dataesr/scientific-paragraphs-categorization huggingface dataset:
, 2016; Nowack et al. , 2018). In addition to determining if the interaction between gaseous boric acid and suspended caesium iodide particles may be relevant enough to affect the source term, this study will provide data, which will be used for the validation of accident analysis codes or for the implementation of the observed phenomena in models. The selected approach is first to acquire data on the effect of possible reaction between gaseous boric acid and caesium iodide particles in a flowing gas. The number and mass concentrations of particles in suspension at the outlet of the TGT under Ar/H 2 O (80/20 vol%) and the amount of gaseous iodine transported to the sampling lines at 450 K will be measured. The second part of the work consists in validating the models implemented in the SOPHAEROS module (version v2.
Analytical methods The percentage of steam at the inlet of the facility was determined by the Gasmet Dx4000 FTIR. The aerosol mass concentration was monitored by Tapered Element Oscillating Microbalance Series 1400a (TEOM). It distinguishes itself from other particulate matter monitoring system by utilizing a direct mass measurement that is not subject to measurement uncertainties found in other surrogate technologies. Data were taken from the analog output, which was run with a range of -100 to +200 mg/m 3 to avoid truncating negative instrument responses. The filter sample flow rate (1 l/min) and temperature (300 K) were used. All TEOM data are reported at standard temperature and pressure. The measurement and the function of the instrument were monitored with RPComm software version 2. 1.
The inlet of the impactor was at atmospheric pressure and the outlet was at 10 4 Pa (absolute). The flow rate through ELPI was 9. 29 ± 0. 20 l/min (NTP). The measurement range of the ELPI was from ca. 7 nm to 10 μm. The measurement uncertainty was ±10%. The data are plotted on a lognormal X-axis. The concentration of molecular iodine in toluene was determined using a PerkinElmer spectrophotometer model Lambda 900. In toluene, the absorption curve of molecular iodine presents two peaks at 306 nm and 497 nm, giving respective molar extinction coefficients of 7901. 0 l mol -1 •cm -1 and 1064. 8 l mol -1 •cm -1. The LOD of iodine in toluene was estimated to be 8. 0•10 - 8  mol/l with a 10-cm glass cuvette. The measurement uncertainty was ±10%. The leaching solutions of the filters 7  containing the transported aerosol particles transported to the liquid traps and the liquid traps were analysed using ICP-MS.
Boric acid transport through the TGT The first test (B-1) was performed in order to assess the behaviour of the gaseous boric acid generated from a crucible. As the boric acid was generated from a crucible which is placed in a thermal gradient (from 450 K to 1000 K), performing thermodynamic equilibrium calculations was required in order to determine the predominant form of the vaporized boron compound in the whole temperature range and to determine the main compound in gaseous phase at the point where the boron meets the caesium iodide aerosols (at 1020 K). The thermodynamic equilibrium calculation were performed: -with FactSage 5. 5 and the FACT 5. 3 compound database  (Bale et al. , 2002) ; -with NucleaToolbox  (Piar, 2016)  and the NUCLEA database developed by IRSN  (Bakardjieva et al.
, 2010; Fischer, 2019). The gaseous and condensed boron species taken into account in the calculation are listed in Table  3  for the two databased utilized. The calculations performed with NucleaToolbox and the NUCLEA database showed that the vaporization of pure boric acid under Ar/H 2 O led mainly to the formation of the trimer of metaboric acid B 3 H 3 O 6 (g). The results obtained with FactSage 5. 5 displayed H 3 B 3 O 3 (g) as the main gaseous species within 400 K and 1000 K (Fig. 5 ). To our knowledge, the thermodynamic data on boric acid vaporization are rather limited. Nevertheless, one can mention the studies conducted by  Stackelberg et al. (1937) ,  Bezzi (1935)  and  Balasubramanian et al. (2008) , using a transpiration method on the H 2 O-B 2 O 3 system and Knudsen effusion mass spectrometry, from which they deduced the variation of H 3 BO 3 (g) vapour pressures, the main species, in the temperature interval  [315-453 K].
Both thermodynamic databases predict the H 3 BO 3 (g) species as the predominant one, in agreement with the experimental data, but higher pressures in the Factsage calculations, of one order of magnitude, which seems to be more consistent with the experimental data even if rather dispersed  (Balasubramanian et al. , 2008; Bezzi, 1935; Pankajavalli et al. , 2007; Stackelberg et al. , 1937). At higher temperatures up to 1000 K, no experimental data seems to be available. The FactSage calculation in this temperature range shows the presence of both H 3 B 3 O 6 (g) and H 3 BO 3 (g) species more or less in equal amount. Above 1060 K,  Meschi et al. (1960)  put in evidence the predominance of HBO 2 (g) (as predicted by both calculations but at higher temperatures) and the minor quantities of H 3 B 3 O 6 (g) and H 3 BO 3 (g) in the gas phase.
8 m). The TGT was modelled as the succession of 40 control volumes. Thermal fluid and outside wall profiles from thermal-hydraulic qualification were used to create the axial mesh of the tube. Input data were deduced from the tests and from qualification tests (mass flow rate of CsI, mass flow rate of H 3 BO 3 , mass flow rate of steam and argon). As the inner wall temperature was not measured experimentally, it was first approximated from CFD analysis tool, CHASER, developed by JAEA based on the commercial ANSYS-FLUENT  (Miwa et al. , 2019a; Miyahara et al. , 2017). Fig. 2  presents the thermal profile with the experimentally measured temperatures and the temperatures approximated by the CFD analysis for the studied atmosphere composition and flow rate. The chemical elements were injected into the first volume with their respective experimental mass flow rates.
The assessment of the main boron species generated from the vaporization of boric acid in Ar/H 2 O atmosphere by NucleaToolbox (B 3 H 3 O 6 (g)) and by FactSage 5. 5 (B 3 H 3 O 6 (g) and H 3 BO 3 (g)) have shown differences. It highlighted the important role of a reliable and validated database. Overall, the ASTEC fission products models allowed performing the evaluation of the experimentally observed results for the analysis of the transport of pure compounds. However, heterogeneous reaction between gaseous boric acid and caesium iodide particles was not reproduced, as the phenomena are not yet taken into account. More work is in progress in order to further investigate this interaction and to determine the need to develop the database and models.
The porosity of the monoliths was further characterised using N 2 adsorption-desorption isotherms at -196ºC (Tristar II from Micromeritics). The BET surface areas (A BET ) and N 2 pore volumes were calculated from these isotherms. The morphology (microstructure) of the xerogel monoliths before and after the compression tests was examined using a scanning electron microscope (SEM, Quanta FEG 650) with an accelerating voltage of 20 kV and a secondary electron detector (EDT, Everhart-Thornley). All samples were metallised with iridium and attached to an aluminium tap using double-sided conductive adhesive tape. The mechanical characterisation was carried out in a controlled environment (20°C average temperature and 50-60% relative humidity), using an INSTRON 5944 universal testing machine equipped with a 2 kN head, set and controlled with the BLUEHILL software.
The compression tests were performed on cylindrical monoliths with length to diameter ratios always lower than 1 (i. e. , lengths < 5. 5 mm), in order to avoid possible bending deformation that would lead to measurement errors. Uniaxial compression tests were performed in the longitudinal direction of the material (see Figure  S1  for details). The full compression characteristics were recorded using the compression set (i. e. , parallel platens with patella) and a head displacement rate of 0. 2 mm min -1  [10, 21]. A maximum load of 1. 6 kN was set to protect the testing machine. The stress-strain (σ com - (3) These data were used to determine the yield strength (σ yi ) of the analysed materials, as well as to obtain the Young's modulus (E com ), according to: / ( 4 ) The Young's modulus was calculated as the slope of the linear part of the stress-strain curve, and the compressive (yield) strength as the stress value for the elastic limit of the material, defined as the maximum stress applied before reaching permanent deformation.
2 mm min -1 was used for performing the measurements  [22] [23] [24] [25] [26] [27]. From the recorded data (i. e. , force and displacement at the midpoint), the stress-strain curve can be calculated, and thus the elastic modulus and flexural strength. The flexural stress for a bending rod of circular cross-section is given by the following equation: = M c / I (5) where σ flex is the stress, M the applied moment, c the distance of the outer surface from the neutral axis, and I the moment of inertia of the cross-section. For a circular crosssection, and considering that the material deformation follows Hooke's law: (6) (7) (8) where a is the moment arm. The moment arm is L 0 /2 in the three-point loading configuration. Hence, the flexural stress becomes: According to the simple beam theory of Euler-Bernoulli, concerning small deflection and small changes in elements length after bending (which is the case of the materials analysed in this work), the flexural modulus (E flex ) is given by the slope of the forcedeflection (δ) curve as expressed by equation  (10).
Acknowledgements The authors gratefully acknowledge the financial support received from the  Consejo Superior de Investigaciones Científicas  (Project  I-LINK1200 ),  Ministerio de Economía, Industria y Competitividad  (Project  CTQ2017-87820-R ) and  Principado de Asturias-FICYT-FEDER  (Project  PCTI-Asturias IDI/2018/000118 ). SLFL is grateful to the  Administración del Principado de Asturias  for her research training grant awarded through the  "Severo Ochoa" program. LARM thanks  CONACYT, México for a postdoctoral grant  ( CVU No 330625 ,  2017 ).
Impulse excitation technique The characterization of tablet natural frequencies was made using an impulse excitation technique and following the methodology presented by  (Mazel and Tchoreloff, 2020). The impulse excitation is obtained for a sample by dropping it on a hard surface from a 1 cm height. The sample free vibrations induced by the impact were recorded using a microphone MM310 (Microtech Gefell GmbH, Gefell, Germany). The data acquisition system was a DEWE-43 coupled with the software Dewesoft X3 (Dewesoft, Trbovlje, Slovenia). Acquisition frequency was set to 200 kHz and as a consequence the maximal detectable frequency was 78. 1 kHz. Time domain amplitude signal was converted into a frequency domain signal to measure the resonance frequencies using a fast Fourier transform (FFT) algorithm.
Finite element calculations Undamped modal analysis was realized using the finite element software Abaqus® 6. 13 (Dassault Systèmes, Vélizy-Villacoublay, France) with the Lanczos algorithm on 3-D free moderately thick cylindrical plates (representing flat-faced cylindrical tablets). Considering that only three natural frequencies can be determined by impact resonance test for some products  (Mazel and Tchoreloff, 2020) , only the first three modes of vibration have been computed. A mesh convergence study was performed and, based on the obtained results, we chose to perform simulations with about 40000 nodes. In order to test the accuracy of the finite element analysis, the fundamental frequency of an isotropic circular plate with a thickness-to-diameter ratio ℎ 5 6 of 0. 2 and a Poisson's ratio of 0.
As it can be seen, ; P ; R 6 shows a linear correlation with. Indeed, by fitting a least squares regression line, the expression of the line obtained is ; P ; R 6 = -2. 03 + 1. 56 and the validation metric R² is 0. 96. Based on these results, for tablets with fixed dimensions, it was decided to use the two frequency-based parameters ; P ; R 6 and ; P ; Q 6 to evaluate the shear ratio ! ! 6. After identifying the frequency-based indices related with the shear ratio, the impact of tablet dimensions was then evaluated with the simulation designs. Both diameter (  5 ) and thickness (ℎ) have an influence on the natural frequencies obtained. Nevertheless, it was found that the frequency-based parameters defined previously remained constant if the thickness-to-diameter ratio ℎ 5 6 was kept fixed (data not shown because the difference between the results obtained for a fixed ℎ 5 6 was exactly 0% for all the studied simulations).
ACKNOWLEDGEMENTS We thank  Prof. J. -M. Lehn  for helpful discussion. FUNDING This work was supported by the  National Natural Science Foundation of China  ( 21821003 ,  21890380 ,  21720102007  and  21701200 ), the  Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program  ( 2017BT01C161 ), the  Fundamental Research Funds for the Central Universities  and the  Sino-French Cai Yuanpei Programme.
Distinctly, DA16MPEG15 clearly self-assembles into remarkable twisted nanotape (nanoribbon) structures. However, all DAmMPEGn samples show the common feature that the self-assembled structures are based on planar 2-dimensional self-assemblies, a conclusion supported by detailed analysis of SAXS data discussed in the following. The presence of intramolecular H-bonding was assessed by FTIR. IR spectroscopy shows vibrations for the N-H stretch at 3238 cm À1 , the CQO stretch at 1632 cm À1 and the amide II at 1564 cm À1 for DAmMPEGn (ESI † Scheme S31) which indicate the presence of intermolecular H-bonding. In contrast, the N-H stretch at 3344 cm À1 , the CQO stretch at 1651 cm À1 and the amide II peak at 1534 cm À1 for MAmDPEGn (ESI † Scheme S32) suggests the absence of threefold intermolecular H-bonds.
The success story of the HSQC spectrum was born and formed the basis for a myriad of 2-to nD spectra used from protein NMR to the analysis of metabolomics samples. Indeed, beyond synthetic chemistry, NMR has found its place in the realm of metabolomics  (Emwas et al. , 2019; Wishart, 2019) , and is together with mass spectrometry the method of choice for characterizing complex mixtures such as biofluids. If throughput is required, the 1D 1 H spectrum remains the general workhorse, whose assignment can be based on database searches, on the spiking of relevant standards within the sample, or on analysis of the corresponding 2D spectra acquired on one or more samples. The 1 H-13 C HSQC spectrum proposed by Bodenhausen and Ruben again is a crucial element in the latter approach, as it spreads out the proton signals according to the 13 C chemical shift of its attached carbons, and allows connection of both in the same time.
Methods All experiments were performed on an Avance III 800 MHz spectrometer (Bruker BioSpin GmbH, Karlsruhe, Germany), equipped with a 1. 7 mm triple-resonance HCP or a 5mm quadruple resonance QCI-P (H/P-C/N/D) cryoprobe and were recorded at 298K. Data were processed with TopSpin 4. 0. 8 (Bruker BioSpin GmbH, Karlsruhe, Germany). All proton spectra were referenced to the methyl proton of 3-trimethylsilylpropionic acid-d4 (TSP-d4). 13 C chemical shifts were determined by indirect referencing  (Markley et al. , 1998).
Both CLIP/CLAP experiments acquired under identical conditions lead to two high quality spectra as shown in Figure  1 (A  &   S1 ). Taking advantage of the sign difference between the  and  components of the doublet in the CLAP experiment (Figure  S2 ), we reduce the resolution and hence the fine structure of both components by processing the CLAP spectrum with 1024 points in the 1 H dimension, yielding to a single peak per component. We developed a python semi-automatic procedure based on the nmrglue package  (Helmus and Jaroniec, 2013)  usable within topspin 4 that can be downloaded from https://github. com/NMRTeamTBI/VirtualDecoupling. While launching the script from TopSpin, the user will have several options that are detailed in the Tutorial available online. The CLAP experiment is processed with 1024 time points to collapse multiplets in a single signal prior automatic peak detection.
This step is performed twice: once on the positive components and once on the negative components of the spectrum and can be performed on the full spectral width or for a user defined region with a threshold that can be adapted if necessary. A clustering step based on 13 C chemical shifts allows a pairwise selection of the signals. If exactly two signals of opposite sign are found with the same 13 C frequency (in points) the script will automatically bring the upfield component extracted from CLIP-HSQC spectrum with full resolution (processed with 16k in the time domain) back to the centre of the doublet therefore creating a virtually decoupled HSQC (vd-HSQC) spectrum (Figure  1. C and Figure  S3 ). In the case of more than two signals identified at a given 13 C frequency value, a user interface will allow selection and clustering of the signals.
The methodology presented here while being robust is rather simplistic and will benefit from the rise of deep learning and artificial intelligence applications to NMR spectra  (Karunanithy et al. , 2021)  to provide a new entry point into metabolite databases. (www. metabohub. fr), and is supported by the Région Midi-Pyrénées, the ERDF, the SICOVAL and the French Minister of Education & Research, who are all gratefully acknowledged.
Acknowledgements The authors thanks  Dr. P Millard  ( INRAE, TBI, Toulouse ) for insightful discussions. We thank  Dr E Cahoreau  and  L. Peyriga  for expert support in the MetaToul (Toulouse metabolomics & fluxomics facilities, www. metatoul. fr)NMR facility. MetaToul is part of the  French National Infrastructure for Metabolomics and Fluxomics MetaboHUB- AR-11-INBS-0010  https://doi. org/10. 5194/mr-2021-48.
Acknowledgements We acknowledge funding from the  European Union  under the  Horizon 2020 research and innovation programs FET-Open  grant  ULTRAQCL 665158 , the  French National Research Agency  ( ANR-18-CE24-0013-02 -"TERASEL" ), the  Swedish Research Council  (project  2017-04287 ) and the  EPSRC (UK)  program grant " HyperTerahertz " ( EP/P021859/1 ).
1] [32]  IRMPD spectroscopy, coupled with quantum chemical calculations of the IR spectra of candidate isomers and conformers, has in fact proven its efficacy in releasing structural information on several anionic species, such as deprotonated natural and phosphorylated amino acids,  33, 34  tyrosine and 3-nitrotyrosine complexed with halide ions,  35  and deprotonated pantothenic acid. 36 everal studies have also assessed that isomeric forms are retained from the solution to the gas phase, given the soft ionization conditions that ESI permits,  [37] [38] [39] [40]  thus confirming IRMPD spectroscopy as a powerful and viable technique to assess the deprotonation sites of anions generated in solution. 39, 40 Spectroscopic data are compared with results of ion-molecule reactions (IMR) in the cell of a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer.
All data analyses were carried out using the MassLynx4. 1 and DriftScope 2. 1 programs provided by Waters. Drift times were correlated to the CCSs using polyalanine oligomers to calibrate the mobility data. 48 RMPD Analysis. IRMPD spectra in the 800-1800 cm -1 frequency range were recorded at the free-electron laser (FEL) beamline of the Centre Laser Infrarouge d'Orsay (CLIO). 49 he FEL beamline (operated at 42. 3 MeV for the present experiments) is coupled with a hybrid FT-ICR tandem mass spectrometer (APEX-Qe Bruker Daltonics)  50  equipped with a 7. 0 T actively shielded magnet and a quadrupole-hexapole interface. The ions of interest were generated by direct injection of the T3 and rT3 solutions into the ESI source of the mass spectrometer, mass isolated in the quadrupole sector, and accumulated in the hexapole for 1 ms before being irradiated in the FT-ICR cell with the IR FEL light operating at a repetition rate of 25 Hz.
The reaction efficiency (ϕ) was calculated by dividing k exp by the collisional rate constant calculated using the parametrized trajectory theory (k ADO ). 55, 56 The reaction efficiency indicates the percentage of reactive collisions. The best-fitting software gmkin (GK) 57 was also employed to analyze the kinetic data, thus obtaining k′ values superimposable with the ones from the semilog plots. Computational Details. Guess structures of [T3-H] -and [rT3-H] -were obtained, combining chemical intuition with a preliminary conformational search using the tool Conformer Distribution, as implemented in the software suite Spartan'16, 58 and the semiempirical method PM6. Subsequently, geometries were optimized at the B3LYP level using the 6-311+G** basis set for light atoms and def2TZVP for iodine.
978 factor to compensate the well-known bias of hybrid DFT functionals to overestimate harmonic vibrational frequencies. This value is consistent with the one used in previous works on similar compounds. 35, 60 CCSs were calculated from the B3LYP-D3 optimized structures with the MobCal software as appropriately modified by Kim et al. for mobility separations employing N 2 as drift gas. 48, 61 RESULTS AND DISCUSSION Tandem Mass Spectrometry and Ion Spectroscopy. Deprotonated triiodothyronine, [T3-H] -, and reverse triiodothyronine, [rT3-H] -, (see Scheme 1) were mass selected and assayed using CID and IRMPD. The resulting (photo)dissociation mass spectra are reported in Figures  S1  and S2  in the Supporting Information (SI). Photofragmentation products are consistent with CID ones, and both experiments replicate the fragmentation pattern already reported in the literature.
Spectroscopic data well correlate with fragmentation behavior, which shows different product ions for the two thyroid hormones. Ion mobilities of [T3-H] -and [rT3-H] -were assayed, obtaining promising results for the establishment of novel separation procedures based on drift times for thyroid hormones. Indeed, the two anions showed different arrival times in a TWIMS sector, which are associated with experimental CCS values in N 2 of 209 and 215 Å for [T3-H] -and [rT3-H] -, respectively. Calculated CCSs were obtained and found to be in good agreement with the experimental data. Furthermore, the theoretical CCSs of carboxylate isomers were found to be consistently lower than the ones of the phenolate structures, suggesting a strong influence of the different negative charge localization in [T3-H] -and [rT3-H] -on their ion mobilities.
■ ACKNOWLEDGMENTS This work was funded by the  Italian Ministry for University and Research -Dipartimenti di Eccellenza   -L. 232/2016  and by the  European Union 's  Horizon 2020 Research and Innovation Programme  under grant agreement no. 731077  ( EU_FT-ICR_MS ) and grant agreement no. 730872  (CAL-IPSO plus). The authors are grateful to the  CLIO team  for their valuable assistance and to  Dr. Francesco Lanucara  for his interest in this work.
In order to avoid the detection of the non-resonantly ionized 52 Cr, the CRIS setup was equipped with a decay detection station, placed behind the end flange of the beamline. The MagneToF detector was removed from the path of the ion beam, and the ionized bunches were implanted into a thin aluminium window with 1 mm thickness allowing the transmission of β particles with energies larger than 0. 6 MeV. The decay station behind this window consisted of a thin and thick scintillator detector (A and B in Fig. 1 ) for a coincidence detection of β-particles. The dimensions of the detectors were 1 mm × 6 cm × 6 cm and 6 cm × 6 cm × 6 cm. The β counts detected in coincidence were recorded by the data acquisition system (DAQ) together with the laser frequency detuning. The DAQ recorded the number of events in the detectors with a timestamp.