dataesr/scientific-paragraphs-categorization huggingface dataset:
Information (SI) available: CVs of P2W15CuAle, Sb2W18Cu3, SbW9CuAle and SiW9CuAle in a pH 5 and pH 1 medium. Table of the value of the catalytic efficiency CAT at different values of the excess parameter    3 - 0 1 medium. This material is available free of charge via the Internet at http://pub. acs/org. ACKNOWLEDGMENT This work was supported by the Ministère de l'Enseignement Supérieur et de la Recherche, the CNRS, the Université de Versailles Saint Quentin en Yvelines, the Université de Strasbourg, the Université Paris XI and a public grant overseen by the French National Research Agency (ANR) as part of the "Investissements d'Avenir" program n°ANR-11-IDEX-0003-02 and the Labex CHARMMMAT ANR-11-LABX-0039. We also thank the Labex CSC of the University of Strasbourg for financial support.
 Information (SI) available: CVs of P2W15CuAle, Sb2W18Cu3, SbW9CuAle and SiW9CuAle in a pH 5 and pH 1 medium. Table of the value of the catalytic efficiency CAT at different values of the excess parameter    3 - 0 1 medium. This material is available free of charge via the Internet at http://pub. acs/org. ACKNOWLEDGMENT This work was supported by the Ministère de l'Enseignement Supérieur et de la Recherche, the CNRS, the Université de Versailles Saint Quentin en Yvelines, the Université de Strasbourg, the Université Paris XI and a public grant overseen by the French National Research Agency (ANR) as part of the "Investissements d'Avenir" program n°ANR-11-IDEX-0003-02 and the Labex CHARMMMAT ANR-11-LABX-0039. We also thank the Labex CSC of the University of Strasbourg for financial support.
The first implementation and use of an in situ size exclusion chromatography (SEC) system on a small-angle neutron scattering instrument (SANS) is described. The possibility of deploying such a system for biological solution scattering at the Institut Laue-Langevin (ILL) has arisen from the fact that current day SANS instruments at ILL now allow datasets to be acquired using small sample volumes with exposure times that are often shorter than a minute. This capability is of particular importance for the study of unstable biological macromolecules where aggregation or denaturation issues are a major problem. The first use of SEC-SANS on ILL's instrument D22 is described for a variety of proteins including one particularly aggregation-prone system.
g. nucleic acid/protein complexes) or by selective deuteration (e. g. protein-protein complexes). SANS data collection is also effectively free of the effects of radiation damage -something that is often a major problem in SAXS work. The growth in the use of SAXS methods by structural biologists over the past 20 years or so has occurred as a result of developments in instrumentation at SR sources, as well as the availability of user-friendly analysis software. There has also been greatly increased use of SANS methods in structural biology in the recent past, with major developments in detector technology, beamline fluxes and sample provision having a strong impact on the uptake of the technique. The high demand for SAS capabilities has meant that a number of central facilities operate dedicated instruments for biological SAXS  (Pernot et al.
, 2013; Tsutakawa et al. , 2007; Tsuruta et al. , 1998)  and SANS  (Heller et al. , 2014). These accommodate efficient sample managing systems that allow high-throughput data collection  (Round et al. , 2015; Martel et al. , 2012; Hura et al. , 2009). One of the more recent developments for SAXS has been the availability of in situ size exclusion chromatography  (David & Perez, 2009; Round et al. , 2013)  (SEC), which allows SAXS data to be collected from freshly purified sample material. In this paper we describe the first SANS measurements carried out in combination with an in situ SEC system on instrument D22 at the Institut Laue-Langevin (ILL). This development has only been possible because the high neutron flux on this instrument allows short exposure times on relatively small sample volumes.
SANS data recording and reduction SANS data were recorded on diffractometers D11 (static measurement of freshly purified sample) and D22 (in situ chromatography) of ILL. The in situ size exclusion chromatography was performed using an AKTAPrime system (GE Healthcare) with a Superdex 75 Column 10/300 GL. The samples were manually injected and then sequentially passed through the size exclusion column, the spectrophotometer Setup of in situ chromatography SANS. The sample is manually injected into the loop (1), then it passes through the size exclusion column (2), the SANS sample cell (3), the UV-visible spectrophotometer (4) and the valve (  5 ), which directs it either to the fraction collector (6) or to the waste container (6 0 ). measurement cell and the SANS measurement cell before being collected in a fraction collector (Fig.
SANS instrument configurations SEC-SANS measurements on instrument D22 were carried out using a neutron wavelength of 6 A ˚AE 10%, detector distances of 8, 4 or 2 m, a rectangular collimation system of 55 Â 40 mm having the same length as the sample-detector distance, and a rectangular sample aperture of 7 Â 10 mm. The sample holder was a Suprasil quartz cell of 1 mm sample thickness placed in the 'stopped-flow head'  (Grillo, 2009). The exposure time was 30 s. Sample injection started at the same time as SANS data acquisition. The whole setup was maintained at a temperature of 288 K. In both experiments, the data were reduced using the GRASP software (https://www. ill. eu/instruments-support/ instruments-groups/groups/lss/grasp/home/) and analyzed using Igor NCNR SANS reduction macros  (Kline, 2006).
Vitamin B12 was visible on the UV absorbance plot but the signal was too small to be analyzed by SANS. The stagger of these plots reflects the time taken for the sample to travel from the SANS measurement cell to the UV absorbance measurement cell and has to be accounted for in concentration normalization. The UV absorbance profile shows that the separated proteins do not re-mix significantly following their passage through the relatively large SANS measurement cell. Even protonated protein in an H 2 O buffer (the worst combination in terms of the contribution to data from hydrogen incoherent scattering) can be successfully subjected to a SEC-SANS analysis. Data recorded during the gel filtration in D 2 O buffer were submitted to a Guinier analysis using the GRASP software, and the results are compared with literature data in Table  1.
Ultracentrifugation measurements later confirmed the presence of trimers and monomers. As we know the oligomeric state of all present species, the SANS curve can then be fitted with the contribution of model oligomers using the FoXS software  (Schneidman-Duhovny et al. , 2010)  or Oligomer from the ATSAS suite  (Konarev et al. , 2003)  to estimate the volume fraction of each mixture component. Such an analysis will be detailed in a later publication, together with results of analytical ultracentrifugation.
Conclusion and future perspectives The high neutron fluxes available on ILL SANS instruments, combined with a low-background spectrometer (like D22), enable the acquisition of high-quality data with short exposure times. However, to fully exploit this flux to characterize aggregation-prone biomacromolecules in solution, an online size exclusion chromatography capability offers major advantages for the study of difficult or complex systems. The results clearly demonstrate the feasibility of the SEC-SANS approach and that it brings real benefits to structural studies of aggregation-prone biomolecules that could not be measured in their monomeric state using a conventional experimental arrangement. The Alba3 results show that the SANS signal from the monomer can be separated from that of its aggregates.
Following this proof of concept, a dedicated chromatography system, integrated with the instrument hardware and control software, will be implemented in order to tackle new 'sensitive' protein structures. Full integration of SEC with the instrument data acquisition will enable us to reduce the flow rate when the protein reaches the scattering measurement cell in order to achieve better statistics (if needed) without affecting the concentration and possible aggregation. In addition, data recorded in streaming mode through the entire sequence will allow finer and better data post processing.
Acknowledgements The authors acknowledge ILL for funding this development and for the beamtime allocated on the D11 and D22 ILL instruments, as well as  David Bowyer  for his participation in the setup of some experiments. VTF acknowledges support from  EPSRC  for grants  GR/R99393/01 ,  EP/C015452/1  under which the  Deuteration Laboratory (D-Lab)  was created within ILL's  Life Sciences group.
The two-dimensional powder diffraction data were then treated using the software FIT2D  (Hammersley, 2016)  in order to obtain intensity I versus Bragg angle plots Ið2Þ. Ið2Þ data obtained for various thin-film depths z were used to compile three-dimensional plots Ið2; zÞ. Other details describing cross-sectional X-ray nanodiffraction can be found in our previous reports  (Keckes et al. , 2012; Bartosik et al. , 2013).
In all three films, the overall nitrogen concentration was approximately stoichiometric. Electron energy loss spectroscopy (not presented here), however, showed an oscillation of nitrogen concentration across the lamellae. The HR-TEM analysis of the film (Fig. 4b ) from position II (cf. Fig. 2a ) indicated (i) that in this region film A consisted of cubic and hexagonal nanolamellae, giving rise to the hexagonal and cubic peaks in Fig. 2 (a), and (ii) that the interfaces between hexagonal Al(Ti)N and cubic Ti(Al)N lamellae were incoherent. HR-TEM data collected from film position I (cf. Fig. 2a ) indicated that hexagonal lamellae were no longer present in the film, which is in agreement with the XRD data from Fig. 2(a). This region of film A consisted of predominantly coherent c-Al(Ti)N and c-Ti(Al)N lamellae, shown in detail in Fig.
Acknowledgements The authors greatly appreciate the support from the  Austrian funding agency FFG  within the project 841137; from the  Austrian Federal Government  (in particular from  Bundesministerium fu ¨r Verkehr, Innovation und Technologie and Bundesministerium fu ¨r Wirtschaft ,  Familie und Jugend ) represented by O ¨sterreichische Forschungsfo ¨rderungsgesellschaft mbH; and from the  Styrian  and the  Tyrolean Provincial Government , represented by  Steirische Wirtschaftsfo ¨rderungsgesellschaft mbH and Standortagentur Tirol , within the framework of the  COMET Funding Programme. A part of the work has received research funding from the  European Union , within the large collaborative project  ISTRESS , grant agreement No. 604646. The nanodiffraction experiments were performed on the ID13 beamline at the  ESRF, Grenoble, France.
Acknowledgements This work was funded by  C'Nano Ile de France  and by the  French ANR agency  (contract no. ANR-11-BS08-02 ,  HIMO2 ). We thank the  Soleil Synchrotron (Saint-Aubin, France)  for the award of beam-time 20130644 and  Javier Perez  for local contact during the SAXS experiments. We thank  V. Peyre ,  O. Tache ,  P. Picot ,  B. Sarrazin  and  D. Petermann  for technical assistance, and  A. Fernandez-Martinez ,  J. C. Gabriel ,  O. Poncelet  and  E. Trizac  for helpful discussions.
[18] On increasing pressure further, both frameworks begin to compress,before plateauing at 1. 15 and 1. 20 GPa in UiO-67 and UiO-abdc,respectively. UiO-67 then remains almost incompressible to 2. 4 GPa, while UiOabdc displays similar behavior to 4. 8 GPa. Theoverall change in unit cell volume of the solvated UiO-abdc of less than 1. 2 % for such al arge pressure regime is highly unusual. Experimental bulk moduli (K)were extracted from the experimental cell volume-pressure relationships using EoS Fit(Supporting Information, Section SI-4). [19] Bulk moduli over as imilar pressure range (0-2 GPa) of 174 GPa and 580 GPa for UiO-67 and UiO-abdc in MeOH were determined from the experimental data, though these numbers cannot be compared to existing literature data owing to the over-solvated state of both frameworks.
In comparison, the effect on the robustness or mechanical stability of the framework is much bigger:asixfold increase in its hydrostatic pressure at which it loses crystallinity. To look at the response of the material under ad ifferent mechanical stimulation, we probed evacuated single crystals of UiO-67 and UiO-abdc by nanoindentation, to determine their Youngs moduli, E,and hardness, H. Single-crystal X-ray diffraction was performed to establish Miller indices of the crystal facets (Supporting Information, Section SI-5). Using the load-displacement data (Supporting Information, Section SI-6) gained during the indentation, E and H were calculated as afunction of depth. Theaverage values for each sample were calculated as E = 20. 02 GPa and H = 1. 27 GPa (UiO-67), and E = 13. 24 GPa and H = 0.
Acknowledgements C. L. H. thanks the  EPSRC  and the  University of Edinburgh  for as tudentship. C. A. M. acknowledges the  UK Car-Parrinello consortium  ( EP/K01465X/1 ) for access to the high performance computing resource ARCHER, as managed by the  Edinburgh Parallel Computing Centre (EPCC). T. D. B. acknowledges  Tr inity Hall (University of Cambridge ) for funding,and  A. K. C. for use of lab facilities. R. S. F. thanks the  Royal Society for receipt of aUniversity Research Fellowship  and  EPSRC  ( EP/L004461/1 ) for funding. F. X. C. a cknowledges the access of HPC resources from  GENCI  (grant  i2015087069 ). We acknowledge  Diamond Light Source  for beamtime. T he authors gratefully acknowledge pump-priming funding from the  EPSRC directed assembly network  ( PP 14 05 03 ). Thed ata which underpin this work are available at http://dx.
Acknowledgements This work was supported by the  EU Graphene Flagship Project , the  Engineering and Physical Sciences Research Council (EPSRC ,  EP/M012700/1 ), the  Royal Society , the  National Academy of Sciences of Ukraine, European Research Council  ( ERC-2012-AdG-320590-MOMB  and  ERC Synergy Grant   Hetero2D ),  LNCMI-CNRS , member of the  European Magnetic Field Laboratory (EMFL) , and by  EPSRC  via its membership to the EMFL ( EP/N01085X/1 ). This work made use of the computing facilities of N8  HPC  provided and funded by the  N8  consortium and  EPSRC  ( EP/K000225/1 ), the  Computational Shared Facility at the University of Manchester , and.
In Section III A we estimate various effects related to current flow in the sample, including the effect of the resulting fields on ARPES and the important question of Joule heating. (with details relegated to Appendices A through E). We note that the analysis of Joule heating is central to our work, since only then can we prove that we observe the nontrivial effects of current flow below the sample T c , rather than the known effects of heating the sample above T c. We should also emphasize that our ARPES measurements were taken when the resistance of the samples with current flow was only one third of the "zero-current" resistance above T c , thus Joule heating was small enough not to raise the sample temperature above T c. In Section III B, we present the ARPES data in the present of current flow and contrast the behavior observed in underdoped and overdoped cuprates.
II. EXPERIMENTAL DETAILS We utilize thin (∼500 Å) films of Bi 2 Sr 2 CaCu 2 O 8+δ (Bi2212) prepared by RF sputtering on SrTiO 3 (STO) substrates. These samples possess ARPES and transport characteristics very similar to those of single crystals, but their small cross sections allow us to obtain high current densities of ∼10 6 A/cm 2 using modest values of the current (≤200mA). The films also display small signals from the structural superlattice distortion (<3% intensity of the main band), thus simplifying the interpretation of ARPES data near the Brillouin zone boundary. The thin film samples were patterned into the shape of two large rectangular pads (3 mm by 2 mm) connected by a narrow bridge of width ∼250 µm and length ∼1 mm as shown in Fig. 1a, b. Two electrical contacts were made by evaporating gold onto those two pads on the top of the sample and then attaching a single copper wire to each with silver paste.
ARPES measurements were carried out using our SES50 movable electron energy analyzer and 4m normal incidence monochromator on the U1 undulator beamline at the Synchrotron Radiation Center in Wisconsin. A moveable analyzer allows the acquisition of data where the energy gap is maximal (antinodal regions of the zone), and a chemical potential reference where the gap is zero (zone diagonals), without moving the sample with respect to the photon beam. The sample is mounted in the geometry where the Cu-O bond direction is parallel to the polarization plane of the photons, with a photon energy of 22 eV employed.
A. ARPES spectroscopy in presence of current When current is flowing in the sample, electric and magnetic fields exist in the vacuum, which deflect the outgoing photoelectrons. We test the effects of these fields empirically by passing a substantial current through a copper plate insulated from the sample and mounted just underneath. The effects of the current are illustrated in Figs. 1d  and 1e , where a ∼1. 5 • deflection is observed with an applied current. The MDCs at E F and EDCs at k F for data with and without the current flow are shown in Figs. 1f  and 1g. E F was determined by integrating EDCs along the momentum cuts and fitting resulting curve with a Fermi function. We do not observe significant distortions of the spectra (other than shifts) that can be created by the highly nonuniform fields.
When the current reaches a critical value, it peaks and then decreases with increasing voltage  [19]. A crucial question is to what extent this negative differential resistance regime in the IV characteristics arises simply due to Joule heating  [18]. This has direct implications on whether the effects seen in the ARPES data in the presence of current flow are entirely due to heating effects, or if they are related to an interesting low temperature resistive state generated by phase slips. From the analysis presented in detail in Appendix C and D, we conclude that there indeed is an increase in the sample temperature above that of the cold finger, nevertheless Joule heating alone cannot account for all of our observations. Specifically, we conclude that the increase in temperature in the presence of current flow still leaves the sample below T c.
This conclusion is based on analyzing the data using two separate methodologies and the simple fact that in this state, the resistance of the samples is significantly below the value measured in the normal state for low currents. In Appendix C, we use a "pure heating model", which makes the worst-case assumption that the IV is entirely dominated by heating. We show that this model is able to describe many aspects of the data, but not all. We argue that its shortcomings imply that this model overestimates the increase in temperature in the regime of interest. Next, in Appendix D, we directly estimate the rise in temperature using the measured IV characteristics of the Bi2212 sample, together with the IV of a thin layer of gold whose resistivity is similar to the normal state of Bi2212. We show that the estimated temperature remains well below T c in the regime of interest for our ARPES data.
In Fig. 2a , we plot a schematic phase diagram of the cuprates and mark the locations where ARPES data was measured. In Fig. 2b , we show the ARPES spectrum of an underdoped (T c =85K) sample at the (π, 0) point of the Brillouin zone as a function of the temperature. Upon increasing the temperature, the quasiparticle peak decreases in intensity and vanishes close to T c  [7] [8] [9] , while the pseudogap persists well above T c  [3, 10]. At a low cold finger temperature, we drive the current through the sample by applying a voltage and measure the spectrum at the (π, 0) point as shown in Fig. 2c. We use the spectrum at (π, 0) rather than k F because it is eas- ier to establish the presence of the coherent peak. The chemical potential is determined at each voltage by measuring the nodal spectrum, where the superconducting gap is zero.
We first note that in the "negative resistance" regime (right side of the current maximum) both curves are qualitatively similar. The current decreases with increasing voltage and reaches a minimum for higher voltage values. For our purposes, this is the most important point, since all the ARPES data shown in this paper were taken in this regime. At very low voltages, there is of course a more significant difference between the two curves. In a 4-point contact measurement, the voltage is measured across a small section of the bridge and does not include the potential drop across the contacts. In the 2-point contact case, the voltage is measured across the whole bridge and contacts. Therefore, V s will remain zero up to a certain value of the current (signifying that the sample is in the zero resistance state).
ACKNOWLEDGMENTS Work at  Ames  and  Argonne  was supported by the  Materials Sciences and Engineering Division, Basic Energy Sciences, Office of Science, U. S. DOE. M. R. was supported by  DOE-BES  Grant No. de-sc0005035. This work was based in part on data acquired at the  Synchrotron Radiation Center, University of Wisconsin-Madison , which was supported by the  National Science Foundation  under Award No. DMR-0537588.
Introduction Nuclear magnetic resonance (NMR) relaxometry consists in the measurement of the relaxation times (T 1 , T 2 ) of a nucleus observable in NMR as a function of the magnetic field. The dependence of the relaxation rates (R 1 = 1/T 1 and R 2 = 1/T 2 ) with the magnetic field bears important information since it gives access to the spectral density and thus to the mechanism of relaxation  [1, 2]. This allows one to probe the molecular dynamics of different systems such as proteins, polymers, and water trapped in porous systems. Relaxometry provides sufficiently extensive experimental datasets so that the relaxation mechanisms can be determined in yet poorly characterized systems containing magnetic entities. This is especially true for water proton relaxation induced by paramagnetic ions  [3]  and superparamagnetic particles used as contrast agents for magnetic resonance imaging  [4].
All exponential fits were carried with the T 1 /T 2 module of the Topspin software. The iron and gadolinium concentrations of the samples were determined by Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES) after microwave digestion in a mixture of nitric acid and hydrogen peroxide. All the relaxation data are presented as relaxivities r 1 , defined as the relaxation rate R 1 = 1/ T 1 normalized by the iron (or gadolinium) concentration.
Conclusion NMRD profiles ranging from very low fields to very high fields were measured with a commercial fast field-cycling device and a shuttle apparatus for PEGylated superparamagnetic iron oxide particles and a polymeric gadolinium chelate. The agreement between the FFC and shuttle-based measurements at their intersection is good. The data were compared to the fit of the usual relaxation theories with a rather good agreement, even if the high-field results are not perfectly reproduced by the fitting. This shows that the complete NMRD profile should be used when trying to refine relaxation theories. Indeed they bear relevant information and are therefore more demanding for the questioned theory. Last but not least, they also allow for the direct evaluation of the efficiency of a potential contrast agent at all fields, including fields typical of clinical and small animal MRI.