.7%) in bluebell, while in bracken they were detected only in stripe and blade in ranges of 2.5-5.5% and 4.4-9.6%, respectively. Pyrophosphate, polyphosphate, scyllo-IP6, phosphonates, found in soil samples, were not detected in any plant parts. In particular, the high abundance of phytate in the soil and in bluebell bulbs, may be related to a mechanism through which bluebells create a recalcitrant phosphorus store which form a key part of their adaptation to nutrient poor conditions.

  9. Inhibition mechanisms of Zn precipitation on aluminum oxide by glyphosate: a 31P NMR and Zn EXAFS study.

    PubMed

    Li, Wei; Wang, Yu-Jun; Zhu, Mengqiang; Fan, Ting-Ting; Zhou, Dong-Mei; Phillips, Brian L; Sparks, Donald L

    2013-05-01

    In this research, the effects of glyphosate (GPS) on Zn sorption/precipitation on γ-alumina were investigated using a batch technique, Zn K-edge EXAFS, and (31)P NMR spectroscopy. The EXAFS analysis revealed that, in the absence of glyphosate, Zn adsorbed on the aluminum oxide surface mainly as bidentate mononuclear surface complexes at pH 5.5, whereas Zn-Al layered double hydroxide (LDH) precipitates formed at pH 8.0. In the presence of glyphosate, the EXAFS spectra of Zn sorption samples at pH 5.5 and 8.0 were very similar, both of which demonstrated that Zn did not directly bind to the mineral surface but bonded with the carboxyl group of glyphosate. Formation of γ-alumina-GPS-Zn ternary surface complexes was further suggested by (31)P solid state NMR data which indicated the glyphosate binds to γ-alumina via a phosphonate group, bridging the mineral surface and Zn. Additionally, we showed the sequence of additional glyphosate and Zn can influence the sorption mechanism. At pH 8, Zn-Al LDH precipitates formed if Zn was added first, and no precipitates formed if glyphosate was added first or simultaneously with Zn. In contrast, at pH 5.5, only γ-alumina-GPS-Zn ternary surface complexes formed regardless of whether glyphosate or Zn was added first or both were added simultaneously. PMID:23550510

  10. Inhibition mechanisms of Zn precipitation on aluminum oxide by glyphosate: a 31P NMR and Zn EXAFS study.

    PubMed

    Li, Wei; Wang, Yu-Jun; Zhu, Mengqiang; Fan, Ting-Ting; Zhou, Dong-Mei; Phillips, Brian L; Sparks, Donald L

    2013-05-01

    In this research, the effects of glyphosate (GPS) on Zn sorption/precipitation on γ-alumina were investigated using a batch technique, Zn K-edge EXAFS, and (31)P NMR spectroscopy. The EXAFS analysis revealed that, in the absence of glyphosate, Zn adsorbed on the aluminum oxide surface mainly as bidentate mononuclear surface complexes at pH 5.5, whereas Zn-Al layered double hydroxide (LDH) precipitates formed at pH 8.0. In the presence of glyphosate, the EXAFS spectra of Zn sorption samples at pH 5.5 and 8.0 were very similar, both of which demonstrated that Zn did not directly bind to the mineral surface but bonded with the carboxyl group of glyphosate. Formation of γ-alumina-GPS-Zn ternary surface complexes was further suggested by (31)P solid state NMR data which indicated the glyphosate binds to γ-alumina via a phosphonate group, bridging the mineral surface and Zn. Additionally, we showed the sequence of additional glyphosate and Zn can influence the sorption mechanism. At pH 8, Zn-Al LDH precipitates formed if Zn was added first, and no precipitates formed if glyphosate was added first or simultaneously with Zn. In contrast, at pH 5.5, only γ-alumina-GPS-Zn ternary surface complexes formed regardless of whether glyphosate or Zn was added first or both were added simultaneously.

  11. Investigation of broad resonances in 31P NMR spectra of the human brain in vivo.

    PubMed

    McNamara, R; Arias-Mendoza, F; Brown, T R

    1994-08-01

    Broad resonances that lie underneath the familiar small molecule profile of in vivo 31P NMR spectra can make accurate spectral integration of these mobile phosphates difficult. The two major broad components are the phosphate contained in the hydroxyapatite in cranial bone and the phosphodiester moiety in partially mobile membrane phospholipids. They can be removed with post-acquisition processing but this results in distortion of lineshapes and intensities and interferes with accurate quantitation. We have employed an off-resonance saturation procedure to eliminate the bone resonance and isolate the signal from the membrane phospholipids by subtraction. Selective saturation of the phospholipid resonance increases the clarity of the sharp peaks downfield from the phosphocreatine peak. Selective saturation 3-D chemical shift imaging techniques were used to create a localized phospholipid profile of the entire brain simultaneously. Monitoring localized phospholipid concentration may be important in studying demyelinating diseases. PMID:7848814

  12. Degradation of black phosphorus: a real-time 31P NMR study

    NASA Astrophysics Data System (ADS)

    Wang, Yue; Yang, Bingchao; Wan, Bensong; Xi, Xuekui; Zeng, Zhongming; Liu, Enke; Wu, Guangheng; Liu, Zhongyuan; Wang, Wenhong

    2016-09-01

    In this work, degradation behaviors and mechanisms of black phosphorus (BP) crystals in air under ambient conditions were investigated by nuclear magnetic resonance spectroscopy. It has been found that the 31P NMR line intensity for BP decreases exponentially during aging even at the very first several hours, suggesting the origin of the degradation of transport properties. In addition to phosphoric acid, new phosphorous acid was also well resolved in the final aging products. Moreover, BP has been found to be stable in water without the presence of oxygen molecules. These findings are relevant for better understanding of degradation behaviors of BP upon aging and should be helpful for overcoming a barrier that might hamper progress toward applications of BP as a 2D material.

  13. (31)P NMR study of post mortem changes in pig muscle.

    PubMed

    Miri, A; Talmant, A; Renou, J P; Monin, G

    1992-01-01

    The rate and the extent of post mortem pH changes in pig muscle largely determine pork quality. Fast pH fall combined with low ultimate pH leads to pale soft exudative (PSE) meat; high ultimate pH leads to dark firm dry (DFD) meat. Post mortem metabolism was studied in pig muscle using(31)P NMR. Fifteen pigs, i.e. 7 Large White pigs and 8 Pietrain pigs, were used. Five pigs of each breed were slaughtered, taking care to minimize preslaughter stress. The other pigs (3 Large Whites and 2 Pietrains) were injected with 0·1 mg adrenaline per kg liveweight before slaughter, in order to increase meat ultimate pH. All the animals were killed by electronarcosis and exsanguination. Three of the adrenaline-treated pigs (1 Large White and 2 Pietrains) gave meat with ultimate pH above 6 (DFD meat). The pigs with normal muscle ultimate pH, i.e. 6 Large Whites and 6 Pietrains, had very variable rates of post mortem muscle metabolism (pH at 30 min after slaughter: 6·17-6·85 in Large Whites; 6·04-6·23 in Pietrains). The relationships between pH and ATP changes were similar in all pigs showing normal muscle ultimate pH, whereas ATP disappeared at a high pH value (on average pH 6·4) in pigs with high ultimate pH. The course of post mortem biochemical changes in a given animal could be predicted rather well by examination of a single(31)P NMR spectrum obtained around 30 min after death. At this time, muscle with a low rate of metabolism simultaneously showed medium to high pH, high ATP content (4-6·8 μmol/g) and rather low Pi content (6-14 μmol/g); muscle with a fast rate of metabolism (PSE-prone muscle) had low pH, low to medium ATP content (1·1-4 μmol/g) and generally high phosphomonoester (PME) content (9-23 μmol/g); muscle with high ultimate pH (DFD-prone muscle) had high pH, low PME content (4-8 μmol/g) and high Pi content (22-27 μmol/g).

  14. Compartmentation of Nucleotides in Corn Root Tips Studied by 31P-NMR and HPLC 1

    PubMed Central

    Hooks, Mark A.; Clark, Robert A.; Nieman, Richard H.; Roberts, Justin K. M.

    1989-01-01

    Corn (Zea mays L.) root tips were subjected to different conditions so that nucleotide levels varied over a wide range. Levels of nucleotides in corn root tips were measured using 31P nuclear magnetic resonance (NMR) spectroscopy and high performance liquid chromatography. Results indicate: (a) Similar amounts of NTP and sugar nucleotides were observed by in vivo NMR and in extracts. In contrast, a significant amount of NDP observed in root tip extracts was not detected by in vivo NMR. Thus, for a given sample, [NTP]/[NDP] ratios determined in vivo by 31P-NMR are always higher than ratios observed in extracts, deviating by ∼4-fold at the highest ratios. The NMR-invisible pool of NDP appeared quite metabolically inert, barely changing in size as total cell NDP changed. We conclude that NDP in corn root tips is compartmented with respect to NMR visibility, and that it is the NMR-visible pool which responds dynamically to metabolic state. The NMR-invisible NDP could either be immobilized (and so have broad, undetectable NMR signals), or be complexed with species that cause the chemical shift of NDP to change (so it does not contribute to the NMR signal of free NDP), or both. (b) 31P-NMR cannot distinguish between bases (A, U, C, and G) of nucleotides. HPLC analysis of root tip extracts showed that the relative amount of each base in the NTP and NDP pools was quite constant in the different samples. (c) In extracts, for each of the nonadenylate nucleotides, [NTP]/[NDP] was linearly proportional to [ATP]/[ADP], indicating near equilibrium in the nucleoside diphosphokinase (NDPK) reaction. However, the apparent equilibrium constants for the phosphorylation of GDP and UDP by ATP were significantly lower than 1, the true equilibrium constant for the NDPK reaction. Thus, for a given sample, [ATP]/[ADP] ∼ [CTP]/[CDP] > [UTP]/[UDP] > [GTP]/[GDP]. This result suggests that the different NDPs in corn root tips do not have equal access to NDPK. PMID:16666649

  15. Using 31P-NMR to investigate dynamics of soil phosphorus compounds in the Rothamsted Long Term Experiments

    NASA Astrophysics Data System (ADS)

    Blackwell, Martin; Turner, Ben; Granger, Steve; Hooper, Tony; Darch, Tegan; Hawkins, Jane; Yuan, Huimin; McGrath, Steve

    2015-04-01

    The technique of 31P-NMR spectroscopy has done more to advance the knowledge of phosphorus forms (especially organic phosphorus) in environmental samples than any other method. The technique has advanced such that specific compounds can be identified where previously only broad categories such as orthophosphate monoesters and diesters were distinguishable. The Soil Archive and Long Term Experiments at Rothamsted Research, UK, potentially provides an unequalled opportunity to use this technique to observe changes in soil phosphorus compounds with time and under different treatments, thereby enhancing our understanding of phosphorus cycling and use by plants. Some of the earliest work using this technique on soils was carried out by Hawkes et al. in 1984 and this used soils from two of the oldest Rothamsted Long Term Experiments, namely Highfield and Park Grass. Here we revisit the samples studied in this early work and reanalyse them using current methodology to demonstrate how the 31P-NMR technique has advanced. We also present results from a study on the phosphorus chemistry in soils along the Hoosfield acid strip (Rothamsted, UK), where a pH gradient from 3.7 to 7.8 occurs in a single soil with little variation in total phosphorus (mean ± standard deviation 399 ± 27 mg P kg-1). Soil pH was found to be an important factor in determining the proportion of phosphomonoesters and phosphodiesters in the soil organic phosphorus, although total organic phosphorus concentrations were a relatively consistent proportion of the total soil phosphorus (36 ± 2%) irrespective of soil pH. Key words. 31P-NMR, soil organic phosphorus, long term experiments, Hoosfield acid strip

  16. 31P NMR Kinetics Study of Cardiac Metabolism under Mild Hypoxia

    NASA Astrophysics Data System (ADS)

    Goudemant, J. F.; Elst, L. V.; Vanhaverbeke, Y.; Muller, R. N.

    The effects of mild hypoxia on the metabolic and mechanical functions of isovolumic perfused rat hearts have been studied. 31P NMR has been used to follow the metabolite concentrations as well as the intracellular pH. Additionally, the energy transfer through the creatine kinase reaction was estimated by the magnetization-transfer technique. The needs of myofibrillar energy and of mitochondrial ATP production have been assessed through mechanical activity and oxygen-consumption rate. It has been observed that mild hypoxia simultaneously impairs contractile and metabolic functions. The aerobic ATP production is maintained under these conditions while anaerobic energy metabolism seems accelerated. The accumulation of some metabolites (ADP and P i) and the decrease of creatine kinase forward flux ( Vfor) tend, however, to prove that ATP availability for myofibrils is lowered. The large aerobic energy production observed must therefore be explained by an energy wastage in the mitochondria. In spite of normal ATP concentration, a contractile dysfunction is observed and can be explained by the P i accumulation, which is known to impair the use of the myofibrillar ATP. Another hypothesis supported by the magnetization transfer experiments is the poor ATP availability resulting from the ATP wastage in the mitochondria and from the inefficient energy transport by the PCr-Cr shuttle.

  17. FTIR and {sup 31}P-NMR spectroscopic analyses of surface species in phosphate-catalyzed lactic acid conversion

    SciTech Connect

    Gunter, G.C.; Tam, M.S.; Miller, D.J.

    1996-11-01

    The surface species present on silica/alumina-supported sodium phosphates, active catalysts for the conversion of lactic acid to acrylic acid and 2,3-pentanedione, are examined by pre- and postreaction MAS {sup 31}P-NMR and FTIR spectroscopies. Species present following lactic acid conversion are identified by transmission FTIR of phosphates supported on silicon disks (as a model catalyst system) and verified by {sup 31}P-NMR and diffuse reflectance IR spectroscopy of actual catalysts used in reaction. Monosodium phosphate (NaH{sub 2}PO{sub 4}) condenses to a mixture of sodium polyphosphate (NaPO{sub 3}){sub n} and sodium trimetaphosphate (Na{sub 3}P{sub 3}O{sub 9}), which exhibit little catalytic activity for converting lactic acid to desired products. Disodium phosphate (Na{sub 2}HPO{sub 4}) condenses to tetrasodium pyrophosphate (Na{sub 4}P{sub 2}O{sub 7}), and proton transfer from lactic acid to pyrophosphate results in the formation of sodium lactate. Trisodium phosphate (Na{sub 3}PO{sub 4}) accepts a proton from lactic acid to form sodium lactate and disodium phosphate, which condenses to pyrophosphate. The presence of pyrophosphate and sodium lactate on supported disodium and trisodium phosphates explains their similar catalytic properties; the larger quantity of sodium lactate present on trisodium phosphate leads to higher conversions at lower temperatures. 40 refs., 14 figs., 2 tabs.

  18. Improvement of (31)P NMR spectral resolution by 8-hydroxyquinoline precipitation of paramagnetic Fe and Mn in environmental samples.

    PubMed

    Ding, Shiming; Xu, Di; Li, Bin; Fan, Chengxin; Zhang, Chaosheng

    2010-04-01

    Solution (31)P nuclear magnetic resonance (NMR) spectroscopy is currently the main method for the characterization of phosphorus (P) forms in environment samples. However, identification and quantification of P compounds may be hampered by poor resolution of spectra caused by paramagnetic Fe and Mn. In this study, a novel technique was developed to improve spectral resolution by removing paramagnetic Fe and Mn from alkaline extracts via 8-hydroxyquinoline (8-HOQ) precipitation. Batch experiments showed that both Fe and Mn were effectively removed by the precipitation at pH 9.0, with the removal efficiencies of 83-91% for Fe and 67-78% for Mn from the extracts of five different environmental samples, while little effect was found on concentration of total P. The (31)P NMR analysis of a model P solution showed that addition of 8-HOQ and its precipitation with metal ions did not alter P forms. Further analyses of the five extracts with (31)P NMR spectroscopy demonstrated that the 8-HOQ precipitation was an ideal method compared with the present postextraction techniques, such as bicarbonate dithionate (BD), EDTA and Chelex-100 treatments, by improving spectral resolution to a large extent with no detrimental effects on P forms. PMID:20201571

  19. Human in vivo phosphate metabolite imaging with 31P NMR.

    PubMed

    Bottomley, P A; Charles, H C; Roemer, P B; Flamig, D; Engeseth, H; Edelstein, W A; Mueller, O M

    1988-07-01

    Phosphorus (31P) spectroscopic images showing the distribution of high-energy phosphate metabolites in the human brain have been obtained at 1.5 T in scan times of 8.5 to 34 min at 27 and 64 cm3 spatial resolution using pulsed phase-encoding gradient magnetic fields and three-dimensional Fourier transform (3DFT) techniques. Data were acquired as free induction decays with a quadrature volume NMR detection coil of a truncated geometry designed to optimize the signal-to-noise ratio on the coil axis on the assumption that the sample noise represents the dominant noise source, and self-shielded magnetic field gradient coils to minimize eddy-current effects. The images permit comparison of metabolic data acquired simultaneously from different locations in the brain, as well as metabolite quantification by inclusion of a vial containing a standard of known 31P concentration in the image array. Values for the NMR visible adenosine triphosphate in three individuals were about 3 mM of tissue. The ratio of NMR detectable phosphocreatine to ATP in brain was 1.15 +/- 0.17 SD in these experiments. Potential sources of random and systematic error in these and other 31P measurements are identified.

  20. Synthesis and sup 31 P NMR spectroscopy of trinuclear, phosphido-bridged iridium and rhodium clusters. Crystal and molecular structures of (M sub 3 (. mu. -PPh sub 2 ) sub 3 (CO) sub n L sub 2 ) (M = Ir or Rh, n = 3, L sub 2 = bis(diphenylphosphino)methane: M = Ir, n = 5, L = t-BuNC)

    SciTech Connect

    Berry, D.E.; Browning, J.; Dehghan, K.; Dixon, K.R.; Meanwell, N.J.; Phillips, A.J. )

    1991-02-06

    Reaction of (Ir{sub 2}(cyclooctene){sub 4}Cl{sub 2}) with CO, NHEt{sub 2}, and PHPh{sub 2} provides a synthetic route to the trinuclear, phosphido-bridged iridium clusters (Ir{sub 3}({mu}-PPh{sub 2}){sub 3}(CO){sub n}L{sub 2}) (n = 3, L = CO or PPh{sub 3}, L{sub 2} = bis(diphenylphosphino)methane (dppm); n = 5, L = t-BuNC). The CO and PPh{sub 3} complexes are analogues of previously known rhodium derivatives, and rhodium analogues of the dppm and t-BuNC complexes are also reported. The crystal structure of both the Ir and Rh complexes was determined and are reported. The molecular structure was also determined. Complete analyses of the {sup 31}P NMR spectra of the prepared complexes are also reported.

  1. In vivo 31P NMR OSIRIS of bioenergetic changes in rabbit kidneys during and after ischaemia: effect of pretreatment with an indeno-indole compound.

    PubMed

    Sørensen, V; Jonsson, O; Pettersson, S; Scherstén, T; Soussi, B

    1998-04-01

    Changes in energy phosphates of rabbit kidneys subjected to ischaemia-reperfusion have been measured in vivo with volume selective 31P NMR spectroscopy. The effects of pretreatment with a new lipid peroxidation inhibitor (indeno-indol derivate--code name H290/51) on the bioenergetic changes were analysed. The left kidney was moved to a subcutaneous pocket to facilitate exact positioning over the surface coil. A 1H NMR image was acquired and a 3.5-mL cube selected for 31P NMR spectra. 31P NMR spectra were recorded before occlusion of the left renal artery, during 1 h of ischaemia and 2 hours of reperfusion. Ischaemia induced drastic changes in the levels of inorganic phosphates and ATP as well as intracellular acidosis. A normalization was observed during reperfusion. Two hours after reperfusion significantly higher values for beta-ATP/Pi and intracellular pH were recorded in the animals pretreated with H290/51. The present technique allows quantitative analyses of changes in kidney bioenergetics in vivo during different experimental conditions. The importance of ischaemia-reperfusion induced lipid peroxidation for mitochondrial function is emphasized.

  2. Detailed Chemical Composition of Condensed Tannins via Quantitative (31)P NMR and HSQC Analyses: Acacia catechu, Schinopsis balansae, and Acacia mearnsii.

    PubMed

    Crestini, Claudia; Lange, Heiko; Bianchetti, Giulia

    2016-09-23

    The chemical composition of Acacia catechu, Schinopsis balansae, and Acacia mearnsii proanthocyanidins has been determined using a novel analytical approach that rests on the concerted use of quantitative (31)P NMR and two-dimensional heteronuclear NMR spectroscopy. This approach has offered significant detailed information regarding the structure and purity of these complex and often elusive proanthocyanidins. More specifically, rings A, B, and C of their flavan-3-ol units show well-defined and resolved absorbance regions in both the quantitative (31)P NMR and HSQC spectra. By integrating each of these regions in the (31)P NMR spectra, it is possible to identify the oxygenation patterns of the flavan-3-ol units. At the same time it is possible to acquire a fingerprint of the proanthocyanidin sample and evaluate its purity via the HSQC information. This analytical approach is suitable for both the purified natural product proanthocyanidins and their commercial analogues. Overall, this effort demonstrates the power of the concerted use of these two NMR techniques for the structural elucidation of natural products containing labile hydroxy protons and a carbon framework that can be traced out via HSQC. PMID:27551744

  3. CD and 31P NMR studies of tachykinin and MSH neuropeptides in SDS and DPC micelles

    NASA Astrophysics Data System (ADS)

    Schneider, Sydney C.; Brown, Taylor C.; Gonzalez, Javier D.; Levonyak, Nicholas S.; Rush, Lydia A.; Cremeens, Matthew E.

    2016-02-01

    Secondary structural characteristics of substance P (SP), neurokinin A (NKA), neurokinin B (NKB), α-melanocyte stimulating hormone peptide (α-MSH), γ1-MSH, γ2-MSH, and melittin were evaluated with circular dichroism in phosphite buffer, DPC micelles, and SDS micelles. CD spectral properties of γ1-MSH and γ2-MSH as well as 31P NMR of DPC micelles with all the peptides are reported for the first time. Although, a trend in the neuropeptide/micelle CD data appears to show increased α-helix content for the tachykinin peptides (SP, NKA, NKB) and increased β-sheet content for the MSH peptides (α-MSH, γ1-MSH, γ2-MSH) with increasing peptide charge, the lack of perturbed 31P NMR signals for all neuropeptides could suggest that the reported antimicrobial activity of SP and α-MSH might not be related to a membrane disruption mode of action.

  4. 31P NMR investigations on the ferromagnetic quantum critical system YbNi4P2

    NASA Astrophysics Data System (ADS)

    Sarkar, R.; Khuntia, P.; Krellner, C.; Geibel, C.; Steglich, F.; Baenitz, M.

    2012-04-01

    We studied the heavy-fermion system YbNi4P2, which presents strong ferromagnetic correlations, using the local 31P NMR probe over a wide field (0.2-8.6 T) and temperature (1.8-200 K) range. The 31P NMR Knight shift provides the static spin susceptibility which tracks the bulk susceptibility whereas the spin-lattice relaxation rate 31(1/T1) provides information about the fluctuations of the Yb 4f moment. The Korringa law is valid over a wide range of temperature and field. The Korringa product 31(1/T1TK2S0)≪1 gives evidence for the presence of strong ferromagnetic correlations. A 31(1/T1T)˜T-3/4 behavior was found over two decades in temperature.

  5. Pyrolysis temperature affects phosphorus transformation in biochar: Chemical fractionation and (31)P NMR analysis.

    PubMed

    Xu, Gang; Zhang, You; Shao, Hongbo; Sun, Junna

    2016-11-01

    Phosphorus (P) recycling or reuse by pyrolyzing crop residue has recently elicited increased research interest. However, the effects of feedstock and pyrolysis conditions on P species have not been fully understood. Such knowledge is important in identifying the agronomic and environmental uses of biochar. Residues of three main Chinese agricultural crops and the biochars (produced at 300°C-600°C) derived from these crops were used to determine P transformations during pyrolysis. Hedley sequential fractionation and (31)P NMR analyses were used in the investigation. Our results showed that P transformation in biochar was significantly affected by pyrolysis temperature regardless of feedstock (Wheat straw, maize straw and peanut husk). Pyrolysis treatment transformed water soluble P into a labile (NaHCO3-Pi) or semi-labile pool (NaOH-Pi) and into a stable pool (Dil. HCl P and residual-P). At the same time, organic P was transformed into inorganic P fractions which was identified by the rapid decomposition of organic P detected with solution (31)P NMR. The P transformation during pyrolysis process suggested more stable P was formed at a higher pyrolysis temperature. This result was also evidenced by the presence of less soluble or stable P species, such as such as poly-P, crandallite (CaAl3(OH)5(PO4)2) and Wavellite (Al3(OH)3(PO4)2·5H2O), as detected by solid-state (31)P NMR in biochars formed at a higher pyrolysis temperature. Furthermore, a significant proportion of less soluble pyrophosphate was identified by solution (2%-35%) and solid-state (8%-53%) (31)P NMR, which was also responsible for the stable P forms at higher pyrolysis temperature although their solubility or stability requires further investigation. Results suggested that a relatively lower pyrolysis temperature retains P availability regardless of feedstock during pyrolysis process.

  6. Structure and motion of phospholipids in human plasma lipoproteins. A sup 31 P NMR study

    SciTech Connect

    Fenske, D.B.; Chana, R.S.; Parmar, Y.I.; Treleaven, W.D.; Cushley, R.J. )

    1990-04-24

    The structure and motion of phospholipids in human plasma lipoproteins have been studied by using {sup 31}P NMR. Lateral diffusion coefficients, D{sub T}, obtained from the viscosity dependence of the {sup 31}P NMR line widths, were obtained for very low density lipoprotein (VLDL), low-density lipoprotein (LDL), high-density lipoproteins (HDL{sub 2}, HDL{sub 3}), and egg PC/TO microemulsions at 25{degree}C, for VLDL at 40{degree}C, and for LDL at 45{degree}C. In order to prove the orientation and/or order of the phospholipid head-group, estimates of the residual chemical shift anistropy, {Delta}{sigma}, have been obtained for all the lipoproteins and the microemulsions from the viscosity and field dependence for the {sup 31}P NMR line widths. These results suggest differences in the orientation and/or ordering of the head-group in the HDLs. The dynamic behavior of the phosphate moiety in LDL and HDL{sub 3} has been obtained from the temperature dependence of the {sup 31}P spin-lattice relaxation rates. Values of the correlation time for phosphate group reorientation and the activation energy for the motion are nearly identical in LDL and HDL{sub 3} and are similar to values obtained for phospholipid bilayers. This argues against long-lived protein-lipid interactions being the source of either the slow diffusion in LDL or the altered head-group orientation in the HDLs.

  7. [sup 31]P NMR study of immobilized artificial membrane surfaces. Structure and dynamics of immobilized phospholipids

    SciTech Connect

    Qiu, X.; Pidgeon, C. )

    1993-11-25

    Chromatography surfaces were prepared by immobilizing a single-chain ether phospholipid at approximately a monolayer density on silica particles. The chromatography particles are denoted as [sup ether]IAM.PC[sup C10/C3], and they are stable to all solvents. The structure and dynamics of the interphase created by immobilizing phospholipids on silica particles were studied by [sup 31]P NMR methods. [sup ether]IAM.PC[sup C10/C3] spontaneously wets when suspended in both aqueous and organic solvents, and [sup 31]P NMR spectra were obtained in water, methanol, chloroform, acetonitrile, and acetone. [sup 31]P NMR spectra were subjected to line-shape analysis. From line-shape analysis, the correlation times for rapid internal motion ([tau]-PLL) and wobbling ([tau]-PRP) of the phospholipid headgroup were calculated for each solvent. Immobilized phospholipid headgroups comprising the IAM interfacial region undergo rapid reorientation similar to the case of the phospholipids forming liposome membranes with [tau]-PLL approximately 1 ns. Phospholipids in liposome membranes exhibit slower wobbling motion ([tau]-PRP approximately 1 ms) in the plane of the membrane. However, the immobilized phospholipids on [sup ether]IAM.PC[sup C10/C3] surfaces wobble with correlation times [tau]-PRP that depend on the solvent bathing the [sup ether]IAM.PC[sup C10/C3] surface. 41 refs., 9 figs., 2 tabs.

  8. Phospholipid composition of plasma and erythrocyte membranes in animal species by 31P NMR.

    PubMed

    Ferlazzo, Alida Maria; Bruschetta, Giuseppe; Di Pietro, Patrizia; Medica, Pietro; Notti, Anna; Rotondo, Enrico

    2011-12-01

    The aim of this study was to provide basal values of phospholipid (PL) composition in different animal species by 31P NMR analysis using detergents. This fast and accurate method allowed a quantitative analysis of PLs without any previous separation. Plasma and erythrocyte membrane PLs were investigated in mammals (pig, cow, horse). Moreover, for the first time, the composition of plasma PLs in avian (chicken and ostrich) was performed by 31P NMR. Significant qualitative and quantitative interspecies differences in plasma PL levels were found. Phosphatidilcholine (PC) and sphingomyelin (SPH) levels were significantly higher (P < 0.001) in chicken plasma than all the other species tested. In erythrocytes, cow PC and phosphatidylcholine diarachidoyl were significantly lower (P < 0.001) than for pigs and horses, whereas pig PC presented intermediate values among cows and horses. Inorganic phosphate and 2,3-diphosphoglycerate levels were also significantly different between the species under investigation. The [SPH/total PLs] molar ratios in erythrocytes confirmed interspecies differences in phospholipid composition while the PC/SPH molar ratios could be related to a distinct erythrocyte flexibility and aggregability. Diet and nutrition may contribute primarily to the interspecies differences in plasma PL amounts detected. Significant differences between chicken plasma PC and SPH levels and those of the other animal species could be ascribed to a fat metabolism specific to egg production.

  9. Synthesis of prostanoids; enantiomeric purity of alcohols by a /sup 31/P NMR technique

    SciTech Connect

    Penning, T.D.

    1985-01-01

    The enone, 2,2-diemthyl-3a..beta.., 6a..beta..-dihydro-4H-cyclopenta-1,3-dioxol-4-one, has been synthesized in six steps from cyclopentadiene, resolved using sulfoximine chemistry, and converted into (-)-prostaglandin E/sub 2/ methyl ester in three steps. Introduction of the optically pure omega side-chain using a conjugate addition of a stabilized organocopper reagent, followed by direct alkylation of the enolate with the ..cap alpha.. side-chain allylic iodide in the presence of hexamethylphosphoramide, afforded a trans, vicinally disubstituted cyclopentanone. Deprotection of the C-15 alcohol, followed by aluminum amalgam reduction of the C-10/oxygen bond, provided (-)-PGE/sub 2/ methyl ester in 47% overall yield from the enone. In an extension of previously described work, 2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide, prepared from l-ephedrine and thiophosphoryl chloride, was used to determine the enantiomeric excess of chiral alcohols in conjunction with /sup 31/P NMR. Chiral primary and secondary alcohols added quantitatively to the phospholidine to give diastereomers which could be analyzed by /sup 31/P NMR and HPLC. A number of other phosphorus heterocycles were also explored as potential chiral derivatizing reagents.

  10. Sediment depth attenuation of biogenic phosphorus compounds measured by 31P NMR.

    PubMed

    Ahlgren, Joakim; Tranvik, Lars; Gogoll, Adolf; Waldeback, Monica; Markides, Karin; Rydin, Emil

    2005-02-01

    Being a major cause of eutrophication and subsequent loss of water quality, the turnover of phosphorus (P) in lake sediments is in need of deeper understanding. A major part of the flux of P to eutrophic lake sediments is organically bound or of biogenic origin. This P is incorporated in a poorly described mixture of autochthonous and allochthonous sediment and forms the primary storage of P available for recycling to the water column, thus regulating lake trophic status. To identify and quantify biogenic sediment P and assess its lability, we analyzed sediment cores from Lake Erken, Sweden, using traditional P fractionation, and in parallel, NaOH extracts were analyzed using 31P NMR. The surface sediments contain orthophosphates (ortho-P) and pyrophosphates (pyro-P), as well as phosphate mono- and diesters. The first group of compounds to disappear with increased sediment depth is pyrophosphate, followed by a steady decline of the different ester compounds. Estimated half-life times of these compound groups are about 10 yr for pyrophosphate and 2 decades for mono- and diesters. Probably, these compounds will be mineralized to ortho-P and is thus potentially available for recycling to the water column, supporting further growth of phytoplankton. In conclusion, 31P NMR is a useful tool to asses the bioavailability of certain P compound groups, and the combination with traditional fractionation techniques makes quantification possible. PMID:15757351

  11. Phosphatidylinositol-specific phospholipase C from Bacillus cereus combines intrinsic phosphotransferase and cyclic phosphodiesterase activities: A sup 31 P NMR study

    SciTech Connect

    Shashidhar, M.S.; Kuppe, A. ); Volwerk, J.J.; Griffith, O.H.

    1990-09-04

    The inositol phosphate products formed during the cleavage of phosphatidylinositol by phosphatidylinositol-specific phospholipase C from Bacillus cereus were analyzed by {sup 31}P NMR. {sup 31}P NMR spectroscopy can distinguish between the inositol phosphate species and phosphatidylinositol. Chemical shift values (with reference to phosphoric acid) observed are {minus}0.41, 3.62, 4.45, and 16.30 ppm for phosphatidylinositol, myo-inositol 1-monophosphate, myo-inositol 2-monophosphate, and myo-inositol 1,2-cyclic monophosphate, respectively. It is shown that under a variety of experimental conditions this phospholipase C cleaves phosphatidylinositol via an intramolecular phosphotransfer reaction producing diacylglycerol and D-myo-inositol 1,2-cyclic monophosphate. The authors also report the new and unexpected observation that the phosphatidylinositol-specific phospholipase C from B. cereus is able to hydrolyze the inositol cyclic phosphate to form D-myo-inositol 1-monophosphate. The enzyme, therefore, possesses phosphotransferase and cyclic phosphodiesterase activities. The second reaction requires thousandfold higher enzyme concentrations to be observed by {sup 31}P NMR. This reaction was shown to be regiospecific in that only the 1-phosphate was produced and stereospecific in that only D-myo-inositol 1,2-cyclic monophosphate was hydrolyzed. Inhibition with a monoclonal antibody specific for the B.cereus phospholipase C showed that the cyclic phosphodiesterase activity is intrinsic to the bacterial enzyme. They propose a two-step mechanism for the phosphatidyl-inositol-specific phospholipase C from B. cereus involving sequential phosphotransferase and cyclic phosphodiesterase activities. This mechanism bears a resemblance to the well-known two-step mechanism of pancreatic ribonuclease, RNase A.

  12. CO2 induced acute respiratory acidosis and brain tissue intracellular pH: a 31P NMR study in swine.

    PubMed

    Martoft, L; Stødkilde-Jørgensen, H; Forslid, A; Pedersen, H D; Jørgensen, P F

    2003-07-01

    High concentration carbon dioxide (CO(2)) is used to promote pre-slaughter anaesthesia in swine and poultry, as well as short-lasting surgical anaesthesia and euthanasia in laboratory animals. Questions related to animal welfare have been raised, as CO(2) anaesthesia does not set in momentarily. Carbon dioxide promotes anaesthesia by lowering the intracellular pH in the brain cells, but the dynamics of the changes in response to a high concentration of CO(2) is not known. Based on (31)P NMR spectroscopy, we describe CO(2)-induced changes in intracellular pH in the brains of five pigs inhaling 90% CO(2) in ambient air for a period of 60 s, and compare the results to changes in arterial blood pH, P(CO2), O(2) saturation and HCO(3)(-) concentration. The intracellular pH paralleled the arterial pH and P(CO2) during inhalation of CO(2); and it is suggested that the acute reaction to CO(2) inhalation mainly reflects respiratory acidosis, and not metabolic regulation as for example transmembrane fluxes of H(+)/HCO(3)(-). The intracellular pH decreased to approximately 6.7 within the 60 s inhalation period, and the situation was metabolically reversible after the end of CO(2) inhalation. The fast decrease in intracellular pH supports the conclusion that high concentration CO(2) leads to anaesthesia soon after the start of inhalation. PMID:12869287

  13. Exploring new Routes for Identifying Phosphorus Species in Terrestrial and Aquatic Ecosystems with 31P NMR

    NASA Astrophysics Data System (ADS)

    Vestergren, Johan; Persson, Per; Sundman, Annelie; Ilstedt, Ulrik; Giesler, Reiner; Schleucher, Jürgen; Gröbner, Gerhard

    2014-05-01

    Phosphorus (P) is the primary growth-limiting nutrient in some of the world's biomes. Rock phosphate is a non-renewable resource and the major source of agricultural fertilizers. Predictions of P consumption indicate that rock phosphate mining may peak within 35 years, with severe impacts on worldwide food production1. Organic P compounds constitute a major fraction of soil P, but little is known about the dynamics and bioavailability of organic P species. Our aim is to develop new liquid and solid state 31P-NMR (nuclear magnetic resonance) techniques to identify P-species in water and soils; information required for correlating P speciation with plant and soil processes2, and eventually to improve P use. Soil organic P is frequently extracted using NaOH/EDTA, followed by characterization of the extract by solution 31P-NMR. However, the obtained NMR spectra usually have poor resolution due to line broadening caused by the presence of paramagnetic ions. Therefore, we successfully developed an approach to avoid paramagnetic line broadening by precipitation of metal sulfides. Sulfide precipitation dramatically reduces NMR line widths for soil extracts, without affecting P-composition. The resulting highly improved resolution allowed us to apply for the first time 2D 1H,31P-NMR methods to identify different P monoesters in spectral regions which are extremely crowded in 1D NMR spectra.3 By exploiting 2D 1H-31P NMR spectra of soil extracts we were able to unambiguously identify individual organic P species by combining 31P and 1H chemical shifts and coupling constants. This approach is even suitable for a structural characterization of unknown P-components and for tracing degradation pathways between diesters and monoesters3,4.Currently we apply our approach on boreal4 and tropical soils with focus on Burkina Faso. In addition we also monitor P-species in aqueos ecosystems. For this purpose stream water from the Krycklan catchment in northern Sweden5 has been used to

  14. In vivo 31P NMR Study of the Metabolism of Murine Mammary 16/C Adenocarcinoma and Its Response to Chemotherapy, X-Radiation, and Hyperthermia

    NASA Astrophysics Data System (ADS)

    Evanochko, W. T.; Ng, T. C.; Lilly, M. B.; Lawson, A. J.; Corbett, T. H.; Durant, J. R.; Glickson, J. D.

    1983-01-01

    31P NMR spectroscopy with surface coils has been used to monitor, in vivo, the phosphate metabolism of subcutaneously implanted mammary 16/C adenocarcinoma in C3H/He mice. This model tumor was studied during untreated tumor growth and after treatment with adriamycin, hyperthermia, and x-radiation. The mammary 16/C tumor exhibited a Gompertzian growth pattern. Levels of high-energy phosphate metabolites--phosphocreatine and ATP--decreased with increases in tumor mass. There was a concomitant increase in the level of Pi and a decrease in the apparent pH of the tumor. These spectral changes appear to reflect changes in tumor vascularization that accompany tumor growth, the tumor becoming progressively more hypoxic. Partial response of this tumor to chemotherapy with adriamycin was reflected in a small but measurable increase in the phosphocreatine resonance, a decrease in Pi, and a return of the intratumor pH to neutral. Hyperthermia resulted in progressive conversion of the 31P NMR spectrum to that of a dead tumor (high levels of Pi, small levels of residual sugar phosphates and pyridine dinucleotides, and acidic pH). X-irradiation (14.0 Gy) led to disappearance of the phosphocreatine peak within 15 min of treatment. Subsequently, this resonance grew back beyond its pretreatment level. As the tumor receded, its spectrum reflected the characteristics of aerobically metabolizing tissue (high levels of phosphocreatine and ATP and low levels of Pi and sugar phosphates).

  15. Modified Prony Method to Resolve and Quantify in Vivo31P NMR Spectra of Tumors

    NASA Astrophysics Data System (ADS)

    Barone, P.; Guidoni, L.; Ragona, R.; Viti, V.; Furman, E.; Degani, H.

    Prony's method, successfully used in processing NMR signals, performs poorly at low signal-to-noise ratios. To overcome this problem, a statistical approach has been adopted by using Prony's method as a sampling device from the distribution associated with the true spectrum. Specifically, Prony's method is applied for each regression order p and number of data points n, both considered in a suitable range, and the estimates of frequencies, amplitudes, and decay factors are pooled separately. A histogram of the pooled frequencies is computed and, looking at the histogram, a lower and an upper frequency bound for each line of interest is determined. All frequency estimates in each of the determined intervals as well as associated decay factors and amplitudes are considered to be independent normal variates. A mean value and a corresponding 95% confidence interval are computed for each parameter. 31P NMR signals from MCF7 human breast cancer cells, inoculated into athymic mice and which developed into tumors, have been processed with traditional methods and with this modified Prony's method. The main components of the phosphomonoester peak, namely those deriving from phosphorylcholine and phosphorylethanolamine, are always well resolved with this new approach and their relative amplitudes can be consequently evaluated. Peak intensities of these two signals show different behavior during treatment of tumors with the antiestrogenic drug tamoxifen. The results of this new approach are compared with those obtainable with traditional techniques.

  16. Activation of dehydrogenase activity and cardiac respiration: A sup 31 P-NMR study

    SciTech Connect

    Katz, L.A.; Koretsky, A.P.; Balaban, R.S. )

    1988-07-01

    {sup 31}P-NMR studies were performed to determine the tissue phosphate and oxygen consumption effects of known maneuvers on the activation of pyruvate dehydrogenase during work jumps in the perfused rat heart. In control studies of the glucose-perfused heart, work jumps, with pacing, resulted in a 32% increase in oxygen consumption ({dot char}Qo{sub 2}) from 1.72 {plus minus} 0.09 to 2.29 {plus minus} 0.12 mmol O{sub 2}{center dot}h{sup {minus}1}{center dot}g dry wt{sup {minus}1}. During this transition no significant change in the high energy phosphates were detected. In contrast, work jumps did cause changes in the phosphates when the activation of pyruvate dehydrogenase was blocked with 2.5 {mu}g of ruthenium red per milliliter or maximally stimulated with 11 mM pyruvate before the increase in work. The observed increase in {dot char}Qo{sub 2} and inorganic phosphate and calculated increase in ADP are consistent with these phosphates controlling mitochondrial respiration under these conditions. These results suggest that the activation of pyruvate dehydrogenase and/or other dehydrogenases may be an important step in the orchestration of work and {dot char}Qo{sub 2}.

  17. /sup 31/P NMR characterization of graded traumatic brain injury in rats

    SciTech Connect

    Vink, R.; McIntosh, T.K.; Yamakami, I.; Faden, A.I.

    1988-01-01

    Irreversible tissue injury following central nervous system trauma is believed to result from both mechanical disruption at the time of primary insult, and more delayed autodestructive processes. These delayed events are associated with various biochemical changes, including alterations in phosphate energy metabolism and intracellular pH. Using /sup 31/P NMR, we have monitored the changes in phosphorus energy metabolism and intracellular pH in a single hemisphere of the rat brain over an 8-h period following graded, traumatic, fluid percussion-induced brain injury. Following trauma the ratio of phosphocreatine to inorganic phosphate (PCr/Pi) declined in each injury group. This decline was transitory with low injury (1.0 +/- 0.5 atm), biphasic with moderate (2.1 +/- 0.4 atm) and high (3.9 +/- 0.9 atm) injury, and sustained following severe injury (5.9 +/- 0.7 atm). The initial PCr/Pi decline in the moderate and high injury groups was associated with intracellular acidosis; however, the second decline occurred in the absence of any pH changes. Alterations in ATP occurred only in severely injured animals and such changes were associated with marked acidosis and 100% mortality rate. After 4h, the posttraumatic PCr/Pi ratio correlated linearly with the severity of injury. We suggest that a reduced posttraumatic PCr/Pi ratio may be indicative of altered mitochondrial energy production and may predict a reduced capacity of the cell to recover from traumatic injury.

  18. Membrane interactions in small fast-tumbling bicelles as studied by 31P NMR.

    PubMed

    Bodor, Andrea; Kövér, Katalin E; Mäler, Lena

    2015-03-01

    Small fast-tumbling bicelles are ideal for studies of membrane interactions at molecular level; they allow analysis of lipid properties using solution-state NMR. In the present study we used 31P NMR relaxation to obtain detailed information on lipid head-group dynamics. We explored the effect of two topologically different membrane-interacting peptides on bicelles containing either dimyristoylphosphocholine (DMPC), or a mixture of DMPC and dimyristoylphosphoglycerol (DMPG), and dihexanoylphosphocholine (DHPC). KALP21 is a model transmembrane peptide, designed to span a DMPC bilayer and dynorphin B is a membrane surface active neuropeptide. KALP21 causes significant increase in bicelle size, as evidenced by both dynamic light scattering and 31P T2 relaxation measurements. The effect of dynorphin B on bicelle size is more modest, although significant effects on T2 relaxation are observed at higher temperatures. A comparison of 31P T1 values for the lipids with and without the peptides showed that dynorphin B has a greater effect on lipid head-group dynamics than KALP21, especially at elevated temperatures. From the field-dependence of T1 relaxation data, a correlation time describing the overall lipid motion was derived. Results indicate that the positively charged dynorphin B decreases the mobility of the lipid molecules--in particular for the negatively charged DMPG--while KALP21 has a more modest influence. Our results demonstrate that while a transmembrane peptide has severe effects on overall bilayer properties, the surface bound peptide has a more dramatic effect in reducing lipid head-group mobility. These observations may be of general importance for understanding peptide-membrane interactions. PMID:25497765

  19. A Wet-Lab Approach to Stereochemistry Using [superscript 31]P NMR Spectroscopy

    ERIC Educational Resources Information Center

    Fenton, Owen S.; Sculimbrene, Bianca R.

    2011-01-01

    Understanding stereochemistry is an important and difficult task for students to master in organic chemistry. In both introductory and advanced courses, students are encouraged to explore the spatial relationships between molecules, but this exploration is often limited either to the lecture hall or the confines of the library. As such, we sought…

  20. Dynamic phosphometabolomic profiling of human tissues and transgenic models by 18O-assisted 31P NMR and mass spectrometry

    PubMed Central

    Nemutlu, Emirhan; Zhang, Song; Gupta, Anu; Juranic, Nenad O.; Macura, Slobodan I.; Terzic, Andre; Jahangir, Arshad

    2012-01-01

    Next-generation screening of disease-related metabolomic phenotypes requires monitoring of both metabolite levels and turnover rates. Stable isotope 18O-assisted 31P nuclear magnetic resonance (NMR) and mass spectrometry uniquely allows simultaneous measurement of phosphometabolite levels and turnover rates in tissue and blood samples. The 18O labeling procedure is based on the incorporation of one 18O into Pi from [18O]H2O with each act of ATP hydrolysis and the distribution of 18O-labeled phosphoryls among phosphate-carrying molecules. This enables simultaneous recording of ATP synthesis and utilization, phosphotransfer fluxes through adenylate kinase, creatine kinase, and glycolytic pathways, as well as mitochondrial substrate shuttle, urea and Krebs cycle activity, glycogen turnover, and intracellular energetic communication. Application of expanded 18O-labeling procedures has revealed significant differences in the dynamics of G-6-P[18O] (glycolysis), G-3-P[18O] (substrate shuttle), and G-1-P[18O] (glycogenolysis) between human and rat atrial myocardium. In human atria, the turnover of G-3-P[18O], which defects are associated with the sudden death syndrome, was significantly higher indicating a greater importance of substrate shuttling to mitochondria. Phosphometabolomic profiling of transgenic hearts deficient in adenylate kinase (AK1−/−), which altered levels and mutations are associated to human diseases, revealed a stress-induced shift in metabolomic profile with increased CrP[18O] and decreased G-1-P[18O] metabolic dynamics. The metabolomic profile of creatine kinase M-CK/ScCKmit−/−-deficient hearts is characterized by a higher G-6-[18O]P turnover rate, G-6-P levels, glycolytic capacity, γ/β-phosphoryl of GTP[18O] turnover, as well as β-[18O]ATP and β-[18O]ADP turnover, indicating altered glycolytic, guanine nucleotide, and adenylate kinase metabolic flux. Thus, 18O-assisted gas chromatography-mass spectrometry and 31P NMR provide a suitable

  1. Characterization of different precursors and activated vanadium phosphate catalysts by [sup 31]P NMR spin echo mapping

    SciTech Connect

    Sananes, M.T. Univ. of Liverpool ); Tuel, A.; Volta, J.C. ); Hutchings, G.J. )

    1994-07-01

    In a previous publication, the authors emphasized the use of the spin echo mapping technique applied to [sup 31]P NMR to obtain information on the valence state of vanadium in different environments of phosphorus for several VPO reference structures. In this paper, the authors describe the use of this technique, combined with knowledge of reference phases, to study VPO catalysts prepared from different precursors and used for the oxidation of n-butane into maleic anhydride. 9 refs., 2 figs., 1 tab.

  2. Phytate degradation by lactic acid bacteria and yeasts during the wholemeal dough fermentation: a 31P NMR study.

    PubMed

    Reale, Anna; Mannina, Luisa; Tremonte, Patrizio; Sobolev, Anatoli P; Succi, Mariantonietta; Sorrentino, Elena; Coppola, Raffaele

    2004-10-01

    myo-Inositol hexaphosphate (IP6) is the main source of phosphorus in cereal grains, and therefore, in bakery products. Different microorganisms such as yeasts and lactic acid bacteria have phytase enzymes able to hydrolyze IP6 during the wholemeal breadmaking. In this paper, the phytase activity of Lactobacillus plantarum, Lactobacillus brevis, Lactobacillus curvatus, and Saccharomyces cerevisiae strains, isolated from southern Italian sourdoughs, is assayed using the (31)P NMR technique. The sourdough technology based on the use of lactic acid bacteria in the breadmaking is finally suggested.

  3. Interaction of antiaggregant molecule ajoene with membranes. An ESR and 1H, 2H, 31P-NMR study.

    PubMed

    Debouzy, J C; Neumann, J M; Hervé, M; Daveloose, D; Viret, J; Apitz-Castro, R

    1989-01-01

    The structure of ajoene, a molecule extracted from garlic, has been studied by 1H-NMR and its interaction with model membranes by 1H-, 2H-, 31-P-NMR and ESR experiments. This study clearly shows that the ajoene molecule is located deep in the layer and is close to the interlayer medium. Moreover while NMR experiments show that the membrane structure is only slightly affected by the presence of ajoene, ESR experiments reveal significant modifications in phospholipid dynamics. This interaction, observed before with the phenothiazine derivative, promazine, results in an increase of the membrane fluidity in its hydrophobic part and could be related to clinical properties of ajoene.

  4. Geographical characterization of greek virgin olive oils (cv. Koroneiki) using 1H and 31P NMR fingerprinting with canonical discriminant analysis and classification binary trees.

    PubMed

    Petrakis, Panos V; Agiomyrgianaki, Alexia; Christophoridou, Stella; Spyros, Apostolos; Dais, Photis

    2008-05-14

    This work deals with the prediction of the geographical origin of monovarietal virgin olive oil (cv. Koroneiki) samples from three regions of southern Greece, namely, Peloponnesus, Crete, and Zakynthos, and collected in five harvesting years (2001-2006). All samples were chemically analyzed by means of 1H and 31P NMR spectroscopy and characterized according to their content in fatty acids, phenolics, diacylglycerols, total free sterols, free acidity, and iodine number. Biostatistical analysis showed that the fruiting pattern of the olive tree complicates the geographical separation of oil samples and the selection of significant chemical compounds. In this way the inclusion of the harvesting year improved the classification of samples, but increased the dimensionality of the data. Discriminant analysis showed that the geographical prediction at the level of three regions is very high (87%) and becomes (74%) when we pass to the thinner level of six sites (Chania, Sitia, and Heraklion in Crete; Lakonia and Messinia in Peloponnesus; Zakynthos). The use of classification and binary trees made possible the construction of a geographical prediction algorithm for unknown samples in a self-improvement fashion, which can be readily extended to other varieties and areas.

  5. Interactions of glycerol monooleate and dimethylsulphoxide with phospholipids. A differential scanning calorimetry and 31P-NMR study.

    PubMed

    Tilcock, C P; Fisher, D

    1982-03-01

    1. A comparative study has been made of the effects of the fusogens glycerol monooleate and dimethyl-sulphoxide on the polymorphic phase behaviour of dipalmitoyl phosphatidylcholine and dipalmitoyl phosphatidylethanolamine by differential scanning calorimetry and 31P-NMR techniques. 2. Glycerol monooleate induces a reduction in the temperature, cooperativity and enthalpy of the gel to liquid-crystal transitions of dipalmitoyl phosphatidylcholine and dipalmitoyl phosphatidylethanolamine, whereas dimethylsulphoxide induces an increase in the temperature and enthalpy and a reduction in the cooperativity of the gel to liquid-crystal transitions for those same phospholipids. 3. Glycerol monooleate induces the formation of isotropic and hexagonal (HII) phases when mixed with either dipalmitoyl phosphatidylcholine or dipalmitoyl phosphatidylethanolamine. By contrast, in the presence of dimethylsulphoxide, those same phospholipids retain the lamellar configuration observed in the absence of fusogen. 4. These results are discussed in terms of the mechanisms of chemically induced cell fusion.

  6. sup 31 P NMR measurements of the ADP concentration in yeast cells genetically modified to express creatine kinase

    SciTech Connect

    Brindle, K.; Braddock, P.; Fulton, S. )

    1990-04-03

    Rabbit muscle creatine kinase has been introduced into the yeast Saccharomyces cerevisiae by transforming cells with a multicopy plasmid containing the coding sequence for the enzyme under the control of the yeast phosphoglycerate kinase promoter. The transformed cells showed creating kinase activities similar to those found in mammalian heart muscle. {sup 31}P NMR measurements of the near-equilibrium concentrations of phosphocreatine and cellular pH together with measurements of the total extractable concentrations of phosphocreatine and creatine allowed calculation of the free ADP/ATP ratio in the cell. The calculated ratio of approximately 2 was considerably higher than the ratio of between 0.06 and 0.1 measured directly in cell extracts.

  7. Observation of myo-inositol 1,2-(cyclic) phosphate in a Morris hepatoma by 31P NMR.

    PubMed

    Graham, R A; Meyer, R A; Szwergold, B S; Brown, T R

    1987-01-01

    We have identified an unusual resonance at 16.5 ppm in the 31P NMR spectrum of a Morris (7777) hepatoma grown in the inguinal fossa of a Buffalo rat as myoinositol 1,2-(cyclic) phosphate. This compound has been observed in all of the 32 tumors examined as well as in cultured cells derived from the tumor, but it has not been observed in normal rat tissues. Its level in the aqueous phase of chloroform/methanol/water extracts of the tumor is 70 +/- 40 nmol/g, wet weight (n = 4). The presence of a breakdown product of phosphatidylinositol at such high levels in a fast growing tumor may provide an important clue for understanding the metabolic defect that results in the malignant growth of this tumor.

  8. 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...

  9. Interaction between beta-Purothionin and dimyristoylphosphatidylglycerol: a (31)P-NMR and infrared spectroscopic study.

    PubMed Central

    Richard, Julie-Andrée; Kelly, Isabelle; Marion, Didier; Pézolet, Michel; Auger, Michèle

    2002-01-01

    The interaction of beta-purothionin, a small basic and antimicrobial protein from the endosperm of wheat seeds, with multilamellar vesicles of dimyristoylphosphatidylglycerol (DMPG) was investigated by (31)P solid-state NMR and infrared spectroscopy. NMR was used to study the organization and dynamics of DMPG in the absence and presence of beta-purothionin. The results indicate that beta-purothionin does not induce the formation of nonlamellar phases in DMPG. Two-dimensional exchange spectroscopy shows that beta-purothionin decreases the lateral diffusion of DMPG in the fluid phase. Infrared spectroscopy was used to investigate the perturbations, induced by beta-purothionin, of the polar and nonpolar regions of the phospholipid bilayers. At low concentration of beta-purothionin, the temperature of the gel-to-fluid phase transition of DMPG increases from 24 degrees C to ~33 degrees C, in agreement with the formation of electrostatic interactions between the cationic protein and the anionic phospholipid. At higher protein concentration, the lipid transition is slightly shifted toward lower temperature and a second transition is observed below 20 degrees C, suggesting an insertion of the protein in the hydrophobic core of the lipid bilayer. The results also suggest that the presence of beta-purothionin significantly modifies the lipid packing at the surface of the bilayer to increase the accessibility of water molecules in the interfacial region. Finally, orientation measurements indicate that the alpha-helices and the beta-sheet of beta-purothionin have tilt angles of ~60 degrees and 30 degrees, respectively, relative to the normal of the ATR crystal. PMID:12324425

  10. 31P NMR conformational studies of non-palindromic DNA duplexes related to HIV-1 enhancer

    NASA Astrophysics Data System (ADS)

    Tisne, C.; Simenel, C.; Hantz, E.; Delepierre, M.

    1998-02-01

    Assignment of all 31P resonances of 16 base-pair DNA duplexes, 5' d(CTGGGGACTTTCCAGG)3' 5' d(CCTGGAAAGTCCCCAG)3', related to the DNA kappaB site of the HIV-1 LTR together with a mutated sequence 5' d(CTGCTCACTTTCCAGG)3' 5' d(CCTGGAAAGTGAGCAG)3' was determined by 2D heteronuclear inverse NMR spectroscopy (HSQC-TOCSY and heteronuclear COSY). ^3JH{3'}-P coupling constants for most of the phosphates of the mutated oligomer were obtained using heteronuclear selective COSY. L'attribution des résonances 31P du fragment d'ADN de seize paires de base 5' d(CTGGGGACTTTCCAGG)3' 5' d(CCTGGAAAGTCCCCAG)3' (16N) correspondant au site kappaB du LTR du HIV-1 et de la séquence mutée 5' d(CTGCTCACTTTCCAGG)3' 5' d(CCTGGAAAGTGAGCAG)3' (16M) a été déterminée à l'aide de méthodes 2D hétéronucléaires à détection indirecte (HSQC-TOCSY et COSY hétéronucléaires). Les constantes de couplage ^3JH{3'}-P ont été mesurées pour la plupart des phosphates de 16 M à l'aide d'expérience COSY hétéronucléaires sélectives.

  11. Intracellular pH and inorganic phosphate content of heart in vivo: A sup 31 P-NMR study

    SciTech Connect

    Katz, L.A.; Swain, J.A.; Portman, M.A.; Balaban, R.S. )

    1988-07-01

    Studies were performed to determine the contribution of red blood cells to the {sup 31}P-nuclear magnetic resonance (NMR) spectrum of the canine heart in vivo and the feasibility of measuring myocardial intracellular phosphate and pH. This was accomplished by replacing whole blood with a perfluorochemical perfusion emulsion blood substitute, Oxypherol, and noting the difference in the {sup 31}P-NMR spectrum of the heart. NMR data were collected with a NMR transmitter-receiver coil on the surface of the distal portion of the left ventricle. These studies demonstrated that a small contribution from 2,3-diphosphoglycerate (2,3-DPG) and phosphodiesters in the blood could be detected. The magnitude and shift of these blood-borne signals permitted the relative quantification of intracellular inorganic phosphate (P{sub i}) content as well as intracellular pH. Under resting conditions, the intracellular ATP/P{sub i} was 7.0 {plus minus} 0.08. This corresponds to a free intracellular P{sub 1} content of {approx} 0.8 {mu}mol./g wet wt. The intracellular pH was 7.10 {plus minus} 0.01. Acute respiratory alkalosis and acidosis, with the arterial pH ranging from {approximately}7.0 to 7.7, resulted in only small changes in the intracellular pH. These latter results demonstrate an effective myocardial intracellular proton-buffering mechanism in vivo.

  12. Influence of temperature on 31P NMR chemical shifts of phospholipids and their metabolites I. In chloroform-methanol-water.

    PubMed

    Estrada, Rosendo; Stolowich, Neal; Yappert, M Cecilia

    2008-09-01

    Spectral overlap of (31)P NMR resonances and the lack of reproducibility in chemical shifts corresponding to phospholipids in organic solvents challenge the accuracy of band assignments and quantification. To alleviate these problems, the use of temperature coefficients is proposed. Changes in temperature enable the resolution of overlapped resonances and provide a facile approach for the computation of temperature coefficients. The coefficients were evaluated for various glycero- and sphingo-phospholipids. Their values suggest that differences in H-bonding between the phosphate and the head groups are responsible for the changes of chemical shift with temperature. Among parent phospholipids, and in addition to sphingomyelin, the smallest temperature coefficient values (closest to zero) were observed for phosphatidylcholine, phosphatidylglycerol, dihydrosphingomyelin, and cardiolipin. The highest values were exhibited by phospholipids with protonated head groups, such as phosphatidylserine and phosphatidylethanolamine. The lowest and, in fact, negative values were measured for phospholipids with an exposed phosphate group: phosphatidic acid, ceramide-1-phosphate, and dihydroceramide-1-phosphate. Diacyl, alkyl-acyl, and alkenyl-acyl phospholipids with the same head group exhibited comparable coefficients but differed slightly in chemical shifts. Compared to their parent glycerophospholipids, all lyso analogs had greater temperature coefficients, possibly due to the presence of an extra OH capable of forming a H-bond with the phosphate group. PMID:18534182

  13. Functional pools of fast and slow twitch fibers observed by /sup 31/P-NMR during exercise of flexor wrist muscles in man

    SciTech Connect

    Park, J.H.; Park, C.R.; Brown, R.L.; Chance, B.

    1987-05-01

    Functional compartments of fast and slow twitch fibers have been observed by /sup 31/P-NMR spectroscopy during exercise of the wrist flexor muscles in a sedentary, young male subject. Values of Pi, phosphocreatine (PCr) and adenine nucleotides were determined at rest and during an exercise protocol. The subject flexed his wrist muscles at 20% of maximum strength every 5 sec for 6 min and then increased his effort in the next two 6 min intervals to 40% and 60% of maximum. With exercise, the Pi/PCr rose rapidly to the exceptionally high value of 2.2 at 60% effort. As the Pi increased, the initial single peak (pH 7.0-6.9) split into two distinct components with pH values of 6.8 and 6.3. Quantitatively, distribution of the Pi was 40% in the pH 6.8 peak and 60% in the pH 6.3 peak as determined by area estimation following curve fitting. This presumably reflects two pools of Pi corresponding to the oxidative (slow twitch, high pH) and glycolytic (fast twitch, low pH) fibers. In the second identical exercise sequence which followed immediately, only one Pi peak (pH 6.8-6.9) appeared. This suggested that the glycolytic contribution to energy production was largely exhausted and the residual energy was derived from oxidative metabolism. During exercise at high levels, total phosphate decreased due primarily to loss of NMR visible adenine nucleotides. Similar phenomena have been observed in three other sedentary individuals, but not in trained athletes.

  14. Local structure of spin Peierls compound TiPO4: 47/49Ti and 31P NMR study

    NASA Astrophysics Data System (ADS)

    Stern, Raivo; Heinmaa, Ivo; Leitmäe, Alexander; Joon, Enno; Tsirlin, Alexander; Kremer, Reinhard; Glaum, Robert

    TiPO4 structure is made of slightly corrugated TiO2 ribbon chains of edge-sharing TiO6 octahedra. The almost perfect 1D spin 1/2 Ti3 + chains are well separated by PO4 tetrahedra. By magnetic susceptibility and MAS-NMR measurements [1] it was shown that TiPO4 has nonmagnetic singlet ground state with remarkably high Spin-Peierls (SP) transition temperature. The high-T magnetic susceptibility of TiPO4 follows well that of a S =1/2 Heisenberg chain with very strong nearest-neighbor AF spin-exchange coupling constant of J =965K. On cooling TiPO4 shows two successive phase transitions at 111K and 74K, with incommensurate (IC) SP phase between them. We studied local structure and dynamics in TiPO4 single crystal using 47/49Ti and 31P NMR in the temperature range 40K to 300K, and determined the principal values and orientation of the magnetic shift tensors for 31P and 47,49Ti nuclei. Since 47,49Ti (S =5/2 and S =7/2, respectively) have quadrupolar moments, we also found the principal axis values and orientations of the electric field gradient (efg) tensor in SP phase and at 295K. In SP phase the structure contains 2 magnetically inequivalent P sites and only one Ti site. From the T-dependence of the relaxation rate of 31P and 47Ti nuclei we determined activation energy Ea = 550 K for spin excitations in SP phase. J. Law et al ., PRB 83, 180414(R) (2011).

  15. Direct Speciation of Phosphorus in Alum-Amended Poultry Litter: Solid-State 31P NMR Investigation

    SciTech Connect

    Hunger, Stefan; Cho, Herman M.; Sims, James T.; Sparks, Donald L.

    2004-02-01

    Amending poultry litter (PL) with aluminum sulfate (alum) has proven to be effective in reducing water-soluble phosphorus (P) in the litter and in runoff from fields that have received PL applications; it has therefore been suggested as a best management practice. Although its effectiveness has been demonstrated on a macroscopic scale in the field, little is known about P speciation in either alumamended or unamended litter. This knowledge is important for the evaluation of the long-term stability and bioavailability of P, which is a necessary prerequisite for the assessment of the sustainability of intensive poultry operations. Both solid state MAS and CP-MAS {sup 31}P NMR as well as {sup 31}P({sup 27}Al) TRAPDOR were used to investigate P speciation in alumamended and unamended PL. The results indicate the presence of a complex mixture of organic and inorganic orthophosphate phases. A calcium phosphate phase, probably a surface precipitate on calcium carbonate, could be identified in both unamended and alum-amended PL, as well as physically bound HPO{sub 4}{sup 2-}. Phosphate associated with Al was found in the alum-amended PL, most probably a mixture of a poorly ordered wavellite and phosphate surface complexes on aluminum hydroxide that had been formed by the hydrolysis of alum. However, a complex mixture of organic and inorganic phosphate species could not be resolved. Phosphate associated with Al comprised on average 40{+-}14% of the total P in alum-amended PL, whereas calcium phosphate phases comprised on average 7{+-}4% in the alum-amended PL and 14{+-}5% in the unamended PL.

  16. Ionization behavior of polyphosphoinositides determined via the preparation of pH titration curves using solid-state 31P NMR.

    PubMed

    Graber, Zachary T; Kooijman, Edgar E

    2013-01-01

    Detailed knowledge of the degree of ionization of lipid titratable groups is important for the evaluation of protein-lipid and lipid-lipid interactions. The degree of ionization is commonly evaluated by acid-base titration, but for lipids localized in a multicomponent membrane interface this is not a suitable technique. For phosphomonoester-containing lipids such as the polyphosphoinositides, phosphatidic acid, and ceramide-1-phosphate, this is more conveniently accomplished by (31)P NMR. Here, we describe a solid-state (31)P NMR procedure to construct pH titration curves to determine the degree of ionization of phosphomonoester groups in polyphosphoinositides. This procedure can also be used, with suitable sample preparation conditions, for other important signaling lipids. Access to a solid-state, i.e., magic angle spinning, capable NMR spectrometer is assumed. The procedures described here are valid for a Bruker instrument, but can be adapted for other spectrometers as needed.

  17. Vacuolar glyphosate-sequestration correlates with glyphosate resistance in ryegrass (Lolium spp.) from Australia, South America, and Europe: a 31P NMR investigation.

    PubMed

    Ge, Xia; d'Avignon, D André; Ackerman, Joseph J H; Collavo, Alberto; Sattin, Maurizio; Ostrander, Elizabeth L; Hall, Erin L; Sammons, R Douglas; Preston, Christopher

    2012-02-01

    Lolium spp., ryegrass, variants from Australia, Brazil, Chile, and Italy showing differing levels of glyphosate resistance were examined by (31)P NMR. Extents of glyphosate (i) resistance (LD(50)), (ii) inhibition of 5-enopyruvyl-shikimate-3-phosphate synthase (EPSPS) activity (IC(50)), and (iii) translocation were quantified for glyphosate-resistant (GR) and glyphosate-sensitive (GS) Lolium multiflorum Lam. variants from Chile and Brazil. For comparison, LD(50) and IC(50) data for Lolium rigidum Gaudin variants from Italy were also analyzed. All variants showed similar cellular uptake of glyphosate by (31)P NMR. All GR variants showed glyphosate sequestration within the cell vacuole, whereas there was minimal or no vacuole sequestration in the GS variants. The extent of vacuole sequestration correlated qualitatively with the level of resistance. Previous (31)P NMR studies of horseweed ( Conyza canadensis (L.) Cronquist) revealed that glyphosate sequestration imparted glyphosate resistance. Data presented herein suggest that glyphosate vacuolar sequestration is strongly contributing, if not the major contributing, resistance mechanism in ryegrass as well.

  18. Effects of pH and cholesterol on DMPA membranes: a solid state 2H- and 31P-NMR study.

    PubMed Central

    Pott, T; Maillet, J C; Dufourc, E J

    1995-01-01

    The effect of pH and cholesterol on the dimyristoylphosphatidic acid (DMPA) model membrane system has been investigated by solid state 2H- and 31P-NMR. It has been shown that each of the three protonation states of the DMPA molecule corresponds to a 31P-NMR powder pattern with characteristic delta sigma values; this implies additionally that the proton exchange on the membrane surface is slow on the NMR time scale (millisecond range). Under these conditions, the 2H-labeled lipid chains sense only one magnetic environment, indicating that the three spectra detected by 31P-NMR are related to charge-dependent local dynamics or orientations of the phosphate headgroup or both. Chain ordering in the fluid phase is also found to depend weakly on the charge at the interface. In addition, it has also been found that the first pK of the DMPA membrane is modified by changes in the lipid lateral packing (gel or fluid phases or in the presence of cholesterol) in contrast to the second pK. The incorporation of 30 mol% cholesterol affects the phosphatidic acid bilayer in a way similar to what has been reported for phosphatidylcholine/cholesterol membranes, but to an extent comparable to 10-20 mol % sterol in phosphatidylcholines. However, the orientation and molecular order parameter of cholesterol in DMPA are similar to those found in dimyristoylphosphatidylcholine. PMID:8580333

  19. Correcting human heart 31P NMR spectra for partial saturation. Evidence that saturation factors for PCr/ATP are homogeneous in normal and disease states

    NASA Astrophysics Data System (ADS)

    Bottomley, Paul A.; Hardy, Christopher J.; Weiss, Robert G.

    Heart PCr/ATP ratios measured from spatially localized 31P NMR spectra can be corrected for partial saturation effects using saturation factors derived from unlocalized chest surface-coil spectra acquired at the heart rate and approximate Ernst angle for phosphor creatine (PCr) and again under fully relaxed conditions during each 31P exam. To validate this approach in studies of normal and disease states where the possibility of heterogeneity in metabolite T1 values between both chest muscle and heart and normal and disease states exists, the properties of saturation factors for metabolite ratios were investigated theoretically under conditions applicable in typical cardiac spectroscopy exams and empirically using data from 82 cardiac 31P exams in six study groups comprising normal controls ( n = 19) and patients with dilated ( n = 20) and hypertrophic ( n = 5) cardiomyopathy, coronary artery disease ( n = 16), heart transplants ( n = 19), and valvular heart disease ( n = 3). When TR ≪ T1,(PCr), with T1(PCr) ⩾ T1(ATP), the saturation factor for PCr/ATP lies in the range 1.5 ± 0.5, regardless of the T1 values. The precise value depends on the ratio of metabolite T1 values rather than their absolute values and is insensitive to modest changes in TR. Published data suggest that the metabolite T1 ratio is the same in heart and muscle. Our empirical data reveal that the saturation factors do not vary significantly with disease state, nor with the relative fractions of muscle and heart contributing to the chest surface-coil spectra. Also, the corrected myocardial PCr/ATP ratios in each normal or disease state bear no correlation with the corresponding saturation factors nor the fraction of muscle in the unlocalized chest spectra. However, application of the saturation correction (mean value, 1.36 ± 0.03 SE) significantly reduced scatter in myocardial PCr/ATP data by 14 ± 11% (SD) ( p ⩽ 0.05). The findings suggest that the relative T1 values of PCr and ATP are

  20. Delineation of conformational preferences in human salivary statherin by 1H, 31P NMR and CD studies: sequential assignment and structure-function correlations.

