dataesr/scientific-paragraphs-categorization huggingface dataset:
Materials Electron beam conditions for 3D FIB-SEM data acquisition. SEM images of newly exposed areas after FIB sectioning were acquired using electron energies ranging from 1. 5 to 2 keV. These values were favorable for achieving charge neutrality at the sample's surface. 37  An electron current ranging from 0. 1 nA to 0. 2 nA (depending on the chemical nature of the analyzed sample) and an electron beam dwell time of 1. 6 ms per pixel were applied. These conditions were not only suitable for avoiding sample degradation under electron beam and lowering charging effects during SEM imaging, but also for achieving an electron penetration depth that was practical for reducing shine-through artifacts. 38  For backscattered electron (BSE) imaging, a EsB detector was used with a potential grid set to 1.
5 kV. Data treatment, image segmentation, 3D reconstruction and quantification. The 3D volume reconstruction of FIB-SEM data, segmentation of structural features and quantification of microporosity (defined in biomaterial science as a pore size of o10 mm) were performed using the Dragonfly s software. 39  For 3D reconstructions, SEM images from the FIB-SEM data were aligned prior to each reconstruction by reducing the standard squared deviations in subsequent images. This enabled us to correct for image drifts and errors related to tracking during serial FIB-SEM acquisitions. Machine learning algorithms incorporated into the software were used for SEM image analysis. The random forest classifier based on pixel comparison features was shown to be well suited for image classification in the data with multiple object categories  40  and was applied in our data treatment.
4b ) and the results were compared to those obtained for the pure inorganic cement (see Fig. 4a ). For both samples, the 3D volume reconstruction was performed using the Dragonfly s software by implementing a stack of more than 700 BSE images. It can be seen from the 3D visualization of the two samples that gelatin induced a modification of the structural organization of the cement. Although needle shaped individual CDHA particles are observed in both samples, a main difference was the high presence of ring-like agglomerates of such needles as well as large ''empty spaces'' (of several nm up to 2300 nm within the observation area) in the CDHA/gelatin sample. While in the pure CDHA cement, the cement was more homogeneously distributed across the sample, the well separated clusters of the ring-like CDHA structures are observed in CDHA/ gelatin.
As phosphate ions are known to dictate the precipitation of calcium phosphate phases, this may have significantly Table  1  Average amount of microporosity and the mean pore sizes of hydrous CDHA and CDHA-polymer mixtures calculated from the FIB-SEM data (10 nm pixel size in the XY plane and 15 nm in the XZ plane). Pores for which the size is below 3 pixels were excluded. Uncertainties were determined by analyzing 4 to 6 regions of each 3D constructed volume and correspond to expanded standard deviations (coverage factor k = 2) Microporosity (%) Mean pore size (nm)  helped for the homogeneous precipitation of the inorganic phases as soon as the preferential nucleation site on the organic macromolecules were occupied by a calcium ion. Larger empty spaces than those observed in the control cement (Fig.
In order to shed light on some of the effects related to dehydration, the structural characterization of CDHA, CDHA/gelatin and CDHA/Si-HA compounds was investigated using FIB-SEM at room temperature and the results were compared to those obtained under cryogenic conditions. The samples were dehydrated prior to the analysis and coated with a thin carbon layer (B50 nm) to ensure the electrical conductivity at the surface. Serial FIB/SEM imaging was carried out on a ROI of each compound and a stack of more than 800 secondary electron images were acquired. 3D volume reconstruction, data analysis and pores segmentation were further performed using the Dragonfly s software (see details in the Methods section). The microstructures of anhydrous CDHA and CDHA-polymer mixtures were observed using SEM (Fig.
These artifacts should be considered when investigating microstructural features or reporting microporosity measurements using cryo-SEM. 57  Using techniques for the characterization of the crystalline structure in depth, such as micro-Raman spectrometry combined with FIB/SEM, the state of vitrification can be evaluated to optimize sample preparation. 58  Sample preparation by HPF would certainly improve the vitrification state and will be explored in the future. Comparing the quantitative structural data obtained from the analysis of samples prepared by plunge-freezing under slush nitrogen, to the same samples cryo-fixed by high pressure freezing, will provide insight into the impact of the freezing method on the structural properties of biomaterials.
Acknowledgements  P. Abellan  and  M. Essani  would like to acknowledge the financial support provided by the  NExT initiative  through the  French National Research Agency (ANR)  under the  Programme d'Investissements d'Avenir  (with reference  ANR-16-IDEX-0007 ). The e -BRIDGE  project also receives financial support from the  Pays de la Loire region  and Nantes Metropole. The FIB/SEM data were collected in the  CIMEN Electron Microscopy Center in Nantes , funded by the  French Contrat Plan E  ´tat-Region and the  European Regional Development Fund of Pays de la Loire.
The Journal of Physical Chemistry B [Tf 2 N], providing two contrasts for each composition. The samples were measured in 1 mm path length and 1 cm wide quartz Hellma cells. Measurements Carried Out on D16. In order to achieve the desired q-range on D16, measurements were carried out at four angles to give a q-range of 0. 08-1. 6 Å -1. The data were processed using a combination of the ILL in-house software LAMP  44  and the NCNR package for IGORPro. 45  Further details of the beamline setup used can be found in the Supporting Information along with fitting parameters (Tables  S4  and S5 ). Raw data are found at 10. 5291/ILL-DATA. 9-10-1720. Measurements Carried Out on SANS2D. Measurements were carried out on SANS2D covering a q-range of 0. 004-0. 97 Å -1 and used a temperature-controlled sample changer set at 20 °C.
Further details of the beamline setup used can be found in the Supporting Information. Raw data are found at 10. 5286/ ISIS. E. RB2220026-1. SAXS Measurements. SAXS employed a Bruker D8 Discover diffractometer equipped with a bespoke temperature-controlled, bored-graphite rod furnace custom built at the University of York. Cu K α (λ = 0. 154056 nm) radiation was used, generated from a 1 mS microfocus source. Diffraction patterns were recorded on a 2048 × 2048 pixel Bruker VANTEC 500 area detector set at a distance of 121 mm from the sample, allowing simultaneous collection of small-and wide-angle scattering data. Mixtures used employed only hydrogenous components. Fitting of the data was carried out using SASView, 46 employing several Lorentzian peaks to describe the observed scattering peaks, with multiple iterations leading to the best fit to the data (Tables  S6  and S7 ).
In some cases, an Ornstein-Zernike model (described as a Lorentzian within the software) is also applied, when the background is not flat. The standard combination of functions used to achieve a good fit to all data collected is a combination of three "peak Lorentz" functions and a Lorentzian. MD Simulations. MD simulations were carried out using DL_POLY 2. 20 and GROMACS 5. 1. 4 packages. [47] [48] [49] [50] [51] [52]  The [C 8 MIM] 1-x [C 8 MIM-F 13 ] x [Tf 2 N] mixtures were modeled using the OPLS/AMBER-like CL&P force field. 26, 27  A scaling factor of α = 0. 8 was applied to the partial charges of the charged part of the cation and the anion. The simulations started from low-density configurations with 2000 ion pairs built with fftool and Packmol software. 53, 54  The runs were performed using 2 fs timesteps and 1.
A Brookfield silicone fluid (97 mPa s, 298 K) was used as a NIST-traceable viscosity standard. The viscosity data were collected between 298 and 328 K using a CP-40 cone. The sample volume used for each experiment was ∼0. 5 mL. The viscosity accuracy was ±1. 0% of the full-scale viscosity range (FSVR), which has been calculated using the equation FSVR [mPa s] = (TK × SMC × 10,000)/rpm (where TK is the DV-II + Pro torque constant and SMC is the spindle multiplier constant). All fluids measured showed Newtonian behavior at 293 K within the range of shear rates examined (7. 50-712. 50 s -1 ). Water content was measured for the pure ILs using a C20S compact Karl Fischer coulometric titrator. Known quantities of the pure ILs were dissolved in known volumes of CH 2 Cl 2 , and water contents for the solutions were compared to that of the solvent used to prepare them to allow the water content of the ILs to be calculated.
Synthesis. The IL [C 8 MIM-F 13 ][Tf 2 N] was prepared by reaction of 1-methylimidazole with 1H,1H,2H,2H-perfluorooctyl iodide in acetonitrile under reflux for an extended period, leading initially to a dark, amber oil which is then purified as described in the Supporting Information. There are, of course, several ways to prepare such materials, but in our experience, the methods adopted, while longer and a little more involved, avoid impurities  56  that can arise from the use of activated carbon  57  and/or alumina  58, 59  in the purification. The purity of these materials is evidenced by the combination of data from NMR spectroscopy, combustion analysis, Karl Fischer titration, and halide testing using AgNO 3. The resulting materials do retain very small amounts of colored impurities, which must have extremely high molar absorption coefficients, as their presence does not adversely influence characterization.
Density. Mixtures with composition [C 8 MIM] 1-x [C 8 MIM- F 13 ] x [Tf 2 N] were prepared for x = 0. 05, 0. 2, 0. 35, 0. 5, 0. 65, 0. 8, and 0. 95, and their densities were measured, from which molar volumes were calculated according to eq 1 in which M x represents the weighted molar mass of the mixture for the particular value of x. = V M (cm mol ) (g mol )/ (g cm ) x x x 3 1 1 3 (1) The Journal of Physical Chemistry B The density data (Table  S1  and plotted in Figure  2a ) for each mixture were compared to the ideal densities/molar volumes calculated from the pure components using a linear mixing law. Percentage deviations are shown in Figure  2b  and highlight that the deviation from ideality is small (<1%), which is likely to be similar to the experimental uncertainty (the main sources of error relating to sample preparation rather than instrument error).
Such features can be seen in the simulations (vide infra� Figure  10 ). Fitting of the SAXS and SANS data showed variation in the positions of the COP and CP with composition (Figure  7b ). The CP moves to longer distances with increasing [C 8 MIM-F 13 ] composition and the COP moves to shorter distances, as shown in Figure  7b. When the COP is taken as representing correlations between like charged ions (e. g. , cation-anion-   The Journal of Physical Chemistry B x-axis is employed here as the q-range spanned is larger and this allows features at low-q to be seen more clearly). Data have been offset in the y-axis to aid visualization, and alternative neutron contrasts are shown in Figures  S5  and S6. The Journal of Physical Chemistry B cation) and the CP representing anion-cation correlations, it is at first sight surprising that these peaks should change at all as a function of composition since the anions and the cationic headgroups of the two ILs are identical.
A better understanding of the origins of the changes seen in the SAXS/SANS data is gained from the complementary atomistic MD simulations that follow. MD Simulations of the Bulk. Figure  8  shows the structure factor functions, S(q), of the [C 8 MIM] 1-x [C 8 MIM-F 13 ] x [Tf 2 N] mixtures, at 300 K, where x = 0, 0. 05, 0. 20, 0. 35, 0. 50, 0. 65, 0. 80, 0. 95, and 1. 00. Since the main interest is in the structural features at the intermolecular level, the analysis focused on the low-q regions of the S(q) functions (0. 2 < q/ Å -1 < 1. 8) to cover the PNPP, COP, and CP. It was observed that the intensity of the PNPP increases, and it shifts slightly to lower q, with the mole fraction of [C 8 MIM-F 13 ][Tf 2 N]. At the same time, the intensity of the COP decreases, and its maximum is slightly shifted to higher values of q, while the CP shifts to lower q-values as x increases.
In this work, we report the use of DPPyDA, an n-type semiconductor with robust thermo-and photo-stability and extended conjugation through the peripheral phenyl groups, to build a series of 6,12-diphenylpyrene diimides (R-DPPyDIs) (Fig. 1 , Scheme 1) and a 6,12-diphenylpyrene-polyimide (DPPyPI) (Fig. 2 ). These compounds can be act as effective metal-free redox-active heterogeneous photocatalysts for visible light-activated organic reactions. We have introduced phenyl groups oriented out of the plane of the pyrene core rings to modify the photophysical properties and reduce π-stacking between the aromatic rings  [18, 49]. To evaluate the effect of the photoactive pyrene unit on catalytic activity, this study also includes the preparation and evaluation of a diphenylperylene-polyimide (DPP-PI) (Fig.
Acknowledgements The authors acknowledge funding support from the  European Union 's  Horizon 2020 research and innovation programme  under grant agreement  800925  ( VECMA  project, www. vecma. eu), the  UK EPSRC  project  Software Environment for Actionable & VVUQ-evaluated Exascale Applications (SEAVEA ), grant no. EP/W007711/1 , and the  UK Consortium on Mesoscale Engineering Sciences (UKCOMES)  under the  UK EPSRC Grant  no. EP/L00030X/1. Simulations were run on ARCHER2 at EPCC,  Edinburgh Parallel Computing Centre  (www. archer2. ac. uk). The authors would like to thank  Prof. Aravind Vijayaraghavan  for several valuable discussions.
40, 41 3] [44] [45]  The analysis of the operando datasets was performed using a chemometric approach including principal component analysis (PCA) and multivariate curve resolution-alternating least squares (MCR-ALS) methods, allowing detailed descriptions of the structural evolution and local environment of the TMs. 46 hese complementary findings are combined to understand in detail the influence of structural modification on the electrochemical behaviour of the investigated PBA. with deionized water and then two times with ethanol, and centrifuged at 20000 rpm before being dried under vacuum. An additional drying step at 100 °C overnight was applied before the characterizations and electrode formulation to ensure that the interstitial water was removed completely. The choice of drying temperature was decided based on thermogravimetric analysis results and is explained in the SI.
Materials characterization and data analysis Powder XRD patterns of the synthetized materials were collected on a Bruker Advance D8 diffractometer with a Cu Kα radiation source (λ = 1. 5418 Å) and a step size of 0. 02 ° in the range of 10-100 °. Lattice parameters were obtained from profile matching method using Fullprof package. 47 ransmission  57  Fe Mössbauer spectra were collected at room temperature with a triangular velocity waveform. A gas-filled counter was used for the detection of γ-rays. A 0. 5 GBq 57 Co:Rh source, kept at room temperature, was the substrate. Velocity calibration was performed with an α-Fe foil at room temperature. Absorbers containing 5 to 25 mg cm -² were protected from air using thermally sealed coffee-bags. The Mössbauer spectra were fitted by using the PC-Mos II computer program with appropriate superpositions of Lorentzian lines.
44 The storage ring was operated at 2. 0 GeV in top-up mode with a typical current of 300 mA. Data were Please do not adjust margins Please do not adjust margins recorded at Mn and Fe K edges in transmission mode using ionization chambers filled with a mixture of Ar, N2, and He to have 10, 70, and 95 % of absorption in the I0, I1, and I2 chambers, respectively. An internal reference of Mn and Fe foils located between the I1 and I2 chambers was used for energy calibration at each scan. This allowed a continuous monitoring of the energy during consecutive scans. Spectra were collected with a constant k-step of 0. 03 Å -1 from 6300 to 8000 eV gathering both Mn and Fe. The energies were calibrated by assigning the first inflection point of the spectra of the Mn and Fe metal to 6539 and 7112 eV, respectively.
The white beam was monochromated using a fixed exit monochromator equipped with a pair of Si(111) crystals. Harmonics were rejected by detuning the second crystal of the monochromator by 30 % of the maximum. XAS spectra were analysed using the Artemis software. 48 Fourier transforms (FT) of the EXAFS data were performed in the 3-10. 5 Å -1 k range, and the fitting was done in the R-space up to 5 Å. All FT of the EXAFS data are shown without phase correction. For the ordinary electrochemical tests, electrode films were prepared by tape-casting on aluminium foil (18 μm, GoodFellow), a slurry obtained by mixing MF21 with Super P carbon (Alfa Aesar) and poly(vinylidene fluoride) (PVdF, Solef ® 5130) as conductive additive and binder, respectively, with a mass ratio of 60/30/10 in N-methyl-2-pyrrolidone (NMP, Sigma Aldrich) in a planetary ball mill.
25 mg cm -2 , whereas it was ≤ 10 mg cm  -2  for the operando XRD and operando XAS measurements. A common chemometric approach based on principal component analysis (PCA) and multivariate curve resolution-alternating least squares (MCR-ALS) analysis, described in detail elsewhere,  46  was applied to analyse the full operando XRD patterns and XAS spectra datasets. In short, PCA is used here to determine the number of independent components contributing to the whole series of collected patterns/spectra during electrochemical cycling. The number of principal components determined in this way is used as the basis for MCR-ALS analysis, which allows the stepwise reconstruction of the "pure" spectral components which are necessary for Please do not adjust margins Please do not adjust margins interpreting the whole multiset of operando spectra.
This spectrum is identical to that obtained after the short plateau in the charge (3. 80 V, Figure  3e ), indicating that this process is well reversible and can be attribute to the redox reaction of the couple HS Fe 3+ /Fe 2+. At the end of discharge (Figure  3d ), the HS Fe 2+ appears again in the Mössbauer spectrum, with almost identical hyperfine parameters as the pristine material. The HS Fe 3+ is still present in the resolved spectrum with a similar amount as before cycling, indicating that the HS Fe 3+ formed in the synthesis is electrochemically inactive. PCA applied on the operando XRD data (Figure  S6 ) shows that at least three independent components are necessary to describe the whole dataset including the charge (depotassiation) and discharging (potassiation). Therefore, MCR-ALS was employed separately on each process with the constraint of unimodality for all components.
In order to simultaneously follow both the redox reactions at the Fe and Mn sites, and to establish a clear correlation between the different reaction steps with specific redox couples, the two Mn and Fe K-edge XAS datasets were analysed independently. PCA was first applied to determine the number of principal components that can express the variance contained in each series of spectra. The results of such analysis showed that the Fe dataset can be described using three principal components (Figure  S8 ), while two components are necessary for Mn series of spectra (Figure  S9 ). MCR-ALS analysis was then carried out for each dataset with the number of principal components obtained from PCA, and unimodality was applied for all components for the charge process. The graphical results of two MCR-ALS analyses are combined in Figure  9.
S10a ). Spectrum #1, representing the pristine phase containing a small amount of HS Fe 3+ , the edge of which lies at a slightly higher energy than that of Component 1. The XANES parts of component 3 and spectrum #20 (corresponding to the EOC phase) are almost identical due to insignificant edge shift when LS Fe 2+ is oxidized (vide supra), despite the presence of this species at the EOC state. For the Mn K-edge spectra, instead, the two components 1 and 2, which perfectly match the first and the last spectra of Mn dataset (Figure  S10b ), represent HS Mn 2+ and Mn 3+ , respectively (Figure  9c ). It is possible to compare the evolution of the concentration of the final components of Fe and Mn, i. e. , Component 3 for the Fe K-edge XAS dataset and Component 2 for the Mn K-edge XAS dataset, by representing the smoothed derivative of their concentration vs.
Acknowledgements This work was part of the  TROPIC  project supported by  Agence Nationale de la Recherche  ( ANR , grant  ANR-19-CE05-0026 ). ANR  is also acknowledged for additional funding through the projects  Labex STORE-EX  (grant  ANR-10-LABX-76-01 ) and  NANOBLUE  (grant  ANR-18-CE09-0012 ). The  Alistore-European Research Institute (ALISTORE-ERI)  is warmly thanked for funding the PhD grant of P. N. L. P. The authors acknowledge the  CERIC-ERIC Consortium  for access to experimental facilities at  Elettra  synchrotron and financial support through project  20207080. Access to several analytical methods available at the Analysis and Characterization  Platform of "Pôle Chimie Montpellier" (PAC-Balard ) is gratefully acknowledged. We This journal is © The  Royal Society of Chemistry 2022 J.
, 2018; Di Genova et al. , 2017a). Indeed, volcanologists have long pursued the experimental investigation of melt viscosity as a function of temperature and composition (e. g. ,  Ishibashi and Sato, 2007; Kolzenburg et al. , 2018; Whittington et al. , 2009) , as well as its subsequent numerical modelling by different approaches including classical linear regression and machine learning  (Giordano et al. , 2008; Hui and Zhang, 2007; Langhammer et al. , 2