    PubMed

    Naganagowda, G A; Gururaja, T L; Levine, M J

    1998-08-01

    Membrane-induced solution structure of human salivary statherin, a 43 amino acid residue acidic phosphoprotein, has been investigated by two-dimensional proton nuclear magnetic resonance (2D 1H NMR) spectroscopy. NMR assignments and structural analysis of this phosphoprotein was accomplished by analyzing the pattern of sequential and medium range NOEs, alphaCH chemical shift perturbations and deuterium exchange measurements of the amide proton resonances. The NMR data revealed three distinct structural motifs in the molecule: (1) an alpha-helical structure at the N-terminal domain comprising Asp1-Tyr16, (2) a polyproline type II (PPII) conformation predominantly occurring at the middle proline-rich domain spanning Gly19-Gln35, and (3) a 3(10)-helical structure at the C-terminal Pro36-Phe43 sequence. Presence of a few weak dalphaN(i,i+2) NOEs suggests that N-terminus also possesses minor population of 3(10)-helical conformation. Of the three secondary structural elements, helical structure formed by the N-terminal residues, Asp1-Ile11 appears to be more rigid as observed by the relatively very slow exchange of amide hydrogens of Glu5-Ile11. 31P NMR experiments clearly indicated that N-terminal domain of statherin exists mainly in disordered state in water whereas, upon addition of structure stabilizing co-solvent, 2,2,2-trifluorethanol (TFE), it showed a strong propensity for helical conformation. Calcium ion interaction studies suggested that the disordered N-terminal region encompassing the two vicinal phosphoserines is essential for the binding of calcium ions in vivo. Results from the circular dichroism (CD) experiments were found to be consistent with and complimentary to the NMR data and provided an evidence that non-aqueous environment such as TFE, could induce the protein to fold into helical conformation. The findings that the statherin possesses blended solvent sensitive secondary structural elements and the requirement of non-structured N-terminal region

  1. [31P-NMR analysis of high energy phosphorous compounds (ATP and phosphocreatine) in the living rat brain--effects of halothane anesthesia and a hypoxic condition].

    PubMed

    Yuasa, T; Miyatake, T; Kuwabara, T; Umeda, M; Eguchi, K

    1983-11-01

    31phosphorus nuclear magnetic resonance (31P-NMR) measurements have provided new and valuable insights for studying the metabolism of living systems. The aim of this paper is to introduce a technique of application of 31P-NMR measurements using a surface coil method, and to discuss the effects of halothane anesthesia and hypoxic hypoxia on the energetic metabolism of intact rat brains. All measurements were made using a JEOL FX 270 spectrometer with a super conducting magnet of 54-mm bore diameter. The magnetic field intensity of this machine is 6.3 tesla, and the resonance frequency used for 31P was 109.14 MHz. We remodelled an ordinary probe to take a live rat, and the animals were made to inhale anesthetic halothane or mixture of oxygen and nitrogen at various concentrations controlled by a flow regulator. The best conditions for measurements with our surface coil method were determined in this study as follows: (1) 90 degrees pulse width and selectivity, Fig. 1 shows signal selectivity in depthwise direction changed with 90 degrees pulse width, which was set to 20 microseconds. (2) Sensitivity and resolution; To obtain a spectrum of 31P-NMR from a rat brain 500 accumulations of free induction decays were considered suitable for both time and space resolution. Fig. 2 shows variations of signal intensity with pulse repetition time, which was set to 2 sec. It took about 17 min for averaging to get a spectrogram. (3) Quantitative accuracy and qualification; As shown in Fig. 3, a linear relationship was found between the signal intensity of beta-phosphate of ATP and the concentration of ATP solutions, thus proving the quantitative accuracy of our systems.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:6661335

  2. /sup 31/P NMR saturation-transfer and /sup 13/C NMR kinetic studies of glycolytic regulation during anaerobic and aerobic glycolysis

    SciTech Connect

    Campbell-Burk, S.L.; den Hollander, J.A.; Alger, J.R.; Shulman, R.G.

    1987-11-17

    /sup 31/P NMR saturation-transfer techniques have been employed in glucose-gown derepressed yeast to determine unidirectional fluxes in the upper part of the Embden-Meyerhof-Parnas pathway. The experiments were performed during anaerobic and aerobic glycolysis by saturating the ATP/sub ..gamma../ resonances and monitoring changes in the phosphomonoester signals from glucose 6-phosphate and fructose 1,6-bisphosphate. These experiments were supplemented with /sup 13/C NMR measurements of glucose utilization rates and /sup 13/C NMR label distribution studies. Combined with data obtained previously from radioisotope measurement, these /sup 31/P and /sup 13/C NMR kinetic studies allowed estimation of the net glycolytic flow in addition to relative flows through phosphofructokinase (PFK) and Fru-1,6-P/sub 2/ase during anaerobic and aerobic glycolysis. The /sup 31/P NMR saturation-transfer results are consistent with previous results obtained from measurements of metabolite levels, radioisotope data, and /sup 13/C NMR studies, providing additional support for in vivo measurement of the flows during glycolysis.

  3. 31P NMR characterization and efficiency of new types of water-insoluble phosphate fertilizers to supply plant-available phosphorus in diverse soil types.

    PubMed

    Erro, Javier; Baigorri, Roberto; Yvin, Jean-Claude; Garcia-Mina, Jose M

    2011-03-01

    Hydroponic plant experiments demonstrated the efficiency of a type of humic acid-based water-insoluble phosphate fertilizers, named rhizosphere controlled fertilizers (RCF), to supply available phosphorus (P) to different plant species. This effect was well correlated to the root release of specific organic acids. In this context, the aims of this study are (i) to study the chemical nature of RCF using solid-state (31)P NMR and (ii) to evaluate the real efficiency of RCF matrix as a source of P for wheat plants cultivated in an alkaline and acid soil in comparison with traditional water-soluble (simple superphosphate, SSP) and water-insoluble (dicalcium phosphate, DCP) P fertilizers. The (31)P NMR study revealed the formation of multimetal (double and triple, MgZn and/or MgZnCa) phosphates associated with chelating groups of the humic acid through the formation of metal bridges. With regard to P fertilizer efficiency, the results obtained show that the RCF matrix produced higher plant yields than SSP in both types of soil, with DCP and the water-insoluble fraction from the RCF matrix (WI) exhibiting the best results in the alkaline soil. By contrast, in the acid soil, DCP showed very low efficiency, WI performed on a par with SSP, and RCF exhibited the highest efficiency, thus suggesting a protector effect of humic acid from soil fixation. PMID:21254775

  4. 31P NMR characterization and efficiency of new types of water-insoluble phosphate fertilizers to supply plant-available phosphorus in diverse soil types.

    PubMed

    Erro, Javier; Baigorri, Roberto; Yvin, Jean-Claude; Garcia-Mina, Jose M

    2011-03-01

    Hydroponic plant experiments demonstrated the efficiency of a type of humic acid-based water-insoluble phosphate fertilizers, named rhizosphere controlled fertilizers (RCF), to supply available phosphorus (P) to different plant species. This effect was well correlated to the root release of specific organic acids. In this context, the aims of this study are (i) to study the chemical nature of RCF using solid-state (31)P NMR and (ii) to evaluate the real efficiency of RCF matrix as a source of P for wheat plants cultivated in an alkaline and acid soil in comparison with traditional water-soluble (simple superphosphate, SSP) and water-insoluble (dicalcium phosphate, DCP) P fertilizers. The (31)P NMR study revealed the formation of multimetal (double and triple, MgZn and/or MgZnCa) phosphates associated with chelating groups of the humic acid through the formation of metal bridges. With regard to P fertilizer efficiency, the results obtained show that the RCF matrix produced higher plant yields than SSP in both types of soil, with DCP and the water-insoluble fraction from the RCF matrix (WI) exhibiting the best results in the alkaline soil. By contrast, in the acid soil, DCP showed very low efficiency, WI performed on a par with SSP, and RCF exhibited the highest efficiency, thus suggesting a protector effect of humic acid from soil fixation.

  5. Studies of uptake and suppresion of Mn/sup 2 +/ migration in highly vacuolated sycamore (Acer pseudoplatanus L) cells by /sup 31/P NMR

    SciTech Connect

    Roby, C.; Bligny, R.; Douce, R.; Pfeffer, P.E.

    1987-04-01

    Recent /sup 31/P NMR studies have demonstrated that Mn/sup 2 +/ appears to invade the cells of heterogeneous excised tissue of corn root tips sequentially, first entering the cytoplasmic compartment, where it complexes with nucleotides and P/sub i/. Under aerobic conditions, further migration across the tonoplast, followed by vacoule trapping was visualized through paramagnetic broadening of the vacoular P/sub i/ resonance. Cultured cells such as Acer pseudoplatanus L offer better opportunities for studying cellular activity by /sup 31/P NMR because of their homogeneity and uniformly rapid response to various metabolic disturbances. In contrast to excised root tissue, Mn/sup 2 +/ showed no measurable accumulation in the cytoplasmic compartments of these cells under aerobic conditions. However, a rapid crossing of the large tonoplast resulted in immediate vacuolar metal ion sequestration. Anoxia did not foster leakage of Mn/sup 2 +/ from the vacuole to the cytoplasm, while hypoxia completely halted all movement of Mn/sup 2 +/ across the plasmalema. This disparity in terms of cell and tissue morphology, membrane permeability and possible tissue trapping of metal ions will be discussed.

  6. Simultaneous beta and gamma spectroscopy

    DOEpatents

    Farsoni, Abdollah T.; Hamby, David M.

    2010-03-23

    A phoswich radiation detector for simultaneous spectroscopy of beta rays and gamma rays includes three scintillators with different decay time characteristics. Two of the three scintillators are used for beta detection and the third scintillator is used for gamma detection. A pulse induced by an interaction of radiation with the detector is digitally analyzed to classify the type of event as beta, gamma, or unknown. A pulse is classified as a beta event if the pulse originated from just the first scintillator alone or from just the first and the second scintillator. A pulse from just the third scintillator is recorded as gamma event. Other pulses are rejected as unknown events.

  7. Analysis of brain metabolism changes induced by acute potassium cyanide intoxication by 31P NMR in vivo using chronically implanted surface coils.

    PubMed

    Decorps, M; Lebas, J F; Leviel, J L; Confort, S; Remy, C; Benabid, A L

    1984-03-12

    Chronic implantation of surface coils on the skull has been developed to record 31P NMR spectra of the brain in unanesthetized rats. Intraperitoneal sublethal potassium cyanide doses induce strong and reversible changes in high-energy phosphate compounds in the brain, similar in part to those induced by ischemia. These effects are dose-dependent as far as phosphocreatine, inorganic orthophosphates and pH are concerned; ATP does not seem to be altered by KCN doses ranging from 3 to 5 mg/kg but starts decreasing at a dose of 6 mg/kg. The fraction of Mg2+ complexed ATP which could be estimated as about 90% was not affected by KCN intoxication. For high doses (6 mg/kg) a new peak, appearing on the upfield side of the inorganic phosphate peak, may correspond to an acidic compartment, the significance of which is discussed.

  8. Analysis of brain metabolism changes induced by acute potassium cyanide intoxication by 31P NMR in vivo using chronically implanted surface coils.

    PubMed

    Decorps, M; Lebas, J F; Leviel, J L; Confort, S; Remy, C; Benabid, A L

    1984-03-12

    Chronic implantation of surface coils on the skull has been developed to record 31P NMR spectra of the brain in unanesthetized rats. Intraperitoneal sublethal potassium cyanide doses induce strong and reversible changes in high-energy phosphate compounds in the brain, similar in part to those induced by ischemia. These effects are dose-dependent as far as phosphocreatine, inorganic orthophosphates and pH are concerned; ATP does not seem to be altered by KCN doses ranging from 3 to 5 mg/kg but starts decreasing at a dose of 6 mg/kg. The fraction of Mg2+ complexed ATP which could be estimated as about 90% was not affected by KCN intoxication. For high doses (6 mg/kg) a new peak, appearing on the upfield side of the inorganic phosphate peak, may correspond to an acidic compartment, the significance of which is discussed. PMID:6705916

  9. Carbon-13, sup 15 N, and sup 31 P NMR studies on 6-hydroxy-L-nicotine oxidase from Arthrobacter oxidans

    SciTech Connect

    Pust, S.; Vervoort, J.; Decker, K.; Bacher, A.; Mueller, F. )

    1989-01-24

    The interaction between the apoprotein of 6-hydroxy-L-nicotine oxidase from Arthrobacter oxidans and the prosthetic group FAD has been investigated by {sup 13}C, {sup 15}N and {sup 31}P NMR techniques. The FAD prosthetic group was selectively enriched in {sup 13}C and {sup 15}N isotopes by adding isotopically labeled riboflavin derivatives to the growth medium of riboflavin-requiring mutant cells. In the oxidized state the chemical shift of the C(7) and C(8) atoms indicates that the xylene moiety of the isoalloxazine ring is embedded in a hydrophobic environment. The binding of the competitive inhibitor, 6-hydroxy-D-nicotine, influences the resonances of the C(4a) and the N(5) atom strongly. It is suggested that these shifts are due to a strong hydrogen-bonding interaction between the N(5) atom and the inhibitor. On reduction all resonances, except those of the C(10a) and the N(1) atoms, shift upfield, indicating the increased electron density in the ring system. It can unambiguously be concluded from the chemical shift of the N(1) atom that the reduced flavin is anionic. The doublet character of the N(3) and N(5) resonances suggests that bulk water has no access to the active center. The strong downfield shift of the N(1) position indicates that this atom is embedded in a polar environment, but it does not indicate the presence of a positively charged residue. The {sup 31}P NMR spectra show that the resonances of the pyrophosphate group of the bound FAD differ slightly from those of free FAD. Besides the {sup 31}P resonances from FAD, four peaks around 0 ppm are observed that belongs to bound phosphorus residues. The residues are not located close to the isoalloxazine ring.

  10. Acid properties of solid acid catalysts characterized by solid-state 31P NMR of adsorbed phosphorous probe molecules.

    PubMed

    Zheng, Anmin; Huang, Shing-Jong; Liu, Shang-Bin; Deng, Feng

    2011-09-01

    A brief review is presented on acidity characterization of solid acid catalysts by means of solid-state phosphor-31 magic-angle-spinning nuclear magnetic resonance ((31)P MAS NMR) spectroscopy using phosphor-containing molecules as probes. It is emphasized that such a simple approach using (31)P MAS NMR of adsorbed phosphorous probe molecules, namely trimethylphosphine (TMP) and trialkylphosphine oxides (R(3)PO), represents a unique technique in providing detailed qualitative and quantitative features, viz. type, strength, distribution, and concentration of acid sites in solid acid catalysts. In particular, it will be shown that when applied with a proper choice of probe molecules with varied sizes and results obtained from elemental analysis, the amounts and locations (intracrystalline vs. extracrystalline) of different types (Brønsted vs. Lewis) of acid sites may be determined. In addition, by incorporating the NMR results with that obtained from theoretical density functional theory (DFT) calculations, correlations between the (31)P chemical shifts (δ(31)P) and acidic strengths of Brønsted and Lewis acid sites may also be derived, facilitating a suitable acidity scale for solid acid catalysts.

  11. In vivo /sup 31/P NMR studies of corn root tissue and its uptake of toxic metals. [Zea mays L

    SciTech Connect

    Pfeffer, P.E.; Tu, S.I.; Gerasimowicz, W.V.; Cavanaugh, J.R.

    1986-01-01

    Excised corn root tissue has been evaluated for its viability, integrity of compartmentation, intracellular pH gradients, total mobile phosphorus content and nucleotide concentrations under different levels of acidity, and mineral stresses using in vivo /sup 31/P nuclear magnetic resonance spectroscopy at 21 to 23/sup 0/C. Perfusion with Al/sup 3 +/ ion at low pH (4.0) for 20 hours caused the overall concentration of nucleotides in the cytoplasm to decrease significantly relative to the control. Respiratory activity as measured by O/sub 2/ uptake decreased by a comparable amount over this time period. The addition of glucose to the Al-containing perfusate negated the inhibitory effects on the respiratory system. Treatment of the tissue with paramagnetic manganese ion while perfusing in the presence of O/sub 2/ allowed for the observation of the sequence of events leading to the irreversible trapping of Mn/sup 2 +/ in the vacuole. Pretreatment of the roots with Mg/sup 2 +/ prevented Mn/sup 2 +/ migration to the vacuole over the time period of this experiment. Hypoxia prevented all but a limited uptake of Mn/sup 2 +/ into the cytoplasm of the root tips. No evidence of Mn/sup 2 +/ complexation of either cytoplasmic or vacuole Pi suggests that the energy derived from O/sub 2/ consuming processes is necessary for the facilitated movement of this divalent cation.

  12. {sup 31}P NMR study of the complexation of TBP with lanthanides and actinides in solution and in a clay matrix

    SciTech Connect

    Hartzell, C.J.

    1994-07-24

    Goal was to use NMR to study TBP/lanthanide complexes in the interlayer or on edge sites of clays. Work in this laboratory yielded details of the complexation of Eu(NO{sub 3}){sub 3} and Pr(NO{sub 3}){sub 3} with TBP in hexane solution; this information is crucial to interpretation of results of NMR studies of the complexes exchanged into clays. The solution {sup 31}P-chemical shift values were improved by repeating the studies on the lanthanide salts dissolved directly into neat TBP. NMR studies of these neat solutions of the Eu(NO{sub 3}){sub 3}{lg_bullet}3TBP-complex and the Pr(NO{sub 3}){sub 3}{lg_bullet}3TBP-complex show that the {sup 31}P chemical shift remains relatively constant for TBP: lanthanide ratios below 3: 1. At higher ratios, the chemical shift approaches that of free TBP, indicating rapid exchange of TBP between the free and complexed state. Exchange of these complexes into the clay hectorite yielded discrete {sup 31}P-NMR signals for the Eu{lg_bullet}TBP complex at -190 ppm and free TBP at -6 ppm. Adsorption of the Pr{lg_bullet}TBP complex yielded broad signals at 76 ppm for the complex and -6 ppm for free TBP. There was no evidence of exchange between the incorporated complex and the free TBP.

  13. Rate equation for creatine kinase predicts the in vivo reaction velocity: /sup 31/P NMR surface coil studies in brain, heart, and skeletal muscle of the living rat

    SciTech Connect

    Bittl, J.A.; DeLayre, J.; Ingwall, J.S.

    1987-09-22

    Brain, heart, and skeletal muscle contain four different creatine kinase isozymes and various concentrations of substrates for the creatine kinase reaction. To identify if the velocity of the creatine kinase reaction under cellular conditions is regulated by enzyme activity and substrate concentrations as predicted by the rate equation, the authors used /sup 31/P NMR and spectrophotometric techniques to measure reaction velocity, enzyme content, isozyme distribution, and concentrations of substrates in brain, heart, and skeletal muscle of living rat under basal or resting conditions. The total tissue activity of creatine kinase in the direction of MgATP synthesis provided an estimate for V/sub max/ and exceeded the NMR-determined in vivo reaction velocities by an order of magnitude. The isozyme composition varied among the three tissues: >99% BB for brain; 14% MB, 61% MM, and 25% mitochondrial for heart; and 98% MM and 2% mitochondrial for skeletal muscle. The NMR-determined reaction velocities agreed with predicted values from the creatine kinase rate equation. The concentrations of free creatine and cytosolic MgADP, being less than or equal to the dissociation constants for each isozyme, were dominant terms in the creatine kinase rate equation for predicting the in vivo reaction velocity. Thus, they observed that the velocity of the creatine kinase reaction is regulated by total tissue enzyme activity and by the concentrations of creatine and MgADP in a manner that is independent of isozyme distribution.

  14. On the use of 31P NMR for the quantification of hydrosoluble phosphorus-containing compounds in coral host tissues and cultured zooxanthellae

    NASA Astrophysics Data System (ADS)

    Godinot, Claire; Gaysinski, Marc; Thomas, Olivier P.; Ferrier-Pagès, Christine; Grover, Renaud

    2016-02-01

    31P Nuclear Magnetic Resonance (NMR) was assessed to investigate the phosphorus-containing compounds present in the tissues of the scleractinian coral Stylophora pistillata as well as of cultured zooxanthellae (CZ). Results showed that phosphorus-containing compounds observed in CZ were mainly phosphate and phosphate esters. Phosphate accounted for 19 ± 2% of the total phosphorus compounds observed in CZ maintained under low P-levels (0.02 μM). Adding 5 mM of dissolved inorganic phosphorus (KH2PO4) to the CZ culture medium led to a 3.1-fold increase in intracellular phosphate, while adding 5 mM of dissolved organic phosphorus led to a reduction in the concentration of phosphorus compounds, including a 2.5-fold intracellular phosphate decrease. In sharp contrast to zooxanthellae, the host mainly contained phosphonates, and to a lesser extent, phosphate esters and phosphate. Two-months of host starvation decreased the phosphate content by 2.4 fold, while bleaching of fed corals did not modify this content. Based on 31P NMR analyses, this study highlights the importance of phosphonates in the composition of coral host tissues, and illustrates the impact of phosphorus availability on the phosphorus composition of host tissues and CZ, both through feeding of the host and inorganic phosphorus enrichment of the CZ.

  15. The effect of ethanol on hydroxyl and carbonyl groups in biopolyol produced by hydrothermal liquefaction of loblolly pine: (31)P-NMR and (19)F-NMR analysis.

    PubMed

    Celikbag, Yusuf; Via, Brian K; Adhikari, Sushil; Buschle-Diller, Gisela; Auad, Maria L

    2016-08-01

    The goal of this study was to investigate the role of ethanol and temperature on the hydroxyl and carbonyl groups in biopolyol produced from hydrothermal liquefaction of loblolly pine (Pinus spp.) carried out at 250, 300, 350 and 390°C for 30min. Water and water/ethanol mixture (1/1, wt/wt) were used as liquefying solvent in the HTL experiments. HTL in water and water/ethanol is donated as W-HTL and W/E-HTL, respectively. It was found that 300°C and water/ethanol solvent was the optimum liquefaction temperature and solvent, yielding up to 68.1wt.% bio-oil and 2.4wt.% solid residue. (31)P-NMR analysis showed that biopolyol produced by W-HTL was rich in phenolic OH while W/E-HTL produced more aliphatic OH rich biopolyols. Moreover, biopolyols with higher hydroxyl concentration were produced by W/E-HTL. Carbonyl groups were analyzed by (19)F-NMR, which showed that ethanol reduced the concentration of carbonyl groups. PMID:27126078

  16. On the use of 31P NMR for the quantification of hydrosoluble phosphorus-containing compounds in coral host tissues and cultured zooxanthellae

    PubMed Central

    Godinot, Claire; Gaysinski, Marc; Thomas, Olivier P.; Ferrier-Pagès, Christine; Grover, Renaud

    2016-01-01

    31P Nuclear Magnetic Resonance (NMR) was assessed to investigate the phosphorus-containing compounds present in the tissues of the scleractinian coral Stylophora pistillata as well as of cultured zooxanthellae (CZ). Results showed that phosphorus-containing compounds observed in CZ were mainly phosphate and phosphate esters. Phosphate accounted for 19 ± 2% of the total phosphorus compounds observed in CZ maintained under low P-levels (0.02 μM). Adding 5 mM of dissolved inorganic phosphorus (KH2PO4) to the CZ culture medium led to a 3.1-fold increase in intracellular phosphate, while adding 5 mM of dissolved organic phosphorus led to a reduction in the concentration of phosphorus compounds, including a 2.5-fold intracellular phosphate decrease. In sharp contrast to zooxanthellae, the host mainly contained phosphonates, and to a lesser extent, phosphate esters and phosphate. Two-months of host starvation decreased the phosphate content by 2.4 fold, while bleaching of fed corals did not modify this content. Based on 31P NMR analyses, this study highlights the importance of phosphonates in the composition of coral host tissues, and illustrates the impact of phosphorus availability on the phosphorus composition of host tissues and CZ, both through feeding of the host and inorganic phosphorus enrichment of the CZ. PMID:26902733

  17. The effect of ethanol on hydroxyl and carbonyl groups in biopolyol produced by hydrothermal liquefaction of loblolly pine: (31)P-NMR and (19)F-NMR analysis.

    PubMed

    Celikbag, Yusuf; Via, Brian K; Adhikari, Sushil; Buschle-Diller, Gisela; Auad, Maria L

    2016-08-01

    The goal of this study was to investigate the role of ethanol and temperature on the hydroxyl and carbonyl groups in biopolyol produced from hydrothermal liquefaction of loblolly pine (Pinus spp.) carried out at 250, 300, 350 and 390°C for 30min. Water and water/ethanol mixture (1/1, wt/wt) were used as liquefying solvent in the HTL experiments. HTL in water and water/ethanol is donated as W-HTL and W/E-HTL, respectively. It was found that 300°C and water/ethanol solvent was the optimum liquefaction temperature and solvent, yielding up to 68.1wt.% bio-oil and 2.4wt.% solid residue. (31)P-NMR analysis showed that biopolyol produced by W-HTL was rich in phenolic OH while W/E-HTL produced more aliphatic OH rich biopolyols. Moreover, biopolyols with higher hydroxyl concentration were produced by W/E-HTL. Carbonyl groups were analyzed by (19)F-NMR, which showed that ethanol reduced the concentration of carbonyl groups.

  18. Conformational transitions of the phosphodiester backbone in native DNA: two-dimensional magic-angle-spinning 31P-NMR of DNA fibers.

    PubMed Central

    Song, Z; Antzutkin, O N; Lee, Y K; Shekar, S C; Rupprecht, A; Levitt, M H

    1997-01-01

    Solid-state 31P-NMR is used to investigate the orientation of the phosphodiester backbone in NaDNA-, LiDNA-, MgDNA-, and NaDNA-netropsin fibers. The results for A- and B-DNA agree with previous interpretations. We verify that the binding of netropsin to NaDNA stabilizes the B form, and find that in NaDNA, most of the phosphate groups adopt a conformation typical of the A form, although there are minor components with phosphate orientations close to the B form. For LiDNA and MgDNA samples, on the other hand, we find phosphate conformations that are in variance with previous models. These samples display x-ray diffraction patterns that correspond to C-DNA. However, we find two distinct phosphate orientations in these samples, one resembling that in B-DNA, and one displaying a twist of the PO4 groups about the O3-P-O4 bisectors. The latter conformation is not in accordance with previous models of C-DNA structure. Images FIGURE 2 FIGURE 3 FIGURE 6 FIGURE 7 FIGURE 8 FIGURE 9 FIGURE 10 FIGURE 14 PMID:9284321

  19. On the use of 31P NMR for the quantification of hydrosoluble phosphorus-containing compounds in coral host tissues and cultured zooxanthellae.

    PubMed

    Godinot, Claire; Gaysinski, Marc; Thomas, Olivier P; Ferrier-Pagès, Christine; Grover, Renaud

    2016-01-01

    (31)P Nuclear Magnetic Resonance (NMR) was assessed to investigate the phosphorus-containing compounds present in the tissues of the scleractinian coral Stylophora pistillata as well as of cultured zooxanthellae (CZ). Results showed that phosphorus-containing compounds observed in CZ were mainly phosphate and phosphate esters. Phosphate accounted for 19 ± 2% of the total phosphorus compounds observed in CZ maintained under low P-levels (0.02 μM). Adding 5 mM of dissolved inorganic phosphorus (KH2PO4) to the CZ culture medium led to a 3.1-fold increase in intracellular phosphate, while adding 5 mM of dissolved organic phosphorus led to a reduction in the concentration of phosphorus compounds, including a 2.5-fold intracellular phosphate decrease. In sharp contrast to zooxanthellae, the host mainly contained phosphonates, and to a lesser extent, phosphate esters and phosphate. Two-months of host starvation decreased the phosphate content by 2.4 fold, while bleaching of fed corals did not modify this content. Based on (31)P NMR analyses, this study highlights the importance of phosphonates in the composition of coral host tissues, and illustrates the impact of phosphorus availability on the phosphorus composition of host tissues and CZ, both through feeding of the host and inorganic phosphorus enrichment of the CZ. PMID:26902733

  20. Comparative differential scanning calorimetric and FTIR and 31P-NMR spectroscopic studies of the effects of cholesterol and androstenol on the thermotropic phase behavior and organization of phosphatidylcholine bilayers.

    PubMed Central

    McMullen, T. P.; Lewis, R. N.; McElhaney, R. N.

    1994-01-01

    We have investigated the comparative effects of the incorporation of increasing quantities of androstenol and cholesterol on the thermotropic phase behavior of aqueous dispersions of members of a homologous series of linear saturated diacyl PCs1 using high sensitivity DSC. We have also employed FTIR and 31P-NMR spectroscopy to study the comparative effects of androstenol and cholesterol incorporation on the organization of the host PC bilayer in both the gel and liquid-crystalline states. The effects of androstenol and cholesterol incorporation on the thermotropic phase behavior of shorter chain PCs like 14:0 PC are generally similar but not identical. The incorporation of either sterol progressively decreases the temperature and enthalpy, but not the cooperativity, of the pretransition and completely abolishes it at sterol concentrations above 5 mol%. Moreover, at sterol concentrations of 1 to 20-25 mol%, both androstenol and cholesterol incorporation produce DSC endotherms consisting of superimposed sharp and broad components, the former due to the hydrocarbon chain melting of sterol-poor and the latter to the melting of sterol-rich 14:0 PC domains. The temperature and cooperativity of the sharp component are reduced slightly with increasing concentration of androstenol or cholesterol, and the enthalpy of the sharp component decreases progressively and becomes zero at 20-25 mol% sterol. As well, at cholesterol or androstenol concentrations above 20-25 mol%, the enthalpy of the broad component also decreases linearly with increasing sterol incorporation and becomes zero at sterol levels of about 50 mol%. However, whereas cholesterol incorporation progressively increases the temperature of the broad component of the DSC endotherm, androstenol incorporation decreases the temperature of this component. In contrast, the effects of androstenol and cholesterol incorporation on the thermotropic phase behavior of the intermediate and longer chain PCs studied here are

  1. 31P NMR analysis of intracellular pH of Swiss Mouse 3T3 cells: effects of extracellular Na+ and K+ and mitogenic stimulation.

    PubMed

    Civan, M M; Williams, S R; Gadian, D G; Rozengurt, E

    1986-01-01

    Swiss mouse 3T3 cells grown on microcarrier beads were superfused with electrolyte solution during continuous NMR analysis. Conventional 31P and 19F probes of intracellular pH (pHc) were found to be impracticable. Cells were therefore superfused with 1 to 4 mM 2-deoxyglucose, producing a large intracellular, pH-sensitive signal of 2-deoxyglucose phosphate (2DGP). The intracellular incorporation of 2DGP inhibited the Embden-Meyerhof pathway. However, intracellular ATP was at least in part retained and the cellular responsivity to changes in extracellular ionic composition and to the application of growth factors proved intact. Transient replacement of external Na+ with choline or K+ reversibly acidified the intracellular fluids. Quiescent cells and mitogenically stimulated cells displayed the same dependence of shifts in pHc on external Na+ concentration (CoNa). PHc also depended on intracellular Na+ concentration (CcNa). Increasing ccNa by withdrawing external K+ (thereby inhibiting the Na,K-pump) caused reversible intracellular acidification; subsequently reducing CoNa produced a larger acid shift in pHc than with external K+ present. Comparison of separate preparations indicated that pHc was higher in stimulated than in quiescent cells. Transient administration of mitogens also reversibly alkalinized quiescent cells studied continuously. This study documents the feasibility of monitoring pHc of Swiss mouse 3T3 cells using 31P NMR analysis of 2DGP. The results support the concept of a Na/H antiport operative in these cells, both in quiescence and after mitogenic stimulation. The data document by an independent technique that cytoplasmic alkalinization is an early event in mitogenesis, and that full activity of the Embden-Meyerhof pathway is not required for the expression of this event.

  2. Monitoring biodegradation of poly(butylene sebacate) by Gel Permeation Chromatography, (1)H-NMR and (31)P-NMR techniques.

    PubMed

    Siotto, Michela; Zoia, Luca; Tosin, Maurizio; Degli Innocenti, Francesco; Orlandi, Marco; Mezzanotte, Valeria

    2013-02-15

    The increasing use of new generation plastics has been accompanied by the development of standard methods for studying their biodegradability. Generally, test methods are based on the measurement of CO(2) production, i.e. the mineralization degree of the tested materials. However, in order to describe the biodegradation process, the determination of the residual amount of tested material which remains in the environment and its chemical characterization can be very important. In this study, the biodegradation in soil of a model polyester (poly(butylene sebacate)) was monitored. Gel Permeation Chromatography and Nuclear Magnetic Resonance ((31)P-NMR and (1)H-NMR) were used in order to obtain information about the polyester structure and the possible by-products that can be found in soil during and at the end of the incubation. The polyester mineralization (i.e. the CO(2) production) was tested according to ASTM 5988 standard method for 245 days. When the polyester mineralization was about 21% and 37% (after 78 and 140 days of incubation) and at the end of the process (63% of mineralization, 100% if compared to the cellulose used as reference material), the soil was extracted with chloroform (solvent of the tested substance) and the extracts were analyzed using GPC and NMR acquisitions. The analytical acquisitions showed high molecular weight polyester in soil during the incubation (78 and 140 days): the polyester concentration decreased but its structure remained almost the same with a slow decreasing in molecular weight. At the end of the test (245 days) no film of the polyester could be extracted from the soil: NMR acquisitions and GPC analyses of the extracts suggested a strong degraded structure of the residual polyester. Even if at the end of the process only 63% of carbon had been lost by mineralization, the whole of the added polyester seems to have disappeared after about eight months of incubation, suggesting substantial biomass formation.

  3. 31P NMR and Genetic Analysis Establish hinT as the only E. coli Purine Nucleoside Phosphoramidase and as Essential for Growth under High Salt Conditions

    PubMed Central

    Chou, Tsui-Fen; Bieganowski, Pawel; Shilinski, Kara; Cheng, Jilin; Brenner, Charles; Wagner, Carston R.

    2008-01-01

    Eukaryotic cells encode AMP-lysine hydrolases related to the rabbit histidine triad nucleotide-binding protein 1 (Hint1) sequence. Bacterial and archaeal cells have Hint homologs annotated in a variety of ways but the enzymes have not been characterized, nor have phenotypes been described due to loss of enzymatic activity. We developed a quantitative 31P NMR assay to determine whether Escherichia coli possesses an adenosine phosphoramidase activity. Indeed, soluble lysates prepared from wild-type laboratory Escherichia coli exhibited activity on the model substrate adenosine monophosphoramidate (AMP-NH2). The Escherichia coli Hint homolog, which had been comprehensively designated ycfF and is here named hinT, was cloned, over-expressed, purified and characterized with respect to purine nucleoside phosphoramidate substrates. Bacterial hinT was several times more active than mammalian Hint on three model substrates. In addition, bacterial and mammalian enzymes preferred guanosine versus adenosine phosphoramidates as substrates. Analysis of the lysates from a constructed hinT knockout strain of Escherichia coli demonstrated that all of the cellular purine nucleoside phosphoramidase activity is due to hinT. Physiological analysis of this mutant revealed that the loss of hinT enzymatic activity results in failure to grow in media containing 0.75 KCl, 0.9 M NaCl, 0.5 M NaOAc and 10 mM MnCl2. Thus, bacteria may possess nucleotidylylated phosphoramidate substrates that must be hydrolyzed to support growth under certain high salt conditions. PMID:15703176

  4. Structural and {sup 31}P NMR investigation of Bi(MM'){sub 2}PO{sub 6} statistic solid solutions: Deconvolution of lattice constraints and cationic influences

    SciTech Connect

    Colmont, Marie; Delevoye, Laurent; Ketatni, El Mostafa; Montagne, Lionel; Mentre, Olivier . E-mail: mentre@ensc-lille.fr

    2006-07-15

    Two solid solutions BiM{sub x} Mg{sub (2-x)}PO{sub 6} (with M {sup 2+}=Zn or Cd) have been studied through {sup 31}P MAS NMR. The analysis has been performed on the basis of refined crystal structures through X-ray diffraction and neutron diffraction. The BiZn {sub x} Mg{sub (2-x)}PO{sub 6} does not provide direct evidence for sensitive changes in the phosphorus local symmetry. This result is in good agreement with structural data which show nearly unchanged lattices and atomic separations through the Zn{sup 2+} for Mg{sup 2+} substitution. On the other hand, the Cd{sup 2+} for Mg{sup 2+} substitution behaves differently. Indeed, up to five resonances are observed, each corresponding to one of the five first-cationic neighbour distributions, i.e. 4Mg/0Cd, 3Mg/1Cd, 2Mg/2Cd, 1Mg/3Cd and 0Mg/4Cd. Their intensities match rather well the expected weight for each configuration of the statistical Cd{sup 2+}/Mg{sup 2+} mixed occupancy. The match is further improved when one takes into account the influence of the 2nd cationic sphere that is available from high-field NMR data (18.8 T). Finally, the fine examination of the chemical shift for each resonance versus x allows to de-convolute the mean Z/a {sup 2} effective field into two sub-effects: a lattice constraint-only term and a chemical-only term whose effects are directly quantifiable. - Graphical abstract: First (CdMg){sub 4} cationic sphere influence on the {sup 31}P NMR signal in Bi(Cd,Mg){sub 2}PO{sub 6}. Display Omitted.

  5. HPLC and 31P NMR characterization of the reaction between antitumor platinum agents and the phosphorothioate chemoprotective agent S-2-(3-aminopropylamino)ethylphosphorothioic acid (WR-2721).

    PubMed

    Thompson, D C; Wyrick, S D; Holbrook, D J; Chaney, S G

    1995-10-26

    In prior studies, we examined the effects of the radioprotective and chemoprotective agent WR-2721 [S-2-(3-aminopropylamino)ethylphosphorothioic acid] on the in vivo biotransformation of the cisplatin [cis-diamminedichloroplatinum(II)] analog ormaplatin [(d,I)trans-1,2-diaminocyclohexanetetrachloroplatinum(IV), Pt(dach)Cl4, (formerly called tetraplatin)]. Those data suggested that a direct interaction between WR-2721 and ormaplatin and/or the corresponding Pt(II) drug, Pt(dach)Cl2, may be occurring in vivo. This would be in contrast to the generally accepted hypothesis that WR-2721 is a prodrug that must first be converted by alkaline phosphatase to a free thiol compound, WR-1065, before any appreciable reactivity would be evident. However, the major biotransformation product observed in the peritoneal fluid, plasma, and all tissues was Pt(dach)(WR-1065). We report here on further investigations into the in vitro reactivity of Pt(dach) compounds with WR-2721 and WR-1065. Separation of reaction products resulting from incubation of Pt(dach)(malonato) with either WR-2721 or WR-1065 under physiological conditions gave profiles that were indistinguishable by reverse phase HPLC and cation exchange HPLC at two different pHs. 31P NMR characterization of the dephosphorylation of WR-2721 revealed essentially no loss of inorganic phosphate for up to 24 hr when incubated in unbuffered water at 30 degrees. In contrast, when incubated with a 1:1 molar ratio of cisplatin under the same conditions, the WR-2721 signal was decreased markedly in the first 5 min, and had disappeared almost completely by 1 hr. The signal corresponding to inorganic phosphate increased in parallel to the decrease in the WR-2721 signal. No intermediate formation of a complex containing both platinum and phosphate could be detected at any time. These data suggest that the reaction between WR-2721 and platinum complexes results in rapid dephosphorylation of WR-2721, and, consequently, that the reaction

  6. Characteristics and degradation of carbon and phosphorus from aquatic macrophytes in lakes: insights from solid-state 13C NMR and solution 31P NMR spectroscopy

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Water extractable organic matter (WEOM) derived from macrophytes plays an important role in biogeochemical cycling of nutrients, including carbon (C), nitrogen (N) and phosphorus (P) in lakes. However, reports of their composition and degradation in natural waters are scarce. Therefore, compositions...

  7. A flow-through probe for in Vivo31P NMR spectroscopy of unanesthetized aquatic vertebrates at 9.4 tesla

    NASA Astrophysics Data System (ADS)

    van den Thillart, Guido; Körner, Frans; van Waarde, Aren; Erkelens, Cees; Lugtenburg, Johan

    A flow cell which fits in a modified bioprobe of a Bruker MSL-400 NMR spectrometer and allows the monitoring of the energy metabolism of an enclosed aquatic vertebrate at a selected temperature, water composition, and oxygen level ranging from 0 to 100% air saturation is described. The animal is pressed against the observation window and immobilized by an inflatable plastic bag. No anesthetics are used during the actual experiment. The signal of the tissue of interest is picked up with a surface coil, which is double-tuned to the phosphorus (162 MHz) and proton (400 MHz) frequencies. The flow cell can be moved vertically to the desired position. The usefulness of the fish probe is demonstrated by spectra of excellent resolution and signal-to-noise, obtained from the myotomal muscles of carp, goldfish, rainbow trout, and tilapia, by high phosphocreatine/ inorganic phosphate ratios, indicating a situation of low stress, and by stability of all NMR-observed parameters over periods of at least one working day (8 h).

  8. Characteristics and assessment of biogenic phosphorus in sediments from the multi-polluted Haihe River, China, using phosphorus fractionation and phosphorus-31 nuclear magnetic resonance (31P-NMR)

    NASA Astrophysics Data System (ADS)

    Zhang, W. Q.; Zhang, H.; Tang, W. Z.; Shan, B. Q.

    2013-10-01

    We studied the phosphorus (P) pollution, as described by concentrations, distribution and transformation potential, of sediments of the water scarce and heavily polluted Fuyang River, a tributary of the Haihe River, using P fractionation and phosphorus-31 nuclear magnetic resonance (31P-NMR).The sediments of the Fuyang River accumulate significant amounts of inorganic phosphorus (Pi) and organic phosphorus (Po) from industrial and domestic wastewater and agricultural non-point pollution. In terms of their contribution to total phosphorus, the rank order of the P fractions was as follows: H2SO4-P > NaOH-Pi > Res-P > NaOH-Po > KCl-P and their average relative proportions were 69.7:47.5:15.9:2.9:1.0 (the proportion was based on the average proportion of the KCl-P). Seven P compounds were detected by the 31P-NMR analysis. Orthophosphate (Ortho-P: 45.2-92.4%) and orthophosphate monoesters (mono-P: 6.6-45.7%) were the dominant forms. Smaller amounts of pyrophosphates (pyro-P: 0.1-6.6%), deoxyribonucleic acid (DNA-P: 0.3-3.9%), phosphonates (phon-P: 0-3.3%), phospholipids (lipids-P: 0-2.7%) and polyphosphate (poly-P: 0-0.04%) were observed in the sediments. Results of P fractionation and 31P-NMR analysis showed that 35% of Pi was labile P, including KCl-P and NaOH-Pi (Fe-P and Al-P). Biogenic-P accounted for 24% of P in the sediments. Analysis of the relationships between P species and water quality indicated that the Po compounds would mineralize to form ortho-P and would be potentially bioavailable for recycling to surface water, supporting further growth of phytoplankton and leading to algal blooms.

  9. Characterizing phosphorus in environmental and agricultural samples by 31P nuclear magnetic resonance spectroscopy.

    PubMed

    Cade-Menun, Barbara J

    2005-04-15

    Phosphorus nuclear magnetic resonance ((31)P-NMR) spectroscopy has advanced our knowledge of organic phosphorus (P) in soils and environmental samples more than any other technique. This paper reviews the use of (31)P-NMR spectroscopy for soil, water and other environmental samples. The requirements for a successful solid-state or solution (31)P-NMR experiment are described, including experimental set-up, sample preparation, extractants, experimental conditions, and post-experimental processing. Next, the literature on solid-state and solution (31)P-NMR spectroscopy in environmental samples is reviewed, including papers on: methods; P transformations; agricultural, forest and natural ecosystem soil studies; humic acid and particle size separations; manure, compost and sludge studies; and water research, including freshwater, estuary and marine studies. Future research needs are also discussed as well as suggestions to improve results, such as increased standardization among research groups.

  10. Multiple Antiferromagnetic Spin Fluctuations and Novel Evolution of Tc in Iron-Based Superconductors LaFe(As1‑xPx)(O1‑yFy) Revealed by 31P-NMR Studies

    NASA Astrophysics Data System (ADS)

    Shiota, Takayoshi; Mukuda, Hidekazu; Uekubo, Masahiro; Engetsu, Fuko; Yashima, Mitsuharu; Kitaoka, Yoshio; Lai, Kwing To; Usui, Hidetomo; Kuroki, Kazuhiko; Miyasaka, Shigeki; Tajima, Setsuko

    2016-05-01

    We report on 31P-NMR studies of LaFe(As1‑xPx)(O1‑yFy) over wide compositions for 0 ≤ x ≤ 1 and 0 ≤ y ≤ 0.14, which provide clear evidence that antiferromagnetic spin fluctuations (AFMSFs) are one of the indispensable elements for enhancing Tc. Systematic 31P-NMR measurements revealed two types of AFMSFs in the temperature evolution, that is, one is the AFMSFs that develop rapidly down to Tc with low-energy characteristics, and the other, with relatively higher energy than the former, develops gradually upon cooling from high temperature. The low-energy AFMSFs in low y (electron doping) over a wide x (pnictogen height suppression) range are associated with the two orbitals of dxz/yz, whereas the higher-energy ones for a wide y region around low x originate from the three orbitals of dxy and dxz/yz. We remark that the nonmonotonic variation of Tc as a function of x and y in LaFe(As1‑xPx)(O1‑yFy) is attributed to these multiple AFMSFs originating from degenerated multiple 3d orbitals inherent to Fe-pnictide superconductors.

  11. Hydrothermal synthesis, X-ray structure refinement, 31P NMR spectra and vibrational study of NaLa(HPO4)2

    NASA Astrophysics Data System (ADS)

    Ben Hassen, C.; Boujelbene, M.; Mhiri, T.

    2013-10-01

    NaLa(HPO4)2 was obtained by hydrothermal synthesis. The structure of NaLa(HPO4)2 was determined by X-ray powder diffraction methods. The results of Rietveld refinement revealed a space group P21/c (No. 14), with lattice parameters of a = 9.7151(17) Å, b = 8.320(12) Å, c = 9.83(2) Å, beta = 114.65(17)°, V = 722 (8) Å3 and Z = 4. Final refinement led to RF = 4.86% and RB = 12.35%.The existence of bound O-H and bound P-O in the structure has been confirmed by IR and Raman spectroscopy. The existence of two crystallographically independent phosphorus atoms in the structure has been confirmed by NMR spectrum. The structure is characterized by LaO6 octahedra which are solely connected to six adjacent HPO4 tetrahedra via common O-corners. This structure contains twelve- and four-membered rings forming channels along [1 1¯ 1]. The cross sections of the channels are given by twelve-membered rings consisting of four lanthanum coordination octahedral and eight hydrogenphosphate groups as well as four-membered rings consisting of two lanthanum coordination octahedra and two hydrogenphosphate tetrahedra. Sodium ions are located within those channels of the twelve-membered rings.

  12. 31P NMR 2D Mapping of Creatine Kinase Forward Flux Rate in Hearts with Postinfarction Left Ventricular Remodeling in Response to Cell Therapy

    PubMed Central

    Gao, Ling; Cui, Weina; Zhang, Pengyuan; Jang, Albert; Zhu, Wuqiang; Zhang, Jianyi

    2016-01-01

    Utilizing a fast 31P magnetic resonance spectroscopy (MRS) 2-dimensional chemical shift imaging (2D-CSI) method, this study examined the heterogeneity of creatine kinase (CK) forward flux rate of hearts with postinfarction left ventricular (LV) remodeling. Immunosuppressed Yorkshire pigs were assigned to 4 groups: 1) A sham-operated normal group (SHAM, n = 6); 2) A 60 minutes distal left anterior descending coronary artery ligation and reperfusion (MI, n = 6); 3) Open patch group; ligation injury plus open fibrin patch over the site of injury (Patch, n = 6); and 4) Cell group, hiPSCs-cardiomyocytes, -endothelial cells, and -smooth muscle cells (2 million, each) were injected into the injured myocardium pass through a fibrin patch (Cell+Patch, n = 5). At 4 weeks, the creatine phosphate (PCr)/ATP ratio, CK forward flux rate (Flux PCr→ATP), and k constant of CK forward flux rate (kPCr→ATP) were severely decreased at border zone myocardium (BZ) adjacent to MI. Cell treatment results in significantly increase of PCr/ATP ratio and improve the value of kPCr→ATP and Flux PCr→ATP in BZ myocardium. Moreover, the BZ myocardial CK total activity and protein expression of CK mitochondria isozyme and CK myocardial isozyme were significantly reduced, but recovered in response to cell treatment. Thus, cell therapy results in improvement of BZ bioenergetic abnormality in hearts with postinfarction LV remodeling, which is accompanied by significantly improvements in BZ CK activity and CK isozyme expression. The fast 2D 31P MR CSI mapping can reliably measure the heterogeneity of bioenergetics in hearts with post infarction LV remodeling. PMID:27606901

  13. 31P NMR 2D Mapping of Creatine Kinase Forward Flux Rate in Hearts with Postinfarction Left Ventricular Remodeling in Response to Cell Therapy.

    PubMed

    Gao, Ling; Cui, Weina; Zhang, Pengyuan; Jang, Albert; Zhu, Wuqiang; Zhang, Jianyi

    2016-01-01

    Utilizing a fast 31P magnetic resonance spectroscopy (MRS) 2-dimensional chemical shift imaging (2D-CSI) method, this study examined the heterogeneity of creatine kinase (CK) forward flux rate of hearts with postinfarction left ventricular (LV) remodeling. Immunosuppressed Yorkshire pigs were assigned to 4 groups: 1) A sham-operated normal group (SHAM, n = 6); 2) A 60 minutes distal left anterior descending coronary artery ligation and reperfusion (MI, n = 6); 3) Open patch group; ligation injury plus open fibrin patch over the site of injury (Patch, n = 6); and 4) Cell group, hiPSCs-cardiomyocytes, -endothelial cells, and -smooth muscle cells (2 million, each) were injected into the injured myocardium pass through a fibrin patch (Cell+Patch, n = 5). At 4 weeks, the creatine phosphate (PCr)/ATP ratio, CK forward flux rate (Flux PCr→ATP), and k constant of CK forward flux rate (kPCr→ATP) were severely decreased at border zone myocardium (BZ) adjacent to MI. Cell treatment results in significantly increase of PCr/ATP ratio and improve the value of kPCr→ATP and Flux PCr→ATP in BZ myocardium. Moreover, the BZ myocardial CK total activity and protein expression of CK mitochondria isozyme and CK myocardial isozyme were significantly reduced, but recovered in response to cell treatment. Thus, cell therapy results in improvement of BZ bioenergetic abnormality in hearts with postinfarction LV remodeling, which is accompanied by significantly improvements in BZ CK activity and CK isozyme expression. The fast 2D 31P MR CSI mapping can reliably measure the heterogeneity of bioenergetics in hearts with post infarction LV remodeling. PMID:27606901

  14. Effect of prior exercise in Pi/PC ratio and intracellular pH during a standardized exercise. A study on human muscle using [31P]NMR.

    PubMed

    Laurent, D; Authier, B; Lebas, J F; Rossi, A

    1992-01-01

    Seven subjects underwent a standard localized exercise of calf muscles in order to investigate whether the metabolic exercise-induced steady-state, as revealed by the evaluation of inorganic phosphate/phosphocreatine ratio, depends on the conditioning of the muscle just prior to the exercise. The experimental protocols consisted of two separate experiments using first [31P]nuclear magnetic resonance spectroscopy and second (on 3 subjects) infrared oxyphotometry to respectively follow variation of energy metabolism and tissular deoxygenation. The exercise consisted of 240 successive plantar flexions (0.5 Hz frequency) against a high load equivalent to 80% of the maximal voluntary contraction. This exercise was accomplished before cold exercise and after warm exercise, a warming-up period bringing to approximately 50% of VO2max. The results showed that: (1) steady-state level of phosphate/phosphocreatine and intracellular acidosis was significantly lowered by warming-up; (2) cold and warm exercise steady-state of calculated adenosine diphosphate values were not significantly different; (3) cold exercise rapidly induced a high tissular deoxygenation that is not observed during warm exercise; and (4) time-constant of phosphocreatine resynthesis is lowered after warm exercise but the initial slope of time-evolution is not modified. Parallel experiments also showed that phosphate/phosphocreatine steady-state was not modified in comparison with warm exercise when the same power of exercise was reached by stepwise incrementation of the charge. From these results we postulate that a better tissue oxygenation due to a global or localized warming-up allows to reach the same mechanical performance with a lower decrease of PCr content, owing to a faster adjustment of oxidative metabolism during the transitional period.(ABSTRACT TRUNCATED AT 250 WORDS)

  15. Simultaneous Conoscopic Holography and Raman Spectroscopy

    NASA Technical Reports Server (NTRS)

    Schramm, Harry F.; Kaiser, Bruce

    2005-01-01

    A new instrument was developed for chemical characterization of surfaces that combines the analytical power of Raman spectroscopy with the three-dimensional topographic information provided by conoscopic holography. The figure schematically depicts the proposed hybrid instrument. The output of the conoscopic holographic portion of the instrument is a topographical map of the surface; the output of the Raman portion of the instrument is hyperspectral Raman data, from which the chemical and/or biological composition of the surface would be deduced. By virtue of the basic principles of design and operation of the instrument, the hyperspectral image data would be inherently spatially registered with the topographical data. In conoscopic holography, the object and reference beams of classical holography are replaced by the ordinary and extraordinary components generated by a single beam traveling through a birefringent, uniaxial crystal. In the basic conoscopic configuration, a laser light is projected onto a specimen and the resulting illuminated spot becomes a point source of diffuse light that propagates in every direction. The laser beam is rasterscanned in two dimensions (x and y) perpendicular to the beam axis (z), and at each x,y location, the pattern of interference between the ordinary and extraordinary rays is recorded. The recorded interferogram constitutes the conoscopic hologram. Of particular significance for the proposed instrument is that the conoscopic hologram contains information on the z coordinate (height) of the illuminated surface spot. Hence, a topographical map of the specimen is constructed point-by-point by rastering the laser beam in the x and y directions and correlating the x and y coordinates with the z information obtained from the interferograms. Conoscopic imaging is an established method, and conoscopic laboratory instruments for surface metrology are commercially available. In Raman spectroscopy of a surface, one measures the spectrum

  16. Theoretical Studies on the Fe-M Interactions and 31P NMR in Fe(CO)3(EtPhPpy)2MX2 (X = NCS, SCN, Cl; M = Zn, Cd, Hg)

    NASA Astrophysics Data System (ADS)

    Huang, Xiao-xuan; Xu, Xuan; Xie, Mei-xiang

    2008-10-01

    To study the Fe-M interactions and their effects on 31P NMR, the structures of Fe(CO)3(EtPhPpy)2 1, Fe(CO)3(EtPhPpy)2M(NCS)2 (2: M = Zn, 3: M = Cd, 4: M = Hg) and Fe(CO)3(EtPhPpy)2CdX2 (5: X = C1, 6: X = SCN) were investigated by density functional theory (DFT) PBE0 method. The stabilities S of complexes follow S(2)>S(3)>S(4) and S(3)approxS(6)>S(5), indicating that 6 is stable and may be synthesized. The complexes with thiocyanate are more stable than that with chloride in Fe(CO)3(EtPhPpy)2CdX2. The strength / of Fe-M interactions follows I(2)approxI(3)

  17. Solution (31)P NMR Study of the Acid-Catalyzed Formation of a Highly Charged {U24Pp12} Nanocluster, [(UO2)24(O2)24(P2O7)12](48-), and Its Structural Characterization in the Solid State Using Single-Crystal Neutron Diffraction.

    PubMed

    Dembowski, Mateusz; Olds, Travis A; Pellegrini, Kristi L; Hoffmann, Christina; Wang, Xiaoping; Hickam, Sarah; He, Junhong; Oliver, Allen G; Burns, Peter C

    2016-07-13

    The first neutron diffraction study of a single crystal containing uranyl peroxide nanoclusters is reported for pyrophosphate-functionalized Na44K6[(UO2)24(O2)24(P2O7)12][IO3]2·140H2O (1). Relative to earlier X-ray studies, neutron diffraction provides superior information concerning the positions of H atoms and lighter counterions. Hydrogen positions have been assigned and reveal an extensive network of H-bonds; notably, most O atoms present in the anionic cluster accept H-bonds from surrounding H2O molecules, and none of the surface-bound O atoms are protonated. The D4h symmetry of the cage is consistent with the presence of six encapsulated K cations, which appear to stabilize the lower symmetry variant of this cluster. (31)P NMR measurements demonstrate retention of this symmetry in solution, while in situ (31)P NMR studies suggest an acid-catalyzed mechanism for the assembly of 1 across a wide range of pH values.

  18. Simultaneous surface plasmon resonance and x-ray absorption spectroscopy

    SciTech Connect

    Serrano, A.; Rodriguez de la Fuente, O.; Collado, V.; Rubio-Zuazo, J.; Castro, G. R.; Monton, C.; Garcia, M. A.

    2012-08-15

    We present an experimental setup for the simultaneous measurement of surface plasmon resonance (SPR) and x-ray absorption spectroscopy (XAS) on metallic thin films at a synchrotron beamline. The system allows measuring in situ and in real time the effect of x-ray irradiation on the SPR curves to explore the interaction of x-rays with matter. It is also possible to record XAS spectra while exciting SPR in order to study changes in the films induced by the excitation of surface plasmons. Combined experiments recording simultaneously SPR and XAS curves while scanning different parameters can be also carried out. The relative variations in the SPR and XAS spectra that can be detected with this setup range from 10{sup -3} to 10{sup -5}, depending on the particular experiment.

  19. Simultaneous surface plasmon resonance and x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Serrano, A.; Rodríguez de la Fuente, O.; Collado, V.; Rubio-Zuazo, J.; Monton, C.; Castro, G. R.; García, M. A.

    2012-08-01

    We present an experimental setup for the simultaneous measurement of surface plasmon resonance (SPR) and x-ray absorption spectroscopy (XAS) on metallic thin films at a synchrotron beamline. The system allows measuring in situ and in real time the effect of x-ray irradiation on the SPR curves to explore the interaction of x-rays with matter. It is also possible to record XAS spectra while exciting SPR in order to study changes in the films induced by the excitation of surface plasmons. Combined experiments recording simultaneously SPR and XAS curves while scanning different parameters can be also carried out. The relative variations in the SPR and XAS spectra that can be detected with this setup range from 10-3 to 10-5, depending on the particular experiment.

  20. A phoswich detector for simultaneous alpha-gamma spectroscopy

    NASA Astrophysics Data System (ADS)

    Moghadam, S. Rajabi; Feghhi, S. A. H.; Safari, M. J.

    2015-11-01

    Phoswich detectors are of value for radiation spectroscopy, especially in cases where a low-cost solution for a mixed radiation field is desired. Meanwhile, simultaneous spectroscopy of alpha particles and gamma-rays has many applications in quantification and distinguishing the alpha-emitting radionuclides which usually occur in the analysis of environmental solid samples. Here, we have developed a system for detection of radioactive actinides (e.g., 241Am) based on the alpha-gamma coincidence technique. The underlying concept, is to assemble two appropriately selected scintillators (i.e., a fast and a slow one) together with a discriminating unit for analysis of their data. Detailed Monte Carlo simulation procedure has been developed using the GEANT4 toolkit to design and find enough knowledge about the response of the system in the studied radiation field. Various comparisons were made between experimental and simulation data which showed appropriate agreement between them. The calibration was performed and the MDA was estimated as 60 mBq for the phoswich system.

  1. Simultaneous NIR-EPR spectroscopy of rat brain oxygenation.

    PubMed

    Sakata, Yasuko S; Grinberg, Oleg Y; Grinberg, Stalina; Springett, Roger; Swartz, Harold M

    2005-01-01

    Changes in cerebral oxygenation were simultaneously monitored by electric paramagnetic resonance (EPR) oximetry and near-infrared spectroscopy (NIRS). The tissue oxygen tension (t-pO2) was measured with an L-band (1.2 GHz) EPR spectrometer with an external loop resonator and the concentration of oxyhemoglobin [HbO2] and deoxyhemoglobin [Hb] were measured with a full-spectral NIRS system. Mean cerebral hemoglobin saturation (SmcO2) was calculated from the absolute [HbO2] and [Hb]. Six adult male rats were implanted with lithium phthalocyanine (LiPc) crystals into the left cerebral cortex. The change in oxygenation of the brain was induced by altering the inspired oxygen fraction (FiO2) in air from 0.30 at baseline to 0.0, 0.05, 0.10, and 0.15 for 1, 2, 5, and 5 minutes, respectively, followed by reoxygenation with an FiO2 = 0.30. Although both t-pO2 and SmcO2 values showed a decrease during reduced FiO2 followed by recovery on reoxygenation, it was found that SmcO2 recovered more rapidly than t-PO2 during the recovery phase. The recovery of t-pO2 is not only related to blood oxygenation, but also to delivery, consumption, and diffusion of oxygen into the tissue from the vascular system. Further studies will be required to determine the exact mechanisms for the delay between the recovery of SmcO2 and t-pO2. PMID:16594173

  2. Posttranslational modification of Klebsiella pneumoniae flavodoxin by covalent attachment of coenzyme A, shown by sup 31 P NMR and electrospray mass spectrometry, prevents electron transfer from the nifJ protein to nitrogenase. A possible new regulatory mechanism for biological nitrogen fixation

    SciTech Connect

    Thorneley, R.N.F.; Ashby, G.A.; Drummond, M.H.; Eady, R.R.; Huff, S.; Macdonald, C.J. ); Abell, C.; Schneier, A. )

    1992-02-04

    A strain of Escherichia coli (71-18) that produces ca. 15% of its soluble cytoplasmic protein as a flavodoxin, the Klebsiella pneumoniae nifF gene product, has been constructed. The flavodoxin was purified using FPLC and resolved into two forms, designated KpFldI and KpFldII, which were shown to have identical N-terminal amino acid sequences (30 residues) in agreement with that predicted by the K. pneumoniae nifF DNA sequence. {sup 31}P NMR, electrospray mass spectrometry, UV-visible spectra, and thiol group estimations showed that the single cysteine residue (position 68) of KpFldI is posttranslationally modified in KpFldII by the covalent, mixed disulfide, attachment of coenzyme A. KpFldII was inactive as an electron carrier between the K. pneumoniae nifJ product (a pyruvate-flavodoxin oxidoreductase) and K. pneumoniae nifH product (the Fe-protein of nitrogenase). This novel posttranslational modification of a flavodoxin is discussed in terms of the regulation of nitrogenase activity in vivo in response to the level of dissolved O{sub 2} and the carbon status of diazotrophic cultures.

  3. Phosphorus-31 nuclear magnetic resonance spectroscopy of toad retina.

    PubMed Central

    Apte, D V; Koutalos, Y; McFarlane, D K; Dawson, M J; Ebrey, T G

    1989-01-01

    Phosphorus-31 nuclear magnetic resonance (31P-NMR) spectra were obtained from living toad retinae and toad retinal extracts at 4 degrees C. Several phosphorus metabolites--nucleoside di- and triphosphates (NTP), phosphocreatine, phosphodiesters, inorganic phosphate, and phosphomonoesters--were identified from the spectra of whole retinae. The intracellular pH was determined to be 7.27 +/- 0.06 at 4 degrees C and the intracellular MgNTP/NTP ratio was at least 0.77. These results are consistent with those reported by other techniques, and they show that 31P-NMR spectroscopy can be used for noninvasively and quantitatively studying the metabolism of living toad retinae, and for monitoring its changes over time. PMID:2506940

  4. Tethered bilayer lipid membranes studied by simultaneous attenuated total reflectance infrared spectroscopy and electrochemical impedance spectroscopy

    PubMed Central

    Erbe, Andreas; Bushby, Richard J.; Evans, Stephen D.; Jeuken, Lars J. C.

    2013-01-01

    The formation of tethered lipid bilayer membranes (tBLMs) from unilamelar vesicles of egg yolk phosphatidylcholine (EggPC) on mixed self–assembled monolayers (SAMs) from varying ratios of 6-mercaptohexanol and EO3Cholesteryl on gold has been monitored by simultaneous attenuated total reflectance fourier transform infrared (ATR–FTIR) spectroscopy and electrochemical impedance spectroscopy (EIS). The influence of the lipid orientation (and hence the anisotropy) of lipids on a gold film on the dichroic ratio was studied by simulations of spectra with a matrix method for anisotropic layers. It is shown that for certain tilt angles of the dielectric tensor of the adsorbed anisotropic layer dispersive and negative absorption bands are possible. The experimental data indicates that the structure of the assemblies obtained varies with varying SAM composition. On SAMs with a high content of EO3Cholesteryl, tBLMs with reduced fluidity are formed. For SAMs with high content of 6-mercaptohexanol, the results are consistent with the adsorption of flattened vesicles, while spherical vesicles have been found in a small range of surface compositions. The kinetics of the adsorption process is consistent with the assumption of spherical vesicles as long–living intermediates for surfaces of high 6-mercaptohexanol content. No long–living spherical vesicles have been detected for surfaces with large fraction of EO3Cholesteryl tethers. The observed differences between the surfaces suggest that for the formation of tBLMs (unlike supported BLMs) no critical surface coverage of vesicles is needed prior to lipid bilayer formation. PMID:17388505

  5. Biogenic phosphorus in oligotrophic mountain lake sediments: differences in composition measured with NMR spectroscopy.

    PubMed

    Ahlgren, Joakim; Reitzel, Kasper; Danielsson, Rolf; Gogoll, Adolf; Rydin, Emil

    2006-12-01

    Phosphorus (P) composition in alkaline sediment extracts from three Swedish oligotrophic mountain lakes was investigated using 31P-NMR spectroscopy. Surface sediments from one natural lake and two mature reservoirs, one of which has received nutrient additions over the last 3 years, were compared with respect to biogenic P composition. The results show significant differences in the occurrence of labile and biogenic P species in the sediments of the different systems. The P compound groups that varied most between these three systems were pyrophosphate and polyphosphates, compound groups known to play an important role in sediment P recycling. The content of these compound groups was lowest in the reservoirs and may indicate a coupling between anthropogenic disturbances (i.e., impoundment) to a water system and the availability of labile P species in the sediment. A statistical study was also conducted to determine the accuracy and reliability of using 31P-NMR spectroscopy for quantification of sediment P forms. PMID:17070896

  6. Simultaneous multi-beam planar array IR (pair) spectroscopy

    DOEpatents

    Elmore, Douglas L.; Rabolt, John F.; Tsao, Mei-Wei

    2005-09-13

    An apparatus and method capable of providing spatially multiplexed IR spectral information simultaneously in real-time for multiple samples or multiple spatial areas of one sample using IR absorption phenomena requires no moving parts or Fourier Transform during operation, and self-compensates for background spectra and degradation of component performance over time. IR spectral information and chemical analysis of the samples is determined by using one or more IR sources, sampling accessories for positioning the samples, optically dispersive elements, a focal plane array (FPA) arranged to detect the dispersed light beams, and a processor and display to control the FPA, and display an IR spectrograph. Fiber-optic coupling can be used to allow remote sensing. Portability, reliability, and ruggedness is enhanced due to the no-moving part construction. Applications include determining time-resolved orientation and characteristics of materials, including polymer monolayers. Orthogonal polarizers may be used to determine certain material characteristics.

  7. Spectroscopy of Solar Prominences Simultaneously From Space and Ground

    NASA Astrophysics Data System (ADS)

    Stellmacher, G.; Wiehr, E.; Dammasch, I. E.

    2003-10-01

    We present a comprehensive set of spectral data from two quiescent solar prominences observed in parallel from space and ground: with the VTT, simultaneous two-dimensional imaging of Hβ4862 Å and Caii 8542 Å yields a constant ratio, indicating small spatial pressure variations over the prominence. With the Gregory, simultaneous spectra of Caii 8542 Å and Hei 10830 Å were taken, their widths yielding 8000 K

  8. An investigation of the potential of 31-phosphorus nuclear magnetic resonance spectroscopy to predict radiation sensitivity

    SciTech Connect

    Bowser, C.L.

    1988-01-01

    The ability of in vivo 31-Phosphorus Nuclear Magnetic Resonance (31-P NMR) Spectroscopy to predict radiation sensitivity following both single and fractionated therapy was evaluated in this study. For Radiation Induced Fibrosarcoma (RIF-1) tumors either, in their natural state or treated with the vasodilator, hydralazine, an increase in the ratio of phosphocreatine to inorganic phosphate (PCr/Pi) and tumor pH were shown to be significantly correlated with radiation sensitivity to a single dose of 15 Grays (Gy) of radiation. After administration of hydralazine to reduce tumor blood flow or flunarizine to increase tumor blood flow, time dependent changes were observed in the 31-P NMR spectrum. After hydralazine, there was a significant decrease in PCr/Pi over time. The opposite pattern was seen flunarizine i.e., decline in Pi, and an increase in PCr and pH. The radiosensitivity of flunarizine treated tumors was substantially greater than that of hydralazine treated tumors.

  9. A new microvascular model for noninvasive nuclear magnetic resonance spectroscopy of the transplanted kidney.

    PubMed

    Haug, C E; Shapiro, J I; Chan, L; Weil, R

    1988-03-01

    The cellular biology of graft rejection is not well understood. Phosphorus-31 nuclear magnetic resonance (31P NMR) spectroscopy is a new noninvasive technique for the measurement of intracellular pH and relative amounts of phosphorus-containing compounds, such as adenosine triphosphate (ATP), inorganic phosphate, phosphocreatine, and sugar phosphates, in any tissue from which a clear signal can be obtained. Biochemical analysis of such precision, without the need for tissue destruction, represents an unusual opportunity for analysis of in vivo cellular metabolism under varying conditions, including graft rejection. 31P NMR study of intra-abdominal viscera has not been feasible in most laboratories without laparotomy because of signal interference from abdominal wall muscle. In this study, to eliminate this interference, a rat kidney was transplanted to the groin, where it could be serially studied without overlying skeletal muscle. This new vascular technique was successful in 11 of 11 attempts and maintained normal serum creatinines in 10 chronic survivors after removal of both native kidneys. The 31P NMR spectroscopic signal from the groin kidney is clear and highly reproducible. This new microvascular model will make it possible to carry out noninvasive long-term spectroscopic studies that could potentially identify a reliable marker for allograft rejection. PMID:3278404

  10. Mitochondrial, acidic, and cytosolic pHs determination by ³¹P NMR spectroscopy: design of new sensitive targeted pH probes.

    PubMed

    Culcasi, Marcel; Thétiot-Laurent, Sophie; Atteia, Ariane; Pietri, Sylvia

    2015-01-01

    (31)P nuclear magnetic resonance (NMR) is a unique technique to monitor noninvasively the energetics of living systems at real time through the detection of a variety of phosphorylated metabolites. Using adequately designed α-aminophosphonates as external probes, we have shown earlier that (31)P NMR can also give access simultaneously to the accurate pH of cytosolic and acidic compartments in normal and stressed cultured cells or isolated perfused organs, a feature that was not possible using endogenous inorganic phosphate as the probe. More recently, we obtained a series of derivatives of these new pH probes that incorporate a triphenylphosphonium cation as a specific vector to the mitochondrion. Here, we describe the synthesis, (31)P NMR pH titrating properties in buffers, and application in cultures of the green alga Chlamydomonas reinhardtii of two of these mitochondria-targeted pH probes in comparison with one nonvectorized, yet still informative α-aminophosphonate.

  11. Mitochondrial, acidic, and cytosolic pHs determination by ³¹P NMR spectroscopy: design of new sensitive targeted pH probes.

    PubMed

    Culcasi, Marcel; Thétiot-Laurent, Sophie; Atteia, Ariane; Pietri, Sylvia

    2015-01-01

    (31)P nuclear magnetic resonance (NMR) is a unique technique to monitor noninvasively the energetics of living systems at real time through the detection of a variety of phosphorylated metabolites. Using adequately designed α-aminophosphonates as external probes, we have shown earlier that (31)P NMR can also give access simultaneously to the accurate pH of cytosolic and acidic compartments in normal and stressed cultured cells or isolated perfused organs, a feature that was not possible using endogenous inorganic phosphate as the probe. More recently, we obtained a series of derivatives of these new pH probes that incorporate a triphenylphosphonium cation as a specific vector to the mitochondrion. Here, we describe the synthesis, (31)P NMR pH titrating properties in buffers, and application in cultures of the green alga Chlamydomonas reinhardtii of two of these mitochondria-targeted pH probes in comparison with one nonvectorized, yet still informative α-aminophosphonate. PMID:25634273

  12. Novel approach to the detection and quantification of phenolic compounds in olive oil based on 31P nuclear magnetic resonance spectroscopy.

    PubMed

    Christophoridou, Stella; Dais, Photis

    2006-02-01

    31P NMR spectroscopy has been employed to detect and quantify phenolic compounds in the polar fraction of virgin olive oil. This novel analytical method is based on the derivatization of the hydroxyl and carboxyl groups of phenolic compounds with 2-chloro-4,4,5,5-tetramethyldioxaphospholane and the identification of the phosphitylated compounds on the basis of the 31P chemical shifts. Quantification of a large number of phenolic compounds in virgin olive oil can be accomplished by integration of the appropriate signals in the 31P NMR spectrum and the use of the phosphitylated cyclohexanol as internal standard. Finally, the validity of this technique for quantitative measurements was thoroughly examined. PMID:16448164

  13. Probing Ion Channel Conformational Dynamics Using Simultaneous Single-Molecule Ultrafast Spectroscopy and Patch-Champ Electric Recording

    SciTech Connect

    Harms, Gregory S.; Orr, Galya; Lu, H Peter

    2004-03-08

    A new approach to probing single-molecule ion channel kinetics and conformational dynamics, patch-clamp confocal fluorescence microscopy (PCCFM), uses simultaneous ultrafast fluorescence spectroscopy and single-channel electric current recording.

  14. Simultaneous measurement of neuronal activity and cortical hemodynamics by unshielded magnetoencephalography and near-infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Seki, Yusuke; Miyashita, Tsuyoshi; Kandori, Akihiko; Maki, Atsushi; Koizumi, Hideaki

    2012-10-01

    The correlation between neuronal activity and cortical hemodynamics, namely, neurovascular coupling (NVC), is important to shed light on the mechanism of a variety of brain functions or neuronal diseases. NVC can be studied by simultaneously measuring neuronal activity and cortical hemodynamics. Consequently, noninvasive measurements of the NVC have been widely studied using both electroencephalography (EEG) and functional magnetic resonance imaging (fMRI). However, electromagnetic interference between EEG and fMRI is still a major problem. On the other hand, near-infrared spectroscopy (NIRS) is another promising tool for detecting cortical hemodynamics because it can be combined with EEG or magnetoencephalography (MEG) without any electromagnetic interference. Accordingly, in the present study, a simultaneous measurement system-combining an unshielded MEG using a two-dimensional gradiometer based on a low-T superconducting quantum interference device (SQUID) and an NIRS using nonmagnetic thin probes-was developed. This combined system was used to simultaneously measure both an auditory-evoked magnetic field and blood flow change in the auditory cortex. It was experimentally demonstrated that the combined unshielded MEG/NIRS system can simultaneously measure neuronal activity and cortical hemodynamics.

  15. Simultaneous composition and thickness measurement of paper using terahertz time-domain spectroscopy.

    PubMed

    Mousavi, Payam; Haran, Frank; Jez, David; Santosa, Fadil; Dodge, John Steven

    2009-11-20

    We present a noncontact method for quantitative composition and thickness monitoring of flat sheet products using terahertz time-domain spectroscopy. We apply the method to obtain simultaneous measurement of thickness and moisture content of paper sheets. The paper is modeled as an effective medium of water mixed with fibers, and model parameters are estimated from fits to the measured transmission amplitude. We demonstrate the method on two different paper samples and obtain uncertainties that are comparable with existing sensor technology. Monte Carlo simulations indicate that these uncertainties can be reduced further by at least an order of magnitude. PMID:19935977

  16. Dynamic High-Resolution H-1 and P-31 NMR Spectroscopy and H-1 T-2 Measurements in Postmortem Rabbit Muscles Using Slow Magic Angle Spinning

    SciTech Connect

    Bertram, Hanne Christine; Hu, Jian Zhi; Rommereim, Donald N.; Wind, Robert A.; Andersen, Henrik J.

    2004-05-05

    Postmortem changes in rabbit muscle tissue with different glycogen status (normal vs low) were followed continuously from 13 min postmortem until 8 h postmortem and again 20 h postmortem using simultaneous magic angle spinning 1H and 31P NMR spectroscopy together with measurement of the transverse relaxation time, T2, of the muscle water. The 1H metabolite spectra were measured using the phase-altered spinning sidebands (PASS) technique at a spinning rate of 40 Hz. pH values calculated from the 31P NMR spectra using the chemical shifts of the C-6 line of histidine in the 1H spectra and the chemical shifts of inorganic phosphate in the 31P spectra confirmed the different muscle glycogen status in the tissues. High-resolution 1H spectra obtained from the PASS technique revealed the presence of a new resonance line at 6.8 ppm during the postmortem period, which were absent in muscles with low muscle glycogen content. This new resonance line may originate from the aminoprotons in creatine, and its appearance may be a result of a pH effect on the exchange rate between the amino and the water protons and thereby the NMR visibility. Alternatively, the new resonance line may originate from the aromatic protons in tyrosine, and its appearance may be a result of a pH-induced protein unfolding exposing hydrophobic amino acid residues to the aqueous environment. Further studies are needed to evaluate these hypotheses. Finally, distributed analysis of the water T2 relaxation data revealed three relaxation populations and an increase in the population believed to reflect extramyofibrillar water through the postmortem period. This increase was significantly reduced (p < 0.0001) in samples from animals with low muscle glycogen content, indicating that the pH is controlling the extent of postmortem expulsion of water from myofibrillar structures. The significance of the postmortem increase in the amount extramyofibrillar water on the water-holding capacity was verified by

  17. Simultaneous measurement of electroencephalography and near-infrared spectroscopy during voluntary motor preparation

    PubMed Central

    Zama, Takuro; Shimada, Sotaro

    2015-01-01

    We investigated the relationship between electrophysiological activity and haemodynamic response during motor preparation by simultaneous recording of electroencephalography (EEG) and near-infrared spectroscopy (NIRS). It is still unknown how exactly EEG signals correlate with the haemodynamic response, although the activation in the premotor area during motor preparation has been captured by EEG and haemodynamic approaches separately. We conducted EEG-NIRS simultaneous recordings over the sensorimotor area with a self-paced button press task. Participants were instructed to press a button at their own pace after a cue was shown. The result showed that the readiness potential (RP), a negative slow potential shift occurring during motor preparation, on C3 in the extended 10–20 system occurred about 1000 ms before the movement onset. An increase in concentration of oxyhaemoglobin (oxyHb) in the premotor cortex during motor preparation was also confirmed by NIRS, which resulted in a significant correlation between the amplitude of the RP and the change in oxyHb concentration (Pearson’s correlation r2 = 0.235, p = 0.03). We show that EEG-NIRS simultaneous recording can demonstrate the correlation between the RP and haemodynamic response in the premotor cortex contralateral to the performing hand. PMID:26574186

  18. Simultaneous Surface-Enhanced Raman Scattering Imaging and Spectroscopy in Confocal Mode.

    NASA Astrophysics Data System (ADS)

    Pristinski, Denis; Erol, Melek; Du, Henry; Sukhishvili, Svetlana

    2007-03-01

    Noble colloidal metal nanoparticles deposited on a planar substrate facilitate ultrasensitive measurements via surface-enhanced Raman scattering (SERS) spectroscopy. Due to the random nature of nanoparticle immobilization, the variation of interparticle distance and possible aggregate formation cause significant fluctuation in SERS signal intensity across the substrate. To study the nature of these intensity fluctuations we have built a microscope capable of simultaneous imaging in epi-fluorescent mode and spectroscopy of a point of interest in confocal mode. Two excitation beams from the same laser (DPSS 532 nm) are mixed to expose the imaged area and to focus on the point of interest through high N.A. objective. The scattered light collected by the same objective is filtered and split between a cooled CCD camera for imaging and a fiber-connected spectrometer for confocal mode spectroscopy. Positively charged Ag nanoparticles prepared by polyethyleneimine-assisted reduction were deposited on glass substrate and used for the assessment of uniformity of SERS signal from subsequently adsorbed anionic molecules and for the identification of proteins. ^1 Department of Chemical, BioMedical, and Materials Engineering ^2 Department of Chemistry and Chemical Biology

  19. Observing Solvation Dynamics with Simultaneous Femtosecond X-ray Emission Spectroscopy and X-ray Scattering.

    PubMed

    Haldrup, Kristoffer; Gawelda, Wojciech; Abela, Rafael; Alonso-Mori, Roberto; Bergmann, Uwe; Bordage, Amélie; Cammarata, Marco; Canton, Sophie E; Dohn, Asmus O; van Driel, Tim Brandt; Fritz, David M; Galler, Andreas; Glatzel, Pieter; Harlang, Tobias; Kjær, Kasper S; Lemke, Henrik T; Møller, Klaus B; Németh, Zoltán; Pápai, Mátyás; Sas, Norbert; Uhlig, Jens; Zhu, Diling; Vankó, György; Sundström, Villy; Nielsen, Martin M; Bressler, Christian

    2016-02-18

    In liquid phase chemistry dynamic solute-solvent interactions often govern the path, ultimate outcome, and efficiency of chemical reactions. These steps involve many-body movements on subpicosecond time scales and thus ultrafast structural tools capable of capturing both intramolecular electronic and structural changes, and local solvent structural changes are desired. We have studied the intra- and intermolecular dynamics of a model chromophore, aqueous [Fe(bpy)3](2+), with complementary X-ray tools in a single experiment exploiting intense XFEL radiation as a probe. We monitored the ultrafast structural rearrangement of the solute with X-ray emission spectroscopy, thus establishing time zero for the ensuing X-ray diffuse scattering analysis. The simultaneously recorded X-ray diffuse scattering patterns reveal slower subpicosecond dynamics triggered by the intramolecular structural dynamics of the photoexcited solute. By simultaneous combination of both methods only, we can extract new information about the solvation dynamic processes unfolding during the first picosecond (ps). The measured bulk solvent density increase of 0.2% indicates a dramatic change of the solvation shell around each photoexcited solute, confirming previous ab initio molecular dynamics simulations. Structural changes in the aqueous solvent associated with density and temperature changes occur with ∼1 ps time constants, characteristic for structural dynamics in water. This slower time scale of the solvent response allows us to directly observe the structure of the excited solute molecules well before the solvent contributions become dominant. PMID:26783685

  20. Beyond hard x-ray photoelectron spectroscopy: Simultaneous combination with x-ray diffraction

    SciTech Connect

    Rubio-Zuazo, Juan; Castro, German R.

    2013-05-15

    Hard x-ray photoelectron spectroscopy (HAXPES) is a powerful and novel emerging technique for the nondestructive determination of electronic properties and chemical composition of bulk, buried interfaces and surfaces. It benefits from the exceptionally large escape depth of high kinetic energy photoelectrons, increasing the information depth up to several tens of nanometers. Complementing HAXPES with an atomic structure sensitive technique (such as x-ray diffraction) opens a new research field with major applications for materials science. At SpLine, the Spanish CRG beamline at the European Synchrotron Radiation Facility, we have developed a novel experimental set-up that combines HAXPES and x-ray diffraction (x-ray reflectivity, surface x-ray diffraction, grazing incidence x-ray diffraction, and reciprocal space maps). Both techniques can be operated simultaneously on the same sample and using the same excitation source. The set-up includes a robust 2S + 3D diffractometer hosting a ultrahigh vacuum chamber equipped with a unique photoelectron spectrometer (few eV < electron kinetic energy < 15 keV), x-ray tube (Mg/Ti), 15 keV electron gun, and auxiliary standard surface facilities (molecular beam epitaxy evaporator, ion gun, low energy electron diffraction, sample heating/cooling system, leak valves, load-lock sample transfer, etc.). This end-station offers the unique possibility of performing simultaneous HAXPES + x-ray diffraction studies. In the present work, we describe the experimental set-up together with two experimental examples that emphasize its outstanding capabilities: (i) nondestructive characterization of the Si/Ge and HfO{sub 2}/SiO{sub 2} interfaces on Ge-based CMOS devices, and (ii) strain study on La{sub 0.7}Ca{sub 0.3}MnO{sub 3} ultrathin films grown on SrTiO{sub 3}(001) substrate.

  1. Simultaneous optimization by neuro-genetic approach for analysis of plant materials by laser induced breakdown spectroscopy

    NASA Astrophysics Data System (ADS)

    Nunes, Lidiane Cristina; da Silva, Gilmare Antônia; Trevizan, Lilian Cristina; Santos Júnior, Dario; Poppi, Ronei Jesus; Krug, Francisco José

    2009-06-01

    A simultaneous optimization strategy based on a neuro-genetic approach is proposed for selection of laser induced breakdown spectroscopy operational conditions for the simultaneous determination of macro-nutrients (Ca, Mg and P), micro-nutrients (B, Cu, Fe, Mn and Zn), Al and Si in plant samples. A laser induced breakdown spectroscopy system equipped with a 10 Hz Q-switched Nd:YAG laser (12 ns, 532 nm, 140 mJ) and an Echelle spectrometer with intensified coupled-charge device was used. Integration time gate, delay time, amplification gain and number of pulses were optimized. Pellets of spinach leaves (NIST 1570a) were employed as laboratory samples. In order to find a model that could correlate laser induced breakdown spectroscopy operational conditions with compromised high peak areas of all elements simultaneously, a Bayesian Regularized Artificial Neural Network approach was employed. Subsequently, a genetic algorithm was applied to find optimal conditions for the neural network model, in an approach called neuro-genetic. A single laser induced breakdown spectroscopy working condition that maximizes peak areas of all elements simultaneously, was obtained with the following optimized parameters: 9.0 µs integration time gate, 1.1 µs delay time, 225 (a.u.) amplification gain and 30 accumulated laser pulses. The proposed approach is a useful and a suitable tool for the optimization process of such a complex analytical problem.

  2. Simultaneous 19F-1H medium resolution NMR spectroscopy for online reaction monitoring

    NASA Astrophysics Data System (ADS)

    Zientek, Nicolai; Laurain, Clément; Meyer, Klas; Kraume, Matthias; Guthausen, Gisela; Maiwald, Michael

    2014-12-01

    Medium resolution nuclear magnetic resonance (MR-NMR) spectroscopy is currently a fast developing field, which has an enormous potential to become an important analytical tool for reaction monitoring, in hyphenated techniques, and for systematic investigations of complex mixtures. The recent developments of innovative MR-NMR spectrometers are therefore remarkable due to their possible applications in quality control, education, and process monitoring. MR-NMR spectroscopy can beneficially be applied for fast, non-invasive, and volume integrating analyses under rough environmental conditions. Within this study, a simple 1/16″ fluorinated ethylene propylene (FEP) tube with an ID of 0.04″ (1.02 mm) was used as a flow cell in combination with a 5 mm glass Dewar tube inserted into a benchtop MR-NMR spectrometer with a 1H Larmor frequency of 43.32 MHz and 40.68 MHz for 19F. For the first time, quasi-simultaneous proton and fluorine NMR spectra were recorded with a series of alternating 19F and 1H single scan spectra along the reaction time coordinate of a homogeneously catalysed esterification model reaction containing fluorinated compounds. The results were compared to quantitative NMR spectra from a hyphenated 500 MHz online NMR instrument for validation. Automation of handling, pre-processing, and analysis of NMR data becomes increasingly important for process monitoring applications of online NMR spectroscopy and for its technical and practical acceptance. Thus, NMR spectra were automatically baseline corrected and phased using the minimum entropy method. Data analysis schemes were designed such that they are based on simple direct integration or first principle line fitting, with the aim that the analysis directly revealed molar concentrations from the spectra. Finally, the performance of 1/16″ FEP tube set-up with an ID of 1.02 mm was characterised regarding the limit of detection (LOQ (1H) = 0.335 mol L-1 and LOQ (19F) = 0.130 mol L-1 for trifluoroethanol in

  3. Simultaneous (19)F-(1)H medium resolution NMR spectroscopy for online reaction monitoring.

    PubMed

    Zientek, Nicolai; Laurain, Clément; Meyer, Klas; Kraume, Matthias; Guthausen, Gisela; Maiwald, Michael

    2014-10-18

    Medium resolution nuclear magnetic resonance (MR-NMR) spectroscopy is currently a fast developing field, which has an enormous potential to become an important analytical tool for reaction monitoring, in hyphenated techniques, and for systematic investigations of complex mixtures. The recent developments of innovative MR-NMR spectrometers are therefore remarkable due to their possible applications in quality control, education, and process monitoring. MR-NMR spectroscopy can beneficially be applied for fast, non-invasive, and volume integrating analyses under rough environmental conditions. Within this study, a simple 1/16″ fluorinated ethylene propylene (FEP) tube with an ID of 0.04″ (1.02mm) was used as a flow cell in combination with a 5mm glass Dewar tube inserted into a benchtop MR-NMR spectrometer with a (1)H Larmor frequency of 43.32MHz and 40.68MHz for (19)F. For the first time, quasi-simultaneous proton and fluorine NMR spectra were recorded with a series of alternating (19)F and (1)H single scan spectra along the reaction time coordinate of a homogeneously catalysed esterification model reaction containing fluorinated compounds. The results were compared to quantitative NMR spectra from a hyphenated 500MHz online NMR instrument for validation. Automation of handling, pre-processing, and analysis of NMR data becomes increasingly important for process monitoring applications of online NMR spectroscopy and for its technical and practical acceptance. Thus, NMR spectra were automatically baseline corrected and phased using the minimum entropy method. Data analysis schemes were designed such that they are based on simple direct integration or first principle line fitting, with the aim that the analysis directly revealed molar concentrations from the spectra. Finally, the performance of 1/16″ FEP tube set-up with an ID of 1.02mm was characterised regarding the limit of detection (LOQ ((1)H)=0.335molL(-1) and LOQ ((19)F)=0.130molL(-1) for trifluoroethanol

  4. High Resolution Electron Energy Loss Spectroscopy with Simultaneous Energy and Momentum Mapping

    NASA Astrophysics Data System (ADS)

    Zhu, Xuetao; Cao, Yanwei; Zhang, Shuyuan; Jia, Xun; Guo, Qinlin; Yang, Fang; Zhu, Linfan; Kesmodel, Larry; Zhang, Jiandi; Plummer, Ward; Guo, Jiandong

    2015-03-01

    High resolution electron energy loss spectroscopy (HREELS) has been demonstrated as a powerful technique to probe vibrational and electronic surface excitations of solids. The dispersion relation of the surface excitations, i.e. energy as a function of momentum, can be obtained via the angle resolved measurements by rotating the sample or the analyzer in a conventional HREELS measurement. The sampling density in the momentum space and the detecting efficiency are restricted by the mechanical rotation. Here we introduce a new design of the HREELS system, by combining the traditional Ibach-type electron source with the mainstream hemispherical electron energy analyzer, which could simultaneously measure the energy and momentum of the scattered electrons without any mechanical rotation. The new system possesses higher efficiency and sampling density of momentum-resolved measurements by at least one order of magnitude than conventional spectrometers without deteriorating the resolution of energy and momentum. Using Bi2Sr2CaCu2O8+δ as an example, we show that an energy loss spectrum can be scanned throughout the first Brillouin zone and a momentum-dependent spectral intensity distribution could be obtained in one measurement.

  5. Multichannel wearable system dedicated for simultaneous electroencephalography/near-infrared spectroscopy real-time data acquisitions

    NASA Astrophysics Data System (ADS)

    Lareau, Etienne; Lesage, Frederic; Pouliot, Philippe; Nguyen, Dang; Le Lan, Jerome; Sawan, Mohamad

    2011-09-01

    Functional neuroimaging is becoming a valuable tool in cognitive research and clinical applications. The clinical context brings specific constraints that include the requirement of a high channel count to cover the whole head, high sensitivity for single event detection, and portability for long-term bedside monitoring. For epilepsy and stroke monitoring, the combination of electroencephalography (EEG) and functional near-infrared spectroscopy (NIRS) is expected to provide useful clinical information, and efforts have been deployed to create prototypes able to simultaneously acquire both measurement modalities. However, to the best of our knowledge, existing systems lack portability, NIRS sensitivity, or have low channel count. We present a battery-powered, portable system with potentially up to 32 EEG channels, 32 NIRS light sources, and 32 detectors. Avalanche photodiodes allow for high NIRS sensitivity and the autonomy of the system is over 24 h. A reduced channel count prototype with 8 EEG channels, 8 sources, and 8 detectors was tested on phantoms. Further validation was done on five healthy adults using a visual stimulation protocol to detect local hemodynamic changes and visually evoked potentials. Results show good concordance with literature regarding functional activations and suggest sufficient performance for clinical use, provided some minor adjustments were made.

  6. Simultaneous measurement of NO and NO(2) by dual-wavelength quantum cascade laser spectroscopy.

    PubMed

    Jágerská, Jana; Jouy, Pierre; Tuzson, Béla; Looser, Herbert; Mangold, Markus; Soltic, Patrik; Hugi, Andreas; Brönnimann, Rolf; Faist, Jérôme; Emmenegger, Lukas

    2015-01-26

    The concept of a multi-wavelength quantum cascade laser emitting at two or more spectrally well-separated wavelengths is highly appealing for applied spectroscopy, as it allows detecting several species with compact and cost-efficient optical setups. Here we present a practical realization of such a dual-wavelength setup, which is based on a room-temperature quantum cascade laser emitting single-mode at 1600 cm-1 and 1900 cm-1 and is thus well-suited for simultaneous NO and NO2 detection. Operated in a time-division multiplexed mode, our spectrometer reaches detection limits of 0.5 and 1.5 ppb for NO2 and NO, respectively. The performance of the system is validated against the well-established chemiluminescence detection while measuring the NOx emissions on an automotive test-bench, as well as upon monitoring the pollution at a suburban site. PMID:25835908

  7. Simultaneous prediction of density and moisture content of wood by terahertz time domain spectroscopy

    NASA Astrophysics Data System (ADS)

    Inagaki, Tetsuya; Ahmed, Belal; Hartley, Ian D.; Tsuchikawa, Satoru; Reid, Matthew

    2014-11-01

    In this study, demonstration of simultaneous prediction of solid wood density and moisture content, both of which are critical in manufacturing operations, of 4 species (Aspen, Birch, Hemlock and Maple) was accomplished using terahertz time-domain spectroscopy (THz-TDS). THz measurements of wood at various moisture contents were taken for two orientations of the THz field (parallel and perpendicular) with respect to the visible grain. The real and imaginary parts of the dielectric function averaged over the frequency range of 0.1 to 0.2 THz had strong correlation with density and moisture content of the wood. We extend a model that has been applied previously to oven-dry wood to include the effects of moisture below the fiber saturation point by combining two effective medium models, which allows the dielectric function of water, air and oven-dry cell wall material to be modeled to give an effective dielectric function for the wood. A strong correlation between measured and predicted values for density and moisture content were observed.

  8. Simultaneous species concentration and temperature measurements using laser induced breakdown spectroscopy with direct spectrum matching

    NASA Astrophysics Data System (ADS)

    McGann, Brendan J.

    Laser induced breakdown spectroscopy (LIBS) is used to simultaneously measure hydrocarbon fuel concentration and temperature in high temperature, high speed, compressible, and reacting flows, a regime in which LIBS has not been done previously. Emission spectra from the plasma produced from a focused laser pulse is correlated in the combustion region of a model scramjet operating in supersonic wind tunnel. A 532 nm Nd:YAG laser operating at 10 Hz is used to induce break-down. The emissions are captured during a 10 ns gate time approximately 75 ns after the first arrival of photons at the measurement location in order to minimize the measurement uncertainty in the turbulent, compressible, high-speed, and reacting environment. Three methods of emission detection are used and a new backward scattering direction method is developed that is beneficial in reducing the amount of optical access needed to perform LIBS measurements. Measurements are taken in the model supersonic combustion and the ignition process is shown to be highly dependent on fuel concentration and gas density as well as combustion surface temperature, concentration gradient, and flow field. Direct spectrum matching method is developed and used for quantitative measurements. In addition, a comprehensive database of spectra covering the fuel concentrations and gas densities found in the wind tunnel of Research Cell 19 at Wright Patterson Air Force Base is created which can be used for further work.

  9. [Simultaneous quantitative analysis of multielements in Al alloy samples by laser-induced breakdown spectroscopy].

    PubMed

    Sun, Lan-Xiang; Yu, Hai-Bin

    2009-12-01

    The multielement components of some aluminium alloy samples were quantified by using laser-induced breakdown spectroscopy (LIBS). The Nd : YAG pulsed laser was used to produce plasma in ambient air. The spectral range of 200-980 nm was simultaneously obtained through a multichannel grating spectrometer and CCD detectors. The authors studied the influences of time delays, energy of the laser, and depth profile of elements in samples on spectral intensity, and optimized the experimental parameters based on the influence analysis. With the optimal experimental parameters, the authors made the calibration curves by four certified aluminum alloy samples for eight elements, Si, Fe, Cu, Mn, Mg, Zn, Sn, and Ni, and quantified the composition of an aluminum sample. The obtained maximum relative standard deviation (RSD) was 5.89%, and relative errors were--20.99%-15%. Experimental results show that LIBS is an effective technique for quantitative analysis of aluminum alloy samples, though the improved accuracy of the quantitative analysis is necessary.

  10. Simultaneous Determination of Amiloride and Hydrochlorothiazide in a Compound Tablet by Diffuse Reflectance Spectroscopy and Chemometrics

    NASA Astrophysics Data System (ADS)

    Tang, J.; Li, X.; Feng, Y.; Liang, B.

    2016-09-01

    This paper studies the simultaneous determination of amiloride hydrochloride (AMH) and hydrochlorothiazide (HCTZ) in amiloride hydrochloride tablets by ultraviolet-visible-shortwave near-infrared diffuse reflectance spectroscopy (UV-Vis-swNIR DRS) and chemometrics. Quantitative models for the two components were established by partial least squares (PLS) and support vector regression (SVR), respectively. For the PLS models of AMH and HCTZ, the determination coefficient R2 of the calibration set was 0.9503 and 0.9538, and the coefficient R2 of the prediction set was 0.8983 and 0.9260, respectively. The root mean square error of the calibration set (RMSEC) was 0.8 mg and 8.1 mg, while the root mean square error of the prediction set (RMSEP) was 1.0 mg and 8.7 mg, respectively. For the SVR models of AMH and HCTZ, the R2 of the calibration set was 0.9668 and 0.9609; the R2 of the prediction set was 0.9145 and 0.9446, respectively. The RMSEC was 0.7 and 7.5 mg, and the RMSEP was 0.9 and 8.9 mg, respectively. The results show that SVR modeling has a satisfactory prediction effect. The proposed method based on UV-vis-swNIR and chemometrics is efficient, nondestructive, and expected to be used for online quality monitoring in the production of drugs.

  11. Regulation of intracellular pH in neuronal and glial tumour cells, studied by multinuclear NMR spectroscopy.

    PubMed

    Flögel, U; Willker, W; Leibfritz, D

    1994-06-01

    The effect of extracellular pH (pHe) on intracellular pH (pHi) and cellular metabolism was examined by multinuclear NMR spectroscopy of cells in vivo and in vitro. A decrease in pHe from 7.4 to 6.4 led to a significant drop in pHi, in both neuronal and glial tumour cells, as detected by in vivo 31P NMR of cells embedded in basement membrane gel threads. A more than 50% decrease in both the phosphocreatine (PCr) level and derivatives of glycolysis (i.e., glycerol 3-phosphate) was observed, concomitantly to the fall in pHi. A 50% decrease in intracellular lactate levels was seen in in vivo 1H NMR spectra under these conditions. Reperfusion with fresh medium (pHe 7.4) resulted in the full recovery of pHi, simultaneously with an increase in both PCr and intracellular lactate back to their control levels. Perchloric acid and lipid extract measurements confirmed the observations made by in vivo 31P and 1H NMR spectroscopy and further showed a decrease both in tricarboxylic acid cycle activity and phospholipid synthesis. The data revealed no significant differences between the neuronal and glial tumour cells investigated. pHi measurements in the presence of inhibitors of the various pH regulatory mechanisms showed that the Na+/H+ exchanger, the carbonic anhydrase and at least one of the bicarbonate-transport systems are involved in pH regulation of both cell types. The results suggest that Na+/H+ exchange is the preferred mechanism by which both neuronal and glial cells regulate their pHi after extracellular acidification.

  12. Simultaneous Quantification of OH and HO_2 in Dimethyl Ether Oxidation Using Faraday Rotation Spectroscopy

    NASA Astrophysics Data System (ADS)

    Brumfield, Brian; Yang, Xueliang; Lefkowitz, Joseph; Ju, Yiguang; Wysocki, Gerard

    2014-06-01

    OH and HO_2 are key radical species that control the autoignition and flame chemistry of fuels. Quantification of these radicals in the low-temperature oxidation of fuels is challenging due to their low concentrations. Strong spectral interference from more abundant non-radical species can further complicate accurate quantification of OH and HO_2. Faraday Rotation Spectroscopy (FRS), a laser-based diagnostic that exploits magneto-optical properties of paramagnetic radical species, can overcome these technical challenges to provide sensitive and selective in situ quantification of radicals. Previously we have been able to illustrate the strengths of FRS in quantification of HO_2 radicals in the low-temperature oxidation of dimethyl ether. Recently we have constructed a dual-wavelength FRS system capable of simultaneous in situ measurement of OH and HO_2. A DFB diode laser operating at 2.8 μm is used to target the Q(1.5e) and Q(1.5f) transitions in the fundamental vibrational band of the 2Π3/2 ground electronic state of OH. An EC-QCL operating at 7.1 μm is used to target a Q-branch spectral feature in the νb{2} vibrational band of HO_2. Concentrations of the target species are extracted from the measured spectra through fitting of an FRS spectral model. Based on preliminary retrievals, 3σ detection limits of <1 ppmv for OH and HO_2 have been estimated from the non-linear least-squares fitting results. In this talk I will discuss the application of dual-wavelength FRS for sensitive measurement of OH and HO_2 radicals generated by oxidation of dimethyl ether in a flow reactor over a 520 K - 1050 K temperature range. B. Brumfield et al., J. Phys. Chem. Lett., 4, 872 (2013) B. Brumfield et al., ``Dual Modulation Faraday Rotation Spectroscopy of HO_2 in a Flow Reactor'' Accepted in Optics Letters (2014) N. Kurimoto et al., ``Quantitative Measurements of HO_2 / H_2O_2 and Intermediate Species in Low and Intermediate Temperature Oxidation of Dimethyl Ether'', Submitted

  13. 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 β- 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.

  14. Complex Mixture Analysis of Organic Compounds in Yogurt by NMR Spectroscopy.

    PubMed

    Lu, Yi; Hu, Fangyu; Miyakawa, Takuya; Tanokura, Masaru

    2016-01-01

    NMR measurements do not require separation and chemical modification of samples and therefore rapidly and directly provide non-targeted information on chemical components in complex mixtures. In this study, one-dimensional (¹H, (13)C, and (31)P) and two-dimensional (¹H-(13)C and ¹H-(31)P) NMR spectroscopy were conducted to analyze yogurt without any pretreatment. ¹H, (13)C, and (31)P NMR signals were assigned to 10 types of compounds. The signals of α/β-lactose and α/β-galactose were separately observed in the ¹H NMR spectra. In addition, the signals from the acyl chains of milk fats were also successfully identified but overlapped with many other signals. Quantitative difference spectra were obtained by subtracting the diffusion ordered spectroscopy (DOSY) spectra from the quantitative ¹H NMR spectra. This method allowed us to eliminate interference on the overlaps; therefore, the correct intensities of signals overlapped with those from the acyl chains of milk fat could be determined directly without separation. Moreover, the ¹H-(31)P HMBC spectra revealed for the first time that N-acetyl-d-glucosamine-1-phosphate is contained in yogurt. PMID:27322339

  15. Complex Mixture Analysis of Organic Compounds in Yogurt by NMR Spectroscopy

    PubMed Central

    Lu, Yi; Hu, Fangyu; Miyakawa, Takuya; Tanokura, Masaru

    2016-01-01

    NMR measurements do not require separation and chemical modification of samples and therefore rapidly and directly provide non-targeted information on chemical components in complex mixtures. In this study, one-dimensional (1H, 13C, and 31P) and two-dimensional (1H-13C and 1H-31P) NMR spectroscopy were conducted to analyze yogurt without any pretreatment. 1H, 13C, and 31P NMR signals were assigned to 10 types of compounds. The signals of α/β-lactose and α/β-galactose were separately observed in the 1H NMR spectra. In addition, the signals from the acyl chains of milk fats were also successfully identified but overlapped with many other signals. Quantitative difference spectra were obtained by subtracting the diffusion ordered spectroscopy (DOSY) spectra from the quantitative 1H NMR spectra. This method allowed us to eliminate interference on the overlaps; therefore, the correct intensities of signals overlapped with those from the acyl chains of milk fat could be determined directly without separation. Moreover, the 1H-31P HMBC spectra revealed for the first time that N-acetyl-d-glucosamine-1-phosphate is contained in yogurt. PMID:27322339

  16. Multibeam long-path differential optical absorption spectroscopy instrument: a device for simultaneous measurements along multiple light paths.

    PubMed

    Pundt, Irene; Mettendorf, Kai Uwe

    2005-08-10

    A novel long-path differential optical absorption spectroscopy (DOAS) apparatus for measuring tropospheric trace gases and the first results from its use are presented: We call it the multibeam instrument. It is the first active DOAS device that emits several light beams simultaneously through only one telescope and with only one lamp as a light source, allowing simultaneous measurement along multiple light paths. In contrast to conventional DOAS instruments, several small mirrors are positioned near the lamp, creating multiple virtual light sources that emit one light beam each in one specific direction. The possibility of error due to scattering between the light beams is negligible. The trace-gas detection limits of NO2, SO2, O3, and H2CO are similar to those of the traditional long-path DOAS instrument. PMID:16114540

  17. Simultaneous Study of Brownian and Néel Relaxation Phenomena in Ferrofluids by Mössbauer Spectroscopy.

    PubMed

    Landers, J; Salamon, S; Remmer, H; Ludwig, F; Wende, H

    2016-02-10

    We demonstrate the ability of Mössbauer spectroscopy to simultaneously investigate Brownian motion and Néel relaxation in ferrofluidic samples. For this purpose, Mössbauer spectra of coated iron oxide nanoparticles with core diameters of 6.0-26.4 nm dissolved in 70 vol % glycerol solution were recorded in the temperature range of 234-287 K and compared to low-temperature spectra without Brownian motion. By comparison to theory, we were able to determine the particle coating thickness and the dynamic viscosity of the fluid from the broadening of the absorption lines (Brownian motion), as well as the state of Néel relaxation. Results from Mössbauer spectroscopy were crosschecked by AC-susceptometry at several temperatures for Brownian motion and in the high-frequency regime (100 Hz-1 MHz) for Néel relaxation. PMID:26788750

  18. Optical emission spectroscopy for simultaneous measurement of plasma electron density and temperature in a low-pressure microwave induced plasma

    SciTech Connect

    Konjevic, N.; Jovicevic, S.; Ivkovic, M.

    2009-10-15

    The simple optical emission spectroscopy technique for diagnostics of low pressure microwave induced plasma (MIP) in hydrogen or in MIP seeded with hydrogen is described and tested. This technique uses the Boltzmann plot of relative line intensities along Balmer spectral series in conjunction with the criterion for partial local thermodynamic equilibrium for low electron density (N{sub e}) plasma diagnostics. The proposed technique is tested in a low pressure MIP discharge for simultaneous determination of electron density N{sub e} (10{sup 17}-10{sup 18} m{sup -3}) and temperature T{sub e}.

  19. Probing ion channel conformational dynamics using simultaneous single-molecule ultrafast spectroscopy and patch-clamp electric recording

    NASA Astrophysics Data System (ADS)

    Harms, Greg; Orr, Galya; Lu, H. Peter

    2004-03-01

    An approach to probing single-molecule ion channel kinetics and conformational dynamics, patch-clamp confocal fluorescence microscopy (PCCFM), uses simultaneous ultrafast fluorescence spectroscopy and single-channel electric current recording. PCCFM is applied to determine single-channel conformational dynamics by probing single-pair fluorescence resonant energy transfer, fluorescence self-quenching, and anisotropy of the dye-labeled gramicidin ion channel incorporated in an artificial lipid bilayer. Hidden conformational changes were observed, which strongly suggests that multiple intermediate conformation states are involved in gramicidin ion channel dynamics.

  20. Frequency Modulation Multiplexing for Simultaneous Detection of Multiple Gases by use of Wavelength Modulation Spectroscopy with Diode Lasers.

    PubMed

    Oh, D B; Paige, M E; Bomse, D S

    1998-04-20

    Modulation frequency multiplexing provides a straightforward method, analogous to television or radio broadcasting, for performing simultaneous detection of multiple gases by use of wavelength modulation spectroscopy with diode lasers. When fiber-optic coupled lasers are used, our approach guarantees that all beams transit the same optical path and impinge on the same detector. Each laser is modulated at a different frequency and the detector output is processed by a set of lock-in amplifiers, one for each laser, to measure the absorbance encountered by each laser. PMID:18273185

  1. 31P-NMR studies of isolated adult heart cells: effect of myoglobin inactivation.

    PubMed

    Gupta, R K; Wittenberg, B A

    1991-10-01

    31P nuclear magnetic resonance (NMR) studies of isolated adult rat heart cells revealed that the cells maintained high-energy phosphates for up to 6 h in polyamide hollow fibers perfused with well-oxygenated nutrient medium. Glucose plus pyruvate superfused heart cells maintained [phosphocreatine]/[ATP] at 1.4 +/- 0.1, internal pH at 7.09 +/- 0.04 (external pH = 7.25), and intracellular free Mg2+ at 0.51 +/- 0.04 mM. In glucose-containing media, hypoxia was accompanied by a reversible decrease in intracellular ATP and phosphocreatine of approximately 50% and 80%, respectively, while the intracellular free Mg2+ was reversibly increased by 40%. However, inhibition of glycolysis by iodoacetate in aerobic pyruvate-containing medium did not significantly alter high-energy phosphate content. Inactivation of intracellular myoglobin with 1-2 mM sodium nitrite, which reduces the steady-state respiratory oxygen consumption rate by 30%, caused a significant (30%) decrease in intracellular phosphocreatine peak, which was reversed upon removal of sodium nitrite. The nitrite-induced decrease in phosphocreatine was also observed in iodoacetate-treated myocytes but not in oligomycin-treated cells. These results indicate that functional myoglobin enhances high-energy phosphate synthesis in well-oxygenated myocytes. PMID:1928397

  2. /sup 31/P NMR studies of ATP synthesis and hydrolysis kinetics in the intact myocardium

    SciTech Connect

    Kingsley-Hickman, P.B.; Sako, E.Y.; Mohanakrishnan, P.; Robitaille, P.M.L.; From, A.H.L.; Foker, J.E.; Ugurbil, K.

    1987-11-17

    The origin of the nuclear magnetic resonance (NMR)-measurable ATP in equilibrium P/sub i/ exchange and whether it can be used to determine net oxidative ATP synthesis rates in the intact myocardium were examined by detailed measurements of ATP in equilibrium P/sub i/ exchange rates in both directions as a function of the myocardial oxygen consumption rate (MVO/sub 2/) in (1) glucose-perfused, isovolumic rat hearts with normal glycolytic activity and (2) pyruvate-perfused hearts where glycolytic activity was reduced or eliminated either by depletion of their endogenous glycogen or by use of the inhibitor iodoacetate. In glucose-perfused hearts, the P/sub i/ ..-->.. ATP rate measured by the conventional two-site saturation transfer (CST) technique remained constant while MVO2 was increased approximately 2-fold. When the glycolytic activity was reduced, the P/sub i/ ..-->.. ATP rate decreased significantly, demonstrating the existence of a significant glycolytic contribution. The ATP ..-->.. P/sub i/ rates and rate:MVO ratios measured by the multiple-site saturation transfer method at two MVO/sub 2/ levels were equal to the corresponding P/sub i/..-->.. ATP rates and rate:MVO ratios obtained in the absence of a glycolytic contribution. The following conclusions are drawn from these studies: (1) unless the glycolytic contribution to the ATP in equilibrium P/sub i/ exchange is inhibited or is specifically shown not to exist, the myocardial P/sub i/ in equilibrium ATP exchange due to oxidative phosphorylation cannot be studied by NMR; (2) at moderate MVO/sub 2/ levels, the reaction catalyzed by the two glycolytic enzymes glyceraldehyde-3-phosphate dehydrogenase and 3-phosphoglycerate kinase is near equilibrium; (3) the ATP synthesis by the mitochondrial H/sup +/-ATPase occurs unidirectionally (i.e., the reaction is far out of equilibrium); (4) the operative P:O ratio in the intact myocardium under our conditions is significantly less than the canonically accepted value of 3.

  3. Gated /sup 31/P NMR study of tetanic contraction in rat muscle depleted of phosphocreatine

    SciTech Connect

    Shoubridge, E.A.; Radda, G.K.

    1987-05-01

    Rats were fed a diet containing 1% ..beta..-guanidino-propionic acid (GPA) for 6-12 wk to deplete their muscles of phosphocreatine (PCr). Gated /sup 31/P nuclear magnetic resonance (NMR) spectra were obtained from the gastrocnemius-plantaris muscle at various time points during either a 1- or 3-s isometric tetanic contraction using a surface coil. The energy cost of a 1-s tetanus in unfatigued control rat muscle was 48.4 ..mu..mol ATP x g dry wt/sup -1/ x s/sup -1/ and was largely supplied by PCr; anaerobic glycogenolysis was negligible. In GPA-fed rats PCr was undetectable after 400 ms. This had no effect on initial force generated per gram, which was not significantly different from controls. Developed tension in a 3-s tetanus in GPA-fed rats could be divided into a peak phase (duration 0.8-0.9 s) and a plateau phase (65% peak tension) in which PCr was undetectable and the (ATP) was < 20% of that in control muscle. Energy from glycogenolysis was sufficient to maintain force generation at this submaximal level. Mean net glycogen utilization per 3-s tetanus was 78% greater than in control muscle. However, the observed decrease in intracellular pH was less than that expected from energy budget calculations, suggesting either increased buffering capacity or modulation of ATP hydrolysis in the muscles of GPA-fed rats. The results demonstrate that the transport role of PCr is not essential in contracting muscle in GPA-fed rats. PCr is probably important in this regard in the larger fibers of control muscle. Although fast-twitch muscles depleted of PCr have nearly twice the glycogen reserves of control muscle, glycogenolysis is limited in its capacity to fill the role of PCr as an energy buffer under conditions of maximum ATP turnover.

  4. Communication: two-dimensional gas-phase coherent anti-Stokes Raman spectroscopy (2D-CARS): simultaneous planar imaging and multiplex spectroscopy in a single laser shot.

    PubMed

    Bohlin, Alexis; Kliewer, Christopher J

    2013-06-14

    Coherent anti-Stokes Raman spectroscopy (CARS) has been widely used as a powerful tool for chemical sensing, molecular dynamics measurements, and rovibrational spectroscopy since its development over 30 years ago, finding use in fields of study as diverse as combustion diagnostics, cell biology, plasma physics, and the standoff detection of explosives. The capability for acquiring resolved CARS spectra in multiple spatial dimensions within a single laser shot has been a long-standing goal for the study of dynamical processes, but has proven elusive because of both phase-matching and detection considerations. Here, by combining new phase matching and detection schemes with the high efficiency of femtosecond excitation of Raman coherences, we introduce a technique for single-shot two-dimensional (2D) spatial measurements of gas phase CARS spectra. We demonstrate a spectrometer enabling both 2D plane imaging and spectroscopy simultaneously, and present the instantaneous measurement of 15,000 spatially correlated rotational CARS spectra in N2 and air over a 2D field of 40 mm(2). PMID:23781772

  5. Communication: Two-dimensional gas-phase coherent anti-Stokes Raman spectroscopy (2D-CARS): Simultaneous planar imaging and multiplex spectroscopy in a single laser shot

    NASA Astrophysics Data System (ADS)

    Bohlin, Alexis; Kliewer, Christopher J.

    2013-06-01

    Coherent anti-Stokes Raman spectroscopy (CARS) has been widely used as a powerful tool for chemical sensing, molecular dynamics measurements, and rovibrational spectroscopy since its development over 30 years ago, finding use in fields of study as diverse as combustion diagnostics, cell biology, plasma physics, and the standoff detection of explosives. The capability for acquiring resolved CARS spectra in multiple spatial dimensions within a single laser shot has been a long-standing goal for the study of dynamical processes, but has proven elusive because of both phase-matching and detection considerations. Here, by combining new phase matching and detection schemes with the high efficiency of femtosecond excitation of Raman coherences, we introduce a technique for single-shot two-dimensional (2D) spatial measurements of gas phase CARS spectra. We demonstrate a spectrometer enabling both 2D plane imaging and spectroscopy simultaneously, and present the instantaneous measurement of 15 000 spatially correlated rotational CARS spectra in N2 and air over a 2D field of 40 mm2.

  6. Communication: Two-dimensional gas-phase coherent anti-Stokes Raman spectroscopy (2D-CARS): Simultaneous planar imaging and multiplex spectroscopy in a single laser shot

    SciTech Connect

    Bohlin, Alexis; Kliewer, Christopher J.

    2013-01-01

    Coherent anti-Stokes Raman spectroscopy (CARS) has been widely used as a powerful tool for chemical sensing, molecular dynamics measurements, and rovibrational spectroscopy since its development over 30 years ago, finding use in fields of study as diverse as combustion diagnostics, cell biology, plasma physics, and the standoff detection of explosives. The capability for acquiring resolved CARS spectra in multiple spatial dimensions within a single laser shot has been a long-standing goal for the study of dynamical processes, but has proven elusive because of both phase-matching and detection considerations. Here, by combining new phase matching and detection schemes with the high efficiency of femtosecond excitation of Raman coherences, we introduce a technique for single-shot two-dimensional (2D) spatial measurements of gas phase CARS spectra. We demonstrate a spectrometer enabling both 2D plane imaging and spectroscopy simultaneously, and present the instantaneous measurement of 15, 000 spatially correlated rotational CARS spectra in N2 and air over a 2D field of 40 mm2.

  7. Simultaneous measurement of the silicon content and physiological parameters by FTIR spectroscopy in diatoms with siliceous cell walls.

    PubMed

    Jungandreas, Anne; Wagner, Heiko; Wilhelm, Christian

    2012-12-01

    Diatoms are the most successful biomass producers worldwide. Therefore, physiological and chemical methods to measure the cell response to a variety of abiotic factors are the focus of recent research. We used the two model diatoms Cyclotella meneghiniana and Skeletonema costatum for the development of Fourier transform infrared (FTIR) spectroscopy-based methods to measure simultaneously the elemental composition of the cells and their cell-specific physiological properties. The cells were grown in chemostat cultures to study the response of Si limitation. The model organisms showed different reactions in terms of their cell properties. Si limitation was accompanied by a drop in the growth rate, a reduced content in Si per cell and a decreased Si : C ratio. Furthermore, the C allocation pattern was changed in both diatoms under Si limitation, as shown by FTIR spectroscopy. Moreover, we used FTIR spectra to develop PLS (partial least square) regression methods to predict the Si content and the Si : C ratio for single as well as multiple species. All PLS regression models were validated by standard chemical methods and showed good prediction accuracy, with the coefficient of determination R(2) being ≥0.93. We could show that it is possible to monitor phytoplankton properties such as C allocation, the Si content and the Si : C ratio at the same time via FTIR spectroscopy. PMID:23104763

  8. Simultaneous measurements of temperature and density in air flows using UV laser spectroscopy

    NASA Technical Reports Server (NTRS)

    Fletcher, D. G.; Mckenzie, R. L.

    1991-01-01

    The simultaneous measurement of temperature and density using laser-induced fluorescence of oxygen in combination with Q-branch Raman scattering of nitrogen and oxygen is demonstrated in a low-speed air flow. The lowest density and temperature measured in the experiment correspond to the freestream values at Mach 5 in the Ames 3.5-Foot Hypersonic Wind Tunnel for stagnation conditions of 100 atm and 1000 K. The experimental results demonstrate the viability of the optical technique for measurements that support the study of compressible turbulence and the validation of numerical codes in supersonic and hypersonic wind tunnel flows.

  9. In Situ Planetary Mineralogy Using Simultaneous Time Resolved Fluorescence and Raman Spectroscopy

    NASA Technical Reports Server (NTRS)

    Blacksberg, J.; Rossman , G.R.

    2011-01-01

    Micro-Raman spectroscopy is one of the primary methods of mineralogical analysis in the laboratory, and more recently in the field. Because of its versatility and ability to interrogate rocks in their natural form it is one of the front runners for the next generation of in situ instruments designed to explore adverse set of solar system bodies (e.g. Mars, Venus, the Moon, and other primitive bodies such as asteroids and the Martian moons Phobos and Deimos), as well as for pre-selection of rock and soil samples for potential cache and return missions.

  10. Versatile fiber-coupled system for simultaneous photon correlation spectroscopy and Fabry-Perot interferometry

    SciTech Connect

    Bogoslovov, R.B.; Shelton, D.P.; Selser, J.C.; Piet, G.; Peng, S.

    2004-10-01

    We demonstrate an experimental setup utilizing fiber-optic detection and coupling of scattered light into existing photon correlation spectroscopy (PCS) and Fabry-Perot (F-P) interferometry systems. The performance of the fiber coupled F-P as a high-resolution interferometer is considered in detail. Several practical issues and limitations are discussed, including the selection of optic and fiber-optic components, collimation, effects of the fiber mode structure and core diameter, and alignment issues. A series of test measurements on standard systems with well known properties shows that the proposed fiber-optic design meets the performance expectations for both PCS and F-P instruments and presents an attractive alternative to the classical pinhole design.

  11. Simultaneously probing two ultrafast condensed-phase molecular symmetry breaking events by two-dimensional infrared spectroscopy.

    PubMed

    Yang, Fan; Yu, Pengyun; Zhao, Juan; Wang, Jianping

    2013-08-01

    In condensed phases, a highly symmetric gas-phase molecule lowers its symmetry under perturbation of the solvent, which is vital to a variety of structural chemistry related processes. However, the dynamical aspects of solvent-mediated symmetry-breaking events remain largely unknown. Herein, direct evidence for two types of solvent-mediated symmetry-breaking events that coexist on the picosecond timescale in a highly symmetric anion, namely, hexacyanocobaltate, is presented: 1) an equilibrium symmetry-breaking event in which a solvent-bound species having lowered symmetry undergoes a population exchange reaction with the symmetry-retaining species; 2) a dynamic symmetry-breaking event that is composed of many dynamic population-exchange reactions under fluctuating solvent interactions. Ultrafast two-dimensional infrared spectroscopy is used to simultaneously observe and dynamically characterize these two events. This work opens a new window into molecular symmetry and structural dynamics under equilibrium and non-equilibrium conditions.

  12. Simultaneous fluorescence and breakdown spectroscopy of fresh and aging transformer oil immersed in paper using ArF excimer laser

    NASA Astrophysics Data System (ADS)

    Parvin, P.; Shoursheini, S. Z.; Khalilinejad, F.; Bavali, A.; Moshgel Gosha, M.; Mansouri, B.

    2012-11-01

    HV transformers are taken into account as the heart of the power distribution system. The on-line monitoring based on the oil analysis offers a rapid diagnostic technique to detect the probable faults. In fact, the transformer malfunctions can be detected using UV laser spectroscopic methods. Here, a novel technique is presented based on simultaneous laser induced fluorescence (LIF) and laser induced breakdown (LIB) spectroscopy for hyper sensitive identification of the oil degradation. Oil is mainly degraded due to the internal transformer faults such as overheating and partial discharge. The spectroscopic characteristics of oil in paper substrate were obtained due to ArF laser irradiation. It was shown that the amplitude of fluorescence signal increases when the oil suffers aging and degradation. A couple of additional characteristic carbon and Hα emissions appear in the corresponding breakdown spectra too.

  13. Methyl oleate as matrix simulacrum for the simultaneous determination of metals in biodiesel samples by flame atomic emission spectroscopy.

    PubMed

    Ferreira, Conny Cerai; Costa, Letícia Malta; Barbeira, Paulo Jorge Sanches

    2015-06-01

    A measurement procedure for direct and simultaneous quantification of Na, K and Ca in biodiesel by flame atomic emission spectroscopy (FAES) was developed. A lab-made device was constructed by coupling a nebulizer/combustion system from a commercial photometer to a continuous emission detector in a spectral range of 255 to 862 nm. Instrumental optimizations were carried out evaluating the most important variables, such as gas flow rates and sample introduction temperature, indicating that a temperature of 50°C enhances the analytical signals and assures good precision. The direct analysis method was properly validated and presented limits of quantification of 0.09, 0.07 and 0.43 μg kg(-1) for Na, K and Ca, respectively. Accuracy of the proposed procedure was checked by comparing the results with those obtained by the standard procedure described in ABNT NBR 15556 and the standard addition method. PMID:25863364

  14. Probing the interaction of U(vi) with phosphonate-functionalized mesoporous silica using solid-state NMR spectroscopy.

    PubMed

    Uribe, Eva C; Mason, Harris E; Shusterman, Jennifer A; Bruchet, Anthony; Nitsche, Heino

    2016-06-21

    The fundamental interaction of U(vi) with diethylphosphatoethyl triethoxysilane functionalized SBA-15 mesoporous silica is studied by macroscopic batch experiments and solid-state NMR spectroscopy. DPTS-functionalized silica has been shown to extract U(vi) from nitric acid solutions at or above pH 3. Extraction is dependent on pH and ionic strength. Single-pulse (31)P NMR on U(vi) contacted samples revealed that U(vi) only interacts with a fraction of the ligands present on the surface. At pH 4 the U(vi) extraction capacity of the material is limited to 27-37% of the theoretical capacity, based on ligand loading. We combined single pulse (31)P NMR on U(vi)-contacted samples with batch studies to measure a ligand-to-metal ratio of approximately 2 : 1 at pH 3 and 4. Batch studies and cross-polarization NMR measurements reveal that U(vi) binds to deprotonated phosphonate and/or silanol sites. We use (31)P-(31)P DQ-DRENAR NMR studies to compare the average dipolar coupling between phosphorus spins for both U(vi)-complexed and non-complexed ligand environments. These measurements reveal that U(vi) extraction is not limited by inadequate surface distribution of ligands, but rather by low stability of the surface phosphonate complex. PMID:27265020

  15. Probing the interaction of U(VI) with phosphonate-functionalized mesoporous silica using solid-state NMR spectroscopy

    DOE PAGES

    Uribe, Eva C.; Mason, Harris E.; Shusterman, Jennifer A.; Bruchet, Anthony; Nitsche, Heino

    2016-05-30

    The fundamental interaction of U(VI) with diethylphosphatoethyl triethoxysilane functionalized SBA-15 mesoporous silica is studied by macroscopic batch experiments and solid-state NMR spectroscopy. DPTS-functionalized silica has been shown to extract U(VI) from nitric acid solutions at or above pH 3. Extraction is dependent on pH and ionic strength. Single-pulse 31P NMR on U(VI) contacted samples revealed that U(VI)only interacts with a fraction of the ligands present on the surface. At pH 4 the U(VI) extraction capacity of the material is limited to 27–37% of the theoretical capacity, based on ligand loading. We combined single pulse 31P NMR on U(VI)-contacted samples withmore » batch studies to measure a ligand-to-metal ratio of approximately 2 : 1 at pH 3 and 4. Batch studies and cross-polarization NMR measurements reveal that U(VI) binds to deprotonated phosphonate and/or silanol sites. We use 31P–31P DQ-DRENAR NMR studies to compare the average dipolar coupling between phosphorus spins for both U(VI)-complexed and non-complexed ligand environments. Furthermore, these measurements reveal that U(VI) extraction is not limited by inadequate surface distribution of ligands, but rather by low stability of the surface phosphonate complex.« less

  16. Simultaneous X-ray and optical spectroscopy of the Oef supergiant λ Cephei

    NASA Astrophysics Data System (ADS)

    Rauw, G.; Hervé, A.; Nazé, Y.; González-Pérez, J. N.; Hempelmann, A.; Mittag, M.; Schmitt, J. H. M. M.; Schröder, K.-P.; Gosset, E.; Eenens, P.; Uuh-Sonda, J. M.

    2015-08-01

    Context. Probing the structures of stellar winds is of prime importance for the understanding of massive stars. Based on their optical spectral morphology and variability, it has been suggested that the stars in the Oef class feature large-scale structures in their wind. Aims: High-resolution X-ray spectroscopy and time-series of X-ray observations of presumably single O-type stars can help us understand the physics of their stellar winds. Methods: We have collected XMM-Newton observations and coordinated optical spectroscopy of the O6 Ief star λ Cep to study its X-ray and optical variability and to analyse its high-resolution X-ray spectrum. We investigate the line profile variability of the He ii λ 4686 and Hα emission lines in our time series of optical spectra, including a search for periodicities. We further discuss the variability of the broadband X-ray flux and analyse the high-resolution spectrum of λ Cep using line-by-line fits as well as a code designed to fit the full high-resolution X-ray spectrum consistently. Results: During our observing campaign, the He ii λ 4686 line varies on a timescale of ~18 h. On the contrary, the Hα line profile displays a modulation on a timescale of 4.1 days which is likely the rotation period of the star. The X-ray flux varies on timescales of days and could in fact be modulated by the same 4.1-day period as Hα, although both variations are shifted in phase. The high-resolution X-ray spectrum reveals broad and skewed emission lines as expected for the X-ray emission from a distribution of wind-embedded shocks. Most of the X-ray emission arises within less than 2 R∗ above the photosphere. Conclusions: The properties of the X-ray emission of λ Cep generally agree with the expectations of the wind-embedded shock model. There is mounting evidence for the existence of large-scale structures that modulate the Hα line and about 10% of the X-ray emission of λ Cep. Based on observations collected with XMM-Newton, an ESA

  17. Simultaneous measurement of deep tissue blood flow and oxygenation using noncontact diffuse correlation spectroscopy flow-oximeter

    PubMed Central

    Li, Ting; Lin, Yu; Shang, Yu; He, Lian; Huang, Chong; Szabunio, Margaret; Yu, Guoqiang

    2013-01-01

    We report a novel noncontact diffuse correlation spectroscopy flow-oximeter for simultaneous quantification of relative changes in tissue blood flow (rBF) and oxygenation (Δ[oxygenation]). The noncontact probe was compared against a contact probe in tissue-like phantoms and forearm muscles (n = 10), and the dynamic trends in both rBF and Δ[oxygenation] were found to be highly correlated. However, the magnitudes of Δ[oxygenation] measured by the two probes were significantly different. Monte Carlo simulations and phantom experiments revealed that the arm curvature resulted in a significant underestimation (~−20%) for the noncontact measurements in Δ[oxygenation], but not in rBF. Other factors that may cause the residual discrepancies between the contact and noncontact measurements were discussed, and further comparisons with other established technologies are needed to identify/quantify these factors. Our research paves the way for noncontact and simultaneous monitoring of blood flow and oxygenation in soft and vulnerable tissues without distorting tissue hemodynamics. PMID:23446991

  18. Simultaneous in situ detection of atmospheric NO3 and N2O5 via cavity ring-down spectroscopy

    NASA Astrophysics Data System (ADS)

    Brown, Steven S.; Stark, Harald; Ciciora, Steven J.; McLaughlin, Richard J.; Ravishankara, A. R.

    2002-09-01

    This article describes the application of cavity ring-down spectroscopy (CaRDS) to the simultaneous concentration measurement of nitrate radical, NO3, and dinitrogen pentoxide, N2O5, in the ambient atmosphere. The sensitivity for detection of both NO3 and N2O5 is 0.5 pptv (2σ) for a 5 s integration, comparable to or better than previous measurements of NO3 (e.g., via DOAS), but with significantly better time resolution. Furthermore, direct measurement of N2O5 represent a previously unavailable capability. Concentrations of both species are measured simultaneously in two separate flow systems and optical cavities pumped by the same pulsed dye laser at 662 nm. One of the flow systems remains at ambient temperature for detection of NO3, while the other is heated to 80 °C to induce thermal decomposition of N2O5 providing a measurement of the sum of the NO3 and N2O5 concentrations. This article outlines a series of laboratory and field tests of the instrument's performance. Important considerations include signal acquisition, zero measurements, aerosol interference, flow system losses, and the conversion efficiency for N2O5 thermolysis to NO3. We describe the limitations of this method and show how they can be quantified and accounted for in field measurements.

  19. Transient Grating Spectroscopy in Magnetic Thin Films: Simultaneous Detection of Elastic and Magnetic Dynamics.

    PubMed

    Janušonis, J; Jansma, T; Chang, C L; Liu, Q; Gatilova, A; Lomonosov, A M; Shalagatskyi, V; Pezeril, T; Temnov, V V; Tobey, R I

    2016-01-01

    Surface magnetoelastic waves are coupled elastic and magnetic excitations that propagate along the surface of a magnetic material. Ultrafast optical techniques allow for a non-contact excitation and detection scheme while providing the ability to measure both elastic and magnetic components individually. Here we describe a simple setup suitable for excitation and time resolved measurements of high frequency magnetoelastic waves, which is based on the transient grating technique. The elastic dynamics are measured by diffracting a probe laser pulse from the long-wavelength spatially periodic structural deformation. Simultaneously, a magnetooptical measurement, either Faraday or Kerr effect, is sensitive to the out-of-plane magnetization component. The correspondence in the response of the two channels probes the resonant interaction between the two degrees of freedom and reveals their intimate coupling. Unraveling the observed dynamics requires a detailed understanding of the spatio-temporal evolution of temperature, magnetization and thermo-elastic strain in the ferromagnet. Numerical solution of thermal diffusion in two dimensions provides the basis on which to understand the sensitivity in the magnetooptic detection. PMID:27377262

  20. Transient Grating Spectroscopy in Magnetic Thin Films: Simultaneous Detection of Elastic and Magnetic Dynamics

    PubMed Central

    Janušonis, J.; Jansma, T.; Chang, C. L.; Liu, Q.; Gatilova, A.; Lomonosov, A. M.; Shalagatskyi, V.; Pezeril, T.; Temnov, V. V.; Tobey, R. I.

    2016-01-01

    Surface magnetoelastic waves are coupled elastic and magnetic excitations that propagate along the surface of a magnetic material. Ultrafast optical techniques allow for a non-contact excitation and detection scheme while providing the ability to measure both elastic and magnetic components individually. Here we describe a simple setup suitable for excitation and time resolved measurements of high frequency magnetoelastic waves, which is based on the transient grating technique. The elastic dynamics are measured by diffracting a probe laser pulse from the long-wavelength spatially periodic structural deformation. Simultaneously, a magnetooptical measurement, either Faraday or Kerr effect, is sensitive to the out-of-plane magnetization component. The correspondence in the response of the two channels probes the resonant interaction between the two degrees of freedom and reveals their intimate coupling. Unraveling the observed dynamics requires a detailed understanding of the spatio-temporal evolution of temperature, magnetization and thermo-elastic strain in the ferromagnet. Numerical solution of thermal diffusion in two dimensions provides the basis on which to understand the sensitivity in the magnetooptic detection. PMID:27377262

  1. Converting spatial to pseudotemporal resolution in laser plasma analysis by simultaneous multifiber spectroscopy

    PubMed

    Bulatov; Krasniker; Schechter

    2000-07-01

    Traditional chemical analysis based on laser plasma spectroscopy (LPS) requires time-gated detectors, to avoid the initial signal from the hot plasma. These detectors are expensive and often need to be cooled and protected against vapor condensation. We suggest a low-cost setup that may replace these gated detectors, while maintaining acceptable analytical performance. The proposed setup is a result of investigation of plasma-front propagation in LPS analysis. It is known that the LPS plasma propagation is similar to the shock wave propagation after a strong explosion in the atmosphere. We found that the propagation of the plasma fits well the Sedov blast wave theory, providing a good agreement between the theoretical and experimental figures. A proper observation geometry, which is perpendicular to the plasma expansion vector, enables converting spatial to temporal resolution. We take advantage of the fact that the plasma reaches a given distance above the analyzed surface at a certain time delay. Therefore, a single optical fiber, positioned at a well-defined geometry, can provide spectral information corresponding to a certain time delay. A multifiber imaging spectrometer provides information corresponding to a series of delay times, which is adequate for analysis of a variety of matrixes. It was found that the performance of the nongated detector observing a narrow solid angle is similar to that of a gated one observing the whole plasma. For one particular example, observing the plasma from a distance of 4.5 mm is equivalent to a delay of 4 micros and integration time of 2 mircos. The ratio of spectral lines of two elements was investigated using the spatially resolved (nongated) setup, and it was found that this mode is advantageous when internal calibration is applied. It was concluded that sensitive LPS analyses can be carried out by less expensive (nongated) detectors. PMID:10905339

  2. Simultaneous determination of titanium, zirconium, and hafnium in aqueous solution by phosphorus-31 nuclear magnetic resonance spectrometry

    SciTech Connect

    Fukumoto, T.; Murata, K.; Ikeda, S.

    1984-01-01

    In acidic solution, the group 4A elements form ternary heteropoly complexes with molybdophosphate, e.g., molybdotitanophosphate, molybdozirconophoaphate, and molybdohafnophosphate. Each ternary heteropoly molybdate gives a different chemical shift in its /sup 31/P NMR spectra, respectively, and its relative peak area increases with increasing metal ion concentration. Simultaneous determination of these elements was found to be possible within accuracies of 1 to 5% and detection limits for Tl, Zr, and Hf were 20, 40, and 60 ppm, respectively, under the proposed experimental condition. The small amounts of these ternary heteropoly molybdates in aqueous solution are extracted quantitatively with cyclohexanone. The optimum acidity for extraction was found to be in the pH range between 1.5 and 2.5 and its recovery in cyclohexanone was more than 95%. 14 references, 3 tables, 4 figures.

  3. Simultaneous detection of trace metal ions in water by solid phase extraction spectroscopy combined with multivariate calibration.

    PubMed

    Wang, Lei; Cao, Peng; Li, Wei; Tong, Peijin; Zhang, Xiaofang; Du, Yiping

    2016-04-15

    Solid Phase Extraction Spectroscopy (SPES) developed in this paper is a technique to measure spectrum directly on the solid phase material where the analytes are concentrated in SPE process. Membrane enrichment and UV-Visible spectroscopy were utilized to fulfill SPES, and multivariate calibration method of partial least squares (PLS) was used to simultaneously detect the concentrations of trace cobalt (II) and zinc (II) in water samples. The proposed method is simple, sensitive and selective. The complexes of analyte ions were collected on the cellulose acetate membranes via membrane filtration after the complexation reaction with 1-2-pyridylazo 2-naphthol (PAN). The spectra of the membranes which contained the complexes of metal ions and PAN were measured directly without eluting. The analytical conditions including pH, reaction time, sample volume, the amount of PAN, and flow rates were optimized. Nonionic surfactant Brij-30 was absorbed on the membranes prior to SPES to modify the membranes for improving the enrichment and spectrum measurement. The interference from other ions to the determination was investigated. Under the optimal condition, the absorbance was linearly related to the concentration at the range of 0.1-3.0 μg/L and 0.1-2.0 μg/L, with the correlation coefficients (R(2)) of 0.9977 and 0.9951 for Co (II) and Zn (II), respectively. The limits of detection were 0.066 μg/L for cobalt (II) and 0.104 μg/L for zinc (II). PLS regression with leave-one-out cross-validation was utilized to build models to detect cobalt (II) and zinc (II) in drinking water samples simultaneously. The correlation coefficient between ion concentration and spectrum of calibration set and independent prediction set were 1.0000 and 0.9974 for cobalt (II) and 1.0000 and 0.9956 for zinc (II). For cobalt (II) and zinc (II), the errors of the prediction set were in the range 0.0406-0.1353 μg/L and 0.0025-0.1884 μg/L.

  4. Simultaneous detection of trace metal ions in water by solid phase extraction spectroscopy combined with multivariate calibration

    NASA Astrophysics Data System (ADS)

    Wang, Lei; Cao, Peng; Li, Wei; Tong, Peijin; Zhang, Xiaofang; Du, Yiping

    2016-04-01

    Solid Phase Extraction Spectroscopy (SPES) developed in this paper is a technique to measure spectrum directly on the solid phase material where the analytes are concentrated in SPE process. Membrane enrichment and UV-Visible spectroscopy were utilized to fulfill SPES, and multivariate calibration method of partial least squares (PLS) was used to simultaneously detect the concentrations of trace cobalt (II) and zinc (II) in water samples. The proposed method is simple, sensitive and selective. The complexes of analyte ions were collected on the cellulose acetate membranes via membrane filtration after the complexation reaction with 1-2-pyridylazo 2-naphthol (PAN). The spectra of the membranes which contained the complexes of metal ions and PAN were measured directly without eluting. The analytical conditions including pH, reaction time, sample volume, the amount of PAN, and flow rates were optimized. Nonionic surfactant Brij-30 was absorbed on the membranes prior to SPES to modify the membranes for improving the enrichment and spectrum measurement. The interference from other ions to the determination was investigated. Under the optimal condition, the absorbance was linearly related to the concentration at the range of 0.1-3.0 μg/L and 0.1-2.0 μg/L, with the correlation coefficients (R2) of 0.9977 and 0.9951 for Co (II) and Zn (II), respectively. The limits of detection were 0.066 μg/L for cobalt (II) and 0.104 μg/L for zinc (II). PLS regression with leave-one-out cross-validation was utilized to build models to detect cobalt (II) and zinc (II) in drinking water samples simultaneously. The correlation coefficient between ion concentration and spectrum of calibration set and independent prediction set were 1.0000 and 0.9974 for cobalt (II) and 1.0000 and 0.9956 for zinc (II). For cobalt (II) and zinc (II), the errors of the prediction set were in the range 0.0406-0.1353 μg/L and 0.0025-0.1884 μg/L.

  5. Simultaneous blood flow and blood oxygenation measurements using a combination of diffuse speckle contrast analysis and near-infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Seong, Myeongsu; Phillips, Zephaniah; Mai, Phuong Minh; Yeo, Chaebeom; Song, Cheol; Lee, Kijoon; Kim, Jae Gwan

    2016-02-01

    A combined diffuse speckle contrast analysis (DSCA)-near-infrared spectroscopy (NIRS) system is proposed to simultaneously measure qualitative blood flow and blood oxygenation changes in human tissue. The system employs an optical switch to alternate two laser sources at two different wavelengths and a CCD camera to capture the speckle image. Therefore, an optical density can be measured from two wavelengths for NIRS measurements and a speckle contrast can be calculated for DSCA measurements. In order to validate the system, a flow phantom test and an arm occlusion protocol for arterial and venous occlusion were performed. Shorter exposure times (<1 ms) show a higher drop (between 50% and 66%) and recovery of 1/KS2 values after occlusion (approximately 150%), but longer exposure time (3 ms) shows more consistent hemodynamic changes. For four subjects, the 1/KS2 values dropped to an average of 82.1±4.0% during the occlusion period and the average recovery of 1/KS2 values after occlusion was 109.1±0.8%. There was also an approximately equivalent amplitude change in oxyhemoglobin (OHb) and deoxyhemoglobin (RHb) during arterial occlusion (max RHb=0.0085±0.0024 mM/DPF, min OHb=-0.0057±0.0044 mM/DPF). The sensitivity of the system makes it a suitable modality to observe qualitative hemodynamic trends during induced physiological changes.

  6. Simultaneous determination of 2-naphthoxyacetic acid and indole-3-acetic acid by first derivation synchronous fluorescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Liu, Xiangxiang; Wan, Yiqun

    2013-07-01

    A simple, rapid, sensitive and selective method for simultaneously determining 2-naphthoxyacetic acid (BNOA) and Indole-3-Acetic Acid (IAA) in mixtures has been developed using derivation synchronous fluorescence spectroscopy based on their synchronous fluorescence. The synchronous fluorescence spectra were obtained with Δλ = 100 nm in a pH 8.5 NaH2PO4-NaOH buffer solution, and the detected wavelengths of quantitative analysis were set at 239 nm for BNOA and 293 nm for IAA respectively. The over lapped fluorescence spectra were well separated by the synchronous derivative method. Under optimized conditions, the limits of detection (LOD) were 0.003 μg/mL for BNOA and 0.012 μg/mL for IAA. This method is simple and expeditious, and it has been successfully applied to the determination of 2-naphthoxyacetic acid and indole-3-acetic acid in fruit juice samples with satisfactory results. The samples were only filtrated through a 0.45 μm membrane filter, which was free from the tedious separation procedures. The obtaining recoveries were in the range of 83.88-87.43% for BNOA and 80.76-86.68% for IAA, and the relative standard deviations were all less than 5.0%. Statistical comparison of the results with high performance liquid chromatography Mass Spectrometry (HPLC-MS) method revealed good agreement and proved that there were no significant difference in the accuracy and precision between these two methods.

  7. Spectroscopy system based on a single quantum cascade laser for simultaneous detection of CO and CO2

    NASA Astrophysics Data System (ADS)

    Wei, Min; Ye, Qing-Hao; Kan, Rui-Feng; Chen, Bing; Yang, Chen-Guang; Xu, Zhen-Yu; Chen, Xiang; Ruan, Jun; Fan, Xue-Li; Wang, Wei; Hu, Mai; Liu, Jian-Guo

    2016-09-01

    A quantum cascade laser (QCL) based system for simultaneous detection of CO and CO2 is developed. The QCL can scan over two neighboring CO (2055.40 cm-1) and CO2 (2055.16 cm-1) lines with a single current scan. The wavelength modulation spectroscopy (f = 20 kHz) is utilized to enhance the signal-to-noise ratio. A white cell with an effective optical path length of 74 m is used. The calibration of the sensor is performed and minimum detection limits of 1.3 ppb (1 × 10-9) for CO and 0.44 ppm (1 × 10-6) for CO2 are achieved. Project supported by the National Key Scientific Instrument and Equipment Development Project of China (Grnat No. 2014YQ060537), the National Basic Research Program of China (Grant No. 2013CB632803), the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant No. XDA05040102), and the National Natural Science Foundation of China (Grant No. 41405134).

  8. Spectroscopy system based on a single quantum cascade laser for simultaneous detection of CO and CO2

    NASA Astrophysics Data System (ADS)

    Wei, Min; Ye, Qing-Hao; Kan, Rui-Feng; Chen, Bing; Yang, Chen-Guang; Xu, Zhen-Yu; Chen, Xiang; Ruan, Jun; Fan, Xue-Li; Wang, Wei; Hu, Mai; Liu, Jian-Guo

    2016-09-01

    A quantum cascade laser (QCL) based system for simultaneous detection of CO and CO2 is developed. The QCL can scan over two neighboring CO (2055.40 cm‑1) and CO2 (2055.16 cm‑1) lines with a single current scan. The wavelength modulation spectroscopy (f = 20 kHz) is utilized to enhance the signal-to-noise ratio. A white cell with an effective optical path length of 74 m is used. The calibration of the sensor is performed and minimum detection limits of 1.3 ppb (1 × 10‑9) for CO and 0.44 ppm (1 × 10‑6) for CO2 are achieved. Project supported by the National Key Scientific Instrument and Equipment Development Project of China (Grnat No. 2014YQ060537), the National Basic Research Program of China (Grant No. 2013CB632803), the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant No. XDA05040102), and the National Natural Science Foundation of China (Grant No. 41405134).

  9. Polymer nanopillar-gold arrays as surface-enhanced Raman spectroscopy substrate for the simultaneous detection of multiple genes.

    PubMed

    Picciolini, Silvia; Mehn, Dora; Morasso, Carlo; Vanna, Renzo; Bedoni, Marzia; Pellacani, Paola; Marchesini, Gerardo; Valsesia, Andrea; Prosperi, Davide; Tresoldi, Cristina; Ciceri, Fabio; Gramatica, Furio

    2014-10-28

    In our study, 2D nanopillar arrays with plasmonic crystal properties are optimized for surface-enhanced Raman spectroscopy (SERS) application and tested in a biochemical assay for the simultaneous detection of multiple genetic leukemia biomarkers. The special fabrication process combining soft lithography and plasma deposition techniques allows tailoring of the structural and chemical parameters of the crystal surfaces. In this way, it has been possible to tune the plasmonic resonance spectral position close to the excitation wavelength of the monochromatic laser light source in order to maximize the enhancing properties of the substrate. Samples are characterized by scanning electron microscopy and reflectance measurements and tested for SERS activity using malachite green. Besides, as the developed substrate had been prepared on a simple glass slide, SERS detection from the support side is also demonstrated. The optimized substrate is functionalized with thiol-modified capture oligonucleotides, and concentration-dependent signal of the target nucleotide is detected in a sandwich assay with labeled gold nanoparticles. Gold nanoparticles functionalized with different DNA and various Raman reporters are applied in a microarray-based assay recognizing a disease biomarker (Wilms tumor gene) and housekeeping gene expressions in the same time on spatially separated microspots. The multiplexing performance of the SERS-based bioassay is illustrated by distinguishing Raman dyes based on their complex spectral fingerprints.

  10. Cerebral hemodynamic responses to seizure in the mouse brain: simultaneous near-infrared spectroscopy-electroencephalography study

    NASA Astrophysics Data System (ADS)

    Lee, Seungduk; Lee, Mina; Koh, Dalkwon; Kim, Beop-Min; Choi, Jee Hyun

    2010-05-01

    We applied near-infrared spectroscopy (NIRS) and electroencephalography (EEG) simultaneously on the mouse brain and investigated the hemodynamic response to epileptic episodes under pharmacologically driven seizure. γ-butyrolactone (GBL) and 4-aminopyridine (4-AP) were applied to induce absence and tonic-clonic seizures, respectively. The epileptic episodes were identified from the single-channel EEG, and the corresponding hemodynamic changes in different regions of the brain were characterized by multichannel frequency-domain NIRS. Our results are the following: (i) the oxyhemoglobin level increases in the case of GBL-treated mice but not 4-AP-treated mice compared to the predrug state; (ii) the dominant response to each absence seizure is a decrease in deoxyhemolobin; (iii) the phase shift between oxy- and deoxyhemoglobin reduces in GBL-treated mice but no 4-AP-treated mice; and (iv) the spatial correlation of hemodynamics increased significantly in 4-AP-treated mice but not in GBL-treated mice. Our results shows that spatiotemporal tracking of cerebral hemodynamics using NIRS can be successfully applied to the mouse brain in conjunction with electrophysiological recording, which will support the study of molecular, cellular, and network origin of neurovascular coupling in vivo.

  11. Fourier transform-plasmon waveguide spectroscopy: a nondestructive multifrequency method for simultaneously determining polymer thickness and apparent index of refraction.

    PubMed

    Bobbitt, Jonathan M; Weibel, Stephen C; Elshobaki, Moneim; Chaudhary, Sumit; Smith, Emily A

    2014-12-16

    Fourier transform (FT)-plasmon waveguide resonance (PWR) spectroscopy measures light reflectivity at a waveguide interface as the incident frequency and angle are scanned. Under conditions of total internal reflection, the reflected light intensity is attenuated when the incident frequency and angle satisfy conditions for exciting surface plasmon modes in the metal as well as guided modes within the waveguide. Expanding upon the concept of two-frequency surface plasmon resonance developed by Peterlinz and Georgiadis [Opt. Commun. 1996, 130, 260], the apparent index of refraction and the thickness of a waveguide can be measured precisely and simultaneously by FT-PWR with an average percent relative error of 0.4%. Measuring reflectivity for a range of frequencies extends the analysis to a wide variety of sample compositions and thicknesses since frequencies with the maximum attenuation can be selected to optimize the analysis. Additionally, the ability to measure reflectivity curves with both p- and s-polarized light provides anisotropic indices of refraction. FT-PWR is demonstrated using polystyrene waveguides of varying thickness, and the validity of FT-PWR measurements are verified by comparing the results to data from profilometry and atomic force microscopy (AFM).

  12. Fourier Transform-Plasmon Waveguide Spectroscopy: A Nondestructive Multifrequency Method for Simultaneously Determining Polymer Thickness and Apparent Index of Refraction

    SciTech Connect

    Bobbitt, Jonathan M; Weibel, Stephen C; Elshobaki, Moneim; Chaudhary, Sumit; Smith, Emily A

    2014-12-16

    Fourier transform (FT)-plasmon waveguide resonance (PWR) spectroscopy measures light reflectivity at a waveguide interface as the incident frequency and angle are scanned. Under conditions of total internal reflection, the reflected light intensity is attenuated when the incident frequency and angle satisfy conditions for exciting surface plasmon modes in the metal as well as guided modes within the waveguide. Expanding upon the concept of two-frequency surface plasmon resonance developed by Peterlinz and Georgiadis [ Opt. Commun. 1996, 130, 260], the apparent index of refraction and the thickness of a waveguide can be measured precisely and simultaneously by FT-PWR with an average percent relative error of 0.4%. Measuring reflectivity for a range of frequencies extends the analysis to a wide variety of sample compositions and thicknesses since frequencies with the maximum attenuation can be selected to optimize the analysis. Additionally, the ability to measure reflectivity curves with both p- and s-polarized light provides anisotropic indices of refraction. FT-PWR is demonstrated using polystyrene waveguides of varying thickness, and the validity of FT-PWR measurements are verified by comparing the results to data from profilometry and atomic force microscopy (AFM).

  13. Microrheology: Structural evolution under static and dynamic conditions by simultaneous analysis of confocal microscopy and diffusing wave spectroscopy

    NASA Astrophysics Data System (ADS)

    Nicolas, Yves; Paques, Marcel; Knaebel, Alexandra; Steyer, Alain; Munch, Jean-Pierre; Blijdenstein, Theo B. J.; van Aken, George A.

    2003-08-01

    An oscillatory shear configuration was developed to improve understanding of structural evolution during deformation. It combines an inverted confocal scanning laser microscope (CSLM) and a special sample holder that can apply to the sample specific deformation: oscillatory shear or steady strain. In this configuration, a zero-velocity plane is created in the sample by moving two plates in opposite directions, thereby providing stable observation conditions of the structural behavior under deformation. The configuration also includes diffusion wave spectroscopy (DWS) to monitor the network properties via particle mobility under static and dynamic conditions. CSLM and DWS can be performed simultaneously and three-dimensional images can be obtained under static conditions. This configuration is mainly used to study mechanistic phenomena like particle interaction, aggregation, gelation and network disintegration, interactions at interfaces under static and dynamic conditions in semisolid food materials (desserts, dressings, sauces, dairy products) and in nonfood materials (mineral emulsions, etc.). Preliminary data obtained with this new oscillatory shear configuration are described that demonstrate their capabilities and the potential contribution to other areas of application also.

  14. Simultaneous and rapid monitoring of biomass and biopolymer production by Sphingomonas paucimobilis using Fourier transform-near infrared spectroscopy.

    PubMed

    Giavasis, Ioannis; Robertson, Ian; McNeil, Brian; Harvey, Linda M

    2003-06-01

    The application of Fourier Transform near infrared spectroscopy (FT-NIRS) to near real-time monitoring of polysaccharide and biomass concentration was investigated using a gellan-producing strain of Sphingomonas paucimobilis grown in a stirred tank reactor. Successful models for both biomass and gellan were constructed despite the physichochemical complexity of the viscous process fluid. Modelling of biomass proved more challenging than for gellan, partly because of the low range of biomass concentration but a model with a good correlation coefficient (0.94) was formulated based on second derivative spectra. The gellan model was highly satisfactory, with an excellent correlation coefficient (0.98), again based on second derivative spectra. No sample pre-treatment was required and all spectral scanning was carried out on whole broth. Additionally, both models should be robust in practice since both were formulated using low numbers of factors. Thus, the near real time simultaneous monitoring of gellan and biomass in this highly complex matrix using FT-NIRS potentially opens the way to greatly improved process control strategies.

  15. Simultaneous infrared reflection absorption spectroscopy and quartz crystal microbalance measurements for in situ studies of the metal/atmosphere interface

    SciTech Connect

    Aastrup, T.; Leygraf, C.

    1997-09-01

    A new experimental setup for in situ studies of the metal/atmosphere interface has been developed based on simultaneous infrared reflection absorption spectroscopy (IRAS) and quartz crystal microbalance (QCM) measurements of a metal surface. It consists of an in situ chamber in which the metal can be exposed to a well-controlled atmosphere. Four external devices are connected to the in situ chamber; a Fourier transform infrared spectrometer with external optical compartments, a QCM sensor probe with a frequency counter, a corrosive air generator, and a corrosive air analyzing system. In order to demonstrate the capability of the IRAS/QCM setup, copper was exposed to purified air at 80% relative humidity and 25 C. Under these exposure conditions, the interface between copper and air consists of cuprous oxide and water physisorbed on the oxide. The kinetics of the cuprous oxide formation could be followed in situ with both techniques. The combined IRAS/QCM results show excellent agreement with previous combined IRAS and cathodic reduction measurements and with optical calculations of the IRAS response. Under these conditions, the detection limit in terms of an equivalent Cu{sub 2}O film thickness is 10 {angstrom} for IRAS in situ analysis and 2 {angstrom} for QCM in situ analysis, respectively.

  16. Simultaneous fingerprint and high-wavenumber fiber-optic Raman spectroscopy improves in vivo diagnosis of esophageal squamous cell carcinoma at endoscopy

    NASA Astrophysics Data System (ADS)

    Wang, Jianfeng; Lin, Kan; Zheng, Wei; Yu Ho, Khek; Teh, Ming; Guan Yeoh, Khay; Huang, Zhiwei

    2015-08-01

    This work aims to evaluate clinical value of a fiber-optic Raman spectroscopy technique developed for in vivo diagnosis of esophageal squamous cell carcinoma (ESCC) during clinical endoscopy. We have developed a rapid fiber-optic Raman endoscopic system capable of simultaneously acquiring both fingerprint (FP)(800-1800 cm-1) and high-wavenumber (HW)(2800-3600 cm-1) Raman spectra from esophageal tissue in vivo. A total of 1172 in vivo FP/HW Raman spectra were acquired from 48 esophageal patients undergoing endoscopic examination. The total Raman dataset was split into two parts: 80% for training; while 20% for testing. Partial least squares-discriminant analysis (PLS-DA) and leave-one patient-out, cross validation (LOPCV) were implemented on training dataset to develop diagnostic algorithms for tissue classification. PLS-DA-LOPCV shows that simultaneous FP/HW Raman spectroscopy on training dataset provides a diagnostic sensitivity of 97.0% and specificity of 97.4% for ESCC classification. Further, the diagnostic algorithm applied to the independent testing dataset based on simultaneous FP/HW Raman technique gives a predictive diagnostic sensitivity of 92.7% and specificity of 93.6% for ESCC identification, which is superior to either FP or HW Raman technique alone. This work demonstrates that the simultaneous FP/HW fiber-optic Raman spectroscopy technique improves real-time in vivo diagnosis of esophageal neoplasia at endoscopy.

  17. Simultaneous fingerprint and high-wavenumber fiber-optic Raman spectroscopy improves in vivo diagnosis of esophageal squamous cell carcinoma at endoscopy

    PubMed Central

    Wang, Jianfeng; Lin, Kan; Zheng, Wei; Yu Ho, Khek; Teh, Ming; Guan Yeoh, Khay; Huang, Zhiwei

    2015-01-01

    This work aims to evaluate clinical value of a fiber-optic Raman spectroscopy technique developed for in vivo diagnosis of esophageal squamous cell carcinoma (ESCC) during clinical endoscopy. We have developed a rapid fiber-optic Raman endoscopic system capable of simultaneously acquiring both fingerprint (FP)(800–1800 cm−1) and high-wavenumber (HW)(2800–3600 cm−1) Raman spectra from esophageal tissue in vivo. A total of 1172 in vivo FP/HW Raman spectra were acquired from 48 esophageal patients undergoing endoscopic examination. The total Raman dataset was split into two parts: 80% for training; while 20% for testing. Partial least squares-discriminant analysis (PLS-DA) and leave-one patient-out, cross validation (LOPCV) were implemented on training dataset to develop diagnostic algorithms for tissue classification. PLS-DA-LOPCV shows that simultaneous FP/HW Raman spectroscopy on training dataset provides a diagnostic sensitivity of 97.0% and specificity of 97.4% for ESCC classification. Further, the diagnostic algorithm applied to the independent testing dataset based on simultaneous FP/HW Raman technique gives a predictive diagnostic sensitivity of 92.7% and specificity of 93.6% for ESCC identification, which is superior to either FP or HW Raman technique alone. This work demonstrates that the simultaneous FP/HW fiber-optic Raman spectroscopy technique improves real-time in vivo diagnosis of esophageal neoplasia at endoscopy. PMID:26243571

  18. Simultaneous fingerprint and high-wavenumber fiber-optic Raman spectroscopy improves in vivo diagnosis of esophageal squamous cell carcinoma at endoscopy.

    PubMed

    Wang, Jianfeng; Lin, Kan; Zheng, Wei; Ho, Khek Yu; Teh, Ming; Yeoh, Khay Guan; Huang, Zhiwei

    2015-08-05

    This work aims to evaluate clinical value of a fiber-optic Raman spectroscopy technique developed for in vivo diagnosis of esophageal squamous cell carcinoma (ESCC) during clinical endoscopy. We have developed a rapid fiber-optic Raman endoscopic system capable of simultaneously acquiring both fingerprint (FP)(800-1800 cm(-1)) and high-wavenumber (HW)(2800-3600 cm(-1)) Raman spectra from esophageal tissue in vivo. A total of 1172 in vivo FP/HW Raman spectra were acquired from 48 esophageal patients undergoing endoscopic examination. The total Raman dataset was split into two parts: 80% for training; while 20% for testing. Partial least squares-discriminant analysis (PLS-DA) and leave-one patient-out, cross validation (LOPCV) were implemented on training dataset to develop diagnostic algorithms for tissue classification. PLS-DA-LOPCV shows that simultaneous FP/HW Raman spectroscopy on training dataset provides a diagnostic sensitivity of 97.0% and specificity of 97.4% for ESCC classification. Further, the diagnostic algorithm applied to the independent testing dataset based on simultaneous FP/HW Raman technique gives a predictive diagnostic sensitivity of 92.7% and specificity of 93.6% for ESCC identification, which is superior to either FP or HW Raman technique alone. This work demonstrates that the simultaneous FP/HW fiber-optic Raman spectroscopy technique improves real-time in vivo diagnosis of esophageal neoplasia at endoscopy.

  19. 31P-nuclear magnetic resonance spectroscopy in vivo of six human melanoma xenograft lines: tumour bioenergetic status and blood supply.

    PubMed Central

    Lyng, H.; Olsen, D. R.; Southon, T. E.; Rofstad, E. K.

    1993-01-01

    Six human melanoma xenograft lines grown s.c. in BALB/c-nu/nu mice were subjected to 31P-nuclear magnetic resonance (31P-NMR) spectroscopy in vivo. The following resonances were detected: phosphomonoesters (PME), inorganic phosphate (Pi), phosphodiesters (PDE), phosphocreatine (PCr) and nucleoside triphosphate gamma, alpha and beta (NTP gamma, alpha and beta). The main purpose of the work was to search for possible relationships between 31P-NMR resonance ratios and tumour pH on the one hand and blood supply per viable tumour cell on the other. The latter parameter was measured by using the 86Rb uptake method. Tumour bioenergetic status [the (PCr + NTP beta)/Pi resonance ratio], tumour pH and blood supply per viable tumour cell decreased with increasing tumour volume for five of the six xenograft lines. The decrease in tumour bioenergetic status was due to a decrease in the (PCr + NTP beta)/total resonance ratio as well as an increase in the Pi/total resonance ratio. The decrease in the (PCr + NTP beta)/total resonance ratio was mainly a consequence of a decrease in the PCr/total resonance ratio for two lines and mainly a consequence of a decrease in the NTP beta/total resonance ratio for three lines. The magnitude of the decrease in the (PCr + NTP beta)/total resonance ratio and the magnitude of the decrease in tumour pH were correlated to the magnitude of the decrease in blood supply per viable tumour cell. Tumour pH decreased with decreasing tumour bioenergetic status, and the magnitude of this decrease was larger for the tumour lines showing a high than for those showing a low blood supply per viable tumour cell. No correlations across the tumour lines were found between tumour pH and tumour bioenergetic status or any other resonance ratio on the one hand and blood supply per viable tumour cell on the other. The differences in the 31P-NMR spectrum between the tumour lines were probably caused by differences in the intrinsic biochemical properties of the tumour

  20. Simultaneous Photometry and Spectroscopy of the Deeply Absorbing Polar MASTER OT J132104.04+560957.8

    NASA Astrophysics Data System (ADS)

    Hoyt, Taylor; Littlefield, Colin; Garnavich, Peter M.

    2016-01-01

    We present photometry and time-resolved spectroscopy of the suspected polar MASTER OT J132104.04+560957.8 (J1321) taken at the Large Binocular Telescope (LBT) simultaneously with the LBC camera and MODS spectrograph in binocular mode. Our V-band photometry confirmed a primary and secondary maximum first identified by Littlefield et al. In the spectra we see unusually deep Balmer and helium absorption features for about 10-15% of a 91 minute orbital period. The absorption lines first appear to the red of the emission peaks then shift bluewards, ultimately dominating the line profile at zero radial velocity. Towards the end of the absorption phase, weak absorption reappears to the blue of the emission lines. When the system is bright the spectra show a broadly-peaked continuum with a maximum around 500nm. We do not see absorption during the secondary bright red phase. Around the minima the continuum is blue and resembles a more typical polar spectrum with strong Balmer, neutral helium and ionized helium emission lines. The Doppler tomograms of J1321 are fuzzy and blobby and resemble those of the asynchronous polar BY Cam. The highly variable width of the secondary maximum remains a mystery along with the lack of a discernible irradiated secondary in the tomograms. We use our observations to constrain the properties of the white dwarf's magnetic field as well as the accretion flow structure. We also discuss evidence of J1321 being in a prolonged low-mass-transfer state in all observations prior to 2007.

  1. Simultaneous determination of CRP and D-dimer in human blood plasma samples with White Light Reflectance Spectroscopy.

    PubMed

    Koukouvinos, Georgios; Petrou, Panagiota; Misiakos, Konstantinos; Drygiannakis, Dimitris; Raptis, Ioannis; Stefanitsis, Gerasimos; Martini, Spyridoula; Nikita, Dimitra; Goustouridis, Dimitrios; Moser, Isabella; Jobst, Gerhard; Kakabakos, Sotirios

    2016-10-15

    A dual-analyte assay for the simultaneous determination of C-reactive protein (CRP) and D-dimer in human blood plasma based on a white light interference spectroscopy sensing platform is presented. Measurement is accomplished in real-time by scanning the sensing surface, on which distinct antibody areas have been created, with a reflection probe used both for illumination of the surface and collection of the reflected interference spectrum. The composition of the transducer, the sensing surface chemical activation and biofunctionalization procedures were optimized with respect to signal magnitude and repeatability. The assay format involved direct detection of CRP whereas for D-dimer a two-site immunoassay employing a biotinylated reporter antibody and reaction with streptavidin was selected. The assays were sensitive with detection limits of 25ng/mL for both analytes, precise with intra- and inter-assay CV values ranging from 3.6% to 7.7%, and from 4.8% to 9.5%, respectively, for both assays, and accurate with recovery values ranging from 88.5% to 108% for both analytes. Moreover, the values determined for the two analytes in 35 human plasma samples were in excellent agreement with those received for the same samples by standard diagnostic laboratory instrumentation employing commercial kits. The excellent agreement of the results supported the validity of the proposed system for clinical application for the detection of multiple analytes since it was demonstrated that up to seven antibody areas can be created on the sensing surface and successfully interrogated with the developed optical set-up. PMID:26675113

  2. [Progress in nuclear magnetic resonance spectroscopy for early cancer diagnosis].

    PubMed

    Gao, Xiu-xiang; Xu, Yi-zhuang; Zhao, Mei-xian; Qi, Jian; Li, Hui-zhen; Wu, Jin-guang

    2008-08-01

    Based on more than 100 references, the present paper reviews the progress in the application of nuclear magnetic resonance (NMR) spectroscopy, an effective method to study the variation in chemical composition and molecular structure in biological samples for early diagnosis of cancer at molecular level. In the past several decades, numerous works have demonstrated that NMR spectroscopy may be developed into a sensitive diagnosis method to detect cancer in early stage. Because of the rapid development of NMR spectroscopic techniques, it becomes possible to record NMR spectra of biological samples in both in-vitro and in-vivo manner. Systematic spectral differences between biological samples from cancer patients and normal controls can be observed from both liquid-state and solid-state 1H, 31P NMR spectra and used to reflect the changes in metabolic behavior of malignant tissues. This paper has summarized NMR spectroscopic investigation on biological fluid, cultured cancerous cells, resected tissues, as well as in-vivo malignant tissues by using various advanced NMR techniques including recently developedhigh-resolution magic angle spinning (HR-MAS)and magnetic resonance spectroscopy and imaging (MRSI) methods. First, characteristic peaks, which are related to choline, phosphocholine (PC) and glycerophosphocholine, can be observed in both 1H and 31P NMR spectra of biological fluid samples from cancer patients. These results indicate that alternation in the metabolic pattern occurs with the progression of cancer. The research on cultured cells by using NMR spectroscopy showed that the signal of various phospholipids and their metabolites such as PME increased significantly in cultured cancer cells. For resected tissues, two methods can be utilized. The first one is to investigate the tissues directly by using HR-MAS spectroscopy. The second method is to extract various metabolites with various solvents such as CHCl3/methonal mixtures, HClO4 solutions, etc. and then

  3. Soil and litter phosphorus-31 nuclear magnetic resonance spectroscopy: extractants, metals, and phosphorus relaxation times.

    PubMed

    Cade-Menun, B J; Liu, C W; Nunlist, R; McColl, J G

    2002-01-01

    Phosphorus-31 nuclear magnetic resonance (NMR) spectroscopy is an excellent tool with which to study soil organic P, allowing quantitative, comparative analysis of P forms. However, for 31P NMR to be tative, all peaks must be completely visible, and in their correct relative proportions. There must be no line broadening, and adequate delay times must be used to avoid saturation of peaks. The objective of this study was to examine the effects of extractants on delay times and peak saturation. Two samples (a forest litter and a mineral soil sample) and three extractants (0.25 M NaOH, NaOH plus Chelex (Bio-Rad Laboratories, Hercules, CA), and NaOH plus EDTA) were used to determine the differences in the concentration of P and cations solubilized by each extractant, and to measure spin-lattice (T1) relaxation times of P peaks in each extract. For both soil and litter, NaOH-Chelex extracted the lowest concentrations of P. For the litter sample, T1 values were short for all extractants due to the high Fe concentration remaining after extraction. For the soil sample, there were noticeable differences among the extractants. The NaOH-Chelex sample had less Fe and Mn remaining in solution after extraction than the other extractants, and the longest delay times used in the study, 6.4 s, were not long enough for quantitative analysis. Delay times of 1.5 to 2 s for the NaOH and NaOH-EDTA were adequate. Line broadening was highest in the NaOH extracts, which had the highest concentration of Fe. On the basis of these results, recommendations for future analyses of soil and litter samples by solution 31P NMR spectroscopy include: careful selection of an extractant; measurement of paramagnetic ions extracted with P; use of appropriate delay times and the minimum number of scans; and measurement of T1 values whenever possible.

  4. Simultaneous probing of bulk liquid phase and catalytic gas-liquid-solid interface under working conditions using attenuated total reflection infrared spectroscopy

    SciTech Connect

    Meemken, Fabian; Müller, Philipp; Hungerbühler, Konrad; Baiker, Alfons

    2014-08-15

    Design and performance of a reactor set-up for attenuated total reflection infrared (ATR-IR) spectroscopy suitable for simultaneous reaction monitoring of bulk liquid and catalytic solid-liquid-gas interfaces under working conditions are presented. As advancement of in situ spectroscopy an operando methodology for gas-liquid-solid reaction monitoring was developed that simultaneously combines catalytic activity and molecular level detection at the catalytically active site of the same sample. Semi-batch reactor conditions are achieved with the analytical set-up by implementing the ATR-IR flow-through cell in a recycle reactor system and integrating a specifically designed gas feeding system coupled with a bubble trap. By the use of only one spectrometer the design of the new ATR-IR reactor cell allows for simultaneous detection of the bulk liquid and the catalytic interface during the working reaction. Holding two internal reflection elements (IRE) the sample compartments of the horizontally movable cell are consecutively flushed with reaction solution and pneumatically actuated, rapid switching of the cell (<1 s) enables to quasi simultaneously follow the heterogeneously catalysed reaction at the catalytic interface on a catalyst-coated IRE and in the bulk liquid on a blank IRE. For a complex heterogeneous reaction, the asymmetric hydrogenation of 2,2,2-trifluoroacetophenone on chirally modified Pt catalyst the elucidation of catalytic activity/enantioselectivity coupled with simultaneous monitoring of the catalytic solid-liquid-gas interface is shown. Both catalytic activity and enantioselectivity are strongly dependent on the experimental conditions. The opportunity to gain improved understanding by coupling measurements of catalytic performance and spectroscopic detection is presented. In addition, the applicability of modulation excitation spectroscopy and phase-sensitive detection are demonstrated.

  5. A multi-wavelength view of AB Doradus outer atmosphere . Simultaneous X-ray and optical spectroscopy at high cadence

    NASA Astrophysics Data System (ADS)

    Lalitha, S.; Fuhrmeister, B.; Wolter, U.; Schmitt, J. H. M. M.; Engels, D.; Wieringa, M. H.

    2013-12-01

    Aims: We study the chromosphere and corona of the ultra-fast rotator AB Dor A at high temporal and spectral resolution using simultaneous observations with XMM-Newton in the X-rays, VLT/UVES in the optical, and the ATCA in the radio. Our optical spectra have a resolving power of ~50 000 with a time cadence of ~1 min. Our observations continuously cover more than one rotational period and include both quiescent periods and three flaring events of different strengths. Methods: From the X-ray observations we investigated the variations in coronal temperature, emission measure, densities, and abundance. We interpreted our data in terms of a loop model. From the optical data we characterised the flaring chromospheric material using numerous emission lines that appear in the course of the flares. A detailed analysis of the line shapes and line centres allowed us to infer physical characteristics of the flaring chromosphere and to coarsely localise the flare event on the star. Results: We specifically used the optical high-cadence spectra to demonstrate that both turbulent and Stark broadening are present during the first ten minutes of the first flare. Also, in the first few minutes of this flare, we find short-lived (one to several minutes) emission subcomponents in the Hα and Ca ii K lines, which we interpret as flare-connected shocks owing to their high intrinsic velocities. Combining the space-based data with the results of our optical spectroscopy, we derive flare-filling factors. Finally, comparing X-ray, optical broadband, and line emission, we find a correlation for two of the three flaring events, while there is no clear correlation for one event. Also, we do not find any correlation of the radio data to any other observed data. Based on observations collected at the European Southern Observatory, Paranal, Chile, 383.D-1002A and on observations obtained with XMM-Newton, an ESA science mission with instruments and contributions directly funded by ESA member

  6. Studies on metabolic regulation using NMR spectroscopy.

    PubMed

    Bachelard, H; Badar-Goffer, R; Ben-Yoseph, O; Morris, P; Thatcher, N

    1993-01-01

    The effects of hypoxia and hypoglycaemia on cerebral metabolism and calcium have been studied using multinuclear magnetic resonance spectroscopy. 13C MRS showed that severe hypoxia did not cause any further increase in metabolic flux into lactate seen in mild hypoxia, but there was a further increase in 13C labelling of alanine and glycerol 3-phosphate. These results are discussed in terms of the ability of lactate dehydrogenase to maintain normal levels of NADH in mild hypoxia, but not in severe hypoxia. We conclude that glycerol 3-phosphate and alanine may provide novel means of monitoring severe hypoxia whereas lactate is a reliable indicator only of mild hypoxia. 19F- and 31P NMR spectroscopy showed that neither hypoxia nor hypoglycaemia alone caused any significant change in [Ca2+]i. Combined sequential insults (hypoxia, followed by hypoxia plus hypoglycaemia), or vice versa, produced a 100% increase in [Ca2+]i, whereas immediate exposure to the combined insult (hypoxia plus hypoglycaemia) resulted in a large 5-fold increase in [Ca2+]i, with severe irreversible effects on the energy state. These results are discussed in terms of metabolic adaptation to the single type of insult, which renders the tissue less vulnerable to the combined insult. The effects of this combined insult are far more severe than those caused by glutamate or NMDA, which throws doubt on the current excitoxic hypothesis of cell damage.

  7. Investigation of the potential of 31-phosphorus nuclear magnetic resonance spectroscopy to predict radiation sensitivity. Doctoral thesis

    SciTech Connect

    Bowser, C.

    1988-01-01

    The ability of in vivo 31-Phosphorus Nuclear Magnetic Resonance (31-PNMR) Spectroscopy to predict radiation sensitivity following both single and fractionated therapy was evaluated in this study. For Radiation Induced Fibrosarcoma (RIF-1) tumors either, in their natural state or treated with the vasodilator, hydralazine, an increase in the ratio of phosphocreatine to inorganic phosphate (PCr/Pi) and tumor pH were shown to be significantly correlated (p < 0.01) with radiation sensitivity to a single dose of 15 Grays (Gy) of radiation. After administration of hydralazine to reduce tumor blood flow or flunarizine to increase tumor blood flow, time dependent changes were observed in the 31-P NMR spectrum. After hydralazine, there was a significant (p < 0.01) decrease in PCr/Pi over time. The opposite pattern was seen for flunarizine i.e., decline in Pi, and an increase tumors was substantially greater (p < 0.05) than that of hydralazine treated tumors.

  8. Dynamics of asymmetric non-polymeric binary glass formers—A nuclear magnetic resonance and dielectric spectroscopy study

    SciTech Connect

    Pötzschner, B.; Mohamed, F.; Lichtinger, A.; Bock, D.; Rössler, E. A.

    2015-10-21

    We study a dynamically asymmetric binary glass former with the low-T{sub g} component m-tri-cresyl phosphate (m-TCP: T{sub g} = 206 K) and a spirobichroman derivative as a non-polymeric high-T{sub g} component (T{sub g} = 382 K) by means of {sup 1}H nuclear magnetic resonance (NMR), {sup 31}P NMR, and dielectric spectroscopy which allow component-selectively probing the dynamics. The entire concentration range is covered, and two main relaxation processes with two T{sub g} are identified, T{sub g1} and T{sub g2}. The slower one is attributed to the high-T{sub g} component (α{sub 1}-process), and the faster one is related to the m-TCP molecules (α{sub 2}-process). Yet, there are indications that a small fraction of m-TCP is associated also with the α{sub 1}-process. While the α{sub 1}-relaxation only weakly broadens upon adding m-TCP, the α{sub 2}-relaxation becomes extremely stretched leading to quasi-logarithmic correlation functions at low m-TCP concentrations—as probed by {sup 31}P NMR stimulated echo experiments. Frequency-temperature superposition does not apply for the α{sub 2}-process and it reflects an isotropic, liquid-like motion which is observed even below T{sub g1}, i.e., in the matrix of the arrested high-T{sub g} molecules. As proven by 2D {sup 31}P NMR, the corresponding dynamic heterogeneities are of transient nature, i.e., exchange occurs within the distribution G(lnτ{sub α2}). At T{sub g1} a crossover is found for the temperature dependence of (mean) τ{sub α2}(T) from non-Arrhenius above to Arrhenius below T{sub g1} which is attributed to intrinsic confinement effects. This “fragile-to-strong” transition also leads to a re-decrease of T{sub g2}(c{sub m−TCP}) at low concentration c{sub m−TCP}, i.e., a maximum is observed in T{sub g2}(c{sub m−TCP}) while T{sub g1}(c{sub m−TCP}) displays the well-known plasticizer effect. Although only non-polymeric components are involved, we re-discover essentially all features previously

  9. Dynamics of asymmetric non-polymeric binary glass formers—A nuclear magnetic resonance and dielectric spectroscopy study

    NASA Astrophysics Data System (ADS)

    Pötzschner, B.; Mohamed, F.; Lichtinger, A.; Bock, D.; Rössler, E. A.

    2015-10-01

    We study a dynamically asymmetric binary glass former with the low-Tg component m-tri-cresyl phosphate (m-TCP: Tg = 206 K) and a spirobichroman derivative as a non-polymeric high-Tg component (Tg = 382 K) by means of 1H nuclear magnetic resonance (NMR), 31P NMR, and dielectric spectroscopy which allow component-selectively probing the dynamics. The entire concentration range is covered, and two main relaxation processes with two Tg are identified, Tg1 and Tg2. The slower one is attributed to the high-Tg component (α1-process), and the faster one is related to the m-TCP molecules (α2-process). Yet, there are indications that a small fraction of m-TCP is associated also with the α1-process. While the α1-relaxation only weakly broadens upon adding m-TCP, the α2-relaxation becomes extremely stretched leading to quasi-logarithmic correlation functions at low m-TCP concentrations—as probed by 31P NMR stimulated echo experiments. Frequency-temperature superposition does not apply for the α2-process and it reflects an isotropic, liquid-like motion which is observed even below Tg1, i.e., in the matrix of the arrested high-Tg molecules. As proven by 2D 31P NMR, the corresponding dynamic heterogeneities are of transient nature, i.e., exchange occurs within the distribution G(lnτα2). At Tg1 a crossover is found for the temperature dependence of (mean) τα2(T) from non-Arrhenius above to Arrhenius below Tg1 which is attributed to intrinsic confinement effects. This "fragile-to-strong" transition also leads to a re-decrease of Tg2(cm-TCP) at low concentration cm-TCP, i.e., a maximum is observed in Tg2(cm-TCP) while Tg1(cm-TCP) displays the well-known plasticizer effect. Although only non-polymeric components are involved, we re-discover essentially all features previously reported for polymer-plasticizer systems.

  10. The Mn₄Ca photosynthetic water-oxidation catalyst studied by simultaneous X-ray spectroscopy and crystallography using an X-ray free-electron laser.

    PubMed

    Tran, Rosalie; Kern, Jan; Hattne, Johan; Koroidov, Sergey; Hellmich, Julia; Alonso-Mori, Roberto; Sauter, Nicholas K; Bergmann, Uwe; Messinger, Johannes; Zouni, Athina; Yano, Junko; Yachandra, Vittal K

    2014-07-17

    The structure of photosystem II and the catalytic intermediate states of the Mn₄CaO₅ cluster involved in water oxidation have been studied intensively over the past several years. An understanding of the sequential chemistry of light absorption and the mechanism of water oxidation, however, requires a new approach beyond the conventional steady-state crystallography and X-ray spectroscopy at cryogenic temperatures. In this report, we present the preliminary progress using an X-ray free-electron laser to determine simultaneously the light-induced protein dynamics via crystallography and the local chemistry that occurs at the catalytic centre using X-ray spectroscopy under functional conditions at room temperature.

  11. The Mn₄Ca photosynthetic water-oxidation catalyst studied by simultaneous X-ray spectroscopy and crystallography using an X-ray free-electron laser.

    PubMed

    Tran, Rosalie; Kern, Jan; Hattne, Johan; Koroidov, Sergey; Hellmich, Julia; Alonso-Mori, Roberto; Sauter, Nicholas K; Bergmann, Uwe; Messinger, Johannes; Zouni, Athina; Yano, Junko; Yachandra, Vittal K

    2014-07-17

    The structure of photosystem II and the catalytic intermediate states of the Mn₄CaO₅ cluster involved in water oxidation have been studied intensively over the past several years. An understanding of the sequential chemistry of light absorption and the mechanism of water oxidation, however, requires a new approach beyond the conventional steady-state crystallography and X-ray spectroscopy at cryogenic temperatures. In this report, we present the preliminary progress using an X-ray free-electron laser to determine simultaneously the light-induced protein dynamics via crystallography and the local chemistry that occurs at the catalytic centre using X-ray spectroscopy under functional conditions at room temperature. PMID:24914152

  12. Simultaneous monitoring of curing shrinkage and degree of cure of thermosets by attenuated total reflection Fourier transform infrared (ATR FT-IR) spectroscopy.

    PubMed

    Fernàndez-Francos, Xavier; Kazarian, Sergei G; Ramis, Xavier; Serra, Àngels

    2013-12-01

    We present a novel methodology to simultaneously monitor of the degree of cure and curing shrinkage of thermosetting formulations. This methodology is based on the observation of changes in the infrared absorption of reactive functional groups and the groups used as a standard reference for normalization. While the optical path length is exact and controlled in transmission infrared spectroscopy, in attenuated total reflection Fourier transform infrared (ATR FT-IR), the exact determination of volume changes requires the measurement of the refractive indices of the studied system throughout the curing process or at least an indirect parallel measurement of this property. The methodology presented here allows one to achieve quantitative measurements of the degree of cure and shrinkage for thermosets using in situ ATR FT-IR spectroscopy.

  13. A tomographic technique for the simultaneous imaging of temperature, chemical species, and pressure in reactive flows using absorption spectroscopy with frequency-agile lasers

    SciTech Connect

    Cai, Weiwei; Kaminski, Clemens F.

    2014-01-20

    This paper proposes a technique that can simultaneously retrieve distributions of temperature, concentration of chemical species, and pressure based on broad bandwidth, frequency-agile tomographic absorption spectroscopy. The technique holds particular promise for the study of dynamic combusting flows. A proof-of-concept numerical demonstration is presented, using representative phantoms to model conditions typically prevailing in near-atmospheric or high pressure flames. The simulations reveal both the feasibility of the proposed technique and its robustness. Our calculations indicate precisions of ∼70 K at flame temperatures and ∼0.05 bars at high pressure from reconstructions featuring as much as 5% Gaussian noise in the projections.

  14. Hemodynamic and Electrophysiological Connectivity in the Language System: Simultaneous Near-Infrared Spectroscopy and Electrocorticography Recordings during Cortical Stimulation

    ERIC Educational Resources Information Center

    Sato, Yosuke; Oishi, Makoto; Fukuda, Masafumi; Fujii, Yukihiko

    2012-01-01

    We applied near-infrared spectroscopy (NIRS) and electrocorticography (ECoG) recordings during cortical stimulation to a temporal lobe epilepsy patient who underwent subdural electrode implantation. Using NIRS, changes in blood concentrations of oxyhemoglobin (HbO[subscript 2]) and deoxyhemoglobin (HbR) during cortical stimulation of the left…

  15. Combining solid-state and solution-state 31P NMR to study in vivo phosphorus metabolism.

    PubMed Central

    Cholli, A L; Yamane, T; Jelinski, L W

    1985-01-01

    Otherwise unavailable information concerning the distribution of phosphorylated compounds in biological systems is obtained by a combined solid-state/solution-state NMR approach, illustrated here for oocytes from Rana pipiens. General methodology is developed, and further extensions are proposed. The following conclusions pertain to the specific system under examination. (i) Nucleoside phosphates can be observed by magic-angle sample spinning of the lyophilized material. (ii) The solid-state NMR technique of dipolar decoupling provides no additional resolution of the phospholipid and phosphoprotein components of the yolk. However, cellular death produces sufficient pH changes to cause the phospholipid and protein phosphate peaks to become resolvable. The concentration of nucleoside phosphates also decreases. (iii) The phospholipid and phosphoprotein components are shown by computer simulation to be present in a ratio of 40:60, respectively. (iv) The amounts of inorganic phosphate, nucleoside phosphates, and sugar phosphates are determined by solution-state NMR observation of the perchloric acid extract of the oocytes. PMID:3871524

  16. 31P NMR relaxation of cortical bone mineral at multiple magnetic field strengths and levels of demineralization.

    PubMed

    Seifert, Alan C; Wright, Alexander C; Wehrli, Suzanne L; Ong, Henry H; Li, Cheng; Wehrli, Felix W

    2013-09-01

    Recent work has shown that solid-state (1) H and (31) P MRI can provide detailed insight into bone matrix and mineral properties, thereby potentially enabling differentiation of osteoporosis from osteomalacia. However, (31) P MRI of bone mineral is hampered by unfavorable relaxation properties. Hence, accurate knowledge of these properties is critical to optimizing MRI of bone phosphorus. In this work, (31) P MRI signal-to-noise ratio (SNR) was predicted on the basis of T1 and T2 * (effective transverse relaxation time) measured in lamb bone at six field strengths (1.5-11.7 T) and subsequently verified by 3D ultra-short echo-time and zero echo-time imaging. Further, T1 was measured in deuterium-exchanged bone and partially demineralized bone. (31) P T2 * was found to decrease from 220.3 ± 4.3 µs to 98.0 ± 1.4 µs from 1.5 to 11.7 T, and T1 to increase from 12.8 ± 0.5 s to 97.3 ± 6.4 s. Deuteron substitution of exchangeable water showed that 76% of the (31) P longitudinal relaxation rate is due to (1) H-(31) P dipolar interactions. Lastly, hypomineralization was found to decrease T1, which may have implications for (31) P MRI based mineralization density quantification. Despite the steep decrease in the T2 */T1 ratio, SNR should increase with field strength as B0 (0.4) for sample-dominated noise and as B0 (1.1) for coil-dominated noise. This was confirmed by imaging experiments. PMID:23505120

  17. Simultaneous detection of ammonia, methane and ethylene at 1.63 μm with diode laser photoacoustic spectroscopy

    NASA Astrophysics Data System (ADS)

    Scotoni, M.; Rossi, A.; Bassi, D.; Buffa, R.; Iannotta, S.; Boschetti, A.

    2006-03-01

    Spectral investigation around 6115 cm-1 for simultaneous detection of ammonia, methane and ethylene in gas samples is presented. Experimental data on the ν2+ν3+ν4 combination band of ammonia are reported with a resolution of 1.5 GHz. A trace gas analyzer based on a resonant photoacoustic cell and an external cavity diode laser has been used for detection. A data fitting procedure has been developed in order to improve the system sensitivity and to limit the need of a reference cell. The selected spectral region allows a sensitivity of about 60 ppm for ammonia, 6 ppm for methane and 30 ppm for ethylene with 0.3 mW laser power. An application of simultaneous detection of such molecules in a mixture reproducing their typical abundances in real gas samples from biomass gasification is discussed.

  18. On the performance of multiway methods for simultaneous quantification of two fluoroquinolones in urine samples by fluorescence spectroscopy and second-order calibration strategies

    NASA Astrophysics Data System (ADS)

    Vosough, Maryam; Eshlaghi, Sara Noroozi; Zadmard, Reza

    2015-02-01

    In the present work, the analytical performance of three multi-way algorithms has been evaluated. The proposed analytical problem was the simultaneous determination of moxifloxacin and ciprofloxacin in human urine samples using fluorescence spectroscopy. Parallel factor analysis (PARAFAC), self-weighted alternating trilinear decomposition (SWATLD) and unfolded partial least squares combined with the residual bilinearization procedure (U-PLS/RBL) have been compared, regarding their ability to solve the proposed problem. In this study, "second-order advantage" was also exploited for the mentioned algorithms through different calibration strategies. The three-way data was obtained via fluorescence spectroscopy, so that excitation-emission matrices (EEM) of the samples were recorded as the analytical signals. The accuracy and precision of each individual algorithm for analyzing the drugs in urine samples were compared using root mean square error of prediction (RMSEP), recovery and elliptical joint confidence region (EJCR) plots. The results revealed that each of the three algorithms could be applied for determination of moxifloxacin and ciprofloxacin, despite different EEM subsets and calibration strategies. However, better analytical performances were observed through PARAFAC and U-PLS/RBL modeling for MOX and CIP, respectively. So, by coupling the multi-way decomposition algorithms with fluorescence spectroscopy, a main part of preliminary sample preparation steps can be eliminated and experimental procedure might be significantly simplified, while achieving desirable analytical performance.

  19. Feasibility of the Simultaneous Determination of Monomer Concentrations and Particle Size in Emulsion Polymerization Using in Situ Raman Spectroscopy

    PubMed Central

    2015-01-01

    An immersion Raman probe was used in emulsion copolymerization reactions to measure monomer concentrations and particle sizes. Quantitative determination of monomer concentrations is feasible in two-monomer copolymerizations, but only the overall conversion could be measured by Raman spectroscopy in a four-monomer copolymerization. The feasibility of measuring monomer conversion and particle size was established using partial least-squares (PLS) calibration models. A simplified theoretical framework for the measurement of particle sizes based on photon scattering is presented, based on the elastic-sphere-vibration and surface-tension models. PMID:26900256

  20. Multi-mode absorption spectroscopy using a quantum cascade laser for simultaneous detection of NO and H2O

    NASA Astrophysics Data System (ADS)

    O'Hagan, S.; Pinto, T.; Ewart, P.; Ritchie, G. A. D.

    2016-08-01

    Detection of multiple transitions in NO and H2O using multi-mode absorption spectroscopy, MUMAS, with a quantum cascade laser, QCL, operating at 5.3 μm at scan rates up to 10 kHz is reported. The linewidth of longitudinal modes of the QCL is derived from pressure-dependent fits to experimental MUMAS data. Variations in the spectral structure of the broadband, multi-mode, output of the commercially available QCL employed are analysed to provide accurate fits of modelled MUMAS signatures to the experimental data.

  1. Spectroscopy analysis for simultaneous determination of lycopene and β-carotene in fungal biomass of Blakeslea trispora.

    PubMed

    Soroka, Iaroslav M; Narushin, Valeriy G; Turiyansky, Yuriy D; Tyurenkov, Alexey A

    2012-01-01

    Blakeslea trispora is a good alternative source for producing such carotenoids as lycopene and β-carotene. The objective of this research was to elaborate a method for the simultaneous determination of lycopene and β-carotene in Blakeslea trispora products using a usual UV-vis spectrophotometer. The standard solutions of the mixture of different concentrations of β-carotene and lycopene were measured with the UV-vis method and correlation formula for the extinction coefficients of 1% standard solution of lycopene in the solvent (hexane) and the ratios of the optical densities at the character peaks of 470 and 502 nm was elaborated. This gives a possibility to calculate the concentrations of lycopene and β-carotene in the mixture. The prediction quality of the UV-vis method was sufficient and the obtained results were very close to the ones, being measured with the HPLC technique. The proposed method can be used for both routine industrial work and academic research, providing the rapid analysis for simultaneous measurements of lycopene and β-carotene.

  2. Simultaneous measurement of two enzyme activities using infrared spectroscopy: A comparative evaluation of PARAFAC, TUCKER and N-PLS modeling.

    PubMed

    Baum, Andreas; Hansen, Per Waaben; Meyer, Anne S; Mikkelsen, Jørn Dalgaard

    2013-08-01

    Enzymes are used in many processes to release fermentable sugars for green production of biofuel, or the refinery of biomass for extraction of functional food ingredients such as pectin or prebiotic oligosaccharides. The complex biomasses may, however, require a multitude of specific enzymes which are active on specific substrates generating a multitude of products. In this paper we use the plant polymer, pectin, to present a method to quantify enzyme activity of two pectolytic enzymes by monitoring their superimposed spectral evolutions simultaneously. The data is analyzed by three chemometric multiway methods, namely PARAFAC, TUCKER3 and N-PLS, to establish simultaneous enzyme activity assays for pectin lyase and pectin methyl esterase. Correlation coefficients Rpred(2) for prediction test sets are 0.48, 0.96 and 0.96 for pectin lyase and 0.70, 0.89 and 0.89 for pectin methyl esterase, respectively. The retrieved models are compared and prediction test sets show that especially TUCKER3 performs well, even in comparison to the supervised regression method N-PLS.

  3. Simultaneous, In-situ Measurement of NO3, N2O5 and NO2 via Cavity Ring-down Spectroscopy aboard an Aircraft

    NASA Astrophysics Data System (ADS)

    Dube, W. P.; Brown, S. S.; Osthoff, H. D.; Ciciora, S. J.; Paris, M. W.; McLaughlin, R. J.; Ravishankara, A. R.

    2006-12-01

    This contribution describes improvements to an existing instrument for aircraft measurements of NO3 and N2O5 in the troposphere via cavity ring-down spectroscopy [Brown, et al., 2002; Dubé, et al., 2006]. The instrument was specifically designed and constructed for operation on the NOAA WP-3. The improvements include the incorporation of two additional cavity ring-down channels, reduced residence time for more rapid sampling and reduced inlet losses; higher reflectivity mirrors to improve instrument sensitivity; and a calibration system based on the conversion of NO3 and N2O5 to NO2. The instrument now consists of a total of four measurement channels, three at 662 nm for measuring NO3, N2O5, and a reference channel to track background changes on a rapid time scale, and one at 532 nm for measurement of NO2 [Osthoff, et al., 2006]. This paper describes the specifics of these design changes, the resultant improvements in the measurement and the performance of the instrument during the TexAQS/GoMACCS campaign in Houston, TX in 2006. Brown, S. S., H. Stark, S. J. Ciciora, R. J. McLaughlin, and A. R. Ravishankara (2002), Simultaneous in-situ detection of atmospheric NO3 and N2O5 via cavity ring-down spectroscopy, Rev. Sci. Instr., 73, 3291-3301. Dube, W. P., S. S. Brown, H. D. Osthoff, M. R. Nunley, S. J. Ciciora, M. W. Paris, R. J. McLaughlin, and A. R. Ravishankara (2006), Aircraft instrument for simultaneous, in-situ measurements of NO3 and N2O5 via cavity ring-down spectroscopy, Rev. Sci. Instr., 77, 034101. Osthoff, H. D., S. S. Brown, T. B. Ryerson, T. J. Fortin, B. M. Lerner, E. J. Williams, A. Pettersson, T. Baynard, W. P. Dube, S. J. Ciciora, and A. R. Ravishankara (2006), Measurement of atmospheric NO2 by pulsed cavity ring-down spectroscopy, J. Geophys. Res., D12305, doi:10.1029/2005JD006942.

  4. Simultaneous Analysis of Major Coenzymes of Cellular Redox Reactions and Energy Using ex Vivo (1)H NMR Spectroscopy.

    PubMed

    Nagana Gowda, G A; Abell, Lauren; Lee, Chi Fung; Tian, Rong; Raftery, Daniel

    2016-05-01

    Coenzymes of cellular redox reactions and cellular energy mediate biochemical reactions fundamental to the functioning of all living cells. Despite their immense interest, no simple method exists to gain insights into their cellular concentrations in a single step. We show that a simple (1)H NMR experiment can simultaneously measure oxidized and reduced forms of nicotinamide adenine dinucleotide (NAD(+) and NADH), oxidized and reduced forms of nicotinamide adenine dinucleotide phosphate (NADP(+) and NADPH), and adenosine triphosphate (ATP) and its precursors, adenosine diphosphate (ADP) and adenosine monophosphate (AMP), using mouse heart, kidney, brain, liver, and skeletal muscle tissue extracts as examples. Combining 1D/2D NMR experiments, chemical shift libraries, and authentic compound data, reliable peak identities for these coenzymes have been established. To assess this methodology, cardiac NADH and NAD(+) ratios/pool sizes were measured using mouse models with a cardiac-specific knockout of the mitochondrial Complex I Ndufs4 gene (cKO) and cardiac-specific overexpression of nicotinamide phosphoribosyltransferase (cNAMPT) as examples. Sensitivity of NAD(+) and NADH to cKO or cNAMPT was observed, as anticipated. Time-dependent investigations showed that the levels of NADH and NADPH diminish by up to ∼50% within 24 h; concomitantly, NAD(+) and NADP(+) increase proportionately; however, degassing the sample and flushing the sample tubes with helium gas halted such changes. The analysis protocol along with the annotated characteristic fingerprints for each coenzyme is provided for easy identification and absolute quantification using a single internal reference for routine use. The ability to visualize the ubiquitous coenzymes fundamental to cellular functions, simultaneously and reliably, offers a new avenue to interrogate the mechanistic details of cellular function in health and disease.

  5. Open-path quantum cascade laser-based system for simultaneous remote sensing of methane, nitrous oxide, and water vapor using chirped-pulse differential optical absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Castillo, Paulo; Diaz, Adrian; Thomas, Benjamin; Gross, Barry; Moshary, Fred

    2015-10-01

    Methane and Nitrous Oxide are long-lived greenhouse gases in the atmosphere with significant global warming effects. We report on application of chirped-pulsed quantum cascade lasers (QCLs) to simultaneous measurements of these trace gases in both open-path fence-line and backscatter systems. The intra-pulse thermal frequency chip in a QCL can be time resolved and calibrated to allow for high resolution differential optical absorption spectroscopy over the spectral window of the chip, which for a DFB-QCL can be reach ~2cm-1 for a 500 nsec pulse. The spectral line-shape of the output from these lasers are highly stable from pulse to pulse over long period of time (> 1 day), and the system does not require frequent calibrations.

  6. Application of Fourier transform near-infrared spectroscopy combined with high-performance liquid chromatography in rapid and simultaneous determination of essential components in crude Radix Scrophulariae.

    PubMed

    Li, Xiaomeng; Fang, Dansi; Cong, Xiaodong; Cao, Gang; Cai, Hao; Cai, Baochang

    2012-12-01

    A method is described using rapid and sensitive Fourier transform near-infrared spectroscopy combined with high-performance liquid chromatography-diode array detection for the simultaneous identification and determination of four bioactive compounds in crude Radix Scrophulariae samples. Partial least squares regression is selected as the analysis type and multiplicative scatter correction, second derivative, and Savitzky-Golay filter were adopted for the spectral pretreatment. The correlation coefficients (R) of the calibration models were above 0.96 and the root mean square error of predictions were under 0.028. The developed models were applied to unknown samples with satisfactory results. The established method was validated and can be applied to the intrinsic quality control of crude Radix Scrophulariae.

  7. Combining Electrochemical Impedance Spectroscopy and Surface Plasmon Resonance into one Simultaneous Read-Out System for the Detection of Surface Interactions

    PubMed Central

    Vandenryt, Thijs; Pohl, Andrea; van Grinsven, Bart; Thoelen, Ronald; De Ceuninck, Ward; Wagner, Patrick; Opitz, Jörg

    2013-01-01

    In this article we describe the integration of impedance spectroscopy (EIS) and surface plasmon resonance (SPR) into one surface analytic device. A polydimethylsiloxane (PDMS) flow cell is created, matching the dimensions of a commercially available sensor chip used for SPR measurements. This flow cell allowed simultaneous measurements between an EIS and a SPR setup. After a successful integration, a proof of principle study was conducted to investigate any signs of interference between the two systems during a measurement. The flow cell was rinsed with 10 mM Tris-HCl and 1× PBS buffer in an alternating manner, while impedance and shifts of the resonance angle were monitored. After achieving a successful proof of principle, a usability test was conducted. It was assessed whether simultaneous detection occurred when: (i) Protein A is adsorbed to the gold surface of the chip; (ii) The non-occupied zone is blocked with BSA molecules and (iii) IgG1 is bound to the Protein A. The results indicate a successful merge between SPR and EIS. PMID:24172282

  8. Simultaneous detection of ethanol, ether and acetone by mid-infrared cavity ring-down spectroscopy at 3.8 μm

    NASA Astrophysics Data System (ADS)

    Zhou, Sheng; Han, Yanling; Li, Bincheng

    2016-07-01

    Mid-infrared cavity ring-down spectroscopy (CRDS) using an external cavity, widely tunable pulsed quantum cascade laser operating at 3.8 μm, was employed for simultaneous detections of ethanol, ether and acetone in this paper. The experiments were performed with a maximum cavity mirror reflectivity of 99.915 % between the wave number 2614 and 2634 cm-1, leading to an effective optical path length of 588 m. The absorption spectra of ethanol, ether and acetone were measured with high spectral resolution in the range of 2614-2634 cm-1, and the spectroscopic analysis of the mixture of ethanol, ether and acetone with overlapping absorption spectra was demonstrated. The experimentally achieved detection limits (3σ, or three times of standard deviation) for ethanol, ether and acetone were 157, 60 and 280 ppb, respectively. The simultaneously measured concentration results were in good agreement with the results with the standard gravimetric method, indicated that the mid-infrared CRDS has the potential for multi-component trace gas detection as well as for spectroscopic measurements of multi-broadband absorbers.

  9. Note: Application of a pixel-array area detector to simultaneous single crystal x-ray diffraction and x-ray absorption spectroscopy measurements

    SciTech Connect

    Sun, Cheng-Jun Brewe, Dale L.; Heald, Steve M.; Zhang, Bangmin; Chen, Jing-Sheng; Chow, G. M.; Venkatesan, T.

    2014-04-15

    X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) are two main x-ray techniques in synchrotron radiation facilities. In this Note, we present an experimental setup capable of performing simultaneous XRD and XAS measurements by the application of a pixel-array area detector. For XRD, the momentum transfer in specular diffraction was measured by scanning the X-ray energy with fixed incoming and outgoing x-ray angles. By selecting a small fixed region of the detector to collect the XRD signal, the rest of the area was available for collecting the x-ray fluorescence for XAS measurements. The simultaneous measurement of XRD and X-ray absorption near edge structure for Pr{sub 0.67}Sr{sub 0.33}MnO{sub 3} film was demonstrated as a proof of principle for future time-resolved pump-probe measurements. A static sample makes it easy to maintain an accurate overlap of the X-ray spot and laser pump beam.

  10. Preliminary study of an offline simultaneous determination of metoprolol tartrate and hydrochlorothiazide in powders and tablets by reflectance near-infrared spectroscopy.

    PubMed

    Vranic, Branko Z; Vandamme, Thierry F

    2015-01-01

    A preliminary study of the feasibility of using near-infrared spectroscopy (NIRS) for the offline simultaneous determination of metoprolol tartrate (MTP) and hydrochlorothiazide (HTZ) in powders and tablets has been carried out. An industrial tableting process was simulated using an instrumented tablet press replicator - Presster™. Conventional reference analytics were replaced with gravimetric analysis. The NIRS models for powder and tablet analysis were developed using 55 samples, and tested on 80 independent samples. Powder mixture components were weighed in glass vials to collect reference values, mixed and manually transferred to a tablet press replicator and compacted to form tablets. NIRS calibration models were developed using spectral and gravimetric reference data. The two model drugs were simultaneously quantified exhibiting root mean-squared error of prediction (RMSEP) of 1.69 and 1.31 mg for HTZ powder and tablet samples, respectively, and RMSEP of 3.15 and 3.00 mg for MTP powder and tablet samples, respectively. NIRS analysis of MTP and HTZ in powder and tablet form has not been reported elsewhere.

  11. Solid-state /sup 13/C nuclear magnetic resonance spectroscopy of simultaneously metabolized acetate and phenol in a soil Pseudomonas sp

    SciTech Connect

    Heiman, A.S.; Copper, W.T.

    1987-01-01

    An investigation was made of the concentration-dependent primary and secondary substrate relationships in the simultaneous metabolism of the ubiquitous pollutant phenol and the naturally occurring substrate acetate by a Pseudomonas sp. soil isolate capable of utilizing either substance as a sole source of carbon and energy. In addition to conventional analytical techniques, solid-state /sup 13/C nuclear magnetic resonance spectroscopy was used to follow the cellular distribution of (1-/sup 13/C)acetate in the presence of unlabeled phenol. These results suggest that, when phenol is present as the primary substrate, acetate is preferentially shuttled into fatty acyl chain synthesis, whereas phenol carbon is funnelled into the tricarboxylic acid cycle. Thus, simultaneous use of a xenobiotic compound and a natural substrate apparently does occur, and the relative concentrations of the two substrates do influence the rate and manner in which the compounds are utilized. These results also demonstrate the unique advantage of using solid-state nuclear magnetic resonance techniques combined with /sup 13/C labeling of specific sites in substrates when doing microbial degradation studies. In this work, the entire cellular biomass was examined directly without extensive extraction, fractionation, or isolation of subcellular units; thus, there is no uncertainty about chemical alteration of substrate metabolites as a result of these often harsh treatments.

  12. Application of multivariate chemometric techniques for simultaneous determination of five parameters of cottonseed oil by single bounce attenuated total reflectance Fourier transform infrared spectroscopy.

    PubMed

    Talpur, M Younis; Kara, Huseyin; Sherazi, S T H; Ayyildiz, H Filiz; Topkafa, Mustafa; Arslan, Fatma Nur; Naz, Saba; Durmaz, Fatih; Sirajuddin

    2014-11-01

    Single bounce attenuated total reflectance (SB-ATR) Fourier transform infrared (FTIR) spectroscopy in conjunction with chemometrics was used for accurate determination of free fatty acid (FFA), peroxide value (PV), iodine value (IV), conjugated diene (CD) and conjugated triene (CT) of cottonseed oil (CSO) during potato chips frying. Partial least square (PLS), stepwise multiple linear regression (SMLR), principal component regression (PCR) and simple Beer׳s law (SBL) were applied to develop the calibrations for simultaneous evaluation of five stated parameters of cottonseed oil (CSO) during frying of French frozen potato chips at 170°C. Good regression coefficients (R(2)) were achieved for FFA, PV, IV, CD and CT with value of >0.992 by PLS, SMLR, PCR, and SBL. Root mean square error of prediction (RMSEP) was found to be less than 1.95% for all determinations. Result of the study indicated that SB-ATR FTIR in combination with multivariate chemometrics could be used for accurate and simultaneous determination of different parameters during the frying process without using any toxic organic solvent. PMID:25127621

  13. Brain cortical mapping by simultaneous recording of functional near infrared spectroscopy and electroencephalograms from the whole brain during right median nerve stimulation.

    PubMed

    Takeuchi, Mikinobu; Hori, Etsuro; Takamoto, Kouichi; Tran, Anh Hai; Satoru, Kohno; Ishikawa, Akihiro; Ono, Taketoshi; Endo, Shunro; Nishijo, Hisao

    2009-11-01

    To investigate relationships between hemodynamic responses and neural activities in the somatosensory cortices, hemodynamic responses by near infrared spectroscopy (NIRS) and electroencephalograms (EEGs) were recorded simultaneously while subjects received electrical stimulation in the right median nerve. The statistical significance of the hemodynamic responses was evaluated by a general linear model (GLM) with the boxcar design matrix convoluted with Gaussian function. The resulting NIRS and EEGs data were stereotaxically superimposed on the reconstructed brain of each subject. The NIRS data indicated that changes in oxy-hemoglobin concentration increased at the contralateral primary somatosensory (SI) area; responses then spread to the more posterior and ipsilateral somatosensory areas. The EEG data indicated that positive somatosensory evoked potentials peaking at 22 ms latency (P22) were recorded from the contralateral SI area. Comparison of these two sets of data indicated that the distance between the dipoles of P22 and NIRS channels with maximum hemodynamic responses was less than 10 mm, and that the two topographical maps of hemodynamic responses and current source density of P22 were significantly correlated. Furthermore, when onset of the boxcar function was delayed 5-15 s (onset delay), hemodynamic responses in the bilateral parietal association cortices posterior to the SI were more strongly correlated to electrical stimulation. This suggests that GLM analysis with onset delay could reveal the temporal ordering of neural activation in the hierarchical somatosensory pathway, consistent with the neurophysiological data. The present results suggest that simultaneous NIRS and EEG recording is useful for correlating hemodynamic responses to neural activity.

  14. Simultaneous near-IR spectroscopy and magnetic resonance imaging to assess cerebral oxygenation and brain water during hypoxia-ischemia in two-week-old rats

    NASA Astrophysics Data System (ADS)

    Shaw, R. A.; Tuor, U. I.; Foniok, T.; Bascaramurty, S.; Ringland, K.; McKenzie, E.; Qiao, M.; Tomanek, B.; Mantsch, Henry H.

    2001-10-01

    Cerebral near-infrared spectroscopy can potentially probe several parameters related to the onset of stroke and the ensuing tissue damage. One obvious marker of ischemia is cerebral oxygenation, which can be lowered sharply in stroke-affected tissue. Also commonly assessed, though less straightforward to recover, is the redox state of the cytochrome aa3 copper center. Finally, parameters that are in principle available but seldom recovered from in vivo near-IR spectra are changes in water concentration and scattering properties of the tissue. We have evaluated the potential for near-IR spectroscopy to detect relevant changes in cerebral oxygenation, blood volume, water content, and scattering properties in an infant rat stroke model that is well characterized by magnetic resonance imaging methods. The specific aim was to acquire near-IR spectra simultaneously with MR images and to correlate stroke-associated changes detected via these two modalities prior to, during and after a hypoxia-ischemia episode within this stroke model. Presented here are results from the design and testing of a near-IR illumination/detection system that is compatible with an MR imaging system, and the recovery of trends in the near-IR spectra that complement the hypoxic-ischemic changes observed in the MR images. Unexpectedly large intensity changes observed for the in vivo near-IR water absorptions are ascribed to hypoxia-induced variations in effective optical pathlength, suggesting that the water absorptions may prove generally useful as a means to track such changes.

  15. Second-derivative synchronous fluorescence spectroscopy for the simultaneous determination of cinnarizine and nicergoline in pharmaceutical preparations.

    PubMed

    Walash, Mohamed I; Belal, Fathalla; El-Enany, Nahed; Abdelal, Amina

    2008-01-01

    A rapid, simple, and highly sensitive second-derivative synchronous fluorometric method has been developed for the simultaneous analysis of binary mixtures of cinnarizine (CN) and nicergoline (NIC). The method is based upon measurement of the native fluorescence of these drugs at constant wavelength difference (Deltalambda) = 80 nm in aqueous methanol (50%, v/v). The different experimental parameters affecting the native fluorescence of the studied drugs were carefully studied and optimized. The fluorescence-concentration plots were rectilinear over the range of 0.025-1.5 and 0.25-5.5 microg/mL for CN and NIC, respectively, with lower detection limits of 0.58 and 0.82 ng/mL and quantitation limits of 1.93 and 2.73 ng/mL for CN and NIC, respectively. The proposed method was successfully applied for the determination of the studied compounds in synthetic mixtures and in commercial tablets. The results obtained were in good agreement with those obtained with reference methods. The high sensitivity attained by the proposed method allowed the determination of CN in real and spiked human plasma. The mean recovery in the case of spiked human plasma [number of trials (n) = 3] was 102.82 +/- 2.17%, while that in real human plasma (n = 3) was 105.25 +/- 2.05. PMID:18476347

  16. Application of near-infrared reflectance spectroscopy to the simultaneous prediction of alkaloids and phenolic substances in green tea leaves.

    PubMed

    Schulz, H; Engelhardt, U H; Wegent, A; Drews, H; Lapczynski, S

    1999-12-01

    A near-infrared reflectance spectroscopic (NIRS) method for the prediction of polyphenol and alkaloid compounds in the leaves of green tea [Camellia sinensis (L.) O. Kuntze] was developed. Reference measurements of the individual catechins, gallic acid, caffeine, and theobromine were performed by reversed-phase HPLC. The total polyphenols were determined according to the colorimetric Folin-Ciocalteu assay. Using the partial least-squares algorithm, very good calibration statistics were obtained for the prediction of gallic acid, (-)-epicatechin, (-)-epigallocatechin, (-)-epicatechin gallate, (-)-epigallocatechin gallate, caffeine, and theobromine (R(2) > 0.85) with standard deviation/standard error of cross-validation (SD/SECV) ratio ranging from 2.00 to 6.27. Simultaneously, the dry matter content of the tea leaves can be analyzed very precisely (R(2) = 0.94; SD/SECV = 4.12). Furthermore, it is possible to discriminate tea leaves of different age by principal component analysis on the basis of the received NIR spectra. Prediction of the total polyphenol content is performed with a lower accuracy, which might be due to the lack of specificity in the colorimetric reference method. The study demonstrates that NIRS technology can be successfully applied as a rapid method not only for breeding and cultivation purposes but also to estimate the quality and taste of green tea and to control industrial processes, for example, decaffeination.

  17. Second-derivative synchronous fluorescence spectroscopy for the simultaneous determination of fluphenazine hydrochloride and nortriptyline hydrochloride in pharmaceutical preparations.

    PubMed

    Walash, M I; El-Brashy, A; El-Enany, N; Kamel, M E

    2009-09-01

    A rapid, simple, and highly sensitive second-derivative synchronous fluorimetric (SDSF) method has been developed for the simultaneous analysis of binary mixtures of fluphenazine hydrochloride (FLZ) and nortriptyline hydrochloride (NTP) in their co-formulated tablets. The method is based upon measurement of the native fluorescence of these drugs at constant wavelength difference (Deltalambda) = 120 nm in acetic acid. The different experimental parameters affecting the fluorescence intensity of the studied drugs were carefully studied and optimized. The fluorescence-concentration plots were rectilinear over the range of 0.25-3.0 and 1-10 microg/ml for FLZ and NTP respectively, with lower detection limits (LOD) of 0.05 and 0.18 microg/ml and quantitation limits of 0.15 and 0.53 microg/ml for FLZ and NTP respectively. The proposed method was successfully applied for the determination of the studied compounds in their synthetic mixtures and in commercial co-formulated tablets. The results obtained were in good agreement with those obtained by the reference methods.

  18. HPLC and chemometrics-assisted UV-spectroscopy methods for the simultaneous determination of ambroxol and doxycycline in capsule

    NASA Astrophysics Data System (ADS)

    Hadad, Ghada M.; El-Gindy, Alaa; Mahmoud, Waleed M. M.

    2008-08-01

    High-performance liquid chromatography (HPLC) and multivariate spectrophotometric methods are described for the simultaneous determination of ambroxol hydrochloride (AM) and doxycycline (DX) in combined pharmaceutical capsules. The chromatographic separation was achieved on reversed-phase C 18 analytical column with a mobile phase consisting of a mixture of 20 mM potassium dihydrogen phosphate, pH 6-acetonitrile in ratio of (1:1, v/v) and UV detection at 245 nm. Also, the resolution has been accomplished by using numerical spectrophotometric methods as classical least squares (CLS), principal component regression (PCR) and partial least squares (PLS-1) applied to the UV spectra of the mixture and graphical spectrophotometric method as first derivative of the ratio spectra ( 1DD) method. Analytical figures of merit (FOM), such as sensitivity, selectivity, analytical sensitivity, limit of quantitation and limit of detection were determined for CLS, PLS-1 and PCR methods. The proposed methods were validated and successfully applied for the analysis of pharmaceutical formulation and laboratory-prepared mixtures containing the two component combination.

  19. Asteroseismology of Hybrid Pulsators Made Possible: Simultaneous MOST Space Photometry and Ground-Based Spectroscopy of γ Peg

    NASA Astrophysics Data System (ADS)

    Handler, G.; Matthews, J. M.; Eaton, J. A.; Daszyńska-Daszkiewicz, J.; Kuschnig, R.; Lehmann, H.; Rodríguez, E.; Pamyatnykh, A. A.; Zdravkov, T.; Lenz, P.; Costa, V.; Díaz-Fraile, D.; Sota, A.; Kwiatkowski, T.; Schwarzenberg-Czerny, A.; Borczyk, W.; Dimitrov, W.; Fagas, M.; Kamiński, K.; Rożek, A.; van Wyk, F.; Pollard, K. R.; Kilmartin, P. M.; Weiss, W. W.; Guenther, D. B.; Moffat, A. F. J.; Rucinski, S. M.; Sasselov, D. D.; Walker, G. A. H.

    2009-06-01

    We have acquired simultaneous high-precision space photometry and radial velocities of the bright hybrid β Cep/Slowly Pulsating B pulsator γ Peg. Frequency analyses reveal the presence of six gravity (g) modes of high radial order together with eight low-order β Cep oscillations in both data sets. Mode identification shows that all pulsations have spherical degrees ell = 0-2. An 8.5 M sun model reproduces the observed pulsation frequencies; all theoretically predicted modes in the β Cep domain are detected. We suggest, contrary to previous authors, that γ Peg is a single star; the claimed orbital variations are due to g-mode pulsation. γ Peg is the first hybrid pulsator for which a sufficiently large number of high-order g modes and low-order pressure (p) and mixed modes have been detected and identified to be usable for in-depth seismic modeling. Based on data from the MOST satellite, a Canadian Space Agency mission operated by Dynacon, Inc., the University of Toronto Institute of Aerospace Studies, and the University of British Columbia, with assistance from the University of Vienna, Austria.

  20. Application of near-infrared reflectance spectroscopy to the simultaneous prediction of alkaloids and phenolic substances in green tea leaves.

    PubMed

    Schulz, H; Engelhardt, U H; Wegent, A; Drews, H; Lapczynski, S

    1999-12-01

    A near-infrared reflectance spectroscopic (NIRS) method for the prediction of polyphenol and alkaloid compounds in the leaves of green tea [Camellia sinensis (L.) O. Kuntze] was developed. Reference measurements of the individual catechins, gallic acid, caffeine, and theobromine were performed by reversed-phase HPLC. The total polyphenols were determined according to the colorimetric Folin-Ciocalteu assay. Using the partial least-squares algorithm, very good calibration statistics were obtained for the prediction of gallic acid, (-)-epicatechin, (-)-epigallocatechin, (-)-epicatechin gallate, (-)-epigallocatechin gallate, caffeine, and theobromine (R(2) > 0.85) with standard deviation/standard error of cross-validation (SD/SECV) ratio ranging from 2.00 to 6.27. Simultaneously, the dry matter content of the tea leaves can be analyzed very precisely (R(2) = 0.94; SD/SECV = 4.12). Furthermore, it is possible to discriminate tea leaves of different age by principal component analysis on the basis of the received NIR spectra. Prediction of the total polyphenol content is performed with a lower accuracy, which might be due to the lack of specificity in the colorimetric reference method. The study demonstrates that NIRS technology can be successfully applied as a rapid method not only for breeding and cultivation purposes but also to estimate the quality and taste of green tea and to control industrial processes, for example, decaffeination. PMID:10606573

  1. Functional near infrared spectroscopy of the sensory and motor brain regions with simultaneous kinematic and EMG monitoring during motor tasks

    PubMed Central

    Sukal-Moulton, Theresa; de Campos, Ana Carolina; Stanley, Christopher J

    2015-01-01

    There are several advantages that functional near-infrared spectroscopy (fNIRS) presents in the study of the neural control of human movement. It is relatively flexible with respect to participant positioning and allows for some head movements during tasks. Additionally, it is inexpensive, light weight, and portable, with very few contraindications to its use. This presents a unique opportunity to study functional brain activity during motor tasks in individuals who are typically developing, as well as those with movement disorders, such as cerebral palsy. An additional consideration when studying movement disorders, however, is the quality of actual movements performed and the potential for additional, unintended movements. Therefore, concurrent monitoring of both blood flow changes in the brain and actual movements of the body during testing is required for appropriate interpretation of fNIRS results. Here, we show a protocol for the combination of fNIRS with muscle and kinematic monitoring during motor tasks. We explore gait, a unilateral multi-joint movement (cycling), and two unilateral single-joint movements (isolated ankle dorsiflexion, and isolated hand squeezing). The techniques presented can be useful in studying both typical and atypical motor control, and can be modified to investigate a broad range of tasks and scientific questions. PMID:25548919

  2. Simultaneous determination of hydrocarbon renewable diesel, biodiesel and petroleum diesel contents in diesel fuel blends using near infrared (NIR) spectroscopy and chemometrics.

    PubMed

    Alves, Julio Cesar Laurentino; Poppi, Ronei Jesus

    2013-11-01

    Highly polluting fuels based on non-renewable resources such as fossil fuels need to be replaced with potentially less polluting renewable fuels derived from vegetable or animal biomass, these so-called biofuels, are a reality nowadays and many countries have started the challenge of increasing the use of different types of biofuels, such as ethanol and biodiesel (fatty acid alkyl esters), often mixed with petroleum derivatives, such as gasoline and diesel, respectively. The quantitative determination of these fuel blends using simple, fast and low cost methods based on near infrared (NIR) spectroscopy combined with chemometric methods has been reported. However, advanced biofuels based on a mixture of hydrocarbons or a single hydrocarbon molecule, such as farnesane (2,6,10-trimethyldodecane), a hydrocarbon renewable diesel, can also be used in mixtures with biodiesel and petroleum diesel fuel and the use of NIR spectroscopy for the quantitative determination of a ternary fuel blend of these two hydrocarbon-based fuels and biodiesel can be a useful tool for quality control. This work presents a development of an analytical method for the quantitative determination of hydrocarbon renewable diesel (farnesane), biodiesel and petroleum diesel fuel blends using NIR spectroscopy combined with chemometric methods, such as partial least squares (PLS) and support vector machines (SVM). This development leads to a more accurate, simpler, faster and cheaper method when compared to the standard reference method ASTM D6866 and with the main advantage of providing the individual quantification of two different biofuels in a mixture with petroleum diesel fuel. Using the developed PLS model the three fuel blend components were determined simultaneously with values of root mean square error of prediction (RMSEP) of 0.25%, 0.19% and 0.38% for hydrocarbon renewable diesel, biodiesel and petroleum diesel, respectively, the values obtained were in agreement with those suggested by

  3. Simultaneous determination of hydrocarbon renewable diesel, biodiesel and petroleum diesel contents in diesel fuel blends using near infrared (NIR) spectroscopy and chemometrics.

    PubMed

    Alves, Julio Cesar Laurentino; Poppi, Ronei Jesus

    2013-11-01

    Highly polluting fuels based on non-renewable resources such as fossil fuels need to be replaced with potentially less polluting renewable fuels derived from vegetable or animal biomass, these so-called biofuels, are a reality nowadays and many countries have started the challenge of increasing the use of different types of biofuels, such as ethanol and biodiesel (fatty acid alkyl esters), often mixed with petroleum derivatives, such as gasoline and diesel, respectively. The quantitative determination of these fuel blends using simple, fast and low cost methods based on near infrared (NIR) spectroscopy combined with chemometric methods has been reported. However, advanced biofuels based on a mixture of hydrocarbons or a single hydrocarbon molecule, such as farnesane (2,6,10-trimethyldodecane), a hydrocarbon renewable diesel, can also be used in mixtures with biodiesel and petroleum diesel fuel and the use of NIR spectroscopy for the quantitative determination of a ternary fuel blend of these two hydrocarbon-based fuels and biodiesel can be a useful tool for quality control. This work presents a development of an analytical method for the quantitative determination of hydrocarbon renewable diesel (farnesane), biodiesel and petroleum diesel fuel blends using NIR spectroscopy combined with chemometric methods, such as partial least squares (PLS) and support vector machines (SVM). This development leads to a more accurate, simpler, faster and cheaper method when compared to the standard reference method ASTM D6866 and with the main advantage of providing the individual quantification of two different biofuels in a mixture with petroleum diesel fuel. Using the developed PLS model the three fuel blend components were determined simultaneously with values of root mean square error of prediction (RMSEP) of 0.25%, 0.19% and 0.38% for hydrocarbon renewable diesel, biodiesel and petroleum diesel, respectively, the values obtained were in agreement with those suggested by

  4. Simultaneous K- and L-band Spectroscopy of Be Stars: Circumstellar Envelope Properties from Hydrogen Emission Lines

    NASA Astrophysics Data System (ADS)

    Granada, A.; Arias, M. L.; Cidale, L. S.

    2010-05-01

    We present medium-resolution K- and L-band spectra of a sample of eight Be stars, obtained with Gemini/NIRI. The IR K and L bands contain many lines of different hydrogen series that are used as a diagnosis to the physical conditions in the circumstellar environments. We make an analysis on the optical depths of the line-forming regions based on the intensity ratios of Pfγ and Brα lines, the behavior of Humphreys' series, and the fluxes of Brα and Brγ lines. All our targets show spectroscopic and photometric long-term variability; thus, time-resolved K- and L-band spectroscopy is an ideal tool for studying the structure and evolution of the innermost regions of the envelope and to test models on the disk-forming mechanism. We note that the instrumental configuration used allowed us to obtain good quality IR observations and to take profit of Gemini band 3 observing time (allocation time for ranked programs in which the observing conditions are relaxed). Based on observations obtained at the Gemini Observatory, which is operated by the Association of Universities for Research in Astronomy, Inc., under a cooperative agreement with the NSF on behalf of the Gemini partnership: the National Science Foundation (USA), the Science and Technology Facilities Council (UK), the National Research Council (Canada), CONICYT (Chile), the Australian Research Council (Australia), Ministério da Ciência e Tecnologia (Brazil), and Ministerio de Ciencia, Tecnología e Innovación Productiva (Argentina).

  5. Processing of emotional words measured simultaneously with steady-state visually evoked potentials and near-infrared diffusing-wave spectroscopy

    PubMed Central

    2010-01-01

    Background Emotional stimuli are preferentially processed compared to neutral ones. Measuring the magnetic resonance blood-oxygen level dependent (BOLD) response or EEG event-related potentials, this has also been demonstrated for emotional versus neutral words. However, it is currently unclear whether emotion effects in word processing can also be detected with other measures such as EEG steady-state visual evoked potentials (SSVEPs) or optical brain imaging techniques. In the present study, we simultaneously performed SSVEP measurements and near-infrared diffusing-wave spectroscopy (DWS), a new optical technique for the non-invasive measurement of brain function, to measure brain responses to neutral, pleasant, and unpleasant nouns flickering at a frequency of 7.5 Hz. Results The power of the SSVEP signal was significantly modulated by the words' emotional content at occipital electrodes, showing reduced SSVEP power during stimulation with pleasant compared to neutral nouns. By contrast, the DWS signal measured over the visual cortex showed significant differences between stimulation with flickering words and baseline periods, but no modulation in response to the words' emotional significance. Conclusions This study is the first investigation of brain responses to emotional words using simultaneous measurements of SSVEPs and DWS. Emotional modulation of word processing was detected with EEG SSVEPs, but not by DWS. SSVEP power for emotional, specifically pleasant, compared to neutral words was reduced, which contrasts with previous results obtained when presenting emotional pictures. This appears to reflect processing differences between symbolic and pictorial emotional stimuli. While pictures prompt sustained perceptual processing, decoding the significance of emotional words requires more internal associative processing. Reasons for an absence of emotion effects in the DWS signal are discussed. PMID:20663220

  6. Simultaneous Determination of Acetaminophen and Synthetic Color(s) by Derivative Spectroscopy in Syrup Formulations and Validation by HPLC: Exposure Risk of Colors to Children.

    PubMed

    Rastogi, Shanya Das; Dixit, Sumita; Tripathi, Anurag; Das, Mukul

    2015-06-01

    Color additives are used in pediatric syrup formulations as an excipient; though not pre-requisite, but pediatric syrup formulations are normally colored. An attempt has been made to measure simultaneously the single drug, acetaminophen (AT), along with the colors, carmoisine (CA), erythrosine (ET), and sunset yellow FCF (SSY) added in it by three derivative spectroscopy methods namely, 1st order, ratio, and differential derivative methods. Moreover, evaluation has been made for the exposure assessment of the colors added as excipient because some colors have been reported to cause allergic reactions and hypersensitivity in children. The present methods provide simple, accurate, and reproducible quantitative determination of the drug, AT, along with the color in synthetic mixtures and commercial drug formulations without any interference. The limit of detection varied from 0.0001-0.31 μg/ml while limit of quantification ranged from 0.002-1.04 μg/ml in all the three methods. The calibration curve of all the three derivative methods exhibited good linear relationship with excellent regression coefficients (0.9986-1.000). Both intra-day and inter-day precisions showed %RSD value less than 2% while the percentage recovery was found between 96.8-103.8%. The sensitivity of the proposed methods is almost comparable to HPLC and thus, can be used for determination of drug AT, and color simultaneously in pharmaceutical formulation on routine basis. The present methods also showed that colors like SSY and ET are saturating more than 50% of acceptable daily intake (ADI) value which is alarming and needs to be considered for modification by regulatory authorities to safeguard the health of children. PMID:25374343

  7. Multivariate classification of edible salts: Simultaneous Laser-Induced Breakdown Spectroscopy and Laser-Ablation Inductively Coupled Plasma Mass Spectrometry Analysis

    NASA Astrophysics Data System (ADS)

    Lee, Yonghoon; Nam, Sang-Ho; Ham, Kyung-Sik; Gonzalez, Jhanis; Oropeza, Dayana; Quarles, Derrick; Yoo, Jonghyun; Russo, Richard E.

    2016-04-01

    Laser-Induced Breakdown Spectroscopy (LIBS) and Laser-Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS), both based on laser ablation sampling, can be employed simultaneously to obtain different chemical fingerprints from a sample. We demonstrated that this analysis approach can provide complementary information for improved classification of edible salts. LIBS could detect several of the minor metallic elements along with Na and Cl, while LA-ICP-MS spectra were used to measure non-metallic and trace heavy metal elements. Principal component analysis using LIBS and LA-ICP-MS spectra showed that their major spectral variations classified the sample salts in different ways. Three classification models were developed by using partial least squares-discriminant analysis based on the LIBS, LA-ICP-MS, and their fused data. From the cross-validation performances and confusion matrices of these models, the minor metallic elements (Mg, Ca, and K) detected by LIBS and the non-metallic (I) and trace heavy metal (Ba, W, and Pb) elements detected by LA-ICP-MS provided complementary chemical information to distinguish particular salt samples.

  8. CW EC-QCL-based sensor for simultaneous detection of H2O, HDO, N2O and CH4 using multi-pass absorption spectroscopy

    DOE PAGES

    Yu, Yajun; Sanchez, Nancy P.; Griffin, Robert J.; Tittel, Frank K.

    2016-05-03

    A sensor system based on a continuous wave, external-cavity quantum-cascade laser (CW EC-QCL) was demonstrated for simultaneous detection of atmospheric H2O, HDO, N2O and CH4 using a compact, dense pattern multi-pass gas cell with an effective path-length of 57.6 m. The EC-QCL with a mode-hop-free spectral range of 1225-1285 cm-1 operating at similar to 7.8 mu m was scanned covering four neighboring absorption lines, for H2O at 1281.161 cm-1, HDO at 1281.455 cm-1, N2O at 1281.53 cm-1 and CH4 at 1281.61 cm-1. A first-harmonic-normalized wavelength modulation spectroscopy with second-harmonic detection (WMS-2f/1f) strategy was employed for data processing. An Allan-Werle deviationmore » analysis indicated that minimum detection limits of 1.77 ppmv for H2O, 3.92 ppbv for HDO, 1.43 ppbv for N2O, and 2.2 ppbv for CH4 were achieved with integration times of 50-s, 50-s, 100-s and 129-s, respectively. In conclusion, experimental measurements of ambient air are also reported.« less

  9. Using UV-Vis spectroscopy for simultaneous geographical and varietal classification of tea infusions simulating a home-made tea cup.

    PubMed

    Diniz, Paulo Henrique Gonçalves Dias; Barbosa, Mayara Ferreira; de Melo Milanez, Karla Danielle Tavares; Pistonesi, Marcelo Fabián; de Araújo, Mário César Ugulino

    2016-02-01

    In this work we proposed a method to verify the differentiating characteristics of simple tea infusions prepared in boiling water alone (simulating a home-made tea cup), which represents the final product as ingested by the consumers. For this purpose we used UV-Vis spectroscopy and variable selection through the Successive Projections Algorithm associated with Linear Discriminant Analysis (SPA-LDA) for simultaneous classification of the teas according to their variety and geographic origin. For comparison, KNN, CART, SIMCA, PLS-DA and PCA-LDA were also used. SPA-LDA and PCA-LDA provided significantly better results for tea classification of the five studied classes (Argentinean green tea; Brazilian green tea; Argentinean black tea; Brazilian black tea; and Sri Lankan black tea). The proposed methodology provides a simpler, faster and more affordable classification of simple tea infusions, and can be used as an alternative approach to traditional tea quality evaluation as made by skilful tasters, which is evidently partial and cannot assess geographic origins.

  10. Direct and simultaneous quantification of tannin mean degree of polymerization and percentage of galloylation in grape seeds using diffuse reflectance fourier transform-infrared spectroscopy.

    PubMed

    Pappas, Christos; Kyraleou, Maria; Voskidi, Eleni; Kotseridis, Yorgos; Taranilis, Petros A; Kallithraka, Stamatina

    2015-02-01

    The direct and simultaneous quantitative determination of the mean degree of polymerization (mDP) and the degree of galloylation (%G) in grape seeds were quantified using diffuse reflectance infrared Fourier transform spectroscopy and partial least squares (PLS). The results were compared with those obtained using the conventional analysis employing phloroglucinolysis as pretreatment followed by high performance liquid chromatography-UV and mass spectrometry detection. Infrared spectra were recorded in solid state samples after freeze drying. The 2nd derivative of the 1832 to 1416 and 918 to 739 cm(-1) spectral regions for the quantification of mDP, the 2nd derivative of the 1813 to 607 cm(-1) spectral region for the degree of %G determination and PLS regression were used. The determination coefficients (R(2) ) of mDP and %G were 0.99 and 0.98, respectively. The corresponding values of the root-mean-square error of calibration were found 0.506 and 0.692, the root-mean-square error of cross validation 0.811 and 0.921, and the root-mean-square error of prediction 0.612 and 0.801. The proposed method in comparison with the conventional method is simpler, less time consuming, more economical, and requires reduced quantities of chemical reagents and fewer sample pretreatment steps. It could be a starting point for the design of more specific models according to the requirements of the wineries. PMID:25588697

  11. Simultaneous determination of penicillin G salts by infrared spectroscopy: Evaluation of combining orthogonal signal correction with radial basis function-partial least squares regression

    NASA Astrophysics Data System (ADS)

    Talebpour, Zahra; Tavallaie, Roya; Ahmadi, Seyyed Hamid; Abdollahpour, Assem

    2010-09-01

    In this study, a new method for the simultaneous determination of penicillin G salts in pharmaceutical mixture via FT-IR spectroscopy combined with chemometrics was investigated. The mixture of penicillin G salts is a complex system due to similar analytical characteristics of components. Partial least squares (PLS) and radial basis function-partial least squares (RBF-PLS) were used to develop the linear and nonlinear relation between spectra and components, respectively. The orthogonal signal correction (OSC) preprocessing method was used to correct unexpected information, such as spectral overlapping and scattering effects. In order to compare the influence of OSC on PLS and RBF-PLS models, the optimal linear (PLS) and nonlinear (RBF-PLS) models based on conventional and OSC preprocessed spectra were established and compared. The obtained results demonstrated that OSC clearly enhanced the performance of both RBF-PLS and PLS calibration models. Also in the case of some nonlinear relation between spectra and component, OSC-RBF-PLS gave satisfactory results than OSC-PLS model which indicated that the OSC was helpful to remove extrinsic deviations from linearity without elimination of nonlinear information related to component. The chemometric models were tested on an external dataset and finally applied to the analysis commercialized injection product of penicillin G salts.

  12. Charge Injection at the Heterointerface in Perovskite CH3NH3PbI3 Solar Cells Studied by Simultaneous Microscopic Photoluminescence and Photocurrent Imaging Spectroscopy.

    PubMed

    Yamashita, Daiki; Handa, Taketo; Ihara, Toshiyuki; Tahara, Hirokazu; Shimazaki, Ai; Wakamiya, Atsushi; Kanemitsu, Yoshihiko

    2016-08-18

    Charge carrier dynamics in perovskite CH3NH3PbI3 solar cells were studied by means of microscopic photoluminescence (PL) and photocurrent (PC) imaging spectroscopy. The PL intensity, PL lifetime, and PC intensity varied spatially on the order of several tens of micrometers. Simultaneous PL and PC image measurements revealed a positive correlation between the PL intensity and PL lifetime, and a negative correlation between PL and PC intensities. These correlations were due to the competition between photocarrier injection from the CH3NH3PbI3 layer into the charge transport layer and photocarrier recombination within the CH3NH3PbI3 layer. Furthermore, we found that the decrease in the carrier injection efficiency under prolonged light illumination leads to a reduction in PC, resulting in light-induced degradation of solar cell devices. Our findings provide important insights for understanding carrier injection at the interface and light-induced degradation in perovskite solar cells. PMID:27482607

  13. Direct and simultaneous quantification of tannin mean degree of polymerization and percentage of galloylation in grape seeds using diffuse reflectance fourier transform-infrared spectroscopy.

    PubMed

    Pappas, Christos; Kyraleou, Maria; Voskidi, Eleni; Kotseridis, Yorgos; Taranilis, Petros A; Kallithraka, Stamatina

    2015-02-01

    The direct and simultaneous quantitative determination of the mean degree of polymerization (mDP) and the degree of galloylation (%G) in grape seeds were quantified using diffuse reflectance infrared Fourier transform spectroscopy and partial least squares (PLS). The results were compared with those obtained using the conventional analysis employing phloroglucinolysis as pretreatment followed by high performance liquid chromatography-UV and mass spectrometry detection. Infrared spectra were recorded in solid state samples after freeze drying. The 2nd derivative of the 1832 to 1416 and 918 to 739 cm(-1) spectral regions for the quantification of mDP, the 2nd derivative of the 1813 to 607 cm(-1) spectral region for the degree of %G determination and PLS regression were used. The determination coefficients (R(2) ) of mDP and %G were 0.99 and 0.98, respectively. The corresponding values of the root-mean-square error of calibration were found 0.506 and 0.692, the root-mean-square error of cross validation 0.811 and 0.921, and the root-mean-square error of prediction 0.612 and 0.801. The proposed method in comparison with the conventional method is simpler, less time consuming, more economical, and requires reduced quantities of chemical reagents and fewer sample pretreatment steps. It could be a starting point for the design of more specific models according to the requirements of the wineries.

  14. Hemodynamic and electrophysiological signals of conflict processing in the Chinese-character Stroop task: a simultaneous near-infrared spectroscopy and event-related potential study

    NASA Astrophysics Data System (ADS)

    Zhai, Jiahuan; Li, Ting; Zhang, Zhongxing; Gong, Hui

    2009-09-01

    A dual-modality method combining continuous-wave near-infrared spectroscopy (NIRS) and event-related potentials (ERPs) was developed for the Chinese-character color-word Stroop task, which included congruent, incongruent, and neutral stimuli. Sixteen native Chinese speakers participated in this study. Hemodynamic and electrophysiological signals in the prefrontal cortex (PFC) were monitored simultaneously by NIRS and ERP. The hemodynamic signals were represented by relative changes in oxy-, deoxy-, and total hemoglobin concentration, whereas the electrophysiological signals were characterized by the parameters P450, N500, and P600. Both types of signals measured at four regions of the PFC were analyzed and compared spatially and temporally among the three different stimuli. We found that P600 signals correlated significantly with the hemodynamic parameters, suggesting that the PFC executes conflict-solving function. Additionally, we observed that the change in deoxy-Hb concentration showed higher sensitivity in response to the Stroop task than other hemodynamic signals. Correlation between NIRS and ERP signals revealed that the vascular response reflects the cumulative effect of neural activities. Taken together, our findings demonstrate that this new dual-modality method is a useful approach to obtaining more information during cognitive and physiological studies.

  15. Simultaneous detection of electronic structure changes from two elements of a bifunctional catalyst using wavelength-dispersive X-ray emission spectroscopy and in situ electrochemistry.

    PubMed

    Gul, Sheraz; Ng, Jia Wei Desmond; Alonso-Mori, Roberto; Kern, Jan; Sokaras, Dimosthenis; Anzenberg, Eitan; Lassalle-Kaiser, Benedikt; Gorlin, Yelena; Weng, Tsu-Chien; Zwart, Petrus H; Zhang, Jin Z; Bergmann, Uwe; Yachandra, Vittal K; Jaramillo, Thomas F; Yano, Junko

    2015-04-14

    Multielectron catalytic reactions, such as water oxidation, nitrogen reduction, or hydrogen production in enzymes and inorganic catalysts often involve multimetallic clusters. In these systems, the reaction takes place between metals or metals and ligands to facilitate charge transfer, bond formation/breaking, substrate binding, and release of products. In this study, we present a method to detect X-ray emission signals from multiple elements simultaneously, which allows for the study of charge transfer and the sequential chemistry occurring between elements. Kβ X-ray emission spectroscopy (XES) probes charge and spin states of metals as well as their ligand environment. A wavelength-dispersive spectrometer based on the von Hamos geometry was used to disperse Kβ signals of multiple elements onto a position detector, enabling an XES spectrum to be measured in a single-shot mode. This overcomes the scanning needs of the scanning spectrometers, providing data free from temporal and normalization errors and therefore ideal to follow sequential chemistry at multiple sites. We have applied this method to study MnOx-based bifunctional electrocatalysts for the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR). In particular, we investigated the effects of adding a secondary element, Ni, to form MnNiOx and its impact on the chemical states and catalytic activity, by tracking the redox characteristics of each element upon sweeping the electrode potential. The detection scheme we describe here is general and can be applied to time-resolved studies of materials consisting of multiple elements, to follow the dynamics of catalytic and electron transfer reactions.

  16. Development and metrological characterization of a tunable diode laser absorption spectroscopy (TDLAS) spectrometer for simultaneous absolute measurement of carbon dioxide and water vapor.

    PubMed

    Pogány, Andrea; Wagner, Steven; Werhahn, Olav; Ebert, Volker

    2015-01-01

    Simultaneous detection of two analytes, carbon dioxide (CO2) and water vapor (H2O), has been realized using tunable diode laser absorption spectroscopy (TDLAS) with a single distributed feedback diode laser at 2.7 μm. The dynamic range of the spectrometer is extended from the low parts per million to the percentage range using two gas cells, a single-pass cell with 0.77 m, and a Herriott-type multipass cell with 76 m path length. Absolute measurements were carried out, i.e., amount fractions of the analytes were calculated based on previously determined spectral line parameters, without the need for an instrument calibration using gas standards. A thorough metrological characterization of the spectrometer is presented. We discuss traceability of all parameters used for amount fraction determination and provide a comprehensive uncertainty assessment. Relative expanded uncertainties (k = 2, 95% confidence level) of the measured amount fractions are shown to be in the 2-3% range for both analytes. Minimum detectable amount fractions are 0.16 μmol/mol for CO2 and 1.1 μmol/mol for H2O for 76 m path length and 5 s averaging time. This corresponds to normalized detection limits of 27 μmol/mol m Hz(-1/2) for CO2 and 221 μmol/mol m Hz(-1/2) for H2O. Precision of the spectrometer, determined using Allan variance analysis, is 3.3 nmol/mol for CO2 and 21 nmol/mol for H2O. The spectrometer has been validated using reference gas mixtures with known CO2 and H2O amount fractions. An application example of the absolute TDLAS spectrometer as a reference instrument to validate other sensors is also presented.

  17. Simultaneous Counter-Ion Co-Deposition a Technique Enabling Matrix Isolation Spectroscopy Studies Using Low-Energy Beams of Mass-Selected Ions

    NASA Astrophysics Data System (ADS)

    Ludwig, Ryan M.; Moore, David T.

    2014-06-01

    Matrix isolation spectroscopy was first developed in Pimentel's group during the 1950's to facilitate spectroscopic studies of transient species. Cryogenic matrices of condensed rare gases provide an inert chemical environment with facile energy dissipation and are transparent at all wavelengths longer than vacuum UV, making them ideal for studying labile and reactive species such as radicals, weakly bound complexes, and ions. Since frozen rare gases are poor electrolytes, studies of ions require near-equal populations of anions and cations in order to stabilize the number densities required for spectroscopic experiments. Many techniques for generation of ions for using in matrix isolation studies satisfy this criterion intrinsically, however when ion beams generated in external sources are deposited, the counter-ions typically arise via secondary processes that are at best loosely controlled. It has long been recognized that it would be desirable to stabilize deposition of mass-selected ions generated in an external source using simultaneous co-deposition of a beam of counter-ions, however previous attempts to achieve this have been reported as unsuccessful. The Moore group at Lehigh has demonstrated successful experiments of this type, using mass-selected anions generated from a metal cluster source, co-deposited with a balanced current of cations generated in a separate electron ionization source. This talk will focus on the details of the technique, and present some results from proof-of-concept studies on anionic copper carbonyl complexes formed in argon matrices following co-deposition of Cu- with Ar+ or Kr+. Funding support from NSF CAREER Award CHE-0955637 is gratefully acknowledged. Whittle et al., J. Chem. Phys. 22, p.1943 (1954); Becker et al., J. Chem. Phys. 25, p.224 (1956). Godbout et al., J. Chem. Phys. 96, p.2892 (1996). Sabo et al., Appl. Spectrosc. 45, p. 535 (1991).

  18. Simultaneous detection of electronic structure changes from two elements of a bifunctional catalyst using wavelength-dispersive X-ray emission spectroscopy and in situ electrochemistry

    DOE PAGES

    Gul, Sheraz; Ng, Jia Wei Desmond; Alonso-Mori, Roberto; Kern, Jan; Sokaras, Dimosthenis; Anzenberg, Eitan; Lassalle-Kaiser, Benedikt; Gorlin, Yelena; Weng, Tsu-Chien; Zwart, Petrus H.; et al

    2015-02-25

    Multielectron catalytic reactions, such as water oxidation, nitrogen reduction, or hydrogen production in enzymes and inorganic catalysts often involve multimetallic clusters. In these systems, the reaction takes place between metals or metals and ligands to facilitate charge transfer, bond formation/breaking, substrate binding, and release of products. In this study, we present a method to detect X-ray emission signals from multiple elements simultaneously, which allows for the study of charge transfer and the sequential chemistry occurring between elements. Kβ X-ray emission spectroscopy (XES) probes charge and spin states of metals as well as their ligand environment. A wavelength-dispersive spectrometer based onmore » the von Hamos geometry was used to disperse Kβ signals of multiple elements onto a position detector, enabling an XES spectrum to be measured in a single-shot mode. This overcomes the scanning needs of the scanning spectrometers, providing data free from temporal and normalization errors and therefore ideal to follow sequential chemistry at multiple sites. We have applied this method to study MnOx-based bifunctional electrocatalysts for the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR). In particular, we investigated the effects of adding a secondary element, Ni, to form MnNiOx and its impact on the chemical states and catalytic activity, by tracking the redox characteristics of each element upon sweeping the electrode potential. In conclusion, the detection scheme we describe here is general and can be applied to time-resolved studies of materials consisting of multiple elements, to follow the dynamics of catalytic and electron transfer reactions.« less

  19. Simultaneous detection of electronic structure changes from two elements of a bifunctional catalyst using wavelength-dispersive X-ray emission spectroscopy and in situ electrochemistry

    SciTech Connect

    Gul, Sheraz; Ng, Jia Wei Desmond; Alonso-Mori, Roberto; Kern, Jan; Sokaras, Dimosthenis; Anzenberg, Eitan; Lassalle-Kaiser, Benedikt; Gorlin, Yelena; Weng, Tsu-Chien; Zwart, Petrus H.; Zhang, Jin Z.; Bergmann, Uwe; Yachandra, Vittal K.; Jaramillo, Thomas F.; Yano, Junko

    2015-02-25

    Multielectron catalytic reactions, such as water oxidation, nitrogen reduction, or hydrogen production in enzymes and inorganic catalysts often involve multimetallic clusters. In these systems, the reaction takes place between metals or metals and ligands to facilitate charge transfer, bond formation/breaking, substrate binding, and release of products. In this study, we present a method to detect X-ray emission signals from multiple elements simultaneously, which allows for the study of charge transfer and the sequential chemistry occurring between elements. Kβ X-ray emission spectroscopy (XES) probes charge and spin states of metals as well as their ligand environment. A wavelength-dispersive spectrometer based on the von Hamos geometry was used to disperse Kβ signals of multiple elements onto a position detector, enabling an XES spectrum to be measured in a single-shot mode. This overcomes the scanning needs of the scanning spectrometers, providing data free from temporal and normalization errors and therefore ideal to follow sequential chemistry at multiple sites. We have applied this method to study MnOx-based bifunctional electrocatalysts for the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR). In particular, we investigated the effects of adding a secondary element, Ni, to form MnNiOx and its impact on the chemical states and catalytic activity, by tracking the redox characteristics of each element upon sweeping the electrode potential. In conclusion, the detection scheme we describe here is general and can be applied to time-resolved studies of materials consisting of multiple elements, to follow the dynamics of catalytic and electron transfer reactions.

  20. Interactions in two-component liposomes studied by 2D correlation spectroscopy

    NASA Astrophysics Data System (ADS)

    Murawska, Agnieszka; Cieślik-Boczula, Katarzyna; Czarnik-Matusewicz, Bogusława

    2010-06-01

    The effect of dipping amphiphilic ICPANs (1-Alkylaminium, N-[2-[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]ethyl]-N,N-dimethyl-, bromide) homologues, characterized by varying alkyl chain length ( n = 8, 10, 12, and 16), into large multilamellar vesicles (MLVs) of dipalmitoylphosphatidylcholine (DPPC) was studied. Attenuated total reflectance infrared (ATR-IR) spectroscopy combined with 31P-NMR enabled observing a cut-off effect for the longest homologue. By employing two-dimensional correlation spectroscopy (2DCOS) for monitoring spectral changes induced by the heating process, detailed information about structural changes was obtained. They confirmed the substantial reorganization in the structure of the interfacial region in the ICPAN-C16/DPPC vesicles compared with the shorter homologues, where mainly the alkyl chains experience significant trans-to-gauche reorganization. Absorbance changes around 1400 cm -1 assigned to the symmetric deformation mode δsym ( +N(CH 3) 3) are a good marker of changes in vesicle shape and are sensitive to the percentage of DPPC molecules directly interacting with the surface of the ATR crystal. This study clearly demonstrates the potential of 2DCOS in investigating interactions in two-component liposomes.

  1. Dynamics of asymmetric binary glass formers. II. Results from nuclear magnetic resonance spectroscopy

    SciTech Connect

    Bock, D.; Kahlau, R.; Pötzschner, B.; Körber, T.; Wagner, E.; Rössler, E. A.

    2014-03-07

    Various {sup 2}H and {sup 31}P nuclear magnetic resonance (NMR) spectroscopy techniques are applied to probe the component dynamics of the binary glass former tripropyl phosphate (TPP)/polystyrene-d{sub 3} (PS) over the full concentration range. The results are quantitatively compared to those of a dielectric spectroscopy (DS) study on the same system previously published [R. Kahlau, D. Bock, B. Schmidtke, and E. A. Rössler, J. Chem. Phys. 140, 044509 (2014)]. While the PS dynamics does not significantly change in the mixtures compared to that of neat PS, two fractions of TPP molecules are identified, one joining the glass transition of PS in the mixture (α{sub 1}-process), the second reorienting isotropically (α{sub 2}-process) even in the rigid matrix of PS, although at low concentration resembling a secondary process regarding its manifestation in the DS spectra. Pronounced dynamical heterogeneities are found for the TPP α{sub 2}-process, showing up in extremely stretched, quasi-logarithmic stimulated echo decays. While the time window of NMR is insufficient for recording the full correlation functions, DS results, covering a larger dynamical range, provide a satisfactory interpolation of the NMR data. Two-dimensional {sup 31}P NMR spectra prove exchange within the broadly distributed α{sub 2}-process. As demonstrated by {sup 2}H NMR, the PS matrix reflects the faster α{sub 2}-process of TPP by performing a spatially highly hindered motion on the same timescale.

  2. Noninvasive quantitation of phosphorus metabolites in human tissue by NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Roth, K.; Hubesch, B.; Meyerhoff, D. J.; Naruse, S.; Gober, J. R.; Lawry, T. J.; Boska, M. D.; Matson, G. B.; Weiner, M. W.

    Quantitation of metabolite concentrations by NMR spectroscopy is complicated by the need to determine the volume from which signals are detected, and by the need to obtain the relative sensitivity of detection within this volume. The use of coils with inhomogeneous B1 fields further complicates these problems. In order to quantify metabolite concentrations using 31P NMR spectroscopy, an external reference of hexamethyl phosphoroustriamide was used. Studies were performed on phantoms, using either a surface coil or a Helmholtz head coil to confirm the accuracy of both the ISIS volume selection technique and the use of an external reference. The limitations of this method are related to contamination and signal loss inherent in the ISIS technique and difficulties with integration of broad overlapping peaks. The method was applied to seven normal human subjects. The integrals for metabolite signals in normal brain and calf muscle were determined by using NMRI software. The T1 values of the signals of all phosphorus metabolites in the selected volume were measured in order to correct for saturation effects. The concentrations for PCr, P i, and ATP were 4.9, 2.0, and 2.5 m M in brain and 36.5, 5.7, and 7.3 m M in muscle. These results are in good agreement with those reported for animals, demonstrating the validity of this quantitation technique.

  3. Simultaneous measurements of CO2, CO and CH4 at an urban site of western India using cavity ring down spectroscopy (CRDS) technique.

    NASA Astrophysics Data System (ADS)

    Negi, N. C.; Sethuraman, V.; Lal, S.

    2014-12-01

    The atmospheric levels of CO2 and CH4 are mainly governed by emissions from several anthropogenic as well as biogenic sources. Anthropogenic sources have different emission characteristics, and emit CO2, CH4 with various other trace gases like CO, NOx, SO2... etc in different ratios. CO is a useful tracer for differentiating between natural and anthropogenic emissions, as the natural source does not affect its levels significantly. Therefore the interrelations of CO2, CH4 with CO and other co-emitted species can be useful for identifying the relative role of emission sectors on the total emission of CO2 and CH4. Simultaneous measurements of CO2, CO and CH4 were made over Ahmedabad (23.03oN, 72.58oE, 55m AMSL), a semi-arid urban site of western India, during the period of autumn (November 2013), winter (December 2013-February 2014) and Monsoon (July 2014) using an online analyser based on the cavity ring-down spectroscopy technique. The measurements show that atmospheric CO correlates well with CO2 during the autumn and winter. The slope of CO and CO2 (∆CO/∆CO2) is found to be in the range of 0.02 and 0.03 which agrees well with the emission ratio for India as per Asian inventory proposed by Street et al., (2003) and connote the influence of mixed sources (fossil fuel as well as biomass burning) during this period. In July , CO doesn't correlate well with CO2 (r2 =0.14), but the slope is around 0.005, indicates the dominance of fossil fuel during this time. The correlation and slope (slope ~ 0.02 and r2 ~ 0.55) of CH4 with CO2 remain fairly constant which demonstrate that the study area does not have significant changes in the source of these gases throughout the study period. Details of the levels, amplitude of diurnal variations of CO2, CO, CH4 as well as their mutual interrelationship will be presented.

  4. Simultaneous determination of estrogens (ethinylestradiol and norgestimate) concentrations in human and bovine serum albumin by use of fluorescence spectroscopy and multivariate regression analysis.

    PubMed

    Hordge, LaQuana N; McDaniel, Kiara L; Jones, Derick D; Fakayode, Sayo O

    2016-05-15

    The endocrine disruption property of estrogens necessitates the immediate need for effective monitoring and development of analytical protocols for their analyses in biological and human specimens. This study explores the first combined utility of a steady-state fluorescence spectroscopy and multivariate partial-least-square (PLS) regression analysis for the simultaneous determination of two estrogens (17α-ethinylestradiol (EE) and norgestimate (NOR)) concentrations in bovine serum albumin (BSA) and human serum albumin (HSA) samples. The influence of EE and NOR concentrations and temperature on the emission spectra of EE-HSA EE-BSA, NOR-HSA, and NOR-BSA complexes was also investigated. The binding of EE with HSA and BSA resulted in increase in emission characteristics of HSA and BSA and a significant blue spectra shift. In contrast, the interaction of NOR with HSA and BSA quenched the emission characteristics of HSA and BSA. The observed emission spectral shifts preclude the effective use of traditional univariate regression analysis of fluorescent data for the determination of EE and NOR concentrations in HSA and BSA samples. Multivariate partial-least-squares (PLS) regression analysis was utilized to correlate the changes in emission spectra with EE and NOR concentrations in HSA and BSA samples. The figures-of-merit of the developed PLS regression models were excellent, with limits of detection as low as 1.6×10(-8) M for EE and 2.4×10(-7) M for NOR and good linearity (R(2)>0.994985). The PLS models correctly predicted EE and NOR concentrations in independent validation HSA and BSA samples with a root-mean-square-percent-relative-error (RMS%RE) of less than 6.0% at physiological condition. On the contrary, the use of univariate regression resulted in poor predictions of EE and NOR in HSA and BSA samples, with RMS%RE larger than 40% at physiological conditions. High accuracy, low sensitivity, simplicity, low-cost with no prior analyte extraction or separation

  5. Quantitative evaluation of noncovalent interactions between glyphosate and dissolved humic substances by NMR spectroscopy.

    PubMed

    Mazzei, Pierluigi; Piccolo, Alessandro

    2012-06-01

    Interactions of glyphosate (N-phosphonomethylglycine) herbicide (GLY) with soluble fulvic acids (FAs) and humic acids (HAs) at pH 5.2 and 7 were studied by (1)H and (31)P NMR spectroscopy. Increasing concentrations of soluble humic matter determined broadening and chemical shift drifts of proton and phosphorus GLY signals, thereby indicating the occurrence of weak interactions between GLY and humic superstructures. Binding was larger for FAs and pH 5.2 than for HAs and pH 7, thus suggesting formation of hydrogen bonds between GLY carboxyl and phosphonate groups and protonated oxygen functions in humic matter. Changes in relaxation and correlation times of (1)H and (31)P signals and saturation transfer difference NMR experiments confirmed the noncovalent nature of GLY-humic interactions. Diffusion-ordered NMR spectra allowed calculation of the glyphosate fraction bound to humic superstructures and association constants (K(a)) and Gibbs free energies of transfer for GLY-humic complex formation at both pH values. These values showed that noncovalent interactions occurred most effectively with FAs and at pH 5.2. Our findings indicated that glyphosate may spontaneously and significantly bind to soluble humic matter by noncovalent interactions at slightly acidic pH and, thus, potentially pollute natural water bodies by moving through soil profiles in complexes with dissolved humus. PMID:22591574

  6. Functional group analysis in coal and on coal surfaces by NMR spectroscopy

    SciTech Connect

    Verkade, J.G.

    1990-01-01

    An accurate knowledge of the oxygen-bearing labile hydrogen functional groups (e.g., carboxylic acids, phenols and alcohols) in coal is required for today's increasingly sophisticated coal cleaning and beneficiation processes. Phospholanes (compounds having the general structure -POCH{sub 2}CH{sub 2}O (1)) are being investigated as reagents for the tagging of liable hydrogen functional groups in coal materials with the NMR-active {sup 31}P nucleus. Of twelve such reagents investigated so far, 2 (2-chloro-1,3-dioxaphospholane, ClPOCH{sub 2}CH{sub 2}O) and 8 (2-chloro-1,3-dithiaphospholane, ClPSCH{sub 2}CH{sub 2}S) have been found to be useful in identifying and quantitating, by {sup 31}P NMR spectroscopy, labile hydrogen functional groups in an Illinois No. 6 coal condensate. Reagent 2 has also been used to quantitate moisture in pyridine extracts of Argonne Premium Coal Samples. Preliminary {sup 119}Sn NMR spectroscopic results on model compounds with the new reagent CF{sub 3}C(O)NHSnMe{sub 3} (N-trimethylstannyltrifluoroacetamide, 14) suggest that labile hydrogen functional groups in coal materials may be more precisely identified with 14 than with phospholanes. 14 refs., 2 figs., 2 tabs.

  7. Synthesis, structure, terahertz spectroscopy and luminescent properties of copper(I) complexes with mercaptan ligands and triphenylphosphine

    NASA Astrophysics Data System (ADS)

    Qiu, Qi-Ming; Liu, Min; Li, Zhong-Feng; Jin, Qiong-Hua; Huang, Xu; Zhang, Zhen-Wei; Zhang, Cun-Lin; Meng, Qing-Xuan

    2014-03-01

    The reactions of copper(I) halides with triphenylphosphine (PPh3) and mercaptan ligand [2-mercapto-6-nitrobenzothiazole (HMNBT), 2-amino-5-mercapto-1,3,4-thiadiazole (HAMTD) and 2-mercapto-5-methyl-benzimidazole (MMBD)] yielded seven complexes, [CuCl(HMNBT)(PPh3)2] (1), [CuX(HMNBT)(PPh3)]2 (X = Cl, Br) (2-3), [Cu(MNBT)(HMNBT)(PPh3)2] (4), [CuBr(HAMTD)(PPh3)2]·CH3OH (5) and [CuX(MMBD)(PPh3)2]·2CH3OH (X = Br, I) (6-7). These complexes were characterized by elemental analysis, X-ray diffraction, 1H NMR and 31P NMR spectroscopy. In these complexes the mercaptan ligands act as monodentate or bridged ligand with S as the coordination atom. In complexes 1 and 4, hydrogen bonds CH⋯X and weak interactions CH⋯π lead to the formation of chains and 2D network respectively, while complexes 2 and 3 are dinuclear. In 5-7, intramolecular hydrogen bonds link the [CuX(thione)(PPh3)2] molecules and the solvated methanol molecules into centrosymmetric dimers. Complexes 1-5 represent first copper(I) halide complexes of HMNBT and HAMTD. The complexes 1, 5, 6 and 7 exhibit interesting fluorescence in the solid state at room temperature and their terahertz (THz) time-domain spectroscopy was also studied.

  8. Simultaneous end-on/side-on coordination modes of a diphosphorus tetrahedral complex imposed by pre-organization of oligometallic Cu(I) acceptors.

    PubMed

    Welsch, Stefan; Lescop, Christophe; Balazs, Gabor; Réau, Régis; Scheer, Manfred

    2011-08-01

    The reaction of the [{CpMo(CO)(2)}(2)(μ,η(2):η(2)-P(2))] (Cp=cyclopentadienyl) metallo-ligand 2 with pre-organized Cu(I) bi- and trimetallic precursors afforded new coordination complexes with unprecedented coordination modes for a Mo(2)P(2) complex. Variable-temperature solution and solid-state (31)P NMR spectroscopy measurements were performed and X-ray diffraction studies revealed an η(2):η(1) coordination mode for the Mo(2)P(2) unit of 2 in the Cu(I) bimetallic complexes 3 and 4. DFT calculations were carried out to highlight the bonding situation of this unprecedented coordination mode in the Cu(I) bimetallic compound 3. It is built up from a side-on coordination of the P-P σ bond to one copper ion and from the interaction of the lone pair of one phosphorus atom with the second copper ion. The remaining available lone pair of the second phosphorus atom can be involved as well to interact with an additional metal centre, as evidenced in the Cu(I) trimetallic compound 5 in which an η(2):η(1):η(1) coordination mode of the ligand 2 is observed. Derivative 3 can be used as a molecular clip to obtain discrete π-stacked dimers through a ligand exchange reaction between acetonitrile ligands and cyano-capped π-conjugated systems, indicating the stability of the new η(2):η(1) coordination mode.

  9. Structural investigations of Pu{sup III} phosphate by X-ray diffraction, MAS-NMR and XANES spectroscopy

    SciTech Connect

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

    2015-10-15

    PuPO{sub 4} 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 β{sup −} decay product of plutonium) in the +III oxidation state was determined based on XANES spectroscopy. High resolution solid state {sup 31}P NMR agrees with the XANES results and the presence of a solid-solution. - Graphical abstract: A full structural analysis of PuPO{sub 4} based on Rietveld analysis of room temperature X-ray diffraction data, XANES and MAS NMR measurements was performed. - Highlights: • The crystal structure of PuPO{sub 4} monazite is solved. • In PuPO{sub 4} plutonium is strictly trivalent. • The presence of a minute amount of Am{sup III} is highlighted. • We propose PuPO{sub 4} as a potential reference material for spectroscopic and microscopic studies.

  10. Simultaneous determination of propranolol and amiloride in synthetic binary mixtures and pharmaceutical dosage forms by synchronous fluorescence spectroscopy: a multivariate approach

    NASA Astrophysics Data System (ADS)

    Divya, O.; Shinde, Mandakini

    2013-07-01

    A multivariate calibration model for the simultaneous estimation of propranolol (PRO) and amiloride (AMI) using synchronous fluorescence spectroscopic data has been presented in this paper. Two multivariate techniques, PCR (Principal Component Regression) and PLSR (Partial Least Square Regression), have been successfully applied for the simultaneous determination of AMI and PRO in synthetic binary mixtures and pharmaceutical dosage forms. The SF spectra of AMI and PRO (calibration mixtures) were recorded at several concentrations within their linear range between wavelengths of 310 and 500 nm at an interval of 1 nm. Calibration models were constructed using 32 samples and validated by varying the concentrations of AMI and PRO in the calibration range. The results indicated that the model developed was very robust and able to efficiently analyze the mixtures with low RMSEP values.

  11. A novel method for simultaneous determination of selected elements in dolomite and magnesia by Inductively Coupled Plasma Atomic Emission Spectroscopy with slurry sample introduction

    NASA Astrophysics Data System (ADS)

    Bok-Badura, Joanna; Jakóbik-Kolon, Agata; Turek, Marian; Szczerba, Jacek; Lemanowicz, Marcin; Karoń, Krzysztof

    2015-11-01

    The slurry nebulization ICP-AES method for simultaneous determination of selected elements in dolomite and magnesia was proposed. Based on the investigation results the optimal conditions for this analysis were as follows: particle size < 40 μm, the nitric acid concentration 10%, the RF power 1.0 kW, aqueous solutions (no dispersing agents) and mixing on magnetic stirrer, during the sample introduction into plasma, as homogenization method. The certified reference materials Dolomite CRM 782-1 and High Purity Magnesia BCS-CRM 389/1 were analyzed. Student's t-test proved that there were no statistically significant differences between determined values and the certified ones. This proves that the slurry sample introduction into plasma in ICP-AES technique can be applied for simultaneous determination of elements in dolomite and magnesia.

  12. PSD Determination using a Simultaneous-Phase Acquisition Interferometer for the Constellation-X Spectroscopy X-ray Telescope (SXT) Mirrors

    NASA Technical Reports Server (NTRS)

    Lehan, J. P.; Saha, T.; Zhang, W. W.

    2006-01-01

    We investigated the use of a simultaneous-phase acquisition interferometer (a 4D FizCamTM 1500) for determining the PSD of the extremely-high aspect ratio (500: 1) glass mirrors for the Constellation-X SXT telescope. We found that the results obtained are strongly influenced by the methodology employed while collecting the data and outline a best method for this type of measurement.

  13. Haemodynamic response associated with both ictal and interictal epileptiform activity using simultaneous video electroencephalography/near infrared spectroscopy in a within-subject study

    PubMed Central

    Monrad, Priya; Sannagowdara, Kumar; Bozarth, Xiuhua; Bhosrekar, Sugandha; Hecox, Kurt; Nwosu, Michelle; Schwabe, Michael; Meyer, Michael; Szabo, Aniko; Prigge, Jenna; Lemke, Russ; Horn, Briana; Whelan, Harry T.

    2015-01-01

    This paper reports the findings from a pilot study of four patients with medically refractory epilepsy undergoing pre-surgical evaluation with ages ranging from 5 to 17 years. Video electroencephalography recordings and data from a near infrared spectroscopy cerebral/somatic oximeter were gathered and related to electrographic seizure onset and offset as determined by a paediatric epileptologist. All four patients showed haemodynamic changes associated with epileptiform activities. The increased blood flow clearly coincided with epileptiform activity and continued to increase as the epileptiform activity built up. Regional cerebral oxygen saturation increased in the epileptogenic focus, perhaps due to loss of cerebrovascular autoregulation. These findings reinforce that near infrared spectroscopy can potentially be used in a wide spectrum of patients with epilepsy regardless of the underlying brain pathology. PMID:26538840

  14. Dynamics of asymmetric binary glass formers. I. A dielectric and nuclear magnetic resonance spectroscopy study.

    PubMed

    Kahlau, R; Bock, D; Schmidtke, B; Rössler, E A

    2014-01-28

    Dielectric spectroscopy as well as (2)H and (31)P nuclear magnetic resonance spectroscopy (NMR) are applied to probe the component dynamics of the binary glass former tripropyl phosphate (TPP)/polystyrene (PS/PS-d3) in the full concentration (cTPP) range. In addition, depolarized light scattering and differential scanning calorimetry experiments are performed. Two glass transition temperatures are found: Tg 1(cTPP) reflects PS dynamics and shows a monotonic plasticizer effect, while the lower Tg 2(cTPP) exhibits a maximum and is attributed to (faster) TPP dynamics, occurring in a slowly moving or immobilized PS matrix. Dielectric spectroscopy probing solely TPP identifies two different time scales, which are attributed to two sub-ensembles. One of them, again, shows fast TPP dynamics (α2-process), the other (α1-process) displays time constants identical with those of the slow PS matrix. Upon heating the α1-fraction of TPP decreases until above some temperature Tc only a single α2-population exists. Inversely, below Tc a fraction of the TPP molecules is trapped by the PS matrix. At low cTPP the α2-relaxation does not follow frequency-temperature superposition (FTS), instead it is governed by a temperature independent distribution of activation energies leading to correlation times which follow Arrhenius laws, i.e., the α2-relaxation resembles a secondary process. Yet, (31)P NMR demonstrates that it involves isotropic reorientations of TPP molecules within a slowly moving or rigid matrix of PS. At high cTPP the super-Arrhenius temperature dependence of τ2(T), as well as FTS are recovered, known as typical of the glass transition in neat systems. PMID:25669557

  15. Interaction of epicatechin gallate with phospholipid membranes as revealed by solid-state NMR spectroscopy.

    PubMed

    Uekusa, Yoshinori; Kamihira-Ishijima, Miya; Sugimoto, Osamu; Ishii, Takeshi; Kumazawa, Shigenori; Nakamura, Kozo; Tanji, Ken-ichi; Naito, Akira; Nakayama, Tsutomu

    2011-06-01

    Epicatechin gallate (ECg), a green tea polyphenol, has various physiological effects. Our previous nuclear Overhauser effect spectroscopy (NOESY) study using solution NMR spectroscopy demonstrated that ECg strongly interacts with the surface of phospholipid bilayers. However, the dynamic behavior of ECg in the phospholipid bilayers has not been clarified, especially the dynamics and molecular arrangement of the galloyl moiety, which supposedly has an important interactive role. In this study, we synthesized [13C]-ECg, in which the carbonyl carbon of the galloyl moiety was labeled by 13C isotope, and analyzed it by solid-state NMR spectroscopy. Solid-state 31P NMR analysis indicated that ECg changes the gel-to-liquid-crystalline phase transition temperature of DMPC bilayers as well as the dynamics and mobility of the phospholipids. In the solid-state 13C NMR analysis under static conditions, the carbonyl carbon signal of the [13C]-ECg exhibited an axially symmetric powder pattern. This indicates that the ECg molecules rotate about an axis tilting at a constant angle to the bilayer normal. The accurate intermolecular-interatomic distance between the labeled carbonyl carbon of [13C]-ECg and the phosphorus of the phospholipid was determined to be 5.3±0.1 Å by 13C-(31)P rotational echo double resonance (REDOR) measurements. These results suggest that the galloyl moiety contributes to increasing the hydrophobicity of catechin molecules, and consequently to high affinity of galloyl-type catechins for phospholipid membranes, as well as to stabilization of catechin molecules in the phospholipid membranes by cation-π interaction between the galloyl ring and quaternary amine of the phospholipid head-group. PMID:21352801

  16. Action of melittin on the DPPC-cholesterol liquid-ordered phase: a solid state 2H-and 31P-NMR study.

    PubMed Central

    Pott, T; Dufourc, E J

    1995-01-01

    Solid-state deuterium and phosphorus-31 nuclear magnetic resonance studies of deuterium-labeled beta--[2,2',3,4,4',6-2H6]-cholesterol and 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine have been undertaken to monitor the action of melittin on model membranes containing 30 mol% cholesterol, both at the molecular and macroscopic level. Cholesterol totally inhibits the toxin-triggered formation of large unilamellar vesicles and strongly restricts the appearance of small discs. The latter remain stable over a wide temperature range (20-60 degrees C) because of an increase in their cholesterol content as the temperature increases. This process is related to a constant disc hydrophobic thickness of approximately 29 A. The system, when not in the form of discs, appears to be composed of very large vesicles on which melittin promotes magnetically induced ellipsoidal deformation. This deformation is the greatest when the maximum of discs is observed. A model to describe both the disc formation and stability is proposed. PMID:7756559

  17. Intra- and extracellular pH of the brain in vivo studied by 31P-NMR during hyper- and hypocapnia.

    PubMed

    Portman, M A; Lassen, N A; Cooper, T G; Sills, A M; Potchen, E J

    1991-12-01

    Studies were performed to determine the pH relationships among the extracellular, intracellular, and arterial blood compartments in the brain in vivo. Resolution of the extracellular monophosphate resonance peak from the intracellular peak in 31P nuclear magnetic resonance (NMR) spectra of sheep brain with the calvarium intact enabled pH measurement in these respective compartments. Sheep were then subjected to both hyper- and hypoventilation, which resulted in a wide range of arterial PCO2 and pH values. Linear regression analysis of pH in these compartments yielded slopes of 0.56 +/- 0.05 for extracellular pH (pHe) vs. arterial pH, 0.43 +/- 0.078 for intracellular pH (pHi) vs. pHe, and 0.23 +/- 0.056 for pHi vs. arterial pH. These data indicate that CO2 buffering capacity is different and decreases from the intracellular to extracellular to arterial blood compartments. Separation of the extracellular space from the vascular space may be a function of the blood-brain barrier, which contributes to the buffering capability of the extracellular compartment. A marked decrease in the pH gradient between the extracellular and intracellular space occurs during hypercarbia and may influence mechanisms of central respiratory control.

  18. Simultaneous characterization of elemental segregation and cementite networks in high carbon steel products by spatially-resolved laser-induced breakdown spectroscopy

    NASA Astrophysics Data System (ADS)

    Boué-Bigne, Fabienne

    2014-06-01

    The reliable characterization of the level of elemental segregation and of the extent of grain-boundary cementite networks in high carbon steel products is a prerequisite for checking product quality, for the purpose of product release to customers, and to investigate the presence of defects that may have led to mechanical property failure of the product. Current methods for the characterization of segregation and cementite networks rely on two different methods of sample etching followed by visual observation, where quality scores are given based on human perception and judgment. With the continuous demand on increasing quality, some of the conventional characterization methods and their associated scoring boards have lost relevance for the precision of characterization that is required today to distinguish between a product that will perform well and one that will not. In order to move away from a qualitative, human perception based situation for the scoring of the severity of segregation and cementite networks, a new method of data evaluation based on spatially-resolved LIBS measurements was developed to provide quantitative and simultaneous characterization of both types of defects. The quantitative assessment of segregation and cementite networks is based on the acquisition of carbon concentration maps. The ability to produce rapid scanning measurements of micro and macro-scale features with adequate spatial resolution makes LIBS the measurement method of preference for this purpose. The characterization of both different defects is extracted simultaneously and from the same carbon concentration map following a series of statistical treatment and data extraction rules. LIBS results were validated against recognized methods and were applied to a significant number of routine samples. The new LIBS method offers a step change improvement in reliability for the characterization of segregation and cementite networks in steel products over the conventional methods

  19. Quasi-simultaneous in-line flue gas monitoring of NO and NO₂ emissions at a caloric power plant employing mid-IR laser spectroscopy.

    PubMed

    Reidl-Leuthner, Christoph; Viernstein, Alexander; Wieland, Karin; Tomischko, Wolfgang; Sass, Ludwig; Kinger, Gerald; Ofner, Johannes; Lendl, Bernhard

    2014-09-16

    Two pulsed thermoelectrically cooled mid-infrared distributed feedback quantum cascade lasers (QCLs) were used for the quasi-simultaneous in-line determination of NO and NO2 at the caloric power plant Dürnrohr (Austria). The QCL beams were combined using a bifurcated hollow fiber, sent through the flue tube (inside diameter: 5.5 m), reflected by a retro-reflector and recorded using a fast thermoelectrically cooled mercury-cadmium-telluride detector. The thermal chirp during 300 ns pulses was about 1.2 cm(-1) and allowed scanning of rotational vibrational doublets of the analytes. On the basis of the thermal chirp and the temporal resolution of data acquisition, a spectral resolution of approximately 0.02 cm(-1) was achieved. The recorded rotational vibrational absorption lines were centered at 1900 cm(-1) for NO and 1630 cm(-1) for NO2. Despite water content in the range of 152-235 g/m(3) and an average particle load of 15.8 mg/m(3) in the flue gas, in-line measurements were possible achieving limits of detection of 73 ppb for NO and 91 ppb for NO2 while optimizing for a single analyte. Quasi-simultaneous measurements resulted in limits of detection of 219 ppb for NO and 164 ppb for NO2, respectively. Influences of temperature and pressure on the data evaluation are discussed, and results are compared to an established reference method based on the extractive measurements presented.

  20. Simultaneous monitoring of organic acids and sugars in fresh and processed apple juice by Fourier transform infrared-attenuated total reflection spectroscopy.

    PubMed

    Irudayaraj, Joseph; Tewari, Jagdish

    2003-12-01

    A combination of Fourier transform infrared spectroscopy (FT-IR) and chemometrics was used as a screening tool for the determination of sugars and organic acids such as sucrose, glucose, fructose, sorbitol, citric acid, and malic acid in processed commercial and extracted fresh apple juices. Prepared samples of synthetic apple juice in different constituent concentration ranges were scanned by attenuated total reflectance (ATR) accessory and the spectral region in the range between 950 and 1500 cm(-1) was selected for calibration model development using partial least squares (PLS) regression and principal component regression (PCR). The calibration models were successfully validated by high-performance liquid chromatography (HPLC) measurements against several commercial juice varieties as well as juice extracted from different apple varieties to provide an overall R2 correlation of 0.998. The present study demonstrates that Fourier transform infrared spectroscopy could be used for rapid and nondestructive determination of multiple constituents in commercial and fresh apple juices. Results indicate this approach to be a rapid and cost-effective tool for routine monitoring of multiple constituents in a fruit juice production facility.

  1. Simultaneous two-voxel localized 1H-observed 13C-edited spectroscopy for in vivo MRS on rat brain at 9.4 T: Application to the investigation of excitotoxic lesions

    NASA Astrophysics Data System (ADS)

    Doan, Bich-Thuy; Autret, Gwennhael; Mispelter, Joël; Méric, Philippe; Même, William; Montécot-Dubourg, Céline; Corrèze, Jean-Loup; Szeremeta, Frédéric; Gillet, Brigitte; Beloeil, Jean-Claude

    2009-05-01

    13C spectroscopy combined with the injection of 13C-labeled substrates is a powerful method for the study of brain metabolism in vivo. Since highly localized measurements are required in a heterogeneous organ such as the brain, it is of interest to augment the sensitivity of 13C spectroscopy by proton acquisition. Furthermore, as focal cerebral lesions are often encountered in animal models of disorders in which the two brain hemispheres are compared, we wished to develop a bi-voxel localized sequence for the simultaneous bilateral investigation of rat brain metabolism, with no need for external additional references. Two sequences were developed at 9.4 T: a bi-voxel 1H-( 13C) STEAM-POCE (Proton Observed Carbon Edited) sequence and a bi-voxel 1H-( 13C) PRESS-POCE adiabatically decoupled sequence with Hadamard encoding. Hadamard encoding allows both voxels to be recorded simultaneously, with the same acquisition time as that required for a single voxel. The method was validated in a biological investigation into the neuronal damage and the effect on the Tri Carboxylic Acid cycle in localized excitotoxic lesions. Following an excitotoxic quinolinate-induced localized lesion in the rat cortex and the infusion of U- 13C glucose, two 1H-( 13C) spectra of distinct (4 × 4 × 4 mm 3) voxels, one centred on the injured hemisphere and the other on the contralateral hemisphere, were recorded simultaneously. Two 1H bi-voxel spectra were also recorded and showed a significant decrease in N-acetyl aspartate, and an accumulation of lactate in the ipsilateral hemisphere. The 1H-( 13C) spectra could be recorded dynamically as a function of time, and showed a fall in the glutamate/glutamine ratio and the presence of a stable glutamine pool, with a permanent increase of lactate in the ipsilateral hemisphere. This bi-voxel 1H-( 13C) method can be used to investigate simultaneously both brain hemispheres, and to perform dynamic studies. We report here the neuronal damage and the

  2. Study of local cerebral hemodynamics by frequency-domain near-infrared spectroscopy and correlation with simultaneously acquired functional magnetic resonance imaging

    NASA Astrophysics Data System (ADS)

    Toronov, Vladislav; Webb, Andrew; Choi, Jee Hyun; Wolf, Martin; Safonova, Larisa; Wolf, Ursula; Gratton, Enrico

    2001-10-01

    The aim of our study was to explore the possibility of detecting hemodynamic changes in the brain using the phase of the intensity modulated optical signal. To obtain optical signals with the highest possible signal-to-noise ratio, we performed a series of simultaneous NIRS-fMRI measurements, with subsequent correlation of the time courses of both measurements. The cognitive paradigm used arithmetic calculations, with optical signals acquired with sensors placed on the forehead. Measurements were done on seven healthy subjects. In five subjects we demonstrated correlation between the hemodynamic signals obtained using NIRS and BOLD fMRI. In four subjects correlation was found for the hemodynamic signal obtained using the phase of the intensity modulated signal.

  3. Study of local cerebral hemodynamics by frequency-domain near-infrared spectroscopy and correlation with simultaneously acquired functional magnetic resonance imaging.

    PubMed

    Toronov, V; Webb, A; Choi, J H; Wolf, M; Safonova, L; Wolf, U; Gratton, E

    2001-10-01

    The aim of our study was to explore the possibility of detecting hemodynamic changes in the brain using the phase of the intensity modulated optical signal. To obtain optical signals with the highest possible signal-to-noise ratio, we performed a series of simultaneous NIRS-fMRI measurements, with subsequent correlation of the time courses of both measurements. The cognitive paradigm used arithmetic calculations, with optical signals acquired with sensors placed on the forehead. Measurements were done on seven healthy subjects. In five subjects we demonstrated correlation between the hemodynamic signals obtained using NIRS and BOLD fMRI. In four subjects correlation was found for the hemodynamic signal obtained using the phase of the intensity modulated signal.

  4. Simultaneous UV and X-ray Spectroscopy of the Seyfert 1 Galaxy NGC 5548. I: Physical Conditions in the UV Absorbers

    NASA Technical Reports Server (NTRS)

    Crenshaw, D. M.; Kraemer, S. B.; Gabel, J. R.; Kaastra, J. S.; Steenbrugge, K. C.; Brinkman, A. C.; Dunn, J. P.; George, I. M.; Liedahl, D. A.; Paerels, F. B. S.

    2003-01-01

    We present new UV spectra of the nucleus of the Seyfert 1 galaxy NGC 5548, which we obtained with the Space Telescope Imaging Spectrograph at high spectral resolution, in conjunction with simultaneous Chandra X-ray Observatory spectra. Taking advantage of the low UV continuum and broad emission-line fluxes, we have determined that the deepest UV absorption component covers at least a portion of the inner, high-ionization narrow-line region (NLR). We find nonunity covering factors in the cores of several kinematic components, which increase the column density measurements of N V and C IV by factors of 1.2 to 1.9 over the full-covering case; however, the revised columns have only a minor effect on the parameters derived from our photoionization models. For the first time, we have simultaneous N V and C IV columns for component 1 (at -1040 km/s), and find that this component cannot be an X-ray warm absorber, contrary to our previous claim based on nonsimultaneous observations. We find that models of the absorbers based on solar abundances severely overpredict the O VI columns previously obtained with the Far Ultraviolet Spectrograph, and present arguments that this is not likely due to variability. However, models that include either enhanced nitrogen (twice solar) or dust, with strong depletion of carbon in either case, are successful in matching all of the observed ionic columns. These models result in substantially lower ionization parameters and total column densities compared to dust-free solar-abundance models, and produce little O VII or O VIII, indicating that none of the UV absorbers are X-ray warm absorbers.

  5. Towards simultaneous measurements of electronic and structural properties in ultra-fast x-ray free electron laser absorption spectroscopy experiments

    SciTech Connect

    Gaudin, J.; Fourment, C.; Cho, B. I.; Engelhorn, K.; Galtier, E.; Harmand, M.; Leguay, P. M.; Lee, H. J.; Nagler, B.; Nakatsutsumi, M.; Ozkan, C.; Störmer, M.; Toleikis, S.; Tschentscher, Th.; Heimann, P. A.; Dorchies, F.

    2014-04-17

    The rapidly growing ultrafast science with X-ray lasers unveils atomic scale processes with unprecedented time resolution bringing the so called “molecular movie” within reach. X-ray absorption spectroscopy is one of the most powerful x-ray techniques providing both local atomic order and electronic structure when coupled with ad-hoc theory. Collecting absorption spectra within few x-ray pulses is possible only in a dispersive setup. We demonstrate ultrafast time-resolved measurements of the LIII-edge x-ray absorption near-edge spectra of irreversibly laser excited Molybdenum using an average of only few x-ray pulses with a signal to noise ratio limited only by the saturation level of the detector. The simplicity of the experimental set-up makes this technique versatile and applicable for a wide range of pump-probe experiments, particularly in the case of non-reversible processes.

  6. Towards simultaneous measurements of electronic and structural properties in ultra-fast x-ray free electron laser absorption spectroscopy experiments

    DOE PAGES

    Gaudin, J.; Fourment, C.; Cho, B. I.; Engelhorn, K.; Galtier, E.; Harmand, M.; Leguay, P. M.; Lee, H. J.; Nagler, B.; Nakatsutsumi, M.; et al

    2014-04-17

    The rapidly growing ultrafast science with X-ray lasers unveils atomic scale processes with unprecedented time resolution bringing the so called “molecular movie” within reach. X-ray absorption spectroscopy is one of the most powerful x-ray techniques providing both local atomic order and electronic structure when coupled with ad-hoc theory. Collecting absorption spectra within few x-ray pulses is possible only in a dispersive setup. We demonstrate ultrafast time-resolved measurements of the LIII-edge x-ray absorption near-edge spectra of irreversibly laser excited Molybdenum using an average of only few x-ray pulses with a signal to noise ratio limited only by the saturation level ofmore » the detector. The simplicity of the experimental set-up makes this technique versatile and applicable for a wide range of pump-probe experiments, particularly in the case of non-reversible processes.« less

  7. Selective Alcohol Oxidation by a Copper TEMPO Catalyst: Mechanistic Insights by Simultaneously Coupled Operando EPR/UV-Vis/ATR-IR Spectroscopy.

    PubMed

    Rabeah, Jabor; Bentrup, Ursula; Stößer, Reinhard; Brückner, Angelika

    2015-09-28

    The first coupled operando EPR/UV-Vis/ATR-IR spectroscopy setup for mechanistic studies of gas-liquid phase reactions is presented and exemplarily applied to the well-known copper/TEMPO-catalyzed (TEMPO=(2,2,6,6-tetramethylpiperidin-1-yl)oxyl) oxidation of benzyl alcohol. In contrast to previous proposals, no direct redox reaction between TEMPO and Cu(I) /Cu(II) has been detected. Instead, the role of TEMPO is postulated to be the stabilization of a (bpy)(NMI)Cu(II) -O2 (⋅-) -TEMPO (bpy=2,2'-bipyridine, NMI=N-methylimidazole) intermediate formed by electron transfer from Cu(I) to molecular O2 .

  8. Towards simultaneous measurements of electronic and structural properties in ultra-fast x-ray free electron laser absorption spectroscopy experiments

    NASA Astrophysics Data System (ADS)

    Gaudin, J.; Fourment, C.; Cho, B. I.; Engelhorn, K.; Galtier, E.; Harmand, M.; Leguay, P. M.; Lee, H. J.; Nagler, B.; Nakatsutsumi, M.; Ozkan, C.; Störmer, M.; Toleikis, S.; Tschentscher, Th; Heimann, P. A.; Dorchies, F.

    2014-04-01

    The rapidly growing ultrafast science with X-ray lasers unveils atomic scale processes with unprecedented time resolution bringing the so called ``molecular movie'' within reach. X-ray absorption spectroscopy is one of the most powerful x-ray techniques providing both local atomic order and electronic structure when coupled with ad-hoc theory. Collecting absorption spectra within few x-ray pulses is possible only in a dispersive setup. We demonstrate ultrafast time-resolved measurements of the LIII-edge x-ray absorption near-edge spectra of irreversibly laser excited Molybdenum using an average of only few x-ray pulses with a signal to noise ratio limited only by the saturation level of the detector. The simplicity of the experimental set-up makes this technique versatile and applicable for a wide range of pump-probe experiments, particularly in the case of non-reversible processes.

  9. Towards simultaneous measurements of electronic and structural properties in ultra-fast x-ray free electron laser absorption spectroscopy experiments.

    PubMed

    Gaudin, J; Fourment, C; Cho, B I; Engelhorn, K; Galtier, E; Harmand, M; Leguay, P M; Lee, H J; Nagler, B; Nakatsutsumi, M; Ozkan, C; Störmer, M; Toleikis, S; Tschentscher, Th; Heimann, P A; Dorchies, F

    2014-04-17

    The rapidly growing ultrafast science with X-ray lasers unveils atomic scale processes with unprecedented time resolution bringing the so called "molecular movie" within reach. X-ray absorption spectroscopy is one of the most powerful x-ray techniques providing both local atomic order and electronic structure when coupled with ad-hoc theory. Collecting absorption spectra within few x-ray pulses is possible only in a dispersive setup. We demonstrate ultrafast time-resolved measurements of the LIII-edge x-ray absorption near-edge spectra of irreversibly laser excited Molybdenum using an average of only few x-ray pulses with a signal to noise ratio limited only by the saturation level of the detector. The simplicity of the experimental set-up makes this technique versatile and applicable for a wide range of pump-probe experiments, particularly in the case of non-reversible processes.

  10. Direct, simultaneous quantification of fructooligosaccharides by FT-MIR ATR spectroscopy and chemometrics for rapid identification of superior, engineered β-fructofuranosidases.

    PubMed

    Trollope, Kim M; Volschenk, Heinrich; Görgens, Johann F; Bro, Rasmus; Nieuwoudt, Hélène H

    2015-02-01

    Fructooligosaccharides (FOS) are popular components of functional foods produced by the enzymatic transfer of fructose units to sucrose. Improving β-fructofuranosidase traits by protein engineering is restricted by the absence of a rapid, direct screening method for the fructooligosaccharide products produced by enzyme variants. The use of standard high-performance liquid chromatography (HPLC) methods involves time-consuming sample preparation and chromatographic and data analysis steps. To overcome these limitations, this work presents a rapid method for screening β-fructofuranosidase variant libraries using Fourier transform mid-infrared attenuated total reflectance (FT-MIR ATR) spectroscopy and calibration using partial least squares (PLS) regression. The method offers notable improvements in terms of sample analysis times and cost, with the added benefit of the absence of toxic eluents. Wavenumber interval selection methods were tested to develop optimised PLS regression models that were successfully applied to quantify of glucose, fructose, sucrose, 1-kestose and nystose, the substrates and products of β-fructofuranosidase activity. To the best of our knowledge, this is the first report on the use of infrared spectroscopy and PLS calibration for the quantification of 1-kestose and nystose. Independent test set-validated results indicated that optimal wavenumber selection by interval PLS (iPLS) served to provide the best models for all sugars, bar glucose. Application of this screening method will facilitate the engineering of β-fructofuranosidases and other glycosyltransferase enzymes by random mutagenesis strategies, as it provides, for the first time, a rapid, direct assay for transferase products that may be adapted to a high-throughput set-up. PMID:25542584

  11. Optimizing phosphorus characterization in animal manures by solution phosphorus-31 nuclear magnetic resonance spectroscopy.

    PubMed

    Turner, Benjamin L

    2004-01-01

    A procedure involving alkaline extraction and solution 31P nuclear magnetic resonance (NMR) spectroscopy was developed and optimized for the characterization of P in animal manures (broiler, swine, beef cattle). Inclusion of ethylenediaminetetraacetic acid (EDTA) in the alkaline extraction solution recovered between 82 and 97% of the total P from the three manures, which represented a significant improvement on recovery in NaOH alone. Low concentrations of paramagnetic ions in all manure extracts meant that relatively long delay times (> 5 s) were required for quantitative analysis by solution 31P NMR spectroscopy. The manures contained inorganic orthophosphate, orthophosphate monoesters, orthophosphate diesters, and inorganic polyphosphates, but results were markedly influenced by the concentration of NaOH in the extractant, which affected both spectral resolution and the apparent P composition of the extracts. For example, extraction of swine manure and broiler litter with 0.5 M NaOH + 50 mM EDTA produced remarkable spectral resolution that allowed accurate quantification of the four signals from phytic acid, the major organic P compound in these manures. In contrast, more dilute NaOH concentrations produced considerable line broadening that obscured individual signals in the orthophosphate monoester region of the spectra. Spectral resolution of cattle manure extracts was relatively unaffected by NaOH concentration. Improvements in spectral resolution of more concentrated NaOH extracts were, however, compromised by the disappearance of phospholipids and inorganic polyphosphates, notably in swine and cattle manure extracts, which indicated either degradation or a change in solubility. The optimum extraction conditions will therefore vary depending on the manure type and the objectives of the study. Phytic acid can be accurately quantified in swine manure and broiler litter by extraction with 0.5 M NaOH + 50 mM EDTA, while a more dilute NaOH concentration should be

  12. High pressure in situ x-ray absorption spectroscopy cell for studying simultaneously the liquid phase and the solid-liquid interface

    SciTech Connect

    Grunwaldt, Jan-Dierk; Ramin, Michael; Rohr, Markus; Michailovski, Alexej; Patzke, Greta R.; Baiker, Alfons

    2005-05-15

    A high pressure in situ x-ray absorption spectroscopy cell with two different path lengths and path positions is presented for studying element-specifically both the liquid phase and the solid-liquid interface at pressures up to 250 bar and temperatures up to 220 deg. C. For this purpose, one x-ray path probes the bottom, while the other x-ray path penetrates through the middle of the in situ cell. The basic design of the cell resembles a 10 ml volume batch reactor, which is equipped with in- and outlet lines to dose compressed gases and liquids as well as a stirrer for good mixing. Due to the use of a polyetheretherketone inset it is also suitable for measurements under corrosive conditions. The characteristic features of the cell are illustrated using case studies from catalysis and solid state chemistry: (a) the ruthenium-catalyzed formylation of an amine in 'supercritical' carbon dioxide in the presence of hydrogen; (b) the cycloaddition of carbon dioxide to propylene oxide in the presence of a solid Zn-based catalyst, and (c) the solvothermal synthesis of MoO{sub 3} nanorods from MoO{sub 3}-2H{sub 2}O.

  13. Utility of surface enhanced Raman spectroscopy (SERS) for elucidation and simultaneous determination of some penicillins and penicilloic acid using hydroxylamine silver nanoparticles.

    PubMed

    El-Zahry, Marwa R; Refaat, Ibrahim H; Mohamed, Horria A; Rosenberg, Erwin; Lendl, Bernhard

    2015-11-01

    Elucidation and quantitative determination of some of commonly used penicillins (ampicillin, penicillin G and carbenicillin) in the presence of their main degradation product (penicilloic acid) were developed. Forced acidic and basic degradation processes were applied at different time intervals. The formed degradation products were elucidated and quantified using surface enhanced Raman spectroscopy (SERS). Silver nanoparticles (AgNPs) prepared by reduction of silver nitrate using hydroxylamine-HCl in alkaline medium were used as SERS substrate. The results obtained in SERS were confirmed by the application of LC/MS method. The concentration range was 100-600 ng/ml in case of the studied penicillins and 100-700 ng/ml in case of penicilloic acid. An excellent correlation coefficient was found in case of ampicillin (r=0.9993) and in the case of penicilloic acid (r=0.9997). Validation procedures were carried out including precision, robustness and accuracy by comparing F- and t-values of both the proposed and reported methods.

  14. Thermal decomposition studies of 1,3,3-trinitroazetidine (TNAZ) and 1-nitroso-3,3-dinitroazetidine (NDNAZ) by simultaneous thermogravimetric modulated beam mass spectroscopy

    SciTech Connect

    Behrens, R. Jr.; Bulusu, S.

    1995-12-01

    The initial results from a study of the thermal decomposition of TNAZ, TNAZ-1-{sup 15}NO{sub 2} and NDNAZ using the simultaneous thermogravimetric modulated beam mass spectrometer (STMBMS) are presented. The major products formed in the decomposition of TNAZ are NO{sub 2} and NO with slightly lesser amounts of H{sub 2}O, HCN, CO/N{sub 2}, CO{sub 2}/N{sub 2}O and NDNAZ. The major product formed in the decomposition of NDNAZ is NO with lesser amounts of H{sub 2}O, HCN, CO/N{sub 2}O. The lower molecular weight products are similar to those observed in RSFTIR and IRMPD studies conducted previously by others. However, this study has shown that the mononitroso analogue of TNAZ, NDNAZ, is an important intermediate formed during the decomposition of TNAZ. It plays an important role in determining the identity of the products formed in the decomposition of TNAZ. The temporal behaviors Of the ion signals associated with the various thermal decomposition products from TNAZ, TNAZ-1-{sup 15}NO{sub 2} and NDNAZ are also presented. The illustrate the evolution sequence of the various products that are associated with the different reaction pathways that control the decomposition of these materials. In particular, the study of the {sup 15}N-labeled sample revealed that NO{sub 2} originates from both the likely sites in the TNAZ molecule and that the cleavage of the nitramine-NO{sub 2} group precedes that of the C-NO{sub 2} cleavage, resulting in similar sequences in the formation of NO and NDNAZ also.

  15. NMR studies of a bacterial cell culture medium (LB broth): cyclic nucleotides in yeast extracts.

    PubMed

    Rayner, M H; Sadler, P J; Scawen, M D

    1990-03-01

    The composition of LB broth (tryptone, yeast extract and NaCl) was investigated by 1H,31P-NMR spectroscopy, FPLC and gel electrophoresis. An unexpected finding was the high level of 2'3'-cyclic nucleotides, detected by characteristic 31P-NMR resonances in the region 20-21 ppm, originating from the yeast component. 31P-NMR resonances for cyclic nucleotides were observed during the autolysis of Saccharomyces cerevisiae cells, and in model reactions of RNase with RNA.

  16. Characterization of plant-derived carbon and phosphorus in lakes by sequential fractionation and NMR spectroscopy.

    PubMed

    Liu, Shasha; Zhu, Yuanrong; Wu, Fengchang; Meng, Wei; He, Zhongqi; Giesy, John P

    2016-10-01

    Although debris from aquatic macrophytes is one of the most important endogenous sources of organic matter (OM) and nutrients in lakes, its biogeochemical cycling and contribution to internal load of nutrients in eutrophic lakes are still poorly understood. In this study, sequential fractionation by H2O, 0.1M NaOH and 1.0M HCl, combined with (13)C and (31)P NMR spectroscopy, was developed and used to characterize organic carbon (C) and phosphorus (P) in six aquatic plants collected from Tai Lake (Ch: Taihu), China. Organic matter, determined by total organic carbon (TOC), was unequally distributed in H2O (21.2%), NaOH (29.9%), HCl (3.5%) and residual (45.3%) fractions. For P in debris of aquatic plants, 53.3% was extracted by H2O, 31.9% by NaOH, and 11% by HCl, with 3.8% in residual fractions. Predominant OM components extracted by H2O and NaOH were carbohydrates, proteins and aliphatic acids. Inorganic P (Pi) was the primary form of P in H2O fractions, whereas organic P (Po) was the primary form of P in NaOH fractions. The subsequent HCl fractions extracted fewer species of C and P. Some non-extractable carbohydrates, aromatics and metal phytate compounds remained in residual fractions. Based on sequential extraction and NMR analysis, it was proposed that those forms of C (54.7% of TOC) and P (96.2% of TP) in H2O, NaOH and HCl fractions are potentially released to overlying water as labile components, while those in residues are stable and likely preserved in sediments of lakes. These results will be helpful in understanding internal loading of nutrients from debris of aquatic macrophytes and their recycling in lakes.

  17. Characterization of plant-derived carbon and phosphorus in lakes by sequential fractionation and NMR spectroscopy.

    PubMed

    Liu, Shasha; Zhu, Yuanrong; Wu, Fengchang; Meng, Wei; He, Zhongqi; Giesy, John P

    2016-10-01

    Although debris from aquatic macrophytes is one of the most important endogenous sources of organic matter (OM) and nutrients in lakes, its biogeochemical cycling and contribution to internal load of nutrients in eutrophic lakes are still poorly understood. In this study, sequential fractionation by H2O, 0.1M NaOH and 1.0M HCl, combined with (13)C and (31)P NMR spectroscopy, was developed and used to characterize organic carbon (C) and phosphorus (P) in six aquatic plants collected from Tai Lake (Ch: Taihu), China. Organic matter, determined by total organic carbon (TOC), was unequally distributed in H2O (21.2%), NaOH (29.9%), HCl (3.5%) and residual (45.3%) fractions. For P in debris of aquatic plants, 53.3% was extracted by H2O, 31.9% by NaOH, and 11% by HCl, with 3.8% in residual fractions. Predominant OM components extracted by H2O and NaOH were carbohydrates, proteins and aliphatic acids. Inorganic P (Pi) was the primary form of P in H2O fractions, whereas organic P (Po) was the primary form of P in NaOH fractions. The subsequent HCl fractions extracted fewer species of C and P. Some non-extractable carbohydrates, aromatics and metal phytate compounds remained in residual fractions. Based on sequential extraction and NMR analysis, it was proposed that those forms of C (54.7% of TOC) and P (96.2% of TP) in H2O, NaOH and HCl fractions are potentially released to overlying water as labile components, while those in residues are stable and likely preserved in sediments of lakes. These results will be helpful in understanding internal loading of nutrients from debris of aquatic macrophytes and their recycling in lakes. PMID:27282495

  18. CW EC-QCL-based sensor for simultaneous detection of H2O, HDO, N2O and CH4 using multi-pass absorption spectroscopy.

    PubMed

    Yu, Yajun; Sanchez, Nancy P; Griffin, Robert J; Tittel, Frank K

    2016-05-16

    A sensor system based on a continuous wave, external-cavity quantum-cascade laser (CW EC-QCL) was demonstrated for simultaneous detection of atmospheric H2O, HDO, N2O and CH4 using a compact, dense pattern multi-pass gas cell with an effective path-length of 57.6 m. The EC-QCL with a mode-hop-free spectral range of 1225-1285 cm-1 operating at ~7.8 µm was scanned covering four neighboring absorption lines, for H2O at 1281.161 cm-1, HDO at 1281.455 cm-1, N2O at 1281.53 cm-1 and CH4 at 1281.61 cm-1. A first-harmonic-normalized wavelength modulation spectroscopy with second-harmonic detection (WMS-2f/1f) strategy was employed for data processing. An Allan-Werle deviation analysis indicated that minimum detection limits of 1.77 ppmv for H2O, 3.92 ppbv for HDO, 1.43 ppbv for N2O, and 2.2 ppbv for CH4 were achieved with integration times of 50-s, 50-s, 100-s and 129-s, respectively. Experimental measurements of ambient air are also reported.

  19. Characterization of phosphorus forms in lake macrophytes and algae by solution (31)P nuclear magnetic resonance spectroscopy.

    PubMed

    Feng, Weiying; Zhu, Yuanrong; Wu, Fengchang; Meng, Wei; Giesy, John P; He, Zhongqi; Song, Lirong; Fan, Mingle

    2016-04-01

    Debris from aquatic macrophytes and algae are important recycling sources of phosphorus (P), which can result in continuing blooms of algae by recycling bioavailable P in the eutrophic lakes. However, knowledge of forms of P in aquatic macrophytes and algae and their contribution to internal loads of P in lakes is limited. Without such knowledge, it is difficult to develop appropriate strategies to remediate and or restore aquatic ecosystems that have become eutrophic. Therefore, in this work, P was extracted from six types of aquatic macrophytes and algae collected from Tai Lake of China and characterized by use of solution (31)P-nuclear magnetic resonance (NMR) spectroscopy. When extracted by 0.5 M NaOH-25 mM EDTA, extraction recovery of total P(TP) and organic P(Po) exceeded 90 %. Concentrations of Po in algae and aquatic macrophytes were 5552 mg kg(-1) and 1005 mg kg(-1) and accounted for 56.0 and 47.2 % of TP, respectively. When Po, including condensed P, was characterized by solution (31)P-NMR Po in algae included orthophosphate monoesters (79.8 %), pyrophosphate (18.2 %), and orthophosphate diester (2.0 %), and Po in aquatic macrophytes included orthophosphate monoesters (90.3 %), pyrophosphate (4.2 %), and orthophosphate diester (5.5 %). Additionally, orthophosphate monoesters in algal debris mainly included β-glycerophosphate (44.1 %), α-glycerophosphate (13.5 %), and glucose 6-phosphate (13.5 %). Orthophosphate monoesters in aquatic macrophytes mainly included β-glycerophosphate (27.9 %), α-glycerophosphate (24.6 %), and adenosine 5' monophosphate (8.2 %). Results derived from this study will be useful in better understanding nutrient cycling, relevant eutrophication processes, and pollution control for freshwater lakes.

  20. Simultaneous high-speed gas property measurements at the exhaust gas recirculation cooler exit and at the turbocharger inlet of a multicylinder diesel engine using diode-laser-absorption spectroscopy.

    PubMed

    Jatana, Gurneesh S; Magee, Mark; Fain, David; Naik, Sameer V; Shaver, Gregory M; Lucht, Robert P

    2015-02-10

    A diode-laser-absorption-spectroscopy-based sensor system was used to perform high-speed (100 Hz to 5 kHz) measurements of gas properties (temperature, pressure, and H(2)O vapor concentration) at the turbocharger inlet and at the exhaust gas recirculation (EGR) cooler exit of a diesel engine. An earlier version of this system was previously used for high-speed measurements of gas temperature and H(2)O vapor concentration in the intake manifold of the diesel engine. A 1387.2 N m tunable distributed feedback diode laser was used to scan across multiple H(2)O absorption transitions, and the direct absorption signal was recorded using a high-speed data acquisition system. Compact optical connectors were designed to conduct simultaneous measurements in the intake manifold, the EGR cooler exit, and the turbocharger inlet of the engine. For measurements at the turbocharger inlet, these custom optical connectors survived gas temperatures as high as 800 K using a simple and passive arrangement in which the temperature-sensitive components were protected from high temperatures using ceramic insulators. This arrangement reduced system cost and complexity by eliminating the need for any active water or oil cooling. Diode-laser measurements performed during steady-state engine operation were within 5% of the thermocouple and pressure sensor measurements, and within 10% of the H(2)O concentration values derived from the CO(2) gas analyzer measurements. Measurements were also performed in the engine during transient events. In one such transient event, where a step change in fueling was introduced, the diode-laser sensor was able to capture the 30 ms change in the gas properties; the thermocouple, on the other hand, required 7.4 s to accurately reflect the change in gas conditions, while the gas analyzer required nearly 600 ms. To the best of our knowledge, this is the first implementation of such a simple and passive arrangement of high-temperature optical connectors as well

  1. Decrease in brain choline-containing compounds following a short period of global ischemia in gerbils as detected by 1H NMR spectroscopy in vivo.

    PubMed

    Kuhmonen, J; Sivenius, J; Riekkinen, P J; Kauppinen, R A

    1994-08-01

    Cerebral metabolism was studied in the postischaemic gerbil brain using surface coil 31P and 1H NMR spectroscopy. The ratio of choline-containing compounds (Cho) to total creatine (Cr) in the brain decreased from 0.46 +/- 0.02 to 0.32 +/- 0.02 by the fifth day following exposure to 5 min of global ischaemia and it remained at this low level for at least 19 days. The amounts of cerebral Cho as quantified by 1H NMR in vivo were 1.70 +/- 0.15 and 1.09 +/- 0.22 mmol/kg in control and postischaemic animals, respectively. The T2 of Cho was longer in the postischaemic cerebral cortex than in the control one. N-acetyl aspartate (NAA) as determined by 1H NMR in vivo did not differ in the two animal groups. High-resolution 1H NMR of acid-extracted brain cortices showed a decrease in total Cho (glycerophosphocholine, phosphocholine and choline) by 31%, but no changes in NAA, total creatine, taurine and myo-inositol, in the brain cortex seven days postischaemia relative to control animals. The decrease in acid extractable Cho was mainly due to the drop in glycerophosphocholine concentration. 31P NMR indicated normal energy state and phosphomonoester/phosphocreatine (PCr) and phosphodiester/PCr ratios in the in vivo brain 7 days postischaemia. Silver impregnation did not reveal neuronal degeneration but immunohistochemical staining showed a number of glial fibrillary acidic protein expressing astrocytes as indicators of reactive gliosis in the postischaemic cerebral cortex. These data show, for the first time, that a 1H NMR decrease in Cho metabolites takes place as a consequence of brief ischaemic episode even in the absence of obvious neuronal degeneration. PMID:7848813

  2. Study of the decomposition pathway of 12-molybdophosphoric acid in aqueous solutions by micro Raman spectroscopy.

    PubMed

    Bajuk-Bogdanović, D; Uskoković-Marković, S; Hercigonja, R; Popa, A; Holclajtner-Antunović, I

    2016-01-15

    Micro Raman spectroscopy was applied to investigate the speciation of heteropoly and isopoly molybdates in 0.05 and 0.005 M aqueous solutions of 12-molybdophosphoric acid at pH values between 1 and 6. For comparative purposes, (31)P NMR spectroscopy was applied too. It is shown that stability of Keggin anion is influenced both by pH and concentration of solution. The Keggin structure is stable in acidic solutions (pH<1.6) while defective Keggin structures are formed with further alkalization (up to pH5.6). Monolacunary anion PMo11O(39)(7-) is the main component in the pH region from 1.6 to 3.4. Further removal of molybdenyl species causes the appearance of other vacant Keggin structures such as PMo9O31(OH)(3)(6-) and PMo6O(25)(9-) at about pH4. At pH5.0, anion PMo6O(25)(9-) is the main species. In solutions with pH greater than 5.0, heteropolymolybdates disappear completely and isopolymolybdates Mo7O(24)(6-) and MoO(4)(2-) are formed in higher amounts. In more diluted solution of 0.005 M, the decomposition scheme of 12-molybdophosphoric acid solution with increasing of pH takes place without observation of significant amounts of Mo7O(24)(6-) species. If alkalinization is performed with 0.5 M instead of 5 M NaOH, there are no significant changes in the Raman spectra of solutions. It is shown that the spectra of evaporated samples may be used for the identification of molecular species in corresponding concentrated solutions. However, Raman spectra of dry residues of more diluted solutions differ from spectra of corresponding solutions due to the reactions performed during the process of drying and cannot be used for unambiguous identification of species in solution. Acidification of 0.05 M solution of Na2MoO4 shows that at pH>5.6, molybdate anion MoO(4)(2-) dominates, while in the pH range between 5.6 and 1, heptamolybdate anion Mo7O(24)(6-) is preferentially formed.

  3. Array-based photoacoustic spectroscopy

    DOEpatents

    Autrey, S. Thomas; Posakony, Gerald J.; Chen, Yu

    2005-03-22

    Methods and apparatus for simultaneous or sequential, rapid analysis of multiple samples by photoacoustic spectroscopy are disclosed. A photoacoustic spectroscopy sample array including a body having at least three recesses or affinity masses connected thereto is used in conjunction with a photoacoustic spectroscopy system. At least one acoustic detector is positioned near the recesses or affinity masses for detection of acoustic waves emitted from species of interest within the recesses or affinity masses.

  4. Imaging with Raman spectroscopy.

    PubMed

    Zhang, Yin; Hong, Hao; Cai, Weibo

    2010-09-01

    Raman spectroscopy, based on the inelastic scattering of a photon, has been widely used as an analytical tool in many research fields. Recently, Raman spectroscopy has also been explored for biomedical applications (e.g. cancer diagnosis) because it can provide detailed information on the chemical composition of cells and tissues. For imaging applications, several variations of Raman spectroscopy have been developed to enhance its sensitivity. This review article will provide a brief summary of Raman spectroscopy-based imaging, which includes the use of coherent anti-Stokes Raman spectroscopy (CARS, primarily used for imaging the C-H bond in lipids), surface-enhanced Raman spectroscopy (SERS, for which a variety of nanoparticles can be used as contrast agents), and single-walled carbon nanotubes (SWNTs, with its intrinsic Raman signal). The superb multiplexing capability of SERS-based Raman imaging can be extremely powerful in future research where different agents can be attached to different Raman tags to enable the interrogation of multiple biological events simultaneously in living subjects. The primary limitations of Raman imaging in humans are those also faced by other optical techniques, in particular limited tissue penetration. Over the last several years, Raman spectroscopy imaging has advanced significantly and many critical proof-of-principle experiments have been successfully carried out. It is expected that imaging with Raman Spectroscopy will continue to be a dynamic research field over the next decade.

  5. Comparison of cerebral tissue oxygenation values in full term and preterm newborns by the simultaneous use of two near-infrared spectroscopy devices: an absolute and a relative trending oximeter

    NASA Astrophysics Data System (ADS)

    Szczapa, Tomasz; Karpiński, Łukasz; Moczko, Jerzy; Weindling, Michael; Kornacka, Alicja; Wróblewska, Katarzyna; Adamczak, Aleksandra; Jopek, Aleksandra; Chojnacka, Karolina; Gadzinowski, Janusz

    2013-08-01

    The aim of this study is to compare a two-wavelength light emitting diode-based tissue oximeter (INVOS), which is designed to show trends in tissue oxygenation, with a four-wavelength laser-based oximeter (FORE-SIGHT), designed to deliver absolute values of tissue oxygenation. Simultaneous values of cerebral tissue oxygenation (StO2) are measured using both devices in 15 term and 15 preterm clinically stable newborns on the first and third day of life. Values are recorded simultaneously in two periods between which oximeter sensor positions are switched to the contralateral side. Agreement between StO2 values before and after the change of sensor position is analyzed. We find that mean cerebral StO2 values are similar between devices for term and preterm babies, but INVOS shows StO2 values spread over a wider range, with wider standard deviations than shown by the FORE-SIGHT. There is relatively good agreement with a bias up to 3.5% and limits of agreement up to 11.8%. Measurements from each side of the forehead show better repeatability for the FORE-SIGHT monitor. We conclude that performance of the two devices is probably acceptable for clinical purposes. Both performed sufficiently well, but the use of FORE-SIGHT may be associated with tighter range and better repeatability of data.

  6. Photoacoustic spectroscopy sample array vessels and photoacoustic spectroscopy methods for using the same

    DOEpatents

    Amonette, James E.; Autrey, S. Thomas; Foster-Mills, Nancy S.

    2006-02-14

    Methods and apparatus for simultaneous or sequential, rapid analysis of multiple samples by photoacoustic spectroscopy are disclosed. Particularly, a photoacoustic spectroscopy sample array vessel including a vessel body having multiple sample cells connected thereto is disclosed. At least one acoustic detector is acoustically positioned near the sample cells. Methods for analyzing the multiple samples in the sample array vessels using photoacoustic spectroscopy are provided.

  7. 31-P NMR studies of intracellular pH (pH/sub i/) of the in vitro resting rat diaphragm (D) exposed to hypercapnia (HC), plus amiloride (HCA)

    SciTech Connect

    Fitzgerald, R.; Howell, S.; Jacobus, W.

    1986-03-05

    The authors have previously reported that the pH/sub i/ of the resting rat D in vitro fell when exposed to HC. Since pH/sub i/ influences cellular functions, it is important to understand mechanisms whereby a tissue maintains its pH/sub i/ One mechanism reported to exist in some vertebrate tissues is a sodium-proton pump which is inhibited by amiloride. If the rat D had the Na/sup +/-H/sup +/ pump, the resting rat D pH/sub i/, when exposed to hypercapnia, would decrease more if amiloride was present than if there was no amiloride. The D was placed in a 25 mm NMR sample tube and superfused with buffer gassed with 95%O/sub 2/-5%CO/sub 2/ at 37/sup 0/C. Two 15 minute pulsed Fourier transform spectra were acquired at 72.89 MHz using 2 sec repetition rate during normocapnia. The D was next superfused for 60 minutes with buffer gassed with 80%O/sub 2/-20%CO/sub 2/ and containing 5 x 10/sup -4/M amiloride (n=5; HCA) or not (n=8; HC). Four 15 minute spectra were obtained; pH/sub i/ was determined from the chemical shift of P/sub i/ resonance. The pH/sub i/ (X vector +/- SE) of HC D's fell from 7.14 +/- .04 to 6.85 +/- .05 at 1 hour of exposure. The pH/sub i/ of HCA D's fell from 6.95 +/- .05 to 6.57 +/- .03. The decrease in pH/sub i/ during hypercapnia is significantly greater (P<0.01) for HCA D's. These data suggest that the rat D uses a Na/sup +/-H/sup +/ pump to regulate pH/sub i/ and that this pump operates in the in vitro resting rat D exposed to hypercapnia.

  8. Interaction Study of an Amorphous Solid Dispersion of Cyclosporin A in Poly-Alpha-Cyclodextrin with Model Membranes by 1H-, 2H-, 31P-NMR and Electron Spin Resonance

    PubMed Central

    Debouzy, Jean-Claude; Bourbon, Fréderic; Lahiani-Skiba, Malika; Skiba, Mohamed

    2014-01-01

    The properties of an amorphous solid dispersion of cyclosporine A (ASD) prepared with the copolymer alpha cyclodextrin (POLYA) and cyclosporine A (CYSP) were investigated by 1H-NMR in solution and its membrane interactions were studied by 1H-NMR in small unilamellar vesicles and by 31P 2H NMR in phospholipidic dispersions of DMPC (dimyristoylphosphatidylcholine) in comparison with those of POLYA and CYSP alone. 1H-NMR chemical shift variations showed that CYSP really interacts with POLYA, with possible adduct formation, dispersion in the solid matrix of the POLYA, and also complex formation. A coarse approach to the latter mechanism was tested using the continuous variations method, indicating an apparent 1 : 1 stoichiometry. Calculations gave an apparent association constant of log Ka = 4.5. A study of the interactions with phospholipidic dispersions of DMPC showed that only limited interactions occurred at the polar head group level (31P). Conversely, by comparison with the expected chain rigidification induced by CYSP, POLYA induced an increase in the fluidity of the layer while ASD formation led to these effects almost being overcome at 298 K. At higher temperature, while the effect of CYSP seems to vanish, a resulting global increase in chain fluidity was found in the presence of ASD. PMID:24883210

  9. Quarkonium spectroscopy

    SciTech Connect

    Scharre, D.L.

    1981-06-01

    Recent experimental investigations of heavy quark-antiquark bound state systems are reviewed. Results from SPEAR on charmonium spectroscopy and from DORIS and CESR on bottomonium spectroscopy are presented. The current status of the search for top is also discussed.

  10. Measurements of the earth`s stratosphere using balloon-borne far infrared spectroscopy: Simultaneous measurements of HO{sub x}, NO{sub x}, and Cl{sub x}

    SciTech Connect

    Chance, K.

    1995-12-31

    The Smithsonian Astrophysical Observatory far-infrared spectrometer (FIRS-2) measures vertical mixing ratio profiles in the stratosphere from a balloon platform. The FIRS-2 is a high-resolution (0.004 cm{sup -1} unapodized) two-beam Fourier transform spectrometer which measures thermal emission in the regions 80-210 cm{sup -1} and 350-700 cm{sup -1}. Observations are made at various elevation angles, with absolute pointing referenced to a gyroscope- and accelerometer-stabilized single-axis platform. Molecules currently measured include OH, HO{sub 2}, H{sub 2}O, H{sub 2}O{sub 2}, O{sub 3}P, O{sub 2}, O{sub 3}, HCl, HF, HBr, HOCl, HOBr, CO, CO{sub 2}, N{sub 2}O, NO{sub 2}, HNO{sub 3}, and HCN. The measurements, the development of the relevant spectroscopy, and the application of the measurements to improving models of the photochemistry of the ozone layer are discussed.

  11. Study of the interactions between sucrose and metal ions (Mg2+ and K+) and their simultaneous quantification in ternary mixture by mid-infrared and 13C nuclear magnetic resonance spectroscopies.

    PubMed

    Rondeau, Philippe; Jhurry, Dhanjay; Sers, Sandrine; Cadet, Frédéric

    2004-07-01

    In this paper, a ternary aqueous mixture of sucrose and two metal ions (Mg(2+) and K(+)) has been examined by mid-infrared spectroscopy coupled with principal component analysis (PCA) and the partial least-squares regression method (PLS). PCA was first used for the description of Fourier transform mid-infrared (mid-FTIR) spectral data of the complex samples. The resulting factorial map, set up with the two most influential component axes, features distinct concentration distribution specific to each component. Prediction equations that linked sucrose, magnesium, and potassium concentrations to the spectral data were established by the partial least-squares regression method. A quite good correlation was obtained between the first 5 axes and the concentration variables, with coefficient values ranging from 0.984 to 0.997. It was thus possible to predict specifically both metal ion concentrations in the ternary mixture with relatively good accuracy. The ternary mixtures of sucrose, Mg(2+), and K(+) were also subjected to (13)C NMR (nuclear magnetic resonance) analysis. From the relative displacements of chemical shifts of the carbon atoms of sucrose, it was possible to determine the influence of each metal ion present in the mixture. PMID:15282047

  12. Study by ³¹P NMR spectroscopy of the triacylglycerol degradation processes in olive oil with different heat-transfer mechanisms.

    PubMed

    Lucas-Torres, Covadonga; Pérez, Angel; Cabañas, Beatriz; Moreno, Andrés

    2014-12-15

    The thermal degradation of olive oil using conventional and microwave heating under the same experimental conditions were compared. A powerful identification and quantification technique based on (31)P NMR has been developed to characterise the differences between the minor components including diacylglycerol and free fatty acids in the heated samples. The (31)P NMR spectra of the degraded olive oils, which contain OH groups derivatised with a phosphorus reagent, showed that conventional heating is more detrimental to the oil than microwave technique. Conventional heating leads to a significant increase in the diacylglycerol and free fatty acid contents as well as in the number of degradation compounds, which damage the olive oil quality. However, the main process that takes place on using microwave heating is isomerisation between diacylglycerols, a change that could give a potential longer shelf life to the olive oil.

  13. Study by ³¹P NMR spectroscopy of the triacylglycerol degradation processes in olive oil with different heat-transfer mechanisms.

    PubMed

    Lucas-Torres, Covadonga; Pérez, Angel; Cabañas, Beatriz; Moreno, Andrés

    2014-12-15

    The thermal degradation of olive oil using conventional and microwave heating under the same experimental conditions were compared. A powerful identification and quantification technique based on (31)P NMR has been developed to characterise the differences between the minor components including diacylglycerol and free fatty acids in the heated samples. The (31)P NMR spectra of the degraded olive oils, which contain OH groups derivatised with a phosphorus reagent, showed that conventional heating is more detrimental to the oil than microwave technique. Conventional heating leads to a significant increase in the diacylglycerol and free fatty acid contents as well as in the number of degradation compounds, which damage the olive oil quality. However, the main process that takes place on using microwave heating is isomerisation between diacylglycerols, a change that could give a potential longer shelf life to the olive oil. PMID:25038644

  14. Mossbauer Spectroscopy.

    ERIC Educational Resources Information Center

    Stevens, John G.; Bowen, Lawrence H.

    1980-01-01

    Reviews current research in Mossbauer spectroscopy, including instrumentation and experimental techniques, spectral analysis, catalysts and surfaces, environmental studies, medical applications and atmospheric air studies. Cites 346 references. (CS)

  15. Simultaneity, relativity and conventionality

    NASA Astrophysics Data System (ADS)

    Janis, Allen I.

    2008-01-01

    The view of simultaneity presented by Max Jammer is almost breathtaking, encompassing, as the book's subtitle suggests, the period from antiquity to the 21st century. Many interesting things are to be found along the way. For example, what Jammer (p. 49) says "may well be regarded as probably the earliest recorded example of an operational definition of distant simultaneity" is due to St. Augustine (in his Confessions, written in 397 A.D.; for a modern translation, see Augustine, 2006). He was arguing against astrology by presenting the story of two women, one rich and one poor, who gave birth simultaneously. Although the two children thus had precisely the same horoscopes, their lives followed quite different courses. And how was it determined that the births were simultaneous? A messenger went from each birth site to the other, leaving the instant the child was born (and, presumably, traveling with equal speeds). Since the messengers met at the midpoint between the locations of the two births, the births must have been simultaneous. This is, of course, quite analogous to Albert Einstein's definition of simultaneity (given more than 1500 years later), which will be discussed in Section 2.1.

  16. Raman Spectroscopy.

    ERIC Educational Resources Information Center

    Gerrard, Donald L.

    1984-01-01

    Reviews literature on Raman spectroscopy from late 1981 to late 1983. Topic areas include: instrumentation and sampling; liquids and solutions; gases and matrix isolation; biological molecules; polymers; high-temperature and high-pressure studies; Raman microscopy; thin films and surfaces; resonance-enhanced and surface-enhanced spectroscopy; and…

  17. Phosphorus-31 nuclear magnetic resonance studies of cellular systems

    SciTech Connect

    Robitaille, P.M.L.

    1986-01-01

    In this study, /sup 31/P-NMR spectroscopy was applied to the study of (1) sipunculan erythrocytes, (2) spermatozoa isolated from several vertebrate and invertebrate species, and (3) unfertilized eggs isolated from the blue crab and the horseshoe crab. /sup 31/P-NMR results center on the identification of key metabolites and on the determination of intracellular pH. In studies involving fish spermatozoa, emphasis was also placed on examining changes in metabolic profiles following (1) an anaerobic insult, (2) motility initiation, or (3) short-term storage. This study also captures several difficulties in spectral interpretation which a spectroscopist is likely to encounter.

  18. Broadband simultaneous multiplane imaging

    NASA Astrophysics Data System (ADS)

    Blanchard, P. M.; Greenaway, A. H.

    2000-09-01

    A technique, using a distorted diffraction grating, which enables the simultaneous imaging of multiple object planes side-by-side on a single camera is described. The chromatic properties of the imaging system are discussed and a modification to allow operation with broadband illumination is demonstrated.

  19. Psychosemantics and Simultaneous Interpretation.

    ERIC Educational Resources Information Center

    Le Ny, Jean-Francois

    A comprehension model of simultaneous interpretation activity raises three types of problems: structure of semantic information stored in long-term memory, modalities of input processing and specific restrictions due to situation. A useful concept of semantic mnesic structures includes: (1) a componential-predicative lexicon; (2) a propositional…

  20. Evaluating Simultaneous Integrals

    ERIC Educational Resources Information Center

    Kwong, Harris

    2012-01-01

    Many integrals require two successive applications of integration by parts. During the process, another integral of similar type is often invoked. We propose a method which can integrate these two integrals simultaneously. All we need is to solve a linear system of equations.

  1. Infrared Spectroscopy

    NASA Astrophysics Data System (ADS)

    Wehling, Randy L.

    Infrared (IR) spectroscopy refers to measurement of the absorption of different frequencies of IR radiation by foods or other solids, liquids, or gases. IR spectroscopy began in 1800 with an experiment by Herschel. When he used a prism to create a spectrum from white light and placed a thermometer at a point just beyond the red region of the spectrum, he noted an increase in temperature. This was the first observation of the effects of IR radiation. By the 1940s, IR spectroscopy had become an important tool used by chemists to identify functional groups in organic compounds. In the 1970s, commercial near-IR reflectance instruments were introduced that provided rapid quantitative determinations of moisture, protein, and fat in cereal grains and other foods. Today, IR spectroscopy is used widely in the food industry for both qualitative and quantitative analysis of ingredients and finished foods.

  2. SIMULTANEOUS DIFFERENTIAL EQUATION COMPUTER

    DOEpatents

    Collier, D.M.; Meeks, L.A.; Palmer, J.P.

    1960-05-10

    A description is given for an electronic simulator for a system of simultaneous differential equations, including nonlinear equations. As a specific example, a homogeneous nuclear reactor system including a reactor fluid, heat exchanger, and a steam boiler may be simulated, with the nonlinearity resulting from a consideration of temperature effects taken into account. The simulator includes three operational amplifiers, a multiplier, appropriate potential sources, and interconnecting R-C networks.

  3. Vibrational spectroscopy of stichtite

    NASA Astrophysics Data System (ADS)

    Frost, Ray L.; Erickson, Kristy L.

    2004-11-01

    Raman spectroscopy complimented with infrared spectroscopy has been used to study the mineral stitchtite, a hydrotalcite of formula Mg 6Cr 2(CO 3)(OH) 16·4H 2O. Two bands are observed at 1087 and 1067 cm -1 with an intensity ratio of ˜2.5/1 and are attributed to the symmetric stretching vibrations of the carbonate anion. The observation of two bands is attributed to two species of carbonate in the interlayer, namely weakly hydrogen bonded and strongly hydrogen bonded. Two infrared bands are found at 1457 and 1381 cm -1 and are assigned to the antisymmetric stretching modes. These bands were not observed in the Raman spectrum. Two infrared bands are observed at 744 and 685 cm -1 and are assigned to the ν4 bending modes. Two Raman bands were observed at 539 and 531 cm -1 attributed to the ν2 bending modes. Importantly the band positions of the paragenically related hydrotalcites stitchtite, iowaite, pyroaurite and reevesite all of which contain the carbonate anion occur at different wavenumbers. Consequently, Raman spectroscopy can be used to distinguish these minerals, particularly in the field where many of these hydrotalcites occur simultaneously in ore zones.

  4. Spectroscopy, scattering, and KK molecules

    SciTech Connect

    Weinstein, J.

    1994-04-01

    The author presents a pedagogical description of a new theoretical technique, based on the multichannel Schroedinger equation, for simultaneously applying the quark model to both meson spectroscopy and meson-meson scattering. This is an extension of an earlier analysis which led to the prediction that the f{sub o}(975) and a{sub o}(980) scalar mesons are K{bar K} molecular states.

  5. Modern Spectroscopy

    ERIC Educational Resources Information Center

    Barrow, Gordon M.

    1970-01-01

    Presents the basic ideas of modern spectroscopy. Both the angular momenta and wave-nature approaches to the determination of energy level patterns for atomic and molecular systems are discussed. The interpretation of spectra, based on atomic and molecular models, is considered. (LC)

  6. Space spectroscopy

    SciTech Connect

    Krupa, Tyler J.

    2000-02-01

    Los Alamos researchers have developed a technique to determine the composition of rock samples despite weather-induced mineral varnish deposited on the rocks. Using laser-induced breakdown spectroscopy (LIBS), the researchers determined the true elemental composition of a Mojave Desert rock sample with a thick weather-induced deposit on it. (AIP) (c)

  7. Simultaneous Determination of Cobalt, Copper, and Nickel by Multivariate Linear Regression.

    ERIC Educational Resources Information Center

    Dado, Greg; Rosenthal, Jeffrey

    1990-01-01

    Presented is an experiment where the concentrations of three metal ions in a solution are simultaneously determined by ultraviolet-vis spectroscopy. Availability of the computer program used for statistically analyzing data using a multivariate linear regression is listed. (KR)

  8. Note on Magnetism and Simultaneity

    ERIC Educational Resources Information Center

    Huggins, Elisha

    2009-01-01

    The paper on "Magnetism and Simultaneity" by Adler provides an excellent new thought experiment involving the lack of simultaneity in Einstein's special relativity. Adler uses the lack of simultaneity rather than the Lorentz contraction to derive the formula for the magnetic force on a moving charged particle. Advantages of his derivation are that…

  9. Simultaneous Immersion Mirau Interferometry

    NASA Astrophysics Data System (ADS)

    Lyulko, Oleksandra

    acquisition challenging. This problem was resolved by integration of polarization optics into the optics of the attachment to enable simultaneous creation and spatial separation of two interferograms, which, combined with the background image, are used to reconstruct the intensity map of the specimen. Giving the name Simultaneous Immersion Mirau Interferometry to this approach, simultaneous acquisition of all interferograms per image has eliminated the issue of vibrations. The designed compound microscope attachment has been manufactured and tested; the system produces images of quality, sufficient to perform targeted cellular irradiation experiments.

  10. Simultaneous Quantum Duel

    NASA Astrophysics Data System (ADS)

    Balthazar, Wagner F.; Huguenin, José A. O.; Schmidt, Alexandre G. M.

    2015-12-01

    We quantize the classical game of simultaneous two-person duel. In this game, the players Alice and Bob, have a two level system, for example, a spin 1/2 particle, which models alive and dead states. Through physical considerations we write up the unitary operator which represents the classical action of firing, which quantum mechanically is represented by flipping the opponent's spin and test its classical limits. We study three representative special cases of such duel where players start the duel: both alive; in a Bell state; and when one of them has her skills decreasing along the duel. We also present a proposal of experimental realization of this quantum game using twin photons produced by spontaneous parametric down conversion.

  11. Frequency comb velocity-modulation spectroscopy.

    PubMed

    Sinclair, Laura C; Cossel, Kevin C; Coffey, Tyler; Ye, Jun; Cornell, Eric A

    2011-08-26

    We have demonstrated a new technique that provides massively parallel comb spectroscopy sensitive specifically to ions through the combination of cavity-enhanced direct frequency comb spectroscopy with velocity-modulation spectroscopy. Using this novel system, we have measured electronic transitions of HfF⁺ and achieved a fractional absorption sensitivity of 3×10⁻⁷ recorded over 1500 simultaneous channels spanning 150  cm⁻¹ around 800 nm with an absolute frequency accuracy of 30 MHz (0.001  cm⁻¹). A fully sampled spectrum consisting of interleaved measurements is acquired in 30 min.

  12. Hypernuclear spectroscopy

    SciTech Connect

    F. Garibaldi, O. Hashimoto, J.J. LeRose, P. Markowitz, S.N. Nakamura, J. Reinhold, L. Tang

    2011-06-01

    A program of hypernuclear spectroscopy experiments encompassing many hypernuclei has been undertaken in both Halls A and C using complimentary approaches. Spectra with sub-MeV resolution have been obtained for Li, B, and N in Hall A, while results from Hall C include He, B, and Al with new data still under analysis for He, Li, Be, B and V. High resolution and high precision in the determination of the single Λ binding energy at various shell levels has been the key success of these experiments using the (e,e'K+) reaction to produce Λ hypernuclei.

  13. Laser Spectroscopy

    NASA Astrophysics Data System (ADS)

    Hollberg, Leo; Bergquist, James Charles; Kasevich, Mark A.

    2008-04-01

    Degenerate gases. Probing vortex pair sizes in the Berezinskii-Kosterlitz-Thouless regime on a two-dimensional lattice of Bose-Einstein condensates / V. Schweikhard ... [et al.]. Interacting Bose-Einstein condensates in random potentials / P. Bouyer ... [et al.]. Towards quantum magnetism with ultracold atoms in optical lattices / I. Bloch -- Precision measurement and fundamental physics. T-violation and the search for a permanent electric dipole moment of the mercury atom / E. N. Fortson -- Quantum information and control I. Quantum information processing and ramsey spectroscopy with trapped ions / C. F. Roos ... [et al.]. Quantum non-demolition counting of photons in a cavity / S. Haroche ... [et al.] -- Ultra-fast control and spectroscopy. Frequency-Comb- assisted mid-infrared spectroscopy / P. de Natale ... [et al.] -- Precision measurement and applications. Precision gravity tests by atom interferometry / G. M. Tino ... [et al.] -- Novel spectroscopic applications. On a variation of the proton-electron mass ratio / W. Ubachs ... [et al.] -- Quantum information and control II. Quantum interface between light and atomic ensembles / H. Krauter ... [et al.] -- Degenerate Fermi gases. An atomic Fermi gas near a P-wave Feshbach resonance / D. S. Jin, J. P. Gaebler and J. T. Stewart. Bragg scattering of correlated atoms from a degenerate Fermi gas / R. J. Ballagh, K. J. Challis and C. W. Gardiner -- Spectroscopy and control of atoms and molecules. Stark and Zeeman deceleration of neutral atoms and molecules / S. D. Hogan ... [et al.]. Generation of coherent, broadband and tunable soft x-ray continuum at the leading edge of the driver laser pulse / A. Jullien ... [et al.]. Controlling neural atoms and photons with optical conveyor belts and ultrathin optical fibers / D. Meschede. W. Alt and A. Rauschenbeutel -- Spectroscopy on the small scale. Wide-field cars-microscopy / C. Heinrich ... [et al.]. Atom nano-optics and nano-lithography / V. I. Balykin ... [et al

  14. A Demonstration of Simultaneous Electrochemiluminescence

    ERIC Educational Resources Information Center

    Ibanez, Jorge G.; Zavala-Araiza, Daniel; Sotomayor-Martinez Barranco, Biaani; Torres-Perez, Jonatan; Camacho-Zuniga, Claudia; Bohrmann-Linde, Claudia; Tausch, Michael W.

    2013-01-01

    Paired (simultaneous) electrochemical processes can increase energy savings in selected cases by using the reactions at both electrodes of an electrochemical cell to perform a desired process, as is the case in the commercially successful chlor-alkali process. In the demonstration described herein, simultaneous blue electrochemiluminescence (ECL)…

  15. Simultaneous Spectral Temporal Adaptive Raman Spectrometer - SSTARS

    NASA Technical Reports Server (NTRS)

    Blacksberg, Jordana

    2010-01-01

    Raman spectroscopy is a prime candidate for the next generation of planetary instruments, as it addresses the primary goal of mineralogical analysis, which is structure and composition. However, large fluorescence return from many mineral samples under visible light excitation can render Raman spectra unattainable. Using the described approach, Raman and fluorescence, which occur on different time scales, can be simultaneously obtained from mineral samples using a compact instrument in a planetary environment. This new approach is taken based on the use of time-resolved spectroscopy for removing the fluorescence background from Raman spectra in the laboratory. In the SSTARS instrument, a visible excitation source (a green, pulsed laser) is used to generate Raman and fluorescence signals in a mineral sample. A spectral notch filter eliminates the directly reflected beam. A grating then disperses the signal spectrally, and a streak camera provides temporal resolution. The output of the streak camera is imaged on the CCD (charge-coupled device), and the data are read out electronically. By adjusting the sweep speed of the streak camera, anywhere from picoseconds to milliseconds, it is possible to resolve Raman spectra from numerous fluorescence spectra in the same sample. The key features of SSTARS include a compact streak tube capable of picosecond time resolution for collection of simultaneous spectral and temporal information, adaptive streak tube electronics that can rapidly change from one sweep rate to another over ranges of picoseconds to milliseconds, enabling collection of both Raman and fluorescence signatures versus time and wavelength, and Synchroscan integration that allows for a compact, low-power laser without compromising ultimate sensitivity.

  16. Blood analysis by Raman spectroscopy.

    PubMed

    Enejder, Annika M K; Koo, Tae-Woong; Oh, Jeankun; Hunter, Martin; Sasic, Slobodan; Feld, Michael S; Horowitz, Gary L

    2002-11-15

    Concentrations of multiple analytes were simultaneously measured in whole blood with clinical accuracy, without sample processing, using near-infrared Raman spectroscopy. Spectra were acquired with an instrument employing nonimaging optics, designed using Monte Carlo simulations of the influence of light-scattering-absorbing blood cells on the excitation and emission of Raman light in turbid medium. Raman spectra were collected from whole blood drawn from 31 individuals. Quantitative predictions of glucose, urea, total protein, albumin, triglycerides, hematocrit, and hemoglobin were made by means of partial least-squares (PLS) analysis with clinically relevant precision (r(2) values >0.93). The similarity of the features of the PLS calibration spectra to those of the respective analyte spectra illustrates that the predictions are based on molecular information carried by the Raman light. This demonstrates the feasibility of using Raman spectroscopy for quantitative measurements of biomolecular contents in highly light-scattering and absorbing media. PMID:18033426

  17. Baryon spectroscopy

    SciTech Connect

    Klempt, Eberhard; Richard, Jean-Marc

    2010-04-15

    About 120 baryons and baryon resonances are known, from the abundant nucleon with u and d light-quark constituents up to the {Xi}{sub b}{sup -}=(bsd), which contains one quark of each generation and to the recently discovered {Omega}{sub b}{sup -}=(bss). In spite of this impressively large number of states, the underlying mechanisms leading to the excitation spectrum are not yet understood. Heavy-quark baryons suffer from a lack of known spin parities. In the light-quark sector, quark-model calculations have met with considerable success in explaining the low-mass excitations spectrum but some important aspects such as the mass degeneracy of positive-parity and negative-parity baryon excitations remain unclear. At high masses, above 1.8 GeV, quark models predict a very high density of resonances per mass interval which is not yet observed. In this review, issues are identified discriminating between different views of the resonance spectrum; prospects are discussed on how open questions in baryon spectroscopy may find answers from photoproduction and electroproduction experiments which are presently carried out in various laboratories.

  18. Amateur spectroscopy

    NASA Astrophysics Data System (ADS)

    Gavin, M. V.

    1998-06-01

    (The 1997 Presidential Address to the British Astronomical Association.) Auguste Comte is remembered for an unfortunate remark. In 1825 he said the chemical composition of stars would never be revealed. Within a decade or so the heart of the atom was being explored in remote stars through the science of spectroscopy. In simplistic terms one can regard the atom as a miniature solar system, but with the novel option that electrons (representing planets) having the ability to 'jump' from one orbit to another. In 'falling' to a lower orbit a photon of light of precise wavelength is released to travel outwards. When the electron 'jumps' to a higher orbit a photon of light is absorbed. This is taking place on a vast scale which we observe as lines in the spectrum - their position and prominence relates to the particular atomic element, temperature and pressure within the stellar atmosphere. It is beyond the scope of this Address to discuss the various processes that affect spectra, or to provide a mathematical explanation which can be found elsewhere. In any case the lack of a deep understanding does not preclude enjoyable or useful observations. Methods and results from amateurs conducting such observations are discussed in this paper.

  19. Simultaneous monitoring of multimetallic atom densities in plasma processes employing a multimicrohollow cathode lamp

    SciTech Connect

    Ohta, Takayuki; Ito, Masafumi; Tachibana, Yoshihiro; Taneda, Satoshi; Takashima, Seigo; Hori, Masaru; Kano, Hiroyuki; Den, Shoji

    2007-06-18

    The authors have developed a simultaneous measurement technique of multimetallic atom densities in process plasmas using absorption spectroscopy employing a multimicrohollow cathode plasma as a light source. The optical emissions of four metallic atoms of Cu, Zn, Fe, and Mo were simultaneously produced from the multimicrohollow cathode plasma of millimeter size. The absolute densities of Cu and Mo in the magnetron sputtering plasma were simultaneously measured using this technique. The simultaneous monitoring of multimetallic atoms is very useful for controlling the plasma processes precisely.

  20. Assessment of skin flap viability using visible diffuse reflectance spectroscopy and auto-fluorescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhu, Caigang; Chen, Shuo; Chui, Christopher Hoe-Kong; Liu, Quan

    2012-12-01

    The accurate assessment of skin flap viability is vitally important in reconstructive surgery. Early identification of vascular compromise increases the change of successful flap salvage. The ability to determine tissue viability intraoperatively is also extremely useful when the reconstructive surgeon must decide how to inset the flap and whether any tissue must be discarded. Visible diffuse reflectance and auto-fluorescence spectroscopy, which yield different sets of biochemical information, have not been used in the characterization of skin flap viability simultaneously to our best knowledge. We performed both diffuse reflectance and fluorescence measurements on a reverse MacFarlane rat dorsal skin flap model to identify the additional value of auto-fluorescence spectroscopy to the assessment of flap viability. Our result suggests that auto-fluorescence spectroscopy appears to be more sensitive to early biochemical changes in a failed flap than diffuse reflectance spectroscopy, which could be a valuable complement to diffuse reflectance spectroscopy for the assessment of flap viability.

  1. Chiroptical Spectroscopy

    NASA Astrophysics Data System (ADS)

    Gurst, Jerome E.

    1995-09-01

    A brief review of the literature, and Chemical and Engineering News in particular, reveals that the determination and use of optical activity is of increasing importance in today's commercial and research laboratories. The classical technique is to measure [alpha]D using a manual or recording polarimeter to provide a single value, the specific rotation at 589 nm. A spectropolarimeter can be used to determine optical activity through the UV-Visible spectrum (Optical Rotatory Dispersion [ORD]). At wavelengths far removed from electronic absorption bands, optical activity arises from circular birefringence, or the difference in the refractive index for left- and right-circularly polarized light; i.e., nL - nR does not equal zero for chiral materials. If the optical activity is measured through an absorption band, complex behavior is observed (a Cotton Effect curve). At an absorption band, chiral materials exhibit circular dichroism (CD), or a difference in the absorption of left- and right-circularly polarized light; epsilon L minus epsilon R does not equal zero. If the spectropolarimeter is set for the measurement of CD spectra, one observes what appears to be a UV-Vis spectrum except that some absorption bands are positive while others may be negative. Just as enantiomers have specific rotations that are equal and opposite at 589 nm (sodium D line), rotations are equal and opposite at all wavelengths, and CD measurements are equal and opposite at all wavelengths. Figure 1 shows the ORD curves for the enantiomeric carvones while Figure 2 contains the CD curves. The enantiomer of carvone that has the positive [alpha]D is obtained from caraway seeds and is known to have the S-configuration while the R-enantiomer is found in spearmint oil. Figure 1. ORD of S-(+)- and R-(-)-carvones Figure 2. CD of S-(+)- and R-(-)-carvones While little can be done to correlate stereochemistry with [alpha]D values, chiroptical spectroscopy (ORD and/or CD) often can be used to assign

  2. Apparent causality affects perceived simultaneity.

    PubMed

    Kohlrausch, Armin; van Eijk, Rob; Juola, James F; Brandt, Inge; van de Par, Steven

    2013-10-01

    The present research addresses the question of how visual predictive information and implied causality affect audio-visual synchrony perception. Previous research has shown a systematic shift in the likelihood of observers to accept audio-leading stimulus pairs as being apparently simultaneous in variants of audio-visual stimulus pairs that differ in (1) the amount of visual predictive information available and (2) the apparent causal relation between the auditory and visual components. An experiment was designed to separate the predictability and causality explanations, and the results indicated that shifts in subjective simultaneity were explained completely by changes in the implied causal relations in the stimuli and that predictability had no added value. Together with earlier findings, these results further indicate that the observed shifts in subjective simultaneity due to causal relations among auditory and visual events do not reflect a mere change in response strategy, but rather result from early multimodal integration processes in event perception.

  3. Nickel(II) complexes containing thiosemicarbazone and triphenylphosphine: Synthesis, spectroscopy, crystallography and catalytic activity

    NASA Astrophysics Data System (ADS)

    Priyarega, S.; Kalaivani, P.; Prabhakaran, R.; Hashimoto, T.; Endo, A.; Natarajan, K.

    2011-09-01

    Four new Ni(II) complexes of the general formula [Ni(PPh 3)(L)] (L = dibasic tridentate ligand derived from 4-diethylamino-salicylaldehyde and thiosemicarbazide or 4-N-substituted thiosemicarbazide) have been reported. The new complexes have been synthesized and characterized by analytical and spectroscopic (IR, electronic, 1H NMR and 31P NMR) techniques. Molecular structure of one of the complexes has been determined by X-ray crystallography. The complex, [Ni(PPh 3)(L4)] (H 2L4 = thiosemicarbazone prepared from 4-diethylamino-salicylaldehyde and 4-phenylthiosemicarbazide) crystallized in monoclinic space group with two molecules per unit cell and has the dimensions of a = 13.232(6) Å, b = 10.181(5) Å, c = 13.574(7) Å, α = 90°, β = 98.483(2)° and γ = 90°. Catalytic activity of the complexes has been explored for aryl-aryl coupling reaction.

  4. Erythrocytes in muscular dystrophy. Investigation with /sup 31/P nuclear magnetic resonance spectroscopy

    SciTech Connect

    Sarpel, G.; Lubansky, H.J.; Danon, M.J.; Omachi, A.

    1981-05-01

    Phosphorus 31 nuclear magnetic resonance (/sup 31/P NMR) signals were recorded from intact human erythrocytes for 16 hours. Total phosphate concentration, which was estimated as the sum of the individual /sup 31/P signals, was 25% lower in erythrocytes from men with myotonic dystrophy than in control erythrocytes. The inorganic-phosphate fraction contained the highest average phosphate concentration over the 16-hour period, and made the major contribution to the difference in total phosphate between the two groups. This result was not observed in erythrocytes from either women with myotonic dystrophy or patients with Duchenne's dystrophy and may be due to a change in cell membrane permeability to inorganic phosphate, which leads to lower steady-state concentrations of the intracellular phosphates.

  5. Erythrocytes in muscular dystrophy. Investigation with 31P nuclear magnetic resonance spectroscopy

    SciTech Connect

    Sarpel, G.; Lubansky, H.J.; Danon, M.J.; Omachi, A.

    1981-05-01

    Phosphorus 31 nuclear magnetic resonance (31P NMR) signals were recorded from intact human erythrocytes for 16 hours. Total phosphate concentration, which was estimated as the sum of the individual 31P signals, was 25% lower in erythrocytes from men with myotonic dystrophy than in control erythrocytes. The inorganic-phosphate fraction contained the highest average phosphate concentration over the 16-hour period, and made the major contribution to the difference in total phosphate between the two groups. This result was not observed in erythrocytes from either women with myotonic dystrophy or patients with Duchenne's dystrophy and may be due to a change in cell membrane permeability to inorganic phosphate, which lead to lower steady-state concentrations of the intracellular phosphates.

  6. Simultaneous RNA-DNA FISH.

    PubMed

    Lai, Lan-Tian; Meng, Zhenyu; Shao, Fangwei; Zhang, Li-Feng

    2016-01-01

    A highly useful tool for studying lncRNAs is simultaneous RNA-DNA FISH, which reveals the localization and quantitative information of RNA and DNA in cellular contexts. However, a simple combination of RNA FISH and DNA FISH often generates disappointing results because the fragile RNA signals are often damaged by the harsh conditions used in DNA FISH for denaturing the DNA. Here, we describe a robust and simple RNA-DNA FISH protocol, in which amino-labeled nucleic acid probes are used for RNA FISH. The method is suitable to detect single-RNA molecules simultaneously with DNA.

  7. Combining Simultaneous with Temporal Masking

    ERIC Educational Resources Information Center

    Hermens, Frouke; Herzog, Michael H.; Francis, Gregory

    2009-01-01

    Simultaneous and temporal masking are two frequently used techniques in psychology and vision science. Although there are many studies and theories related to each masking technique, there are no systematic investigations of their mutual relationship, even though both techniques are often applied together. Here, the authors show that temporal…

  8. Local simultaneity in general relativity

    SciTech Connect

    Olivert, J.

    1980-07-01

    In this paper the existence of simultaneous points, in the Landau sense, in the neighborhood of an observer P is studied. It is shown that the set of such points has the structure of a regular submanifold of the space--time manifold.

  9. Best Practices and Simultaneous Compliance

    EPA Science Inventory

    This wrap-up presentation to the workshop covers several topics concerning how lead and copper compliance under the Lead and Copper Rule should be integrated into an overall “simultaneous compliance” framework with other organizations. The LCR requires “optimization” of lead leve...

  10. Envisioning Curriculum as Six Simultaneities

    ERIC Educational Resources Information Center

    Hussain, Hanin; Conner, Lindsey; Mayo, Elaine

    2014-01-01

    This paper uses the discourse of complexity thinking to envision curriculum as six partial and coupled facets that exist simultaneously: curriculum as structure, curriculum as process, curriculum as content, curriculum as teaching, curriculum as learning and curriculum as activity. Such a curriculum is emergent and self-organising. It is emergent…

  11. Bimodal BCI using simultaneously NIRS and EEG.

    PubMed

    Tomita, Yohei; Vialatte, François-Benoît; Dreyfus, Gérard; Mitsukura, Yasue; Bakardjian, Hovagim; Cichocki, Andrzej

    2014-04-01

    Although noninvasive brain-computer interfaces (BCI) based on electroencephalographic (EEG) signals have been studied increasingly over the recent decades, their performance is still limited in two important aspects. First, the difficulty of performing a reliable detection of BCI commands increases when EEG epoch length decreases, which makes high information transfer rates difficult to achieve. Second, the BCI system often misclassifies the EEG signals as commands, although the subject is not performing any task. In order to circumvent these limitations, the hemodynamic fluctuations in the brain during stimulation with steady-state visual evoked potentials (SSVEP) were measured using near-infrared spectroscopy (NIRS) simultaneously with EEG. BCI commands were estimated based on responses to a flickering checkerboard (ON-period). Furthermore, an "idle" command was generated from the signal recorded by the NIRS system when the checkerboard was not flickering (OFF-period). The joint use of EEG and NIRS was shown to improve the SSVEP classification. For 13 subjects, the relative improvement in error rates obtained by using the NIRS signal, for nine classes including the "idle" mode, ranged from 85% to 53 %, when the epoch length increase from 3 to 12 s. These results were obtained from only one EEG and one NIRS channel. The proposed bimodal NIRS-EEG approach, including detection of the idle mode, may make current BCI systems faster and more reliable.

  12. Heterodyne laser spectroscopy system

    DOEpatents

    Wyeth, Richard W.; Paisner, Jeffrey A.; Story, Thomas

    1989-01-01

    A heterodyne laser spectroscopy system utilizes laser heterodyne techniques for purposes of laser isotope separation spectroscopy, vapor diagnostics, processing of precise laser frequency offsets from a reference frequency and the like, and provides spectral analysis of a laser beam.

  13. Heterodyne laser spectroscopy system

    DOEpatents

    Wyeth, Richard W.; Paisner, Jeffrey A.; Story, Thomas

    1990-01-01

    A heterodyne laser spectroscopy system utilizes laser heterodyne techniques for purposes of laser isotope separation spectroscopy, vapor diagnostics, processing of precise laser frequency offsets from a reference frequency, and provides spectral analysis of a laser beam.

  14. Electron-impact spectroscopy

    NASA Technical Reports Server (NTRS)

    Trajmar, S.

    1990-01-01

    The methods of electron impact spectroscopy and cross section measurements are discussed and compared to optical spectroscopy. A brief summary of the status of this field and the available data is given.

  15. Optical spectroscopy of novel materials

    NASA Astrophysics Data System (ADS)

    Reijnders, Anjan A.

    Optical Spectroscopy is a well-established experimental technique for the study of solids, gasses, and liquids. This thesis focuses on two broad topics related to optical spectroscopy; experimental instrumentation, and its application to novel materials. The first half of the thesis discusses the design and construction of a novel, multifunctional magneto-optical spectroscopy apparatus with exceptional repeatability. Included are the operating principles of FTIR reflectance and transmittance spectroscopy, and the optical ray-tracing design, physical design, and characterization of a custom built magneto-optical spectroscopy apparatus. The second half of the thesis discusses the experimental results of a comprehensive spectroscopic study of Topological Insulators and thermoelectric Pb0.77Sn0.23Se. Topological Insulators (TIs) are a recently discovered phase of matter in which highly conductive free carriers are found on the surface of small band-gap insulators. A challenge in TI research is the experimental isolation of conductive surface states from the bulk states, which are frequently plagued by residual conductivity due to impurities. In this work, optical spectroscopy is used to simultaneously probe the bulk and surface states to study their individual optical properties, in addition to their coupling. Using variable temperature, crystal orientation, and a broad frequency range, we identify compounds with the most resistive bulk states, and provide new insights into carrier dynamics, surface state conductance suppression as a function of temperature, and practical material optimization guidelines for application purposes. A comprehensive optical investigation of Pb0.77Sn0.23Se is also discussed. This is a promising thermoelectric, which exhibits a temperature dependent band inversion, associated with a topological phase transition. We find clear evidence for this band inversion, and find a bulk carrier lifetime dominated by electron-acoustic phonon scattering

  16. Frequency Comb Velocity Modulation Spectroscopy

    NASA Astrophysics Data System (ADS)

    Cossel, Kevin C.; Sinclair, Laura C.; Coffey, Tyler; Cornell, Eric; Ye, Jun

    2011-06-01

    We have developed a novel technique for rapid ion-sensitive spectroscopy over a broad spectral bandwidth by combining the high sensitivity of velocity modulation spectroscopy (VMS) with the parallel nature and high frequency accuracy of cavity-enhanced direct frequency comb spectroscopy. Prior to this research, no techniques have been capable of high sensitivity velocity modulation spectroscopy on every parallel detection channel over such a broad spectral range. We have demonstrated the power of this technique by measuring the A^2Π_u - X^2Σ_g^+ (4,2) band of N_2^+ at 830 nm with an absorption sensitivity of 1×10-6 for each of 1500 simultaneous measurement channels spanning 150 Cm-1. A densely sampled spectrum consisting of interleaved measurements to achieve 75 MHz spacing is acquired in under an hour. This technique is ideally suited for high resolution survey spectroscopy of molecular ions with applications including chemical physics, astrochemistry, and precision measurement. Currently, this system is being used to map the electronic transitions of HfF^+ for the JILA electron electric dipole moment (eEDM) experiment. The JILA eEDM experiment uses trapped molecular ions to significantly increase the coherence time of the measurement in addition to utilizing the strong electric field enhancement available from molecules. Previous theoretical work has shown that the metastable ^3Δ_1 state in HfF^+ and ThF^+ provides high sensitivity to the eEDM and good cancellation of systematic effects; however, the electronic level structure of these species have not previously been measured, and the theoretical uncertainties are hundreds to thousands of wavenumbers. This necessitates broad-bandwidth, high-resolution survey spectroscopy provided by frequency comb VMS in the 700-900 nm spectral window. F. Adler, M. J. Thorpe, K. C. Cossel, and J. Ye. Annu. Rev. Anal. Chem. 3, 175-205 (2010) A. E. Leanhardt, et. al. arXiv:1008.2997v2 E. Meyer, J. L. Bohn, and M. P. Deskevich

  17. Terahertz Spectroscopy of Biochars and Related Aromatic Compounds

    NASA Astrophysics Data System (ADS)

    Lepodise, L. M.; Horvat, J.; Lewis, R. A.

    2016-07-01

    A recent application of terahertz spectroscopy is to biochar, the agricultural charcoal produced by pyrolysis of various organic materials. Biochars simultaneously improve soil fertility and assist in carbon sequestration. Terahertz spectroscopy allows different biochars to be distinguished. However, the origin of the absorption features observed has not been clear. Given that biochar-based fertilizers are rich in aromatic compounds, we have investigated simple aromatic compounds as an approach to unravelling the complex biochar spectrum.

  18. Simultaneous time and frequency resolved fluorescence microscopy of single molecules.

    SciTech Connect

    Hayden, Carl C.; Gradinaru, Claudiu C.; Chandler, David W.; Luong, A. Khai

    2005-01-01

    Single molecule fluorophores were studied for the first time with a new confocal fluorescence microscope that allows the wavelength and emission time to be simultaneously measured with single molecule sensitivity. In this apparatus, the photons collected from the sample are imaged through a dispersive optical system onto a time and position sensitive detector. This detector records the wavelength and emission time of each detected photon relative to an excitation laser pulse. A histogram of many events for any selected spatial region or time interval can generate a full fluorescence spectrum and correlated decay plot for the given selection. At the single molecule level, this approach makes entirely new types of temporal and spectral correlation spectroscopy of possible. This report presents the results of simultaneous time- and frequency-resolved fluorescence measurements of single rhodamine 6G (R6G), tetramethylrhodamine (TMR), and Cy3 embedded in thin films of polymethylmethacrylate (PMMA).

  19. SIMULTANEOUS MEASUREMENT OF CIRCULAR DICHROISM AND FLUORESCENCE POLARIZATION ANISOTROPY.

    SciTech Connect

    SUTHERLAND,J.C.

    2002-01-19

    Circular dichroism and fluorescence polarization anisotropy are important tools for characterizing biomolecular systems. Both are used extensively in kinetic experiments involving stopped- or continuous flow systems as well as titrations and steady-state spectroscopy. This paper presents the theory for determining circular dichroism and fluorescence polarization anisotropy simultaneously, thus insuring the two parameters are recorded under exactly the same conditions and at exactly the same time in kinetic experiments. The approach to measuring circular dichroism is that used in almost all conventional dichrographs. Two arrangements for measuring fluorescence polarization anisotropy are described. One uses a single fluorescence detector and signal processing with a lock-in amplifier that is similar to the measurement of circular dichroism. The second approach uses classic ''T'' format detection optics, and thus can be used with conventional photon-counting detection electronics. Simple extensions permit the simultaneous measurement of the absorption and excitation intensity corrected fluorescence intensity.

  20. Positional isotope exchange studies on enzyme using NMR spectroscopy

    SciTech Connect

    Matsunaga, T.O.

    1987-01-01

    The isotopically enriched compounds, /sup 18/O-..beta..,..gamma..-ATP and /sup 18/O bridge-labeled pyrophosphate, synthesized previously in this laboratory, were used to investigate and measure the exchange vs. turnover of substrates and products from their central complexes in four selected enzyme systems. Using hi-field /sup 31/P NMR, we were able to differentiate between /sup 18/O labeled in the bridge vs. the non-bridge positions by virtue of the isotope shift upon the phosphorus nuclei. The bridge to non-bridge scrambling of the label was quantitated and the exchange vs. turnover ratios under a variety of conditions was determined. Using the substrate inhibitor carboxycreatinine, PIX experiments with /sup 18/O-..beta..,..gamma..-ATP and creatine kinase were conducted. It was shown that carboxycreatinine and creatine kinase promoted exchange of the /sup 18/O label as determined by NMR. We have concluded that carboxycreatinine is either a substrate that catalyzes very slow turnover or it catalyzes exchange by a dissociative (SN/sub 1//sub P/) type of mechanism

  1. Coherent frequency combs and spectroscopy

    NASA Astrophysics Data System (ADS)

    Ye, Jun

    2010-03-01

    Optical frequency combs maintain precise phase coherence across the entire visible spectrum and they have profoundly changed optical frequency metrology and ultrafast science, with breakthrough developments in optical atomic clocks, optical frequency synthesis, direct frequency comb spectroscopy (DFCS), high-resolution quantum control, coherent pulse synthesis and amplification, and control of sub-femtosecond electron dynamics in atoms and molecules. DFCS [1] is a new spectroscopic approach that realizes simultaneously broad spectral coverage, high spectral resolution, many parallel detection channels, ultrahigh sensitivity, and real-time analysis [2]. These powerful capabilities have been demonstrated in a series of experiments where identification and quantification of many different molecular states or species are achieved in a massively parallel fashion [3].[4pt] [1] A. Marian et al., Science 306, 2063 (2004). [0pt] [2] M. J. Thorpe et al., Science 311, 1595 (2006). [0pt] [3] M. J. Thorpe & J. Ye, Appl. Phys. B 91, 397 (2008).

  2. Coherent frequency combs and spectroscopy

    NASA Astrophysics Data System (ADS)

    Ye, Jun

    2010-03-01

    Optical frequency combs possessing precise phase coherence across the entire visible spectrum have profoundly changed optical frequency metrology and ultrafast science, with breakthrough developments in optical atomic clocks, optical frequency synthesis, direct frequency comb spectroscopy (DFCS), high-resolution quantum control, coherent pulse synthesis and amplification, and control of sub-femtosecond electron dynamics in atoms and molecules. DFCS [1] is a new spectroscopic approach that embraces simultaneously broad spectral coverage, fine spectral resolution, numerous detection channels, ultrahigh sensitivity, and real-time analysis [2]. These powerful capabilities have been demonstrated in a series of experiments where identification and quantification of many different molecular states or species are achieved in a massively parallel fashion [3]. A range of interesting scientific applications will be discussed. [4pt] [1] A. Marian et al., Science 306, 2063 (2004). [0pt] [2] M. J. Thorpe et al., Science 311, 1595 (2006). [0pt] [3] M. J. Thorpe & J. Ye, Appl. Phys. B 91, 397 (2008).

  3. Sub-Equimolar Hydrolysis and Condensation of Organophosphates

    DOE PAGES

    Alam, Todd M.; Kinnan, Mark K.; Wilson, Brendan W.; Wheeler, David R.

    2016-07-16

    We characterized the in-situ hydrolysis and subsequent condensation reaction of the chemical agent simulant diethyl chlorophosphate (DECP) by high-resolution 31P NMR spectroscopy following the addition of water in sub-equimolar concentrations. Moreover, the identification and quantification of the multiple pyrophosphate and larger polyphosphate chemical species formed through a series of self-condensation reactions are reported. Finally, the DECP hydrolysis kinetics and distribution of breakdown species was strongly influenced by the water concentration and reaction temperature.

  4. Influence of natural organic matter on the bioavailability and preservation of organic phosphorus in lake sediments

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Organic P (Po) was sequentially extracted by H2O and NaOH-EDTA in the sediments from algae- and macrophyte-dominated regions of Lake Taihu, China and then analyzed by enzymatic hydrolysis and solution 31P-NMR spectroscopy. The amount of H2O-Po was 0.8-2.0 mg kg-1, 45.5% to 89.4% of which could be hy...

  5. Simultaneous multislice (SMS) imaging techniques

    PubMed Central

    Barth, Markus; Breuer, Felix; Koopmans, Peter J.; Poser, Benedikt A.

    2015-01-01

    Simultaneous multislice imaging (SMS) using parallel image reconstruction has rapidly advanced to become a major imaging technique. The primary benefit is an acceleration in data acquisition that is equal to the number of simultaneously excited slices. Unlike in‐plane parallel imaging this can have only a marginal intrinsic signal‐to‐noise ratio penalty, and the full acceleration is attainable at fixed echo time, as is required for many echo planar imaging applications. Furthermore, for some implementations SMS techniques can reduce radiofrequency (RF) power deposition. In this review the current state of the art of SMS imaging is presented. In the Introduction, a historical overview is given of the history of SMS excitation in MRI. The following section on RF pulses gives both the theoretical background and practical application. The section on encoding and reconstruction shows how the collapsed multislice images can be disentangled by means of the transmitter pulse phase, gradient pulses, and most importantly using multichannel receiver coils. The relationship between classic parallel imaging techniques and SMS reconstruction methods is explored. The subsequent section describes the practical implementation, including the acquisition of reference data, and slice cross‐talk. Published applications of SMS imaging are then reviewed, and the article concludes with an outlook and perspective of SMS imaging. Magn Reson Med 75:63–81, 2016. © 2015 The Authors. Magnetic Resonance in Medicine Published by Wiley Periodicals, Inc. on behalf of International Society of Medicine in Resonance. PMID:26308571

  6. Simultaneous multislice (SMS) imaging techniques.

    PubMed

    Barth, Markus; Breuer, Felix; Koopmans, Peter J; Norris, David G; Poser, Benedikt A

    2016-01-01

    Simultaneous multislice imaging (SMS) using parallel image reconstruction has rapidly advanced to become a major imaging technique. The primary benefit is an acceleration in data acquisition that is equal to the number of simultaneously excited slices. Unlike in-plane parallel imaging this can have only a marginal intrinsic signal-to-noise ratio penalty, and the full acceleration is attainable at fixed echo time, as is required for many echo planar imaging applications. Furthermore, for some implementations SMS techniques can reduce radiofrequency (RF) power deposition. In this review the current state of the art of SMS imaging is presented. In the Introduction, a historical overview is given of the history of SMS excitation in MRI. The following section on RF pulses gives both the theoretical background and practical application. The section on encoding and reconstruction shows how the collapsed multislice images can be disentangled by means of the transmitter pulse phase, gradient pulses, and most importantly using multichannel receiver coils. The relationship between classic parallel imaging techniques and SMS reconstruction methods is explored. The subsequent section describes the practical implementation, including the acquisition of reference data, and slice cross-talk. Published applications of SMS imaging are then reviewed, and the article concludes with an outlook and perspective of SMS imaging.

  7. Cerebral lateralization in simultaneous interpretation.

    PubMed

    Fabbro, F; Gran, L; Basso, G; Bava, A

    1990-07-01

    Cerebral asymmetries for L1 (Italian), L2 (English), and L3 (French, German, Spanish, or Russian) were studied, by using a verbal-manual interference paradigm, in a group of Italian right-handed polyglot female students at the Scuola Superiore di Lingue Moderne per Interpreti e Traduttori (SSLM-School for Interpreters and Translators) of the University of Trieste and in a control group of right-handed monolingual female students at the Medical School of the University of Trieste. In an automatic speech production task no significant cerebral lateralization was found for the mother tongue (L1) either in the interpreting students or in the control group; the interpreting students were not significantly lateralized for the third language (L3), while weak left hemispheric lateralization was shown for L2. A significantly higher degree of verbal-manual interference was found for L1 than for L2 and L3. A significantly higher disruption rate occurred in the meaning-based mode of simultaneous interpretation (from L2 into L1 and vice versa) than in the word-for-word mode (from L2 into L1 and vice versa). No significant overall or hemispheric differences were found during simultaneous interpretation from L1 into L2 or from L2 into L1. PMID:2207622

  8. Simultaneous ion sputter polishing and deposition

    NASA Technical Reports Server (NTRS)

    Rutledge, S.; Banks, B.; Brdar, M.

    1981-01-01

    Results of experiments to study ion beam sputter polishing in conjunction with simultaneous deposition as a mean of polishing copper surfaces are presented. Two types of simultaneous ion sputter polishing and deposition were used in these experiments. The first type utilized sputter polishing simultaneous with vapor deposition, and the second type utilized sputter polishing simultaneous with sputter deposition. The etch and deposition rates of both techniques were studied, as well as the surface morphology and surface roughness.

  9. Single atom identification by energy dispersive x-ray spectroscopy

    SciTech Connect

    Lovejoy, T. C.; Dellby, N.; Krivanek, O. L.; Ramasse, Q. M.; Falke, M.; Kaeppel, A.; Terborg, R.; Zan, R.

    2012-04-09

    Using aberration-corrected scanning transmission electron microscope and energy dispersive x-ray spectroscopy, single, isolated impurity atoms of silicon and platinum in monolayer and multilayer graphene are identified. Simultaneously acquired electron energy loss spectra confirm the elemental identification. Contamination difficulties are overcome by employing near-UHV sample conditions. Signal intensities agree within a factor of two with standardless estimates.

  10. Synthesis of triazole-linked morpholino oligonucleotides via CuI catalysed cycloaddition† †Electronic supplementary information (ESI) available: Full experimental details and copies of 1H, 13C, 31P NMR spectra for all compounds. See DOI: 10.1039/c6ob00007j Click here for additional data file.

    PubMed Central

    Palframan, Matthew J.; Alharthy, Rima D.; Powalowska, Paulina K.

    2016-01-01

    Triazole-linked morpholino (TLMO) oligonucleic acids were synthesised using the CuI catalysed (3 + 2) azide–alkyne cycloaddition (CuAAC) reaction. The modified DNA analogues were incorporated into 13-mer sequences via solid phase synthesis. UV melting experiments showed that the TLMO modification gives higher T m values than the corresponding TLDNA modification. PMID:26905296

  11. Differential Optical Dispersion Spectroscopy for Comparative Molecular Quantification

    NASA Astrophysics Data System (ADS)

    Nikodem, Michal; Brumfield, Brian; Wysocki, Gerard

    2013-06-01

    A new spectroscopic technique that is based on molecular dispersion spectroscopy and enables new capabilities in chemical detection as compared to well-established laser absorption spectroscopy will be discussed in this paper. Differential optical dispersion spectroscopy (DODiS) enables simultaneous measurement and comparison of two gas samples. This is performed through simultaneous detection of molecular absorption that is additive and molecular dispersion that provides differential information about the samples. Therefore DODiS performs true optical addition/subtraction of absorption/dispersion spectra, which is a unique property not available with any conventional absorption-based techniques. The DODiS measurement principle and proof-of-concept experiments involving comparative measurements with a well-known reference gas mixture utilized as a real-time system calibration, as well as mitigation of unwanted spectral interference from other molecules achieved through DODiS optical subtraction will be presented. G. Wysocki and D. Weidmann, Opt. Express 18, 26123 (2010).

  12. BATSE spectroscopy analysis system

    NASA Technical Reports Server (NTRS)

    Schaefer, Bradley E.; Bansal, Sandhia; Basu, Anju; Brisco, Phil; Cline, Thomas L.; Friend, Elliott; Laubenthal, Nancy; Panduranga, E. S.; Parkar, Nuru; Rust, Brad

    1992-01-01

    The Burst and Transient Source Experiment (BATSE) Spectroscopy Analysis System (BSAS) is the software system which is the primary tool for the analysis of spectral data from BATSE. As such, Guest Investigators and the community as a whole need to know its basic properties and characteristics. Described here are the characteristics of the BATSE spectroscopy detectors and the BSAS.

  13. Metallomic EPR spectroscopy.

    PubMed

    Hagen, Wilfred R

    2009-09-01

    Based on explicit definitions of biomolecular EPR spectroscopy and of the metallome, this tutorial review positions EPR in the field of metallomics as a unique method to study native, integrated systems of metallobiomolecular coordination complexes subject to external stimuli. The specific techniques of whole-system bioEPR spectroscopy are described and their historic, recent, and anticipated applications are discussed.

  14. Europium (III) coordination complex with a novel phosphonated ligand

    NASA Astrophysics Data System (ADS)

    Villemin, E.; Elias, B.; Marchand-Brynaert, J.

    2013-02-01

    An original Eu(III) complex with a phosphonated half-cage ligand (CCNPh) was synthesized and characterized. Coordination between Eu(III) and the selected ligand was investigated by FT-IR, 1H, 13C and 31P NMR spectroscopies. The stoichiometry of the Eu(III) complex in acetonitrile was determined by titrations using 1H, 31P NMR and photoluminescence. The 1M:2L stoichiometry, i.e. two CCNPh ligands for one Eu(III), has been measured. In contrast, the 1M:3L stoichiometry occurred in the solid state, from the elemental analysis. This particular behavior may be explained by the addition of a third CCNPh ligand to Eu(III) metallic core during the treatment and evaporation process for the obtention of the solid sample. An antenna effect has been observed consisting in the energy transfer from N-Ph (λexc = 276 nm) to Eu(III) (λem = 618 nm).

  15. Fiber Optic Switch For Broadband Emission Spectroscopy

    NASA Technical Reports Server (NTRS)

    De Groot, Wim; Myers, Roger; Zube, Dieter

    1994-01-01

    Many high-temperature processes comprise large-scale phenomena. Studying spatial and temporal correlations of physical processes between several locations within characteristic scales provides desired information on macroscopic physical processes. Achieved with emission spectroscopy by use of multiple optical fibers. Simultaneous coupling of light from these fibers into single available spectrometer and/or monochromator not accomplished without added expense of two-dimensional array and increased complexity of calibration. Quasi-simultaneous coupling, while maintaining optimum alignment and maximum throughput of broadband emission, achieved by use of fiber optic multiscanner. Instrument used successfully in study of frozen-flow losses internal to flow of plasma inside nozzle of arc jet. Instrument includes two hollow disks of different sizes and stepping motor.

  16. Advanced Flicker Spectroscopy of Fluid Membranes

    NASA Astrophysics Data System (ADS)

    Döbereiner, Hans-Günther; Gompper, Gerhard; Haluska, Christopher; Kroll, Daniel; Petrov, Peter; Riske, Karin

    2003-07-01

    The bending elasticity of a fluid membrane is characterized by its modulus and spontaneous curvature. We present a new method, advanced flicker spectroscopy of giant nonspherical vesicles, which makes it possible to simultaneously measure both parameters for the first time. Our analysis is based on the generation of a large set of reference data from Monte Carlo simulations of randomly triangulated surfaces. As an example of the potential of the procedure, we monitor thermal trajectories of vesicle shapes and discuss the elastic response of zwitterionic membranes to transmembrane pH gradients. Our technique makes it possible to easily characterize membrane curvature as a function of environmental conditions.

  17. [Simultaneous bilateral pneumothorax. Case report].

    PubMed

    Paolini, A; Caminiti, F; Tosato, F; Ruggieri, M; Paolini, G; Carnevale, L; Corsini, F; Marano, S; Monsellato, I

    2001-04-01

    A case report of a 44 year-old white man admitted to the surgical unit for a bilateral simultaneous pneumothorax is presented. The pneumothorax occurred on day one after a surgical operation for discal hernia; in the past the patient already presented a right spontaneous pneumothorax at 32 years of age and a left pneumothorax at 37 years of age, both treated with a pleural drainage. A thoracic drain was bilaterally positioned with a good result only in the right side. The persistence of the left pneumothorax induced the authors to perform a postero-lateral thoracotomy bullae excision and pleurectomy with a good postoperative course. After a few months a new right pneumothorax occurred and the patient was treated with a right postero-lateral thoracotomy, bullae resection and pleurectomy. On the basis of the case reported, the authors consider the different opportunities in the treatment of spontaneous pneumothorax in relation to the present knowledges and technologies. Surgical procedure is to be preferred in case of persistence of pneumothorax despite a pleural drain and in case of pneumothorax in high risk subjects. Even if thoracoscopy seems to give better results regarding postoperative pain, it is not always possible with such a method to perform a careful pleurectomy neither to obtain it in all cases (above all in secondary pneumothorax). Every case must then be carefully studied to choose the best treatment at present available. PMID:11353349

  18. Heteronuclear probes of coal structure and reactivity. Quarterly report, January--March 1994

    SciTech Connect

    Verkade, J.G.; Hall, G.

    1994-04-30

    One of the goals of the proposal is to employ solution {sup 31}P NMR spectroscopy in tandem with HPLC to speciate and quantitate phenols in coal resids. As solution {sup 31}P NMR tagging agents, we are using both 1 and 2 since the {sup 31}P chemical shifts provided by each are different for identical phenols. This allows a cross-check on the indentity of phenols (especially isomeric examples) as well as their concentration. By building a library of {sup 31}P chemical shifts of a wide variety of phenols derivatized with 1 and 2, speciation of phenols in coal liquids, for example, can be accomplished. Using preparative HPLC, we can separate the phenols and also derivatize them with 1 and 2 for speciation. Tables III and IV list chemical shifts for phenols derivatized with 1 and 2, respectively. In Table V we hst the total phenol contents of three Consol coal reaids using reagent 1 and a {sup 31}P NMR procedure we reported earlier. We are gratified to note how well our quantitations compare with those reported in the literature using FTER spectroscopy. Because sample 3 contained paramagnetic species, speciation of phenols was precluded, owing to peak breadth and overlap. However, samples 1 and 2 produced well-resolved signals. We are now in the process of identifying the phenols responsible for these peaks.

  19. VSWIR Microimaging Spectroscopy for Geologic History and Identifying and Quantifying Mineral, Ice, and Organic Abundances on Planetary Surfaces

    NASA Astrophysics Data System (ADS)

    Ehlmann, B. L.; Blaney, D. L.; Green, R. O.; Mouroulis, P.

    2016-10-01

    VSWIR microimaging spectroscopy is a key tool for landed planetary missions, acquiring simultaneous composition and texture. It has been matured to TRL 6 as UCIS and is presently being used for meteorite and terrestrial earth science studies.

  20. Ultrasensitive Laser Spectroscopy.

    ERIC Educational Resources Information Center

    Kliger, David S.

    1985-01-01

    Examines techniques used to make ultrasensitive spectroscopic measurements. They include excitation, thermal lens, photo acoustic, and ionization spectroscopies. Guidelines and methods are provided for each technique; common uses and applications are explained. (DH)

  1. Spectroscopy of divertor plasmas

    SciTech Connect

    Isler, R.C.

    1995-12-31

    The requirements for divertor spectroscopy are treated with respect to instrumentation and observations on present machines. Emphasis is placed on quantitative measurements.of impurity concentrations from the interpretation of spectral line intensities. The possible influence of non-Maxwellian electron distributions on spectral line excitation in the divertor is discussed. Finally the use of spectroscopy for determining plasma temperature, density, and flows is examined.

  2. Spectroscopy of D Mesons

    SciTech Connect

    Bianco, Stefano

    2006-02-11

    The scenario of heavy quark meson spectroscopy underwent recently a major revolution, after the observation of BABAR and CLEO, confirmed by BELLE, of DsJ L=1 excited states, and by further evidences by SELEX. These experimental results have cast doubts on the incarnations of the ideas of Heavy Quark Effective Theory in heavy quark spectroscopy. I shall review the status of experimental data, discuss implications and sketch an outlook.

  3. Auger resonant Raman spectroscopy

    SciTech Connect

    Azuma, Y.; LeBrun, T.; MacDonald, M.; Southworth, S.H.

    1995-08-01

    As noted above, traditional spectroscopy of the electronic structure of the inner shells of atoms, molecules, and solids is limited by the lifetime broadening of the core-excited states. This limitation can also be avoided with the non-radiative analog of X-ray Raman scattering - resonant Auger Raman spectroscopy. We have used this technique to study the K-shell excitation spectrum of argon as the photon energy is continuously scanned across threshold.

  4. Electronic Spectroscopy & Dynamics

    SciTech Connect

    Mark Maroncelli, Nancy Ryan Gray

    2010-06-08

    The Gordon Research Conference (GRC) on Electronic Spectroscopy and Dynamics was held at Colby College, Waterville, NH from 07/19/2009 thru 07/24/2009. The Conference was well-attended with participants (attendees list attached). The attendees represented the spectrum of endeavor in this field coming from academia, industry, and government laboratories, both U.S. and foreign scientists, senior researchers, young investigators, and students. The GRC on Electronic Spectroscopy & Dynamics showcases some of the most recent experimental and theoretical developments in electronic spectroscopy that probes the structure and dynamics of isolated molecules, molecules embedded in clusters and condensed phases, and bulk materials. Electronic spectroscopy is an important tool in many fields of research, and this GRC brings together experts having diverse backgrounds in physics, chemistry, biophysics, and materials science, making the meeting an excellent opportunity for the interdisciplinary exchange of ideas and techniques. Topics covered in this GRC include high-resolution spectroscopy, biological molecules in the gas phase, electronic structure theory for excited states, multi-chromophore and single-molecule spectroscopies, and excited state dynamics in chemical and biological systems.

  5. 5 CFR 1651.11 - Simultaneous death.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 5 Administrative Personnel 3 2014-01-01 2014-01-01 false Simultaneous death. 1651.11 Section 1651.11 Administrative Personnel FEDERAL RETIREMENT THRIFT INVESTMENT BOARD DEATH BENEFITS § 1651.11 Simultaneous death. If a beneficiary dies at the same time as the participant, the beneficiary will be...

  6. 5 CFR 1651.11 - Simultaneous death.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 5 Administrative Personnel 3 2010-01-01 2010-01-01 false Simultaneous death. 1651.11 Section 1651.11 Administrative Personnel FEDERAL RETIREMENT THRIFT INVESTMENT BOARD DEATH BENEFITS § 1651.11 Simultaneous death. If a beneficiary dies at the same time as the participant, the beneficiary will be...

  7. 5 CFR 1651.11 - Simultaneous death.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 5 Administrative Personnel 3 2011-01-01 2011-01-01 false Simultaneous death. 1651.11 Section 1651.11 Administrative Personnel FEDERAL RETIREMENT THRIFT INVESTMENT BOARD DEATH BENEFITS § 1651.11 Simultaneous death. If a beneficiary dies at the same time as the participant, the beneficiary will be...

  8. 5 CFR 1651.11 - Simultaneous death.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 5 Administrative Personnel 3 2012-01-01 2012-01-01 false Simultaneous death. 1651.11 Section 1651.11 Administrative Personnel FEDERAL RETIREMENT THRIFT INVESTMENT BOARD DEATH BENEFITS § 1651.11 Simultaneous death. If a beneficiary dies at the same time as the participant, the beneficiary will be...

  9. 5 CFR 1651.11 - Simultaneous death.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 5 Administrative Personnel 3 2013-01-01 2013-01-01 false Simultaneous death. 1651.11 Section 1651.11 Administrative Personnel FEDERAL RETIREMENT THRIFT INVESTMENT BOARD DEATH BENEFITS § 1651.11 Simultaneous death. If a beneficiary dies at the same time as the participant, the beneficiary will be...

  10. Simultaneous and spontaneous bilateral quadriceps tendons rupture.

    PubMed

    Celik, Evrim Coşkun; Ozbaydar, Mehmet; Ofluoglu, Demet; Demircay, Emre

    2012-07-01

    Simultaneous and spontaneous bilateral quadriceps tendon rupture is an uncommon injury that is usually seen in association with multiple medical conditions and some medications. We report a case of simultaneous and spontaneous bilateral quadriceps tendon rupture that may be related to the long-term use of a statin.

  11. 5 CFR 532.413 - Simultaneous action.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 5 Administrative Personnel 1 2014-01-01 2014-01-01 false Simultaneous action. 532.413 Section 532.413 Administrative Personnel OFFICE OF PERSONNEL MANAGEMENT CIVIL SERVICE REGULATIONS PREVAILING RATE SYSTEMS Pay Administration § 532.413 Simultaneous action. (a) If an employee becomes entitled to more...

  12. 5 CFR 532.413 - Simultaneous action.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 5 Administrative Personnel 1 2012-01-01 2012-01-01 false Simultaneous action. 532.413 Section 532.413 Administrative Personnel OFFICE OF PERSONNEL MANAGEMENT CIVIL SERVICE REGULATIONS PREVAILING RATE SYSTEMS Pay Administration § 532.413 Simultaneous action. (a) If an employee becomes entitled to more...

  13. 5 CFR 532.413 - Simultaneous action.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 5 Administrative Personnel 1 2011-01-01 2011-01-01 false Simultaneous action. 532.413 Section 532.413 Administrative Personnel OFFICE OF PERSONNEL MANAGEMENT CIVIL SERVICE REGULATIONS PREVAILING RATE SYSTEMS Pay Administration § 532.413 Simultaneous action. (a) If an employee becomes entitled to more...

  14. 5 CFR 532.413 - Simultaneous action.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 5 Administrative Personnel 1 2010-01-01 2010-01-01 false Simultaneous action. 532.413 Section 532.413 Administrative Personnel OFFICE OF PERSONNEL MANAGEMENT CIVIL SERVICE REGULATIONS PREVAILING RATE SYSTEMS Pay Administration § 532.413 Simultaneous action. (a) If an employee becomes entitled to more...

  15. 5 CFR 532.413 - Simultaneous action.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 5 Administrative Personnel 1 2013-01-01 2013-01-01 false Simultaneous action. 532.413 Section 532.413 Administrative Personnel OFFICE OF PERSONNEL MANAGEMENT CIVIL SERVICE REGULATIONS PREVAILING RATE SYSTEMS Pay Administration § 532.413 Simultaneous action. (a) If an employee becomes entitled to more...

  16. Simultaneous double interphalangeal dislocation in one finger.

    PubMed

    Takami, H; Takahashi, S; Ando, M

    2000-01-01

    Isolated dislocation of the proximal or distal interphalangeal joint of a finger is common, but simultaneous dislocation of both joints is rare. Three cases of simultaneous dislocations of both interphalangeal joints in the same finger are reported. Closed reduction was easily achieved in all cases.

  17. Crystallinity and compositional changes in carbonated apatites: Evidence from {sup 31}P solid-state NMR, Raman, and AFM analysis

    SciTech Connect

    McElderry, John-David P.; Zhu, Peizhi; Mroue, Kamal H.; Xu, Jiadi; Pavan, Barbara; Fang, Ming; Zhao, Guisheng; McNerny, Erin; Kohn, David H.; Franceschi, Renny T.; Holl, Mark M.Banaszak; Tecklenburg, Mary M.J.; Ramamoorthy, Ayyalusamy; Morris, Michael D.

    2013-10-15

    Solid-state (magic-angle spinning) NMR spectroscopy is a useful tool for obtaining structural information on bone organic and mineral components and synthetic model minerals at the atomic-level. Raman and {sup 31}P NMR spectral parameters were investigated in a series of synthetic B-type carbonated apatites (CAps). Inverse {sup 31}P NMR linewidth and inverse Raman PO{sub 4}{sup 3−}ν{sub 1} bandwidth were both correlated with powder XRD c-axis crystallinity over the 0.3–10.3 wt% CO{sub 3}{sup 2−} range investigated. Comparison with bone powder crystallinities showed agreement with values predicted by NMR and Raman calibration curves. Carbonate content was divided into two domains by the {sup 31}P NMR chemical shift frequency and the Raman phosphate ν{sub 1} band position. These parameters remain stable except for an abrupt transition at 6.5 wt% carbonate, a composition which corresponds to an average of one carbonate per unit cell. This near-binary distribution of spectroscopic properties was also found in AFM-measured particle sizes and Ca/P molar ratios by elemental analysis. We propose that this transition differentiates between two charge-balancing ion-loss mechanisms as measured by Ca/P ratios. These results define a criterion for spectroscopic characterization of B-type carbonate substitution in apatitic minerals. - Graphical abstract: Carbonated apatite shows an abrupt change in spectral (NMR, Raman) and morphological (AFM) properties at a composition of about one carbonate substitution per unit cell. Display Omitted - Highlights: • Crystallinity (XRD), particle size (AFM) of carbonated apatites and bone mineral. • Linear relationships among crystallinity, {sup 31}P NMR and Raman inverse bandwidths. • Low and high carbonated apatites use different charge-balancing ion-loss mechanism.

  18. Combined fiber probe for fluorescence lifetime and Raman spectroscopy

    PubMed Central

    Dochow, Sebastian; Ma, Dinglong; Latka, Ines; Bocklitz, Thomas; Hartl, Brad; Bec, Julien; Fatakdawala, Hussain; Marple, Eric; Urmey, Kirk; Wachsmann-Hogiu, Sebastian; Schmitt, Michael; Marcu, Laura; Popp, Jürgen

    2016-01-01

    In this contribution we present a dual modality fiber optic probe combining fluorescence lifetime imaging (FLIm) and Raman spectroscopy for in vivo endoscopic applications. The presented multi-spectroscopy probe enables efficient excitation and collection of fluorescence lifetime signals for FLIm in the UV/visible wavelength region, as well as of Raman spectra in the near-IR for simultaneous Raman/FLIm imaging. The probe was characterized in terms of its lateral resolution and distance dependency of the Raman and FLIm signals. In addition, the feasibility of the probe for in vivo FLIm and Raman spectral characterization of tissue was demonstrated. PMID:26093843

  19. Identification and characterization of a novel high affinity metal-binding site in the hammerhead ribozyme.

    PubMed Central

    Hansen, M R; Simorre, J P; Hanson, P; Mokler, V; Bellon, L; Beigelman, L; Pardi, A

    1999-01-01

    A novel metal-binding site has been identified in the hammerhead ribozyme by 31P NMR. The metal-binding site is associated with the A13 phosphate in the catalytic core of the hammerhead ribozyme and is distinct from any previously identified metal-binding sites. 31P NMR spectroscopy was used to measure the metal-binding affinity for this site and leads to an apparent dissociation constant of 250-570 microM at 25 degrees C for binding of a single Mg2+ ion. The NMR data also show evidence of a structural change at this site upon metal binding and these results are compared with previous data on metal-induced structural changes in the core of the hammerhead ribozyme. These NMR data were combined with the X-ray structure of the hammerhead ribozyme (Pley HW, Flaherty KM, McKay DB. 1994. Nature 372:68-74) to model RNA ligands involved in binding the metal at this A13 site. In this model, the A13 metal-binding site is structurally similar to the previously identified A(g) metal-binding site and illustrates the symmetrical nature of the tandem G x A base pairs in domain 2 of the hammerhead ribozyme. These results demonstrate that 31P NMR represents an important method for both identification and characterization of metal-binding sites in nucleic acids. PMID:10445883

  20. The effect of binding of spider-derived antimicrobial peptides, oxyopinins, on lipid membranes.

    PubMed

    Nomura, Kaoru; Corzo, Gerardo

    2006-09-01

    Oxyopinins (Oxki1 and Oxki2) are antimicrobial peptides isolated from the crude venom of the wolf spider Oxyopes kitabensis. The effect of oxyopinins on lipid bilayers was investigated using high-sensitivity titration calorimetry and (31)P solid-state NMR spectroscopy. High-sensitivity titration calorimetry experiments showed that the binding of oxyopinins was exothermic, and the binding enthalpies (DeltaH) to 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphatidylcholine (POPC) small unilamellar vesicles (SUVs) were -18.1 kcal/mol and -15.0 kcal/mol for Oxki1 and Oxki2, respectively, and peptide partition coefficient (K(p)) was found to be 3.9x10(3) M(-1). (31)P NMR spectra of 1,2-dielaidoyl-sn-glycero-3-phosphoethanolamine (DEPE) membranes in the presence of oxyopinins indicated that they induced a positive curvature in lipid bilayers. The induced positive curvature was stronger in the presence of Oxki2 than in the presence of Oxki1. (31)P NMR spectra of phosphaditylcholine (PC) membranes in the presence of Oxki2 showed that Oxki2 produced micellization of membranes at low peptide concentrations, but unsaturated PC membranes or acidic phospholipids prevented micellization from occurring. Furthermore, (31)P NMR spectra using membrane lipids from E. coli suggested that Oxki1 was more disruptive to bacterial membranes than Oxki2. These results strongly correlate to the known biological activity of the oxyopinins.

  1. Contributions of nuclear magnetic resonance to renal biochemistry

    SciTech Connect

    Ross, B.; Freeman, D.; Chan, L.

    1986-01-01

    /sup 31/P NMR as a descriptive technique is of interest to nephrologists. Particular contributions of /sup 31/P NMR to our understanding of renal function may be enumerated.: Free metabolite levels are different from those classically accepted; in particular, ADP and Pi are low with implications for the control of renal metabolism and Pi transport, and, via the phosphorylation potential, for Na+ transport. Renal pH is heterogeneous; between cortex, outer medulla, and papilla, and between cell and lumen, a large pH gradient exists. Also, quantitation between cytosol and mitochondrion of the pH gradient is now feasible. In acute renal failure of either ischemic or nonischemic origin, both ATP depletion and acidification of the renal cell result in damage, with increasing evidence for the importance of the latter. Measurements of renal metabolic rate in vivo suggest the existence of a prodromal phase of acute renal failure, which could lead to its detection at an earlier and possibly reversible stage. Human renal cancers show a unique /sup 31/P NMR spectrum and a very acidic environment. Cancer chemotherapy may alter this and detection of such changes with NMR offers a method of therapeutic monitoring with significance beyond nephrology. Renal cortex and medulla have a different T1 relaxation time, possibly due to differences in lipid composition. It seems that NMR spectroscopy has much to offer to the future understanding of the relationship between renal biochemistry and function. 56 references.

  2. Crystallinity and compositional changes in carbonated apatites: Evidence from 31P solid-state NMR, Raman, and AFM analysis

    PubMed Central

    McElderry, John-David P.; Zhu, Peizhi; Mroue, Kamal H.; Xu, Jiadi; Pavan, Barbara; Fang, Ming; Zhao, Guisheng; McNerny, Erin; Kohn, David H.; Franceschi, Renny T.; Holl, Mark M. Banaszak; Tecklenburg, Mary M.J.; Ramamoorthy, Ayyalusamy; Morris, Michael D.

    2013-01-01

    Solid-state (magic-angle spinning) NMR spectroscopy is a useful tool for obtaining structural information on bone organic and mineral components and synthetic model minerals at the atomic-level. Raman and 31P NMR spectral parameters were investigated in a series of synthetic B-type carbonated apatites (CAps). Inverse 31P NMR linewidth and inverse Raman PO43− ν1 bandwidth were both correlated with powder XRD c-axis crystallinity over the 0.3–10.3 wt% CO32− range investigated. Comparison with bone powder crystallinities showed agreement with values predicted by NMR and Raman calibration curves. Carbonate content was divided into two domains by the 31P NMR chemical shift frequency and the Raman phosphate ν1 band position. These parameters remain stable except for an abrupt transition at 6.5 wt% carbonate, a composition which corresponds to an average of one carbonate per unit cell. This near-binary distribution of spectroscopic properties was also found in AFM-measured particle sizes and Ca/P molar ratios by elemental analysis. We propose that this transition differentiates between two charge-balancing ion-loss mechanisms as measured by Ca/P ratios. These results define a criterion for spectroscopic characterization of B-type carbonate substitution in apatitic minerals. PMID:24273344

  3. Simultaneous topography and recognition imaging using force microscopy.

    PubMed

    Stroh, Cordula M; Ebner, Andreas; Geretschläger, Manfred; Freudenthaler, Günter; Kienberger, Ferry; Kamruzzahan, A S M; Smith-Gill, Sandra J; Gruber, Hermann J; Hinterdorfer, Peter

    2004-09-01

    We present a method for simultaneously recording topography images and localizing specific binding sites with nm positional accuracy by combining dynamic force microscopy with single molecule recognition force spectroscopy. For this we used lysozyme adsorbed to mica, the functionality of which was characterized by enzyme immunoassays. The topography and recognition images were acquired using tips that were magnetically oscillated during scanning and contained antibodies directed against lysozyme. For cantilevers with low Q-factor (approximately 1 in liquid) driven at frequencies below resonance, the surface contact only affected the downward deflections (minima) of the oscillations, whereas binding of the antibody on the tip to lysozyme on the surface only affected the upwards deflections (maxima) of the oscillations. The recognition signals were therefore well separated from the topographic signals, both in space (Delta z approximately 5 nm) and time (approximately 0.1 ms). Topography and recognition images were simultaneously recorded using a specially designed electronic circuit with which the maxima (U(up)) and the minima (U(down)) of each sinusoidal cantilever deflection period were depicted. U(down) was used for driving the feedback loop to record the height (topography) image, and U(up) provided the data for the recognition image. PMID:15345574

  4. Dielectric spectroscopy in agrophysics

    NASA Astrophysics Data System (ADS)

    Skierucha, W.; Wilczek, A.; Szypłowska, A.

    2012-04-01

    The paper presents scientific foundation and some examples of agrophysical applications of dielectric spectroscopy techniques. The aim of agrophysics is to apply physical methods and techniques for studies of materials and processes which occur in agriculture. Dielectric spectroscopy, which describes the dielectric properties of a sample as a function of frequency, may be successfully used for examinations of properties of various materials. Possible test materials may include agrophysical objects such as soil, fruit, vegetables, intermediate and final products of the food industry, grain, oils, etc. Dielectric spectroscopy techniques enable non-destructive and non-invasive measurements of the agricultural materials, therefore providing tools for rapid evaluation of their water content and quality. There is a limited number of research in the field of dielectric spectroscopy of agricultural objects, which is caused by the relatively high cost of the respective measurement equipment. With the fast development of modern technology, especially in high frequency applications, dielectric spectroscopy has great potential of expansion in agrophysics, both in cognitive and utilitarian aspects.

  5. Simultaneous spectrophotometric and mechanical property characterization of skin

    NASA Astrophysics Data System (ADS)

    Bunegin, Leonid; Moore, Jeffery B.

    2006-02-01

    Both reflectance spectroscopy and the determination Young's Modulus of skin have shown promise for identifying skin pathology. At present, these determinations are carried out using separate methodologies. This study demonstrates a new technology combining digital UV/VIS reflectance spectroscopy and vacuum aspiration for simultaneously determining the reflectance spectrum and mechanical properties of human skin tissue. A small hand held prototype device incorporating fiber-optic light guides into a vacuum channel was calibrated using various elastic materials subjected to increments of stress by vacuum from 0 to 25 in Hg. The intensity of a UV/VIS light beam reflected from the material at each vacuum increment was compared to the resulting material strain. The reflected beam was also spectrophotometrically analyzed. Skin types were similarly evaluated comparing normal and scar tissue and skin of various ages and coloration. An exponential relationship between reflected beam intensity and the amount of strain resulting from vacuum increments was observed. Young's Modulus (calculated from Aoki et. al equation) and spectra from normal skin and scar tissue were in agreement with previously published observations. Age related decreases in skin elasticity were also demonstrated. In the reflectance spectra, oxy and deoxy-hemoglobin absorbance bands were detected, becoming significantly enhanced at increased levels of vacuum. Melanin absorbance was also easily detected and appeared to correlate with skin coloration. Since superficial skin pathologies have characteristic spectroscopic and mechanical properties, this technique may provide a promising new approach for rapid, non-invasive method for the evaluation of skin lesions.

  6. The question of simultaneity in multisensory integration

    NASA Astrophysics Data System (ADS)

    Leone, Lynnette; McCourt, Mark E.

    2012-03-01

    Early reports of audiovisual (AV) multisensory integration (MI) indicated that unisensory stimuli must evoke simultaneous physiological responses to produce decreases in reaction time (RT) such that for unisensory stimuli with unequal RTs the stimulus eliciting the faster RT had to be delayed relative to the stimulus eliciting the slower RT. The "temporal rule" states that MI depends on the temporal proximity of unisensory stimuli, the neural responses to which must fall within a window of integration. Ecological validity demands that MI should occur only for simultaneous events (which may give rise to non-simultaneous neural activations). However, spurious neural response simultaneities which are unrelated to singular environmental multisensory occurrences must somehow be rejected. Using an RT/race model paradigm we measured AV MI as a function of stimulus onset asynchrony (SOA: +/-200 ms, 50 ms intervals) under fully dark adapted conditions for visual (V) stimuli that were either weak (scotopic 525 nm flashes; 511 ms mean RT) or strong (photopic 630 nm flashes; 356 ms mean RT). Auditory (A) stimulus (1000 Hz pure tone) intensity was constant. Despite the 155 ms slower mean RT to the scotopic versus photopic stimulus, facilitative AV MI in both conditions nevertheless occurred exclusively at an SOA of 0 ms. Thus, facilitative MI demands both physical and physiological simultaneity. We consider the mechanisms by which the nervous system may take account of variations in response latency arising from changes in stimulus intensity in order to selectively integrate only those physiological simultaneities that arise from physical simultaneities.

  7. Information extraction during simultaneous motion processing.

    PubMed

    Rideaux, Reuben; Edwards, Mark

    2014-02-01

    When confronted with multiple moving objects the visual system can process them in two stages: an initial stage in which a limited number of signals are processed in parallel (i.e. simultaneously) followed by a sequential stage. We previously demonstrated that during the simultaneous stage, observers could discriminate between presentations containing up to 5 vs. 6 spatially localized motion signals (Edwards & Rideaux, 2013). Here we investigate what information is actually extracted during the simultaneous stage and whether the simultaneous limit varies with the detail of information extracted. This was achieved by measuring the ability of observers to extract varied information from low detail, i.e. the number of signals presented, to high detail, i.e. the actual directions present and the direction of a specific element, during the simultaneous stage. The results indicate that the resolution of simultaneous processing varies as a function of the information which is extracted, i.e. as the information extraction becomes more detailed, from the number of moving elements to the direction of a specific element, the capacity to process multiple signals is reduced. Thus, when assigning a capacity to simultaneous motion processing, this must be qualified by designating the degree of information extraction. PMID:24333279

  8. Fabricating Nanometer-Thick Simultaneously Oleophobic/Hydrophilic Polymer Coatings via a Photochemical Approach.

    PubMed

    Wang, Yongjin; Dugan, Michael; Urbaniak, Brian; Li, Lei

    2016-07-01

    The simultaneously oleophobic/hydrophilic coatings are highly desirable in antifogging, oil-water separation, and detergent-free cleaning. However, such coatings require special chemical structure, i.e., perfluorinated backbone and polar end-groups, and are too expensive for real-life application. Here, we have developed an UV-based photochemical approach to make nanometer-thick perfluoropolyethers without polar end-groups, which are not intrinsically simultaneously oleophobic/hydrophilic but cost-effective, become simultaneously oleophobic/hydrophilic. The contact angle, ellipsometry, and X-ray photoelectron spectroscopy (XPS) results indicated that the UV irradiation results in the covalent bonding between the polymer and the substrate, which renders more ordered packing of polymer chains and thus the appropriately small interchain distance. As a result, the small water molecules penetrate the polymer network while large oil molecules do not. As a result, the oil contact angle is larger than the water contact angle and the coating shows the simultaneous oleophobicity/hydrophilicity. Moreover, we also demonstrated that this nanometer-thick simultaneously oleophobic/hydrophilic coating has improved long-term antifogging performance and detergent-free cleaning capability and is mechanically robust. The photochemical approach established here potentially can be applied on many other polymers and greatly accelerate the development and application of simultaneously oleophobic/hydrophilic coatings. PMID:27249169

  9. Fabricating Nanometer-Thick Simultaneously Oleophobic/Hydrophilic Polymer Coatings via a Photochemical Approach.

    PubMed

    Wang, Yongjin; Dugan, Michael; Urbaniak, Brian; Li, Lei

    2016-07-01

    The simultaneously oleophobic/hydrophilic coatings are highly desirable in antifogging, oil-water separation, and detergent-free cleaning. However, such coatings require special chemical structure, i.e., perfluorinated backbone and polar end-groups, and are too expensive for real-life application. Here, we have developed an UV-based photochemical approach to make nanometer-thick perfluoropolyethers without polar end-groups, which are not intrinsically simultaneously oleophobic/hydrophilic but cost-effective, become simultaneously oleophobic/hydrophilic. The contact angle, ellipsometry, and X-ray photoelectron spectroscopy (XPS) results indicated that the UV irradiation results in the covalent bonding between the polymer and the substrate, which renders more ordered packing of polymer chains and thus the appropriately small interchain distance. As a result, the small water molecules penetrate the polymer network while large oil molecules do not. As a result, the oil contact angle is larger than the water contact angle and the coating shows the simultaneous oleophobicity/hydrophilicity. Moreover, we also demonstrated that this nanometer-thick simultaneously oleophobic/hydrophilic coating has improved long-term antifogging performance and detergent-free cleaning capability and is mechanically robust. The photochemical approach established here potentially can be applied on many other polymers and greatly accelerate the development and application of simultaneously oleophobic/hydrophilic coatings.

  10. Recent advances in the use of NIR spectroscopy for qualitative control and protection of extra virgin olive oil

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Recent studies on the use of near infrared (NIR) spectroscopy for the qualitative characterization of extra virgin olive oil, are reported and discussed in this paper. Research results confirms that NIR spectroscopy, combined with chemometric data analysis, allows to simultaneously evaluate all qual...

  11. Vibrational Spectroscopy of Biomembranes

    NASA Astrophysics Data System (ADS)

    Schultz, Zachary D.; Levin, Ira W.

    2011-07-01

    Vibrational spectroscopy, commonly associated with IR absorption and Raman scattering, has provided a powerful approach for investigating interactions between biomolecules that make up cellular membranes. Because the IR and Raman signals arise from the intrinsic properties of these molecules, vibrational spectroscopy probes the delicate interactions that regulate biomembranes with minimal perturbation. Numerous innovative measurements, including nonlinear optical processes and confined bilayer assemblies, have provided new insights into membrane behavior. In this review, we highlight the use of vibrational spectroscopy to study lipid-lipid interactions. We also examine recent work in which vibrational measurements have been used to investigate the incorporation of peptides and proteins into lipid bilayers, and we discuss the interactions of small molecules and drugs with membrane structures. Emerging techniques and measurements on intact cellular membranes provide a prospective on the future of vibrational spectroscopic studies of biomembranes.

  12. Cham and Charmoniium Spectroscopy

    SciTech Connect

    Petersen, Brian Aa.; /Stanford U., Phys. Dept.

    2006-10-20

    The last few years have seen a revival of interest in charm spectroscopy with more than a dozen new states being reported and hundreds of new theoretical investigations being published. The advent of the B-factories [1,2], with their large, charm-rich data samples, has proven crucial to the discovery and investigation of new charm hadron states, but other experiments have confirmed and complemented the B-factory observations. Much interest has been generated by several new states that do not appear to be easily incorporated in the conventional picture of charm and charmonium mesons. Here, the focus is on the latest experimental results in charm spectroscopy and the determination of the nature of the recently discovered states. Recent experimental results in charm and charmonium spectroscopy are reviewed.

  13. Spectroscopy for the Masses

    NASA Astrophysics Data System (ADS)

    Le Roy, Robert J.; Hopkins, Scott; Power, William P.; Leung, Tong; Hepburn, John

    2015-06-01

    Undergraduate students in all areas of science encounter one or more types of spectroscopy as an essential tool in their discipline, but most never take the advanced physics or chemistry courses in which the subject is normally taught. To address this problem, for over 20 years our department has been teaching a popular Introductory Spectroscopy course that assumes as background only a one-term introductory chemistry course containing a unit on atomic theory, and a familiarity with rudimentary calculus. This survey course provides an introduction to microwave, infrared, Raman, electronic, photoelectron and NMR spectroscopy in a manner that allows students to understand many of these phenomena as intuitive generalizations of the problem of a particle in a 1-D box or a particle-on-a-ring, and does not require any high level mathematics.

  14. Scanning, non-contact, hybrid broadband diffuse optical spectroscopy and diffuse correlation spectroscopy system

    PubMed Central

    Johansson, Johannes D.; Mireles, Miguel; Morales-Dalmau, Jordi; Farzam, Parisa; Martínez-Lozano, Mar; Casanovas, Oriol; Durduran, Turgut

    2016-01-01

    A scanning system for small animal imaging using non-contact, hybrid broadband diffuse optical spectroscopy (ncDOS) and diffuse correlation spectroscopy (ncDCS) is presented. The ncDOS uses a two-dimensional spectrophotometer retrieving broadband (610-900 nm) spectral information from up to fifty-seven source-detector distances between 2 and 5 mm. The ncDCS data is simultaneously acquired from four source-detector pairs. The sample is scanned in two dimensions while tracking variations in height. The system has been validated with liquid phantoms, demonstrated in vivo on a human fingertip during an arm cuff occlusion and on a group of mice with xenoimplanted renal cell carcinoma. PMID:26977357

  15. Dual-axis vapor cell for simultaneous laser frequency stabilization on disparate optical transitions

    SciTech Connect

    Jayakumar, Anupriya Plotkin-Swing, Benjamin; Jamison, Alan O.; Gupta, Subhadeep

    2015-07-15

    We have developed a dual-axis ytterbium (Yb) vapor cell and used it to simultaneously address the two laser cooling transitions in Yb at wavelengths 399 nm and 556 nm, featuring the disparate linewidths of 2π × 29 MHz and 2π × 182 KHz, respectively. By utilizing different optical paths for the two wavelengths, we simultaneously obtain comparable optical densities suitable for saturated absorption spectroscopy for both the transitions and keep both the lasers frequency stabilized over several hours. We demonstrate that by appropriate control of the cell temperature profile, two atomic transitions differing in relative strength across a large range of over three orders of magnitude can be simultaneously addressed, making the device adaptable to a variety of spectroscopic needs. We also show that our observations can be understood with a simple theoretical model of the Yb vapor.

  16. Electrochemical piezoelectric-excited millimeter-sized cantilever (ePEMC) for simultaneous dual transduction biosensing.

    PubMed

    Johnson, Blake N; Mutharasan, Raj

    2013-11-01

    A dual mode electrochemical piezoelectric-excited millimeter cantilever (ePEMC) sensor is reported for simultaneous in-liquid biochemical sensing. The ePEMC incorporates mass-sensing measurement of dynamic-mode cantilevers with electrochemical impedance spectroscopy (EIS) commonly employed for transduction in sensitive electrochemical biosensors. Such an integrated design allows for simultaneous and continuous measurement of resonant frequency shift (Δf) and charge transfer resistance (RCT) as a target analyte binds to the sensor gold surface (0.5 mm(2)) via electromechanical and electrochemical impedance spectroscopy, respectively. The properties of ePEMC are demonstrated in three experiments: (1) resonant frequency response to electrochemically-deposited metal thin-films, (2) resonant frequency response to adsorption of thiolated ssDNA and model proteins with subsequent EIS sensing, and (3) simultaneous resonant frequency and charge transfer resistance response to model chemisorption of a short-chain thiol molecule, mercaptohexanol. Adsorption of all model binding analytes caused decrease in sensor resonant frequency and increase in charge transfer resistance. Comparison of sensor response to binding of protein and thiol molecules showed the two simultaneously transduced signals were proportional and showed the same kinetics.

  17. Electrochemical piezoelectric-excited millimeter-sized cantilever (ePEMC) for simultaneous dual transduction biosensing.

    PubMed

    Johnson, Blake N; Mutharasan, Raj

    2013-11-01

    A dual mode electrochemical piezoelectric-excited millimeter cantilever (ePEMC) sensor is reported for simultaneous in-liquid biochemical sensing. The ePEMC incorporates mass-sensing measurement of dynamic-mode cantilevers with electrochemical impedance spectroscopy (EIS) commonly employed for transduction in sensitive electrochemical biosensors. Such an integrated design allows for simultaneous and continuous measurement of resonant frequency shift (Δf) and charge transfer resistance (RCT) as a target analyte binds to the sensor gold surface (0.5 mm(2)) via electromechanical and electrochemical impedance spectroscopy, respectively. The properties of ePEMC are demonstrated in three experiments: (1) resonant frequency response to electrochemically-deposited metal thin-films, (2) resonant frequency response to adsorption of thiolated ssDNA and model proteins with subsequent EIS sensing, and (3) simultaneous resonant frequency and charge transfer resistance response to model chemisorption of a short-chain thiol molecule, mercaptohexanol. Adsorption of all model binding analytes caused decrease in sensor resonant frequency and increase in charge transfer resistance. Comparison of sensor response to binding of protein and thiol molecules showed the two simultaneously transduced signals were proportional and showed the same kinetics. PMID:24040646

  18. Spectroscopy of francium

    SciTech Connect

    Simsarian, J. E.; Grossman, J. S.; Orozco, L. A.; Pearson, M.; Sprouse, G. D.; Zhao, W. Z.

    1999-01-15

    Francium is the least studied of the alkali atoms because it has no stable isotopes. We have performed precision spectroscopy on cold Fr atoms in a magneto optical trap. We have determined the location of the first two excited states of the S series by two-photon spectroscopy. We have measured the lifetimes of the 7p levels with a precision better than 0.5%. Our measurements test the many-body perturbation theory ab initio calculations of the dipole matrix element to very high accuracy in this relativistic alkali.

  19. Submillimeter Fourier transform spectroscopy

    NASA Astrophysics Data System (ADS)

    Serabyn, Eugene

    1998-07-01

    At submillimeter wavelengths, broadband spectroscopy is currently possible only with a Fourier transform spectrometer (FTS). As a result, FTSes are quite useful for observations of objects in which spectral lines either cover a large frequency range, or where lines are broadened either by pressure or kinematics. Sources matching these descriptions include galaxies, hot, dense cores in interstellar molecular clouds, and planetary atmospheres. In the following, a tour of the classes of observations enabled by broadband spectroscopy is presented. As meaningful results call for attention to calibration, relevant calibration issues are discussed in the context of these observations.

  20. An algorithmically optimized combinatorial library screened by digital imaging spectroscopy.

    PubMed

    Goldman, E R; Youvan, D C

    1992-12-01

    Combinatorial cassettes based on a phylogenetic "target set" were used to simultaneously mutagenize seven amino acid residues on one face of a transmembrane alpha helix comprising a bacteriochlorophyll binding site in the light harvesting II antenna of Rhodobacter capsulatus. This pigmented protein provides a model system for developing complex mutagenesis schemes, because simple absorption spectroscopy can be used to assay protein expression, structure, and function. Colony screening by Digital Imaging Spectroscopy showed that 6% of the optimized library bound bacteriochlorophyll in two distinct spectroscopic classes. This is approximately 200 times the throughput (ca. 0.03%) of conventional combinatorial cassette mutagenesis using [NN(G/C)]. "Doping" algorithms evaluated in this model system are generally applicable and should enable simultaneous mutagenesis at more positions in a protein than currently possible, or alternatively, decrease the screening size of combinatorial libraries.

  1. Simultaneous bilateral tibial tubercle avulsion fracture.

    PubMed

    Maar, D C; Kernek, C B; Pierce, R O

    1988-11-01

    Bilateral simultaneous tibial tubercle avulsion fractures are extremely rare. The present case was a 16-year-old boy who sustained bilateral simultaneous tibial tubercle avulsion fractures (Watson-Jones Type III) from jumping while playing basketball. Both fractures were treated successfully by open reduction and internal fixation with screws. Three years later, the patient had the screws removed because of knee pain and tenderness over the screws.

  2. An approach to directly probe simultaneity

    NASA Astrophysics Data System (ADS)

    Kipreos, Edward T.; Balachandran, Riju S.

    2016-08-01

    The theory of special relativity derives from the Lorentz transformation. The Lorentz transformation implies differential simultaneity and light speed isotropy. Experiments to probe differential simultaneity should be able to distinguish the Lorentz transformation from a kinematically-similar alternate transformation that predicts absolute simultaneity, the absolute Lorentz transformation. Here, we describe how published optical tests of light speed isotropy/anisotropy cannot distinguish between the two transformations. We show that the shared equations of the two transformations, from the perspective of the “stationary” observer, are sufficient to predict null results in optical resonator experiments and in tests of frequency changes in one-way light paths. In an influential 1910 exposition on differential simultaneity, Comstock described how a “stationary” observer would observe different clock readings for spatially-separated “moving” clocks. The difference in clock readings is an integral aspect of differential simultaneity. We derive the equation for the difference in clock readings and show that it is equivalent to the Sagnac correction that describes light speed anisotropies in satellite communications. We describe an experimental strategy that can measure the differences in spatially-separated clock times to allow a direct probe of the nature of simultaneity.

  3. Fourier transform infrared spectroscopy

    SciTech Connect

    Ferraro, J.R.; Basile, L.J.

    1985-01-01

    The final and largest volume to complete this four-volume treatise is published in response to the intense commercial and research interest in Fourier Transform Interferometry. Volume 4 introduces new information on, for example, applications of Diffuse Reflectance Spectroscopy in the Far-infrared Region. The editors place emphasis on surface studies and address advances in Capillary Gas Chromatography-Fourier Transform Interferometry.

  4. Spectroscopy with Supersonic Jets.

    ERIC Educational Resources Information Center

    Skinner, Anne R.; Chandler, Dean W.

    1980-01-01

    Discusses a new technique that enables spectroscopists to study gas phase molecules at temperatures below 1 K, without traditional cryogenic apparatus. This technique uses supersonic jets as samples for gas molecular spectroscopy. Highlighted are points in the theory of supersonic flow which are important for applications in molecular…

  5. FTIR Rotational Spectroscopy.

    ERIC Educational Resources Information Center

    Woods, Ron; Henderson, Giles

    1987-01-01

    Presented are representative examples of the spectra and the analyses for a linear molecule (HC1), a symmetric top molecule (NH3), and an asymmetric top (H2O). Any combination of these projects could be incorporated in a physical chemistry or molecular spectroscopy laboratory. (RH)

  6. Advanced Spectroscopy Technique for Biomedicine

    NASA Astrophysics Data System (ADS)

    Zhao, Jianhua; Zeng, Haishan

    This chapter presents an overview of the applications of optical spectroscopy in biomedicine. We focus on the optical design aspects of advanced biomedical spectroscopy systems, Raman spectroscopy system in particular. Detailed components and system integration are provided. As examples, two real-time in vivo Raman spectroscopy systems, one for skin cancer detection and the other for endoscopic lung cancer detection, and an in vivo confocal Raman spectroscopy system for skin assessment are presented. The applications of Raman spectroscopy in cancer diagnosis of the skin, lung, colon, oral cavity, gastrointestinal tract, breast, and cervix are summarized.

  7. Broadband Rotational Spectroscopy

    NASA Astrophysics Data System (ADS)

    Pate, Brooks

    2014-06-01

    The past decade has seen several major technology advances in electronics operating at microwave frequencies making it possible to develop a new generation of spectrometers for molecular rotational spectroscopy. High-speed digital electronics, both arbitrary waveform generators and digitizers, continue on a Moore's Law-like development cycle that started around 1993 with device bandwidth doubling about every 36 months. These enabling technologies were the key to designing chirped-pulse Fourier transform microwave (CP-FTMW) spectrometers which offer significant sensitivity enhancements for broadband spectrum acquisition in molecular rotational spectroscopy. A special feature of the chirped-pulse spectrometer design is that it is easily implemented at low frequency (below 8 GHz) where Balle-Flygare type spectrometers with Fabry-Perot cavity designs become technologically challenging due to the mirror size requirements. The capabilities of CP-FTMW spectrometers for studies of molecular structure will be illustrated by the collaborative research effort we have been a part of to determine the structures of water clusters - a project which has identified clusters up to the pentadecamer. A second technology trend that impacts molecular rotational spectroscopy is the development of high power, solid state sources in the mm-wave/THz regions. Results from the field of mm-wave chirped-pulse Fourier transform spectroscopy will be described with an emphasis on new problems in chemical dynamics and analytical chemistry that these methods can tackle. The third (and potentially most important) technological trend is the reduction of microwave components to chip level using monolithic microwave integrated circuits (MMIC) - a technology driven by an enormous mass market in communications. Some recent advances in rotational spectrometer designs that incorporate low-cost components will be highlighted. The challenge to the high-resolution spectroscopy community - as posed by Frank De

  8. Simultaneous X-Ray and UV Spectroscopy of the Symbiotic HD 154791

    NASA Technical Reports Server (NTRS)

    Chakrabarty, Deepto

    2005-01-01

    Our program consisted of three observations of the symbiotic neutron stadred giant binary 4U 1700+24/HD154791. Using an earlier 2002 TOO observation made in response to a new transient X-ray outburst, we had previously discovered a redshifted O VII line and submitted a paper on this discovery to the journal Astronomy and Astrophysics. In these new observations, we from analysis of the 2002 TOO observation of the symbiotic neutron-star binary 4U 1700+24, made in response to detection of a new transient outburst, we discovered a redshifted Oxygen VIII line (in collaboration with A. Tiengo of UVA), and submitted a paper on this result to A&A. Analysis of the three subsequent observations has found a number of other features also due to ionized oxygen, which we have found to vary as the source transits from outburst to quiescence. A paper describing these observations is being prepared for submission to the Astrophysical Journal, led by Co-I Duncan Galloway.

  9. Simultaneous solution-based generation and characterization of crystalline bismuth thin film by femtosecond laser spectroscopy

    SciTech Connect

    Zhu, Liangdong; Keszler, Douglas A.; Fang, Chong; Saha, Sumit; Liu, Weimin; Wang, Yanli

    2015-08-10

    We demonstrate generation and characterization of crystalline bismuth thin film from triphenyl bismuth in methanol. Upon ultraviolet (267 nm) femtosecond laser irradiation of the solution, a thin film of elemental bismuth forms on the inner side of the sample cuvette, confirmed by detection of the coherent A{sub 1g} optical phonon mode of crystalline bismuth at ∼90 cm{sup −1}. Probe pulses at 267 and 400 nm are used to elucidate the excited state potential energy surface and photochemical reaction coordinate of triphenyl bismuth in solution with femtosecond resolution. The observed phonon mode blueshifts with increasing irradiation time, likely due to the gradual thickening of nascent bismuth thin film to ∼80 nm in 90 min. From transient absorption with the 400 nm probe, we observe a dominant ∼4 ps decay time constant of the excited-state absorption signal, which is attributed to a characteristic metal-ligand bond-weakening/breaking intermediate enroute to crystalline metallic thin film from the solution precursor molecules. Our versatile optical setup thus opens an appealing avenue to characterize the laser-induced crystallization process in situ and prepare high-quality thin films and nanopatterns directly from solution phase.

  10. Simultaneous Determination of Metamizole, Thiamin and Pyridoxin Using UV-Spectroscopy in Combination with Multivariate Calibration

    PubMed Central

    Chotimah, Chusnul; Sudjadi; Riyanto, Sugeng; Rohman, Abdul

    2015-01-01

    Purpose: Analysis of drugs in multicomponent system officially is carried out using chromatographic technique, however, this technique is too laborious and involving sophisticated instrument. Therefore, UV-VIS spectrophotometry coupled with multivariate calibration of partial least square (PLS) for quantitative analysis of metamizole, thiamin and pyridoxin is developed in the presence of cyanocobalamine without any separation step. Methods: The calibration and validation samples are prepared. The calibration model is prepared by developing a series of sample mixture consisting these drugs in certain proportion. Cross validation of calibration sample using leave one out technique is used to identify the smaller set of components that provide the greatest predictive ability. The evaluation of calibration model was based on the coefficient of determination (R2) and root mean square error of calibration (RMSEC). Results: The results showed that the coefficient of determination (R2) for the relationship between actual values and predicted values for all studied drugs was higher than 0.99 indicating good accuracy. The RMSEC values obtained were relatively low, indicating good precision. The accuracy and presision results of developed method showed no significant difference compared to those obtained by official method of HPLC. Conclusion: The developed method (UV-VIS spectrophotometry in combination with PLS) was succesfully used for analysis of metamizole, thiamin and pyridoxin in tablet dosage form. PMID:26819934

  11. Photothermal deflection spectroscopy and detection

    SciTech Connect

    Jackson, W. B.; Amer, Nabil M.; Boccara, A. C.; Fournier, D.

    1981-04-15

    The theory for a sensitive spectroscopy based on the photothermal deflection of a laser beam is developed. We consider cw and pulsed cases of both transverse and collinear photothermal deflection spectroscopy for solids, liquids, gases, and thin films. The predictions of the theory are experimentally verified, its implications for imaging and microscopy are given, and the sources of noise are analyzed. The sensitivity and versatility of photothermal deflection spectroscopy are compared with thermal lensing and photoacoustic spectroscopy.

  12. Experimental demonstration of quantitation errors in MR spectroscopy resulting from saturation corrections under changing conditions

    NASA Astrophysics Data System (ADS)

    Galbán, Craig J.; Ellis, Scott J.; Spencer, Richard G. S.

    2003-04-01

    Metabolite concentration measurements in in vivo NMR are generally performed under partially saturated conditions, with correction for partial saturation performed after data collection using a measured saturation factor. Here, we present an experimental test of the hypothesis that quantitation errors can occur due to application of such saturation factor corrections in changing systems. Thus, this extends our previous theoretical work on quantitation errors due to varying saturation factors. We obtained results for two systems frequently studied by 31P NMR, the ischemic rat heart and the electrically stimulated rat gastrocnemius muscle. The results are interpreted in light of previous theoretical work which defined the degree of saturation occurring in a one-pulse experiment for a system with given spin-lattice relaxation times, T1s, equilibrium magnetizations, M0s, and reaction rates. We found that (i) the assumption of constancy of saturation factors leads to quantitation errors on the order of 40% in inorganic phosphate; (ii) the dominant contributor to the quantitation errors in inorganic phosphate is most likely changes in T1; (iii) T1 and M0 changes between control and intervention periods, and chemical exchange contribute to different extents to quantitation errors in phosphocreatine and γ-ATP; (iv) relatively small increases in interpulse delay substantially decreased quantitation errors for metabolites in ischemic rat hearts; (v) random error due to finite SNR led to approximately 4% error in quantitation, and hence was a substantially smaller contributor than were changes in saturation factors.

  13. Multidimensional spectroscopy of photoreactivity

    PubMed Central

    Ruetzel, Stefan; Diekmann, Meike; Nuernberger, Patrick; Walter, Christof; Engels, Bernd; Brixner, Tobias

    2014-01-01

    Coherent multidimensional electronic spectroscopy is commonly used to investigate photophysical phenomena such as light harvesting in photosynthesis in which the system returns back to its ground state after energy transfer. By contrast, we introduce multidimensional spectroscopy to study ultrafast photochemical processes in which the investigated molecule changes permanently. Exemplarily, the emergence in 2D and 3D spectra of a cross-peak between reactant and product reveals the cis–trans photoisomerization of merocyanine isomers. These compounds have applications in organic photovoltaics and optical data storage. Cross-peak oscillations originate from a vibrational wave packet in the electronically excited state of the photoproduct. This concept isolates the isomerization dynamics along different vibrational coordinates assigned by quantum-chemical calculations, and is applicable to determine chemical dynamics in complex photoreactive networks. PMID:24639540

  14. Precision Muonium Spectroscopy

    NASA Astrophysics Data System (ADS)

    Jungmann, Klaus P.

    2016-09-01

    The muonium atom is the purely leptonic bound state of a positive muon and an electron. It has a lifetime of 2.2 µs. The absence of any known internal structure provides for precision experiments to test fundamental physics theories and to determine accurate values of fundamental constants. In particular ground state hyperfine structure transitions can be measured by microwave spectroscopy to deliver the muon magnetic moment. The frequency of the 1s-2s transition in the hydrogen-like atom can be determined with laser spectroscopy to obtain the muon mass. With such measurements fundamental physical interactions, in particular quantum electrodynamics, can also be tested at highest precision. The results are important input parameters for experiments on the muon magnetic anomaly. The simplicity of the atom enables further precise experiments, such as a search for muonium-antimuonium conversion for testing charged lepton number conservation and searches for possible antigravity of muons and dark matter.

  15. Charm and Charm Spectroscopy

    SciTech Connect

    Santoro, Valentina; /Ferrara U.

    2011-11-23

    Recent developements in D mixing physics and charm spectroscopy will be discussed. Focus will be on the BaBar experimental results for the D mixing: first evidence of the D{sup 0}-mixing (hadronic D{sup 0} decays), lifetime difference and time-dependent Dalitz plot analysis of D{sup 0} {yields} K{sup +}{pi}{sup -}{pi}{sup 0}. Then, recent results on charm spectroscopy will be presented with particular focus on the new Ds states that have been discovered in the last few years. Some of these states were not expected theoretically: their masses, widths, quantum numbers, and decay modes do not fit the existing spectroscopic classication, which is based mostly on potential model calculations.

  16. Chiral rotational spectroscopy

    NASA Astrophysics Data System (ADS)

    Cameron, Robert P.; Götte, Jörg B.; Barnett, Stephen M.

    2016-09-01

    We introduce chiral rotational spectroscopy, a technique that enables the determination of the orientated optical activity pseudotensor components BX X, BY Y, and BZ Z of chiral molecules, in a manner that reveals the enantiomeric constitution of a sample and provides an incisive signal even for a racemate. Chiral rotational spectroscopy could find particular use in the analysis of molecules that are chiral solely by virtue of their isotopic constitution and molecules with multiple chiral centers. A basic design for a chiral rotational spectrometer together with a model of its functionality is given. Our proposed technique offers the more familiar polarizability components αX X, αY Y, and αZ Z as by-products, which could see it find use even for achiral molecules.

  17. Photothermal absorption correlation spectroscopy.

    PubMed

    Octeau, Vivien; Cognet, Laurent; Duchesne, Laurence; Lasne, David; Schaeffer, Nicolas; Fernig, David G; Lounis, Brahim

    2009-02-24

    Fluorescence correlation spectroscopy (FCS) is a popular technique, complementary to cell imaging for the investigation of dynamic processes in living cells. Based on fluorescence, this single molecule method suffers from artifacts originating from the poor fluorophore photophysics: photobleaching, blinking, and saturation. To circumvent these limitations we present here a new correlation method called photothermal absorption correlation spectroscopy (PhACS) which relies on the absorption properties of tiny nano-objects. PhACS is based on the photothermal heterodyne detection technique and measures akin FCS, the time correlation function of the detected signals. Application of this technique to the precise determination of the hydrodynamic sizes of different functionalized gold nanoparticles are presented, highlighting the potential of this method. PMID:19236070

  18. Ultrafast spectroscopy of novel materials

    NASA Astrophysics Data System (ADS)

    Hardison, Lindsay M.

    My research focused on steady state and time-resolved photophysical characterization of a series of semiconductor nanoparticles and water soluble conjugated polyelectrolytes. Several studies have shown that the electronic structure and relaxation dynamics in CdSe nanocrystals are not only size but are also shape and passivation dependent; however, there is no detailed comparison of the photophysical properties of ZnCdSe particles with different relative amounts of Zn. This dissertation presents data collected for colloidal CdSe, CdSe/ZnSe and ZnCdSe nanoparticles with rod-like architectures synthesized and investigated in our labs to determine how size, shape, passivation and composition affect the quantum confinement and dynamics. In addition, a series of different polymer repeat unit lengths of a linear conjugated polyelectrolyte (CPE) with a carboxylate ionic side chain have been synthesized and their photophysical properties have been explored. Spectral shifts and line broadening exhibited within the Raman spectroscopy, UV-Vis spectroscopy and photoluminescence aided in determining the extent of alloying and compositional disorder created during the alloying process. The photoluminescence quantum yield of ZnCdSe nanorods is higher than that from pristine CdSe nanorods indicating a higher binding energy of the exciton. This effect is speculated to be due to increased localization of the exciton as a result of fluctuations in the composition, ultimately resulting in increases in luminescence efficiencies. Moreover, time-resolved photoluminescence characterized lifetimes of nanoparticles with similar shape but different composition. Emission of an inhomogeneous population distribution (different sizes, shapes or composition) leads to the simultaneous probing of particles with different decaying rates. A stretched exponential function, I(t)= A*exp[-(t/tau) beta], can be used to describe these systems, where beta <1 corresponds to disperse populations. In the

  19. 2008 Vibrational Spectroscopy

    SciTech Connect

    Philip J. Reid

    2009-09-21

    The conference focuses on using vibrational spectroscopy to probe structure and dynamics of molecules in gases, liquids, and interfaces. The goal is to bring together a collection of researchers who share common interests and who will gain from discussing work at the forefront of several connected areas. The intent is to emphasize the insights and understanding that studies of vibrations provide about a variety of systems.

  20. Theory and spectroscopy

    NASA Astrophysics Data System (ADS)

    Stanton, John F.

    2015-05-01

    The interaction between quantum-mechanical theory and spectroscopy is one of the most fertile interfaces in all of science, and has a richly storied history. Of course it was spectroscopy that provided essentially all of the evidence that not all was well (or, perhaps more correctly put, complete) with the world of 19th century classical physics. From the discoveries of the dark lines in the solar spectrum by Fraunhöfer in 1814 to the curiously simple geometric formula discovered seventy years later that described the hydrogen atom spectrum, spectroscopy and spectroscopists have consistently identified the areas of atomic and molecular science that are most in need of hard thinking by theoreticians. The rest of the story, of course, is well-known: spectroscopic results were used to understand and motivate the theory of radioactivity and ultimately the quantum theory, first in its immature form that was roughly contemporaneous with the first World War, and then the Heisenberg-Schrödinger-Dirac version that has withstood the test of time. Since the basic principles of quantum mechanics ware first understood, the subject has been successfully used to understand the patterns found in spectra, and how these relate to molecular structure, symmetry, energy levels, and dynamics. But further understanding required to attain these intellectual achievements has often come only as a result of vital and productive interactions between theoreticians and spectroscopists (of course, many people have strengths in both areas). And indeed, a field that might be termed "theoretical spectroscopy" was cultivated and is now an important part of modern molecular science.

  1. The Goodness of Simultaneous Fits in ISIS

    NASA Astrophysics Data System (ADS)

    Kühnel, Matthias; Falkner, Sebastian; Grossberger, Christoph; Ballhausen, Ralf; Dauser, Thomas; Schwarm, Fritz-Walter; Kreykenbohm, Ingo; Nowak, Michael A.; Pottschmidt, Katja; Ferrigno, Carlo; Rothschild, Richard E.; Martínez-Núñez, Silvia; Torrejón, José Miguel; Fürst, Felix; Klochkov, Dmitry; Staubert, Rüdiger; Kretschmar, Peter; Wilms, Jörn

    2016-02-01

    In a previous work, we introduced a tool for analyzing multiple datasets simultaneously, which has been implemented into ISIS. This tool was used to fit many spectra of X-ray binaries. However, the large number of degrees of freedom and individual datasets raise an issue about a good measure for a simultaneous fit quality. We present three ways to check the goodness of these fits: we investigate the goodness of each fit in all datasets, we define a combined goodness exploiting the logical structure of a simultaneous fit, and we stack the fit residuals of all datasets to detect weak features. These tools are applied to all RXTE-spectra from GRO 1008-57, revealing calibration features that are not detected significantly in any single spectrum. Stacking the residuals from the best-fit model for the Vela X-1 and XTE J1859+083 data evidences fluorescent emission lines that would have gone undetected otherwise.

  2. Layman friendly spectroscopy

    NASA Astrophysics Data System (ADS)

    Sentic, Stipo; Sessions, Sharon

    Affordable consumer grade spectroscopes (e.g. SCiO, Qualcomm Tricorder XPRIZE) are becoming more available to the general public. We introduce the concepts of spectroscopy to the public and K12 students and motivate them to delve deeper into spectroscopy in a dramatic participatory presentation and play. We use diffraction gratings, lasers, and light sources of different spectral properties to provide a direct experience of spectroscopy techniques. Finally, we invite the audience to build their own spectroscope--utilizing the APS SpectraSnapp cell phone application--and study light sources surrounding them in everyday life. We recontextualize the stigma that science is hard (e.g. ``Math, Science Popular Until Students Realize They're Hard,'' The Wall Street Journal) by presenting the material in such a way that it demonstrates the scientific method, and aiming to make failure an impersonal scientific tool--rather than a measure of one's ability, which is often a reason for shying away from science. We will present lessons we have learned in doing our outreach to audiences of different ages. This work is funded by the APS Outreach Grant ``Captain, we have matter matters!'' We thank New Mexico Tech Physics Department and Physics Club for help and technical equipment.

  3. High Resolution Laboratory Spectroscopy

    NASA Astrophysics Data System (ADS)

    Brünken, S.; Schlemmer, S.

    2016-05-01

    In this short review we will highlight some of the recent advancements in the field of high-resolution laboratory spectroscopy that meet the needs dictated by the advent of highly sensitive and broadband telescopes like ALMA and SOFIA. Among these is the development of broadband techniques for the study of complex organic molecules, like fast scanning conventional absorption spectroscopy based on multiplier chains, chirped pulse instrumentation, or the use of synchrotron facilities. Of similar importance is the extension of the accessible frequency range to THz frequencies, where many light hydrides have their ground state rotational transitions. Another key experimental challenge is the production of sufficiently high number densities of refractory and transient species in the laboratory, where discharges have proven to be efficient sources that can also be coupled to molecular jets. For ionic molecular species sensitive action spectroscopic schemes have recently been developed to overcome some of the limitations of conventional absorption spectroscopy. Throughout this review examples demonstrating the strong interplay between laboratory and observational studies will be given.

  4. Instrumentation for the spectroscopy of hot plasmas

    NASA Astrophysics Data System (ADS)

    Schnopper, H. W.; Silver, E. H.; Westergaard, N. J.

    Current and planned instruments and observational capabilities for studying X-ray spectra from celestial sources using space-based instruments are described. Concentration systems will provide high sensitivity using 0.5-2.0 arcmin angular resolution. The X-80 mission will feature a grazing incidence telescope coupled to an Anger gas scintillation proportional counter and will scan the 0.2-10 keV range. Inclusion of a transmission grating after the telescope will permit 2000 lines/mm resolution. Bragg crystal spectroscopy, a potential part of the X-80, XMM, and AXAF spacecraft, will provide data for calculating the emission line sensitivities for cosmically abundant elements. Finally, a spherical crystal imaging spectrometer will provide high sensitivity simultaneously at several wavelengths. The three instruments will allow closer estimates of gas temperatures, densities, ionization states, and velocities.

  5. Simultaneous sampling technique for two spectral sources

    NASA Technical Reports Server (NTRS)

    Jarrett, Olin, Jr.

    1987-01-01

    A technique is described that uses a bundle of fiber optics to simultaneously sample a dye laser and a spectral lamp. By the use of a real-time display with this technique, the two signals can be superimposed, and the effect of any spectral adjustments can be immediately accessed. In the NASA's CARS system used for combustion diagnostics, the dye laser mixes with a simultaneously pulsed Nd:YAG laser at 532 nm to probe the vibrational levels of nitrogen. An illustration of the oscilloscopic display of the system is presented.

  6. Simultaneous wireless electrophysiological and neurochemical monitoring

    NASA Astrophysics Data System (ADS)

    Murari, Kartikeya; Mollazadeh, Mohsen; Thakor, Nitish; Cauwenberghs, Gert

    2008-08-01

    Information processing and propagation in the central nervous system is mostly electrical in nature. At synapses, electrical signals cause the release of neurotransmitters like dopamine, glutamate etc., that are sensed by post-synaptic neurons resulting in signal propagation or inhibition. It can be very informative to monitor electrical and neurochemical signals simultaneously to understand the mechanisms underlying normal or abnormal brain function. We present an integrated system for the simultaneous wireless acquisition of neurophysiological and neurochemical activity. Applications of the system to neuroscience include monitoring EEG and glutamate in rat somatosensory cortex following global ischemia.

  7. Mass exchange during simultaneous grinding and dissolution

    SciTech Connect

    Aksel'rud, G.A.; Semenishin, E.M.; Kopyt, S.Ya.; Trotskii, V.I.

    1988-03-20

    Extraction of ore components of interest has a number of disadvantages, one of which being low efficiency. Combining the grinding and dissolution steps in one apparatus makes the process more efficient. Adoption of this technology, however, requires theoretical and mathematical studies. This paper reports the kinetics of simultaneous grinding and dissolution of copper-containing minerals. Simultaneous grinding and dissolution accelerated several fold the mass transfer of components of interest in the interaction of malachite and azurite with sulfuric acid solutions. The complete dissolution time was determined by adding the experimental rates of dissolution and abrasion.

  8. Theranostic Fibers for Simultaneous Imaging and Drug Delivery.

    PubMed

    Jin, Miao; Yu, Deng-Guang; Geraldes, Carlos F G C; Williams, Gareth R; Bligh, S W Annie

    2016-07-01

    New methods for creating theranostic systems with simultaneous encapsulation of therapeutic, diagnostic, and targeting agents are much sought after. This work reports for the first time the use of coaxial electrospinning to prepare such systems in the form of core-shell fibers. Eudragit S100 was used to form the shell of the fibers, while the core comprised poly(ethylene oxide) loaded with the magnetic resonance contrast agent Gd(DTPA) (Gd(III) diethylenetriaminepentaacetate hydrate) and indomethacin as a model therapeutic agent. The fibers had linear cylindrical morphologies with clear core-shell structures, as demonstrated by electron microscopy. X-ray diffraction and differential scanning calorimetry proved that both indomethacin and Gd(DTPA) were present in the fibers in the amorphous physical form. This is thought to be a result of intermolecular interactions between the different components, the presence of which was suggested by infrared spectroscopy. In vitro dissolution tests indicated that the fibers could provide targeted release of the active ingredients through a combined mechanism of erosion and diffusion. The proton relaxivities for Gd(DTPA) released from the fibers into tris buffer increased (r1 = 4.79-9.75 s(-1) mM(-1); r2 = 7.98-14.22 s(-1) mM(-1)) compared with fresh Gd(DTPA) (r1 = 4.13 s(-1) mM(-1) and r2 = 4.40 s(-1) mM(-1)), which proved that electrospinning has not diminished the contrast properties of the complex. The new systems reported herein thus offer a new platform for delivering therapeutic and imaging agents simultaneously to the colon. PMID:27280491

  9. Simultaneous drug release at different rates from biodegradable polyurethane foams.

    PubMed

    Sivak, Wesley N; Zhang, Jianying; Petoud, Stephané; Beckman, Eric J

    2009-09-01

    In this study, we present an approach for the simultaneous release of multiple drug compounds at different rates from single-phase polyurethane foams constructed from lysine diisocyanate (LDI) and glycerol. The anti-cancer compounds DB-67 and doxorubicin were covalently incorporated into polyurethane foams, whereby drug release can then occur in concert with material degradation. To begin, the reactions of DB-67 and doxorubicin with LDI in the presence of a tertiary amine catalyst were monitored with infrared spectroscopy; each compound formed urethane linkages with LDI. Fluorescent spectra of DB-67 and doxorubicin were then recorded in phosphate-buffered saline, pH 7.4 (PBS), to ensure that each anti-cancer compound could be quantitatively detected alone and in combination. Doxorubicin and DB-67 were then incorporated into a series of degradable LDI-glycerol polyurethane foams alone and in combination with one another. The sol content, average porosity and drug distribution throughout each foam sample was measured and found to be similar amongst all foam samples. The stability of DB-67 and doxorubicin's fluorescent signal was then assessed over a 2-week period at 70 degrees C. Release rates of the compounds from the foams were assessed over a 10-week period at 4, 22, 37 and 70 degrees C by way of fluorescence spectroscopy. Release was found to be temperature-dependent, with rates related to the chemical structure of the incorporated drug. This study demonstrates that differential release of covalently bound drugs is possible from simple single-phase, degradable polyurethane foams. PMID:19398389

  10. Simultaneous Visual Discrimination in Asian Elephants

    ERIC Educational Resources Information Center

    Nissani, Moti; Hoefler-Nissani, Donna; Lay, U. Tin; Htun, U. Wan

    2005-01-01

    Two experiments explored the behavior of 20 Asian elephants ("Elephas aximus") in simultaneous visual discrimination tasks. In Experiment 1, 7 Burmese logging elephants acquired a white+/black- discrimination, reaching criterion in a mean of 2.6 sessions and 117 discrete trials, whereas 4 elephants acquired a black+/white- discrimination in 5.3…

  11. Intelligibility of Speech Produced during Simultaneous Communication

    ERIC Educational Resources Information Center

    Whitehead, Robert L.; Schiavetti, Nicholas; MacKenzie, Douglas J.; Metz, Dale Evan

    2004-01-01

    This study investigated the overall intelligibility of speech produced during simultaneous communication (SC). Four hearing, experienced sign language users were recorded under SC and speech alone (SA) conditions speaking Boothroyd's (1985) forced-choice phonetic contrast material designed for measurement of speech intelligibility. Twelve…

  12. Preventing Simultaneous Conduction In Switching Transistors

    NASA Technical Reports Server (NTRS)

    Mclyman, William T.

    1990-01-01

    High voltage spikes and electromagnetic interference suppressed. Power-supply circuit including two switching transistors easily modified to prevent simultaneous conduction by both transistors during switching intervals. Diode connected between collector of each transistor and driving circuit for opposite transistor suppresses driving signal to transistor being turned on until transistor being turned off ceases to carry current.

  13. Baseline estimation from simultaneous satellite laser tracking

    NASA Technical Reports Server (NTRS)

    Dedes, George C.

    1987-01-01

    Simultaneous Range Differences (SRDs) to Lageos are obtained by dividing the observing stations into pairs with quasi-simultaneous observations. For each of those pairs the station with the least number of observations is identified, and at its observing epochs interpolated ranges for the alternate station are generated. The SRD observables are obtained by subtracting the actually observed laser range of the station having the least number of observations from the interpolated ranges of the alternate station. On the basis of these observables semidynamic single baseline solutions were performed. The aim of these solutions is to further develop and implement the SRD method in the real data environment, to assess its accuracy, its advantages and disadvantages as related to the range dynamic mode methods, when the baselines are the only parameters of interest. Baselines, using simultaneous laser range observations to Lageos, were also estimated through the purely geometric method. These baselines formed the standards the standards of comparison in the accuracy assessment of the SRD method when compared to that of the range dynamic mode methods. On the basis of this comparison it was concluded that for baselines of regional extent the SRD method is very effective, efficient, and at least as accurate as the range dynamic mode methods, and that on the basis of a simple orbital modeling and a limited orbit adjustment. The SRD method is insensitive to the inconsistencies affecting the terrestrial reference frame and simultaneous adjustment of the Earth Rotation Parameters (ERPs) is not necessary.

  14. Simultaneous dislocation of all five carpometacarpal joints.

    PubMed

    Fayman, M; Hugo, B; de Wet, H

    1988-07-01

    A case of unique combination of simultaneous dislocation of all five carpometacarpal joints is presented. The mechanism of injury in this case seems to be some manner of punching with a closed fist rather than direct violence. Satisfactory results were achieved using simple principles of manipulation under anesthesia, open reduction, and skeletal fixation, followed by intensive physiotherapy.

  15. The rheo-Raman microscope: Simultaneous chemical, conformational, mechanical, and microstructural measures of soft materials

    NASA Astrophysics Data System (ADS)

    Kotula, Anthony P.; Meyer, Matthew W.; De Vito, Francesca; Plog, Jan; Hight Walker, Angela R.; Migler, Kalman B.

    2016-10-01

    The design and performance of an instrument capable of simultaneous Raman spectroscopy, rheology, and optical microscopy are described. The instrument couples a Raman spectrometer and optical microscope to a rotational rheometer through an optically transparent base, and the resulting simultaneous measurements are particularly advantageous in situations where flow properties vary due to either chemical or conformational changes in molecular structure, such as in crystallization, melting, gelation, or curing processes. Instrument performance is demonstrated on two material systems that show thermal transitions. First, we perform steady state rotational tests, Raman spectroscopy, and polarized reflection microscopy during a melting transition in a cosmetic emulsion. Second, we perform small amplitude oscillatory shear measurements along with Raman spectroscopy and polarized reflection microscopy during crystallization of a high density polyethylene. The instrument can be applied to study structure-property relationships in a variety of soft materials including thermoset resins, liquid crystalline materials, colloidal suspensions undergoing sol-gel processes, and biomacromolecules. Official contribution of the National Institute of Standards and Technology; not subject to copyright in the United States.

  16. OPTOPUS spectroscopy of galaxies

    NASA Astrophysics Data System (ADS)

    Schnur, G. F. O.

    The spectra of selected H II regions in the center of the starburst galaxy NGC 1808 and of many faint galaxies surrounding the NGC 1808 were obtained simultaneously, using the Optopus fiber-optics spectrograph facility (described by Lund, 1986) at the ESO 3.6-m telescope. The preparation of Optopus plates (each of which employed more than 40 fibers), observations, and the procedures of data processing and Optopus calibration are described together with the problems caused by cosmic ray events. Preliminary results are included.

  17. Theory of femtosecond stimulated Raman spectroscopy.

    PubMed

    Lee, Soo-Y; Zhang, Donghui; McCamant, David W; Kukura, Philipp; Mathies, Richard A

    2004-08-22

    Femtosecond broadband stimulated Raman spectroscopy (FSRS) is a new technique that produces high-resolution (time-resolved) vibrational spectra from either the ground or excited electronic states of molecules, free from background fluorescence. FSRS uses simultaneously a narrow bandwidth approximately 1-3 ps Raman pump pulse with a continuum approximately 30-50 fs Stokes probe pulse to produce sharp Raman gains, at positions corresponding to vibrational transitions in the sample, riding on top of the continuum Stokes probe spectrum. When FSRS is preceded by a femtosecond actinic pump pulse that initiates the photochemistry of interest, time-resolved Raman spectroscopy can be carried out. We present two theoretical approaches to FSRS: one is based on a coupling of Raman pump and probe light waves with the vibrations in the medium, and another is a quantum-mechanical description. The latter approach is used to discuss the conditions of applicability and limitations of the coupled-wave description. Extension of the quantum-mechanical description to the case where the Raman pump beam is on resonance with an excited electronic state, as well as when FSRS is used to probe a nonstationary vibrational wave packet prepared by an actinic pump pulse, is also discussed. PMID:15303930

  18. Noninvasive glucose sensing by transcutaneous Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Shih, Wei-Chuan; Bechtel, Kate L.; Rebec, Mihailo V.

    2015-05-01

    We present the development of a transcutaneous Raman spectroscopy system and analysis algorithm for noninvasive glucose sensing. The instrument and algorithm were tested in a preclinical study in which a dog model was used. To achieve a robust glucose test system, the blood levels were clamped for periods of up to 45 min. Glucose clamping and rise/fall patterns have been achieved by injecting glucose and insulin into the ear veins of the dog. Venous blood samples were drawn every 5 min and a plasma glucose concentration was obtained and used to maintain the clamps, to build the calibration model, and to evaluate the performance of the system. We evaluated the utility of the simultaneously acquired Raman spectra to be used to determine the plasma glucose values during the 8-h experiment. We obtained prediction errors in the range of ˜1.5-2 mM. These were in-line with a best-case theoretical estimate considering the limitations of the signal-to-noise ratio estimates. As expected, the transition regions of the clamp study produced larger predictive errors than the stable regions. This is related to the divergence of the interstitial fluid (ISF) and plasma glucose values during those periods. Two key contributors to error beside the ISF/plasma difference were photobleaching and detector drift. The study demonstrated the potential of Raman spectroscopy in noninvasive applications and provides areas where the technology can be improved in future studies.

  19. Noninvasive glucose sensing by transcutaneous Raman spectroscopy

    PubMed Central

    Shih, Wei-Chuan; Bechtel, Kate L.; Rebec, Mihailo V.

    2015-01-01

    Abstract. We present the development of a transcutaneous Raman spectroscopy system and analysis algorithm for noninvasive glucose sensing. The instrument and algorithm were tested in a preclinical study in which a dog model was used. To achieve a robust glucose test system, the blood levels were clamped for periods of up to 45 min. Glucose clamping and rise/fall patterns have been achieved by injecting glucose and insulin into the ear veins of the dog. Venous blood samples were drawn every 5 min and a plasma glucose concentration was obtained and used to maintain the clamps, to build the calibration model, and to evaluate the performance of the system. We evaluated the utility of the simultaneously acquired Raman spectra to be used to determine the plasma glucose values during the 8-h experiment. We obtained prediction errors in the range of ∼1.5−2  mM. These were in-line with a best-case theoretical estimate considering the limitations of the signal-to-noise ratio estimates. As expected, the transition regions of the clamp study produced larger predictive errors than the stable regions. This is related to the divergence of the interstitial fluid (ISF) and plasma glucose values during those periods. Two key contributors to error beside the ISF/plasma difference were photobleaching and detector drift. The study demonstrated the potential of Raman spectroscopy in noninvasive applications and provides areas where the technology can be improved in future studies. PMID:25688542

  20. Euv spectroscopy in astrophysics

    NASA Astrophysics Data System (ADS)

    Kowalski, M.; Cruddace, R.; Wood, K.; Barstow, M.

    The bulk of radiation from million-degree plasmas is emitted at EUV wavelengths. Such plasmas are ubiquitous in astrophysics, and examples include the atmospheres of white dwarfs, accretion phenomena in cataclysmic variables, the coronae of active stars, and the interstellar medium (ISM) of our own galaxy and as well as that of others. EUV wavelengths encompass critical spectral features with diagnostic information often not available at other wavelengths. For example in the ISM the bound free continuum of He II (< 228 Angstroms) and the resonance line at 304 Angstroms are the only useful diagnostics of the He II density. EUVE and the ROSAT WFC left a tremendous legacy in broad-band photometry at EUV wavelengths, and the former introduced EUV spectroscopy. However the termination of EUVE left a gap that CHIPS fills only partially as it is optimized for diffuse emission. Moreover, while Chandra has demonstrated the promise of high-resolution X-ray spectroscopy, EUV spectrometers have had modest resolution and effective area (EUVE: 1 cm2, Resolution 400; CHIPS: Resolution 150) until recently. Our sounding rocket instrument J-PEX has now made the first successful high-resolution (effective area 3 cm2, Resolution 3000) spectral observation in the EUV, and future instruments with effective area >30 cm2 and Resolution>10,000 are now practical. We will highlight EUV spectroscopy results in non-solar astrophysics and trace the development of instrument capabilities that lead to the next generation of high-resolution EUV spectrometers. This work is supported by the Office of Naval Research and NRL, and by NASA Space Astrophysics and Research Analysis grants.

  1. Active Beam Spectroscopy

    NASA Astrophysics Data System (ADS)

    von Hellermann, M. G.; Delabie, E.; Jaspers, R. J. E.; Biel, W.; Marchuk, O.; Summers, H. P.; Whiteford, A.; Giroud, C.; Hawkes, N. C.; Zastrow, K. D.

    2008-03-01

    Charge eXchange Recombination Spectroscopy (CXRS) plays a pivotal role in the diagnostics of hot fusion plasmas and is implemented currently in most of the operating devices. In the present report the main features of CXRS are summarized and supporting software packages encompassing "Spectral Analysis Code CXSFIT", "Charge Exchange Analysis Package CHEAP", and finally "Forward Prediction of Spectral Features" are described. Beam Emission Spectroscopy (BES) is proposed as indispensable cross-calibration tool for absolute local impurity density measurements and also for the continuous monitoring of the neutral beam power deposition profile. Finally, a full exploitation of the `Motional Stark Effect' pattern is proposed to deduce local pitch angles, total magnetic fields and possibly radial electric fields. For the proposed active beam spectroscopy diagnostic on ITER comprehensive performance studies have been carried out. Estimates of expected spectral signal-to-noise ratios are based on atomic modelling of neutral beam stopping and emissivities for CXRS, BES and background continuum radiation as well as extrapolations from present CXRS diagnostic systems on JET, Tore Supra, TEXTOR and ASDEX-UG. Supplementary to thermal features a further promising application of CXRS has been proposed recently for ITER, that is a study of slowing-down alpha particles in the energy range up to 2 MeV making use of the 100 keV/amu DNB (Diagnostic Neutral Beam) and the 500 keV/amu HNB (Heating Neutral Beam). Synthetic Fast Ion Slowing-Down spectra are evaluated in terms of source rates and slowing-down parameters

  2. Dark Matter Velocity Spectroscopy.

    PubMed

    Speckhard, Eric G; Ng, Kenny C Y; Beacom, John F; Laha, Ranjan

    2016-01-22

    Dark matter decays or annihilations that produce linelike spectra may be smoking-gun signals. However, even such distinctive signatures can be mimicked by astrophysical or instrumental causes. We show that velocity spectroscopy-the measurement of energy shifts induced by relative motion of source and observer-can separate these three causes with minimal theoretical uncertainties. The principal obstacle has been energy resolution, but upcoming experiments will have the precision needed. As an example, we show that the imminent Astro-H mission can use Milky Way observations to separate possible causes of the 3.5-keV line. We discuss other applications. PMID:26849582

  3. Dark Matter Velocity Spectroscopy.

    PubMed

    Speckhard, Eric G; Ng, Kenny C Y; Beacom, John F; Laha, Ranjan

    2016-01-22

    Dark matter decays or annihilations that produce linelike spectra may be smoking-gun signals. However, even such distinctive signatures can be mimicked by astrophysical or instrumental causes. We show that velocity spectroscopy-the measurement of energy shifts induced by relative motion of source and observer-can separate these three causes with minimal theoretical uncertainties. The principal obstacle has been energy resolution, but upcoming experiments will have the precision needed. As an example, we show that the imminent Astro-H mission can use Milky Way observations to separate possible causes of the 3.5-keV line. We discuss other applications.

  4. Spectroscopy of implants

    NASA Astrophysics Data System (ADS)

    Afanasyeva, Natalia I.

    1994-01-01

    The spectral criteria of selection of soft intraocular lens (IOL) implants of long service in an organism have been defined for ophthalmology. The analysis of Fourier Transform Infrared (FTIR) spectra provides the required and sufficient level of material polymerization for manufacturing non-toxic lenses for the eye. The spectral limits for determining the biocompatibility of samples can be related to the intensity ratio of two bands only in the FTIR spectra of siloxane. Siloxane-poly(urethane) block copolymers and other materials for implants have been studied. Passivated surfaces of implants have been obtained and registered by methods of Fourier Transform Spectroscopy.

  5. Standoff photo acoustic spectroscopy

    SciTech Connect

    Van Neste, Charles W; Senesac, Larry R; Thundat, Thomas George

    2008-01-01

    Here, we demonstrate a variation of photoacoustic spectroscopy that can be used for obtaining spectroscopic information of surface adsorbed chemicals in a standoff fashion. Pulsed light scattered from a target excites an acoustic resonator and the variation of the resonance amplitude as a function of illumination wavelength yields a representation of the absorption spectrum of the target. We report sensitive and selective detection of surface adsorbed compounds such as tributyl phosphate and residues of explosives such as trinitrotoluene at standoff distances ranging from 0.5-20 m, with a detection limit on the order of 100 ng/cm{sup 2}.

  6. Nanosecond fluorescence spectroscopy

    SciTech Connect

    Leskovar, B.

    1985-03-01

    This article is a summary of a short course lecture given in conjunction with the 1984 Nuclear Science Symposium. Measuring systems for nanosecond fluorescence spectroscopy using single-photon counting techniques are presented. These involve systems based on relaxation-type spark gap light pulser and synchronously pumped mode-locked dye lasers. Furthermore, typical characteristics and optimization of operating conditions of the critical components responsible for the system time resolution are discussed. A short comparison of the most important deconvolution methods for numerical analysis of experimental data is given particularly with respect to the signal-to-noise ratio of the fluorescence signal. 22 refs., 8 figs.

  7. [System of ns time-resolved spectroscopy diagnosis and radioprotection].

    PubMed

    Yao, Wei-Bo; Guo, Jian-Ming; Zhang, Yong-min; Tang, Jun-Ping; Cheng, Liang; Xu, Qi-fuo

    2014-06-01

    Cathode plasma of high current electron beam diode is an important research on high power microwave and strong pulsed radio accelerator. It is a reliable method to study cathode plasma by diagnosing the cathode plasma parameters with non-contact spectroscopy measurement system. The present paper introduced the work principle, system composition and performance of the nanosecond (ns) time-resolved spectroscopy diagnosis system. Furthermore, it introduced the implementing method and the temporal relation of lower jitter synchronous trigger system. Simultaneously, the authors designed electromagnetic and radio shield room to protect the diagnosis system due to the high electromagnetic and high X-ray and γ-ray radiation, which seriously interferes with the system. Time-resolved spectroscopy experiment on brass (H62) cathode shows that, the element and matter composition of cathode plasma is clearly increase with the increase in the diode pulsed voltage and current magnitude. The spectroscopy diagnosis system could be of up to 10 ns time resolve capability. It's least is 2 ns. Synchronous trigger system's jitter is less than 4 ns. The spectroscopy diagnosis system will open a new way to study the cathode emission mechanism in depth. PMID:25358142

  8. Visible Light Spectroscopy of GEO Debris

    NASA Technical Reports Server (NTRS)

    Seitzer, Patrick; Lederer, Susan M.; Cowardin, Heather; Barker, Edwin S.; Abercromby, Kira J.

    2012-01-01

    Our goal is to understand the physical characteristics of debris at geosynchronous orbit (GEO). Our approach is to compare the observed reflectance as a function of wavelength with laboratory measurements of typical spacecraft surfaces to understand what the materials are likely to be. Because debris could be irregular in shape and tumbling at an unknown rate, rapid simultaneous measurements over a range of wavelengths are required. Acquiring spectra of optically faint objects with short exposure times to minimize these effects requires a large telescope. We describe optical spectroscopy obtained during 12-14 March 2012 with the IMACS imaging spectrograph on the 6.5-m 'Walter Baade' Magellan telescope at Las Campanas Observatory in Chile. When used in f/2 imaging mode for acquisition, this instrument has a field of view of 30 arc-minutes in diameter. After acquisition and centering of a GEO object, a 2.5 arc-second wide slit and a grism are moved into the beam for spectroscopy. We used a 200 l/mm grism blazed at 660 nm for wavelength coverage in the 500-900 nm region. Typical exposure times for spectra were 15-30 seconds. Spectra were obtained for five objects in the GEO regime listed as debris in the US Space Command public catalog, and one high area to mass ratio GEO object. In addition spectra were obtained of three cataloged IDCSP (Initial Defense Communications Satellite Program) satellites with known initial properties just below the GEO regime. All spectra were calibrated using white dwarf flux standards and solar analog stars. We will describe our experiences using Magellan, a telescope never used previously for orbital debris spectroscopy, and our initial results.

  9. Industrial applications of photon density wave spectroscopy for in-line particle sizing [Invited].

    PubMed

    Hass, Roland; Münzberg, Marvin; Bressel, Lena; Reich, Oliver

    2013-03-01

    Optical spectroscopy in highly turbid liquid material is often restricted by simultaneous occurrence of absorption and scattering of light. Photon Density Wave (PDW) spectroscopy is one of the very few, yet widely unknown, technologies for the independent quantification of these two optical processes. Here, a concise overview about modern PDW spectroscopy is given, including all necessary equations concerning the optical description of the investigated material, dependent light scattering, particle sizing, and PDW spectroscopy itself. Additionally, it is shown how the ambiguity in particle sizing, arising from Mie theory, can be correctly solved. Due to its high temporal resolution, its applicability to highest particle concentrations, and its purely fiber-optical probe, PDW spectroscopy possesses all fundamental characteristics for optical in-line process analysis. Several application examples from the chemical industry are presented.

  10. Sequential or simultaneous visual processing deficit in developmental dyslexia?

    PubMed

    Lassus-Sangosse, Delphine; N'guyen-Morel, Marie-Ange; Valdois, Sylviane

    2008-03-01

    The ability of dyslexic children with or without phonological problems to process simultaneous and sequential visual information was assessed using two tasks requiring the oral report of simultaneously or sequentially displayed letter-strings. The two groups were found to exhibit a simultaneous visual processing deficit but preserved serial processing skills. However, the impairment in simultaneous processing was larger in the dyslexic group with no phonological disorder. Although sequential and simultaneous processing skills both related to reading performance, simultaneous processing alone significantly contributed to reading speed and accuracy. These findings suggest that a simultaneous processing disorder might contribute to developmental dyslexia.

  11. Multiple quantum coherence spectroscopy.

    PubMed

    Mathew, Nathan A; Yurs, Lena A; Block, Stephen B; Pakoulev, Andrei V; Kornau, Kathryn M; Wright, John C

    2009-08-20

    Multiple quantum coherences provide a powerful approach for studies of complex systems because increasing the number of quantum states in a quantum mechanical superposition state increases the selectivity of a spectroscopic measurement. We show that frequency domain multiple quantum coherence multidimensional spectroscopy can create these superposition states using different frequency excitation pulses. The superposition state is created using two excitation frequencies to excite the symmetric and asymmetric stretch modes in a rhodium dicarbonyl chelate and the dynamic Stark effect to climb the vibrational ladders involving different overtone and combination band states. A monochromator resolves the free induction decay of different coherences comprising the superposition state. The three spectral dimensions provide the selectivity required to observe 19 different spectral features associated with fully coherent nonlinear processes involving up to 11 interactions with the excitation fields. The different features act as spectroscopic probes of the diagonal and off-diagonal parts of the molecular potential energy hypersurface. This approach can be considered as a coherent pump-probe spectroscopy where the pump is a series of excitation pulses that prepares a multiple quantum coherence and the probe is another series of pulses that creates the output coherence. PMID:19507812

  12. Nanowire Electron Scattering Spectroscopy

    NASA Technical Reports Server (NTRS)

    Hunt, Brian; Bronikowsky, Michael; Wong, Eric; VonAllmen, Paul; Oyafuso, Fablano

    2009-01-01

    Nanowire electron scattering spectroscopy (NESS) has been proposed as the basis of a class of ultra-small, ultralow-power sensors that could be used to detect and identify chemical compounds present in extremely small quantities. State-of-the-art nanowire chemical sensors have already been demonstrated to be capable of detecting a variety of compounds in femtomolar quantities. However, to date, chemically specific sensing of molecules using these sensors has required the use of chemically functionalized nanowires with receptors tailored to individual molecules of interest. While potentially effective, this functionalization requires labor-intensive treatment of many nanowires to sense a broad spectrum of molecules. In contrast, NESS would eliminate the need for chemical functionalization of nanowires and would enable the use of the same sensor to detect and identify multiple compounds. NESS is analogous to Raman spectroscopy, the main difference being that in NESS, one would utilize inelastic scattering of electrons instead of photons to determine molecular vibrational energy levels. More specifically, in NESS, one would exploit inelastic scattering of electrons by low-lying vibrational quantum states of molecules attached to a nanowire or nanotube.

  13. Wave mixing spectroscopy

    SciTech Connect

    Smith, R.W.

    1980-08-01

    Several new aspects of nonlinear or wave mixing spectroscopy were investigated utilizing the polarization properties of the nonlinear output field and the dependence of this field upon the occurrence of multiple resonances in the nonlinear susceptibility. First, it is shown theoretically that polarization-sensitive detection may be used to either eliminate or controllably reduce the nonresonant background in coherent anti-Stokes Raman spectroscopy, allowing weaker Raman resonances to be studied. The features of multi-resonant four-wave mixing are examined in the case of an inhomogeneously broadened medium. It is found that the linewidth of the nonlinear output narrows considerably (approaching the homogeneous width) when the quantum mechanical expressions for the doubly- and triply-resonant susceptibilities are averaged over a Doppler or strain broadened profile. Experimental studies of nonlinear processes in Pr/sup +3/:LaF/sub 3/ verify this linewidth narrowing, but indicate that this strain broadened system cannot be treated with a single broadening parameter as in the case of Doppler broadening in a gas. Several susceptibilities are measured from which are deduced dipole matrix elements and Raman polarizabilities related to the /sup 3/H/sub 4/, /sup 3/H/sub 6/, and /sup 3/P/sub 0/ levels of the praseodymium ions.

  14. Simultaneous, Isolated Traumatic Bilateral Patella Fractures

    PubMed Central

    Madi, Sandesh; Naik, Monappa; Rao, Sharath; Vijayan, Sandeep

    2016-01-01

    Introduction Isolated traumatic fractures of both Patellae, occurring at the same time, in an otherwise healthy person, are very rare. The Patella, as a subcutaneous and a cancellous bone, is vulnerable to injury. However, simultaneous injury to both Patellae without the involvement of any other bony injuries occurs infrequently, and only a few cases have been reported in the literature. Case Presentation We report a rare case of isolated, traumatic bilateral Patella fracture with unusual fracture patterns and briefly review the literature. Conclusions In simultaneous bilateral Patella fractures, good functional outcome can be expected following a stable surgical fixation and a structured rehabilitation regime. However, personality of the fracture determines salvage versus sacrifice of the Patella. PMID:27218047

  15. Simultaneous CARS and Interferometric Rayleigh Scattering

    NASA Technical Reports Server (NTRS)

    Bivolaru, Daniel; Danehy, Paul M.; Grinstead, Keith D., Jr.; Tedder, Sarah; Cutler, Andrew D.

    2006-01-01

    This paper reports for the first time the combination of a dual-pump coherent anti-Stokes Raman scattering system with an interferometric Rayleigh scattering system (CARS - IRS) to provide time-resolved simultaneous measurement of multiple properties in combustion flows. The system uses spectrally narrow green (seeded Nd:YAG at 532 nm) and yellow (552.9 nm) pump beams and a spectrally-broad red (607 nm) beam as the Stokes beam. A spectrometer and a planar Fabry-Perot interferometer used in the imaging mode are used to record the spectrally broad CARS spectra and the spontaneous Rayleigh scattering spectra, respectively. Time-resolved simultaneous measurement of temperature, absolute mole fractions of N2, O2, and H2, and two components of velocity in a Hencken burner flame were performed to demonstrate the technique.

  16. Continuous Simultaneous Detection in Mass Spectrometry

    SciTech Connect

    Schilling, G. D.; Andrade, Francisco J.; Barnes IV., James H.; Sperline, Roger P.; Denton, M. Bonner; Barinaga, Charles J.; Koppenaal, David W.; Hieftje, Gary M.

    2007-10-15

    In mass spectrometry, several advantages can be derived when multiple mass-to-charge values are detected simultaneously. One such advantage is an improved duty cycle, which leads to superior limits of detection, better precision, shorter analysis times, and reduced sample sizes. A second advantage is the ability to reduce correlated noise by taking the ratio of two or more simultaneously collected signals, enabling greatly enhanced isotope ratio data. A final advantage is the elimination of spectral skew, leading to more accurate transient signal analysis. Here, these advantages are demonstrated by means of a novel Faraday-strip array detector coupled to a Mattauch-Herzog mass spectrograph. The same system is used to monitor elemental fractionation phenomena in laser ablation inductively coupled plasma mass spectrometry.

  17. Tool For Driving Many Fasteners Simultaneously

    NASA Technical Reports Server (NTRS)

    Cook, Joseph S., Jr.

    1995-01-01

    Proposed tool tightens or loosens several bolts, screws, nuts, or other threaded fasteners arranged in circle on compressor head, automotive wheel, pipe-end flange, or similar object. Enables assembly or disassembly in fraction of time needed to tighten fasteners one at a time. Simultaneously applies same torque to all fasteners, preventing distortion and enhancing reliability. Concept not limited to circular fastener patterns. Adapted to rectangular configurations like on engine intake manifolds, by adding gears to drive train to provide proper spacing. Designed to deliver fixed or adjustable maximum torque. To ensure even seal loading, piston pressure simultaneously ramped from initial to final values to maintain relatively constant torque loading on all fasteners until final specifications limit achieved.

  18. Simultaneous dynamic optical and electrical properties of endothelial cell attachment on indium tin oxide bioelectrodes.

    PubMed

    Choi, Chang K; English, Anthony E; Kihm, Kenneth D; Margraves, Charles H

    2007-01-01

    This study quantifies the dynamic attachment and spreading of porcine pulmonary artery endothelial cells (PPAECs) on optically thin, indium tin oxide (ITO) biosensors using simultaneous differential interference contrast microscopy (DICM) and electrical microimpedance spectroscopy. A lock-in amplifier circuit monitored the impedance of PPAECs cultivated on the transparent ITO bioelectrodes as a function of frequency between 10 Hz and 100 kHz and as a function of time, while DICM images were simultaneously acquired. A digital image processing algorithm quantified the cell-covered electrode area as a function of time. The results of this study show that the fraction of the cell-covered electrode area is in qualitative agreement with the electrical impedance during the attachment phase following the cell settling on the electrode surface. The possibility of several distinctly different states of electrode coverage and cellular attachment giving rise to similar impedance signals is discussed. PMID:18163844

  19. Understanding catalyst behavior during in situ heating through simultaneous secondary and transmitted electron imaging

    PubMed Central

    2014-01-01

    By coupling techniques of simultaneous secondary (SE) and transmitted electron (TE) imaging at high resolution in a modern scanning transmission electron microscope (STEM), with the ability to heat specimens using a highly stable MEMS-based heating platform, we obtained synergistic information to clarify the behavior of catalysts during in situ thermal treatments. Au/iron oxide catalyst 'leached' to remove surface Au was heated to temperatures as high as 700°C. The Fe2O3 support particle structure tended to reduce to Fe3O4 and formed surface terraces; the formation, coalescence, and mobility of 1- to 2-nm particles on the terraces were characterized in SE, STEM-ADF, and TEM-BF modes. If combined with simultaneous nanoprobe spectroscopy, this approach will open the door to a new way of studying the kinetics of nano-scaled phenomena. PMID:25419195

  20. Note: Time-gated 3D single quantum dot tracking with simultaneous spinning disk imaging

    SciTech Connect

    DeVore, M. S.; Stich, D. G.; Keller, A. M.; Phipps, M. E.; Hollingsworth, J. A.; Goodwin, P. M.; Werner, J. H.; Cleyrat, C.; Lidke, D. S.; Wilson, B. S.

    2015-12-15

    We describe recent upgrades to a 3D tracking microscope to include simultaneous Nipkow spinning disk imaging and time-gated single-particle tracking (SPT). Simultaneous 3D molecular tracking and spinning disk imaging enable the visualization of cellular structures and proteins around a given fluorescently labeled target molecule. The addition of photon time-gating to the SPT hardware improves signal to noise by discriminating against Raman scattering and short-lived fluorescence. In contrast to camera-based SPT, single-photon arrival times are recorded, enabling time-resolved spectroscopy (e.g., measurement of fluorescence lifetimes and photon correlations) to be performed during single molecule/particle tracking experiments.

  1. Quantitative Comparison of Tumor Delivery for Multiple Targeted Nanoparticles Simultaneously by Multiplex ICP-MS

    NASA Astrophysics Data System (ADS)

    Elias, Andrew; Crayton, Samuel H.; Warden-Rothman, Robert; Tsourkas, Andrew

    2014-07-01

    Given the rapidly expanding library of disease biomarkers and targeting agents, the number of unique targeted nanoparticles is growing exponentially. The high variability and expense of animal testing often makes it unfeasible to examine this large number of nanoparticles in vivo. This often leads to the investigation of a single formulation that performed best in vitro. However, nanoparticle performance in vivo depends on many variables, many of which cannot be adequately assessed with cell-based assays. To address this issue, we developed a lanthanide-doped nanoparticle method that allows quantitative comparison of multiple targeted nanoparticles simultaneously. Specifically, superparamagnetic iron oxide (SPIO) nanoparticles with different targeting ligands were created, each with a unique lanthanide dopant. Following the simultaneous injection of the various SPIO compositions into tumor-bearing mice, inductively coupled plasma mass spectroscopy was used to quantitatively and orthogonally assess the concentration of each SPIO composition in serial blood and resected tumor samples.

  2. Quantitative Comparison of Tumor Delivery for Multiple Targeted Nanoparticles Simultaneously by Multiplex ICP-MS

    PubMed Central

    Elias, Andrew; Crayton, Samuel H.; Warden-Rothman, Robert; Tsourkas, Andrew

    2014-01-01

    Given the rapidly expanding library of disease biomarkers and targeting agents, the number of unique targeted nanoparticles is growing exponentially. The high variability and expense of animal testing often makes it unfeasible to examine this large number of nanoparticles in vivo. This often leads to the investigation of a single formulation that performed best in vitro. However, nanoparticle performance in vivo depends on many variables, many of which cannot be adequately assessed with cell-based assays. To address this issue, we developed a lanthanide-doped nanoparticle method that allows quantitative comparison of multiple targeted nanoparticles simultaneously. Specifically, superparamagnetic iron oxide (SPIO) nanoparticles with different targeting ligands were created, each with a unique lanthanide dopant. Following the simultaneous injection of the various SPIO compositions into tumor-bearing mice, inductively coupled plasma mass spectroscopy was used to quantitatively and orthogonally assess the concentration of each SPIO composition in serial blood and resected tumor samples. PMID:25068300

  3. Note: Time-gated 3D single quantum dot tracking with simultaneous spinning disk imaging.

    PubMed

    DeVore, M S; Stich, D G; Keller, A M; Cleyrat, C; Phipps, M E; Hollingsworth, J A; Lidke, D S; Wilson, B S; Goodwin, P M; Werner, J H

    2015-12-01

    We describe recent upgrades to a 3D tracking microscope to include simultaneous Nipkow spinning disk imaging and time-gated single-particle tracking (SPT). Simultaneous 3D molecular tracking and spinning disk imaging enable the visualization of cellular structures and proteins around a given fluorescently labeled target molecule. The addition of photon time-gating to the SPT hardware improves signal to noise by discriminating against Raman scattering and short-lived fluorescence. In contrast to camera-based SPT, single-photon arrival times are recorded, enabling time-resolved spectroscopy (e.g., measurement of fluorescence lifetimes and photon correlations) to be performed during single molecule/particle tracking experiments.

  4. Photoelectron photoion molecular beam spectroscopy

    SciTech Connect

    Trevor, D.J.

    1980-12-01

    The use of supersonic molecular beams in photoionization mass spectroscopy and photoelectron spectroscopy to assist in the understanding of photoexcitation in the vacuum ultraviolet is described. Rotational relaxation and condensation due to supersonic expansion were shown to offer new possibilities for molecular photoionization studies. Molecular beam photoionization mass spectroscopy has been extended above 21 eV photon energy by the use of Stanford Synchrotron Radiation Laboratory (SSRL) facilities. Design considerations are discussed that have advanced the state-of-the-art in high resolution vuv photoelectron spectroscopy. To extend gas-phase studies to 160 eV photon energy, a windowless vuv-xuv beam line design is proposed.

  5. Simultaneous Multiple-Location Separation Control

    NASA Technical Reports Server (NTRS)

    Greenblatt, David (Inventor)

    2009-01-01

    A method of controlling a shear layer for a fluid dynamic body introduces first periodic disturbances into the fluid medium at a first flow separation location. Simultaneously, second periodic disturbances are introduced into the fluid medium at a second flow separation location. A phase difference between the first and second periodic disturbances is adjusted to control flow separation of the shear layer as the fluid medium moves over the fluid dynamic body.

  6. Chemically modified Si(111) surfaces simultaneously demonstrating hydrophilicity, resistance against oxidation, and low trap state densities

    NASA Astrophysics Data System (ADS)

    Brown, Elizabeth S.; Hlynchuk, Sofiya; Maldonado, Stephen

    2016-03-01

    Chemically modified Si(111) surfaces have been prepared through a series of wet chemical surface treatments that simultaneously show resistance towards surface oxidation, selective reactivity towards chemical reagents, and areal defect densities comparable to unannealed thermal oxides. Specifically, grazing angle attenuated total reflectance infrared and X-ray photoelectron (XP) spectroscopies were used to characterize allyl-, 3,4-methylenedioxybenzene-, or 4-[bis(trimethylsilyl)amino]phenyl-terminated surfaces and the subsequently hydroxylated surfaces. Hydroxylated surfaces were confirmed through reaction with 4-(trifluoromethyl)benzyl bromide and quantified by XP spectroscopy. Contact angle measurements indicated all surfaces remained hydrophilic, even after secondary backfilling with CH3sbnd groups. Surface recombination velocity measurements by way of microwave photoconductivity transients showed the relative defect-character of as-prepared and aged surfaces. The relative merits for each investigated surface type are discussed.

  7. Large-scale Growth and Simultaneous Doping of Molybdenum Disulfide Nanosheets

    NASA Astrophysics Data System (ADS)

    Kim, Seong Jun; Kang, Min-A.; Kim, Sung Ho; Lee, Youngbum; Song, Wooseok; Myung, Sung; Lee, Sun Sook; Lim, Jongsun; An, Ki-Seok

    2016-04-01

    A facile method that uses chemical vapor deposition (CVD) for the simultaneous growth and doping of large-scale molybdenum disulfide (MoS2) nanosheets was developed. We employed metalloporphyrin as a seeding promoter layer for the uniform growth of MoS2 nanosheets. Here, a hybrid deposition system that combines thermal evaporation and atomic layer deposition (ALD) was utilized to prepare the promoter. The doping effect of the promoter was verified by X-ray photoelectron spectroscopy and Raman spectroscopy. In addition, the carrier density of the MoS2 nanosheets was manipulated by adjusting the thickness of the metalloporphyrin promoter layers, which allowed the electrical conductivity in MoS2 to be manipulated.

  8. Simultaneous parallel inclined readout image technique.

    PubMed

    Paley, Martyn N J; Lee, Kuan J; Wild, James M; Griffiths, Paul D; Whitby, Elspeth H

    2006-06-01

    Sensitivity-encoded phase undersampling has been combined with simultaneous slice excitation to produce a parallel MRI method with a high volumetric acquisition acceleration factor without the need for auxiliary stepped field coils. Dual-slice excitation was produced by modulating both spin and gradient echo sequences at +/-6 kHz. Frequency aliasing of simultaneously excited slices was prevented by using an additional gradient applied along the slice axis during data acquisition. Data were acquired using a four-channel receiver array and x4 sensitivity encoding on a 1.5 T MR system. The simultaneous parallel inclined readout image technique has been successfully demonstrated in both phantoms and volunteers. A multiplicative image acquisition acceleration factor of up to x8 was achieved. Image SNR and resolution was dependent on the ratio of the readout gradient to the additional slice gradient. A ratio of approximately 2:1 produced acceptable image quality. Use of RF pulses with additional excitation bands should enable the technique to be extended to volumetric acquisition acceleration factors in the range of x16-24 without the SNR limitations of pure partially parallel phase reduction methods.

  9. Simultaneous Statistical Inference for Epigenetic Data

    PubMed Central

    Schildknecht, Konstantin; Olek, Sven; Dickhaus, Thorsten

    2015-01-01

    Epigenetic research leads to complex data structures. Since parametric model assumptions for the distribution of epigenetic data are hard to verify we introduce in the present work a nonparametric statistical framework for two-group comparisons. Furthermore, epigenetic analyses are often performed at various genetic loci simultaneously. Hence, in order to be able to draw valid conclusions for specific loci, an appropriate multiple testing correction is necessary. Finally, with technologies available for the simultaneous assessment of many interrelated biological parameters (such as gene arrays), statistical approaches also need to deal with a possibly unknown dependency structure in the data. Our statistical approach to the nonparametric comparison of two samples with independent multivariate observables is based on recently developed multivariate multiple permutation tests. We adapt their theory in order to cope with families of hypotheses regarding relative effects. Our results indicate that the multivariate multiple permutation test keeps the pre-assigned type I error level for the global null hypothesis. In combination with the closure principle, the family-wise error rate for the simultaneous test of the corresponding locus/parameter-specific null hypotheses can be controlled. In applications we demonstrate that group differences in epigenetic data can be detected reliably with our methodology. PMID:25965389

  10. Freeform object design and simultaneous manufacturing

    NASA Astrophysics Data System (ADS)

    Zhang, Wei; Zhang, Weihan; Lin, Heng; Leu, Ming C.

    2003-04-01

    Today's product design, especially the consuming product design, focuses more and more on individuation, originality, and the time to market. One way to meet these challenges is using the interactive and creationary product design methods and rapid prototyping/rapid tooling. This paper presents a novel Freeform Object Design and Simultaneous Manufacturing (FODSM) method that combines the natural interaction feature in the design phase and simultaneous manufacturing feature in the prototyping phase. The natural interactive three-dimensional design environment is achieved by adopting virtual reality technology. The geometry of the designed object is defined through the process of "virtual sculpting" during which the designer can touch and visualize the designed object and can hear the virtual manufacturing environment noise. During the designing process, the computer records the sculpting trajectories and automatically translates them into NC codes so as to simultaneously machine the designed part. The paper introduced the principle, implementation process, and key techniques of the new method, and compared it with other popular rapid prototyping methods.

  11. Simultaneous Dual-Species Atom Interferometry

    NASA Astrophysics Data System (ADS)

    Bonnin, Alexis; Zahzam, Nassim; Bidel, Yannick; Bresson, Alexandre; Sensors; Micro Technologie unit Team

    2015-05-01

    In the context of testing the Weak Equivalence Principle (WEP) with matter-wave accelerometers, some projects under development aim to compare the acceleration of two different atomic species during few seconds of free fall in order to achieve highly sensitive measurements. A simultaneous interrogation of both atomic species is crucial to fully take advantage of a differential measurement. We report the realization of an atom interferometer based on Raman transitions which simultaneously interrogates both isotopes of Rubidium. The simultaneous aspect of our experiment allows the resolution of the differential accelerometer to remain lower than 7.10-9 g even with vibration levels up to 3.10-3 g thanks to common-mode vibration noise rejection. These results exhibit a rejection ratio of 90 dB. An atom based test of the WEP has been carried out leading to a differential free fall measurement between both isotopes of Δg / g =(1 . 2 +/- 3 . 2) ×10-7 .

  12. Simultaneous nano-tracking of multiple motor proteins via spectral discrimination of quantum dots

    PubMed Central

    Kakizuka, Taishi; Ikezaki, Keigo; Kaneshiro, Junichi; Fujita, Hideaki; Watanabe, Tomonobu M.; Ichimura, Taro

    2016-01-01

    Simultaneous nanometric tracking of multiple motor proteins was achieved by combining multicolor fluorescent labeling of target proteins and imaging spectroscopy, revealing dynamic behaviors of multiple motor proteins at the sub-diffraction-limit scale. Using quantum dot probes of distinct colors, we experimentally verified the localization precision to be a few nanometers at temporal resolution of 30 ms or faster. One-dimensional processive movement of two heads of a single myosin molecule and multiple myosin molecules was successfully traced. Furthermore, the system was modified for two-dimensional measurement and applied to tracking of multiple myosin molecules. Our approach is useful for investigating cooperative movement of proteins in supramolecular nanomachinery. PMID:27446684

  13. Simultaneous Temperature and Velocity Measurements in a Large-Scale, Supersonic, Heated Jet

    NASA Technical Reports Server (NTRS)

    Danehy, P. M.; Magnotti, G.; Bivolaru, D.; Tedder, S.; Cutler, A. D.

    2008-01-01

    Two laser-based measurement techniques have been used to characterize an axisymmetric, combustion-heated supersonic jet issuing into static room air. The dual-pump coherent anti-Stokes Raman spectroscopy (CARS) measurement technique measured temperature and concentration while the interferometric Rayleigh scattering (IRS) method simultaneously measured two components of velocity. This paper reports a preliminary analysis of CARS-IRS temperature and velocity measurements from selected measurement locations. The temperature measurements show that the temperature along the jet axis remains constant while dropping off radially. The velocity measurements show that the nozzle exit velocity fluctuations are about 3% of the maximum velocity in the flow.

  14. Nuclear resonant spectroscopy

    NASA Astrophysics Data System (ADS)

    Sturhahn, Wolfgang

    2004-02-01

    Nuclear resonant scattering techniques with synchrotron radiation (SR) are introduced on a basic level. We focus on the theoretical background and on experimental aspects of two popular methods with a widening range of applications, nuclear resonant inelastic x-ray scattering and synchrotron Mössbauer spectroscopy. The inelastic method provides specific vibrational information, e.g., the phonon density of states. The Mössbauer method permits determination of hyperfine interactions. All nuclear resonance techniques take full advantage of the unique properties of SR: intensity, collimation, time structure, and polarization. As a result both methods discussed here have led to novel applications for materials under extreme conditions, proteins with biological functionality, and magnetic nanostructures.

  15. Resonant ultrasound spectroscopy

    DOEpatents

    Migliori, Albert

    1991-01-01

    A resonant ultrasound spectroscopy method provides a unique characterization of an object for use in distinguishing similar objects having physical differences greater than a predetermined tolerance. A resonant response spectrum is obtained for a reference object by placing excitation and detection transducers at any accessible location on the object. The spectrum is analyzed to determine the number of resonant response peaks in a predetermined frequency interval. The distribution of the resonance frequencies is then characterized in a manner effective to form a unique signature of the object. In one characterization, a small frequency interval is defined and stepped though the spectrum frequency range. Subsequent objects are similarly characterized where the characterizations serve as signatures effective to distinguish objects that differ from the reference object by more than the predetermined tolerance.

  16. Transient infrared transmission spectroscopy

    SciTech Connect

    Jones, R.W.; McClelland, J.F. )

    1990-10-15

    Transient infrared transmission spectroscopy is a new method that can acquire analytically useful transmission spectra from moving, optically thick solids. No sample preparation is required. The spectra are of sufficient quality for accurate quantitative compositional analysis. The method works by the creation of a thin, short-lived, chilled layer at the sample surface. Blackbody-like thermal emission from the bulk of the sample is selectively absorbed as it passes through the chilled layer, so the transmission spectrum of the layer is superimposed on the observed thermal emission. Spectra of polycarbonate, beeswax, and copolymers of methyl and butyl methacrylate are presented. Compositional analysis of the methacrylate copolymers with a standard error or prediction of only 0.87 mol % is demonstrated.

  17. Transient infrared transmission spectroscopy.

    PubMed

    Jones, R W; McClelland, J F

    1990-10-15

    Transient infrared transmission spectroscopy is a new method that can acquire analytically useful transmission spectra from moving, optically thick solids. No sample preparation is required. The spectra are of sufficient quality for accurate quantitative compositional analysis. The method works by the creation of a thin, short-lived, chilled layer at the sample surface. Blackbody-like thermal emission from the bulk of the sample is selectively absorbed as it passes through the chilled layer, so the transmission spectrum of the layer is superimposed on the observed thermal emission. Spectra of polycarbonate, beeswax, and copolymers of methyl and butyl methacrylate are presented. Compositional analysis of the methacrylate copolymers with a standard error of prediction of only 0.87 mol % is demonstrated.

  18. Quantitative velocity modulation spectroscopy

    NASA Astrophysics Data System (ADS)

    Hodges, James N.; McCall, Benjamin J.

    2016-05-01

    Velocity Modulation Spectroscopy (VMS) is arguably the most important development in the 20th century for spectroscopic study of molecular ions. For decades, interpretation of VMS lineshapes has presented challenges due to the intrinsic covariance of fit parameters including velocity modulation amplitude, linewidth, and intensity. This limitation has stifled the growth of this technique into the quantitative realm. In this work, we show that subtle changes in the lineshape can be used to help address this complexity. This allows for determination of the linewidth, intensity relative to other transitions, velocity modulation amplitude, and electric field strength in the positive column of a glow discharge. Additionally, we explain the large homogeneous component of the linewidth that has been previously described. Using this component, the ion mobility can be determined.

  19. Hadron spectroscopy at RHIC

    SciTech Connect

    Chung, S.U.; Kern, W.; Willutzki, H.J.

    1990-08-01

    A description is given of the physics opportunities at RHIC regarding quark-gluon spectroscopy. The basic idea is to isolate with appropriate triggers the subprocesses pomeron + pomeron {yields} hadrons and {gamma}* + {gamma}* {yields} hadrons with the net effective mass of hadrons in the range of 1.0 to 3.0 GeV, in order to study the hadronic states composed of u, d, and s and gluons. The double-pomeron interactions are expected to produce glueballs and hybrids preferentially, while the two-offshell-photon initial states should couple predominantly to quarkonia and multiquark states. A plethora of J{sup PC}-exotic mesons can be produced either directly in both types of interactions or in association with a single recoil photon in the final state. 8 refs., 2 figs.

  20. Electron spectroscopy analysis

    NASA Technical Reports Server (NTRS)

    Gregory, John C.

    1992-01-01

    The Surface Science Laboratories at the University of Alabama in Huntsville (UAH) are equipped with x-ray photoelectron spectroscopy (XPS or ESCA) and Auger electron spectroscopy (AES) facilities. These techniques provide information from the uppermost atomic layers of a sample, and are thus truly surface sensitive. XPS provides both elemental and chemical state information without restriction on the type of material that can be analyzed. The sample is placed into an ultra high vacuum (UHV) chamber and irradiated with x-rays which cause the ejection of photoelectrons from the sample surface. Since x-rays do not normally cause charging problems or beam damage, XPS is applicable to a wide range of samples including metals, polymers, catalysts, and fibers. AES uses a beam of high energy electrons as a surface probe. Following electronic rearrangements within excited atoms by this probe, Auger electrons characteristic of each element present are emitted from the sample. The main advantage of electron induced AES is that the electron beam can be focused down to a small diameter and localized analysis can be carried out. On the rastering of this beam synchronously with a video display using established scanning electron microscopy techniques, physical images and chemical distribution maps of the surface can be produced. Thus very small features, such as electronic circuit elements or corrosion pits in metals, can be investigated. Facilities are available on both XPS and AES instruments for depth-profiling of materials, using a beam of argon ions to sputter away consecutive layers of material to reveal sub-surface (and even semi-bulk) analyses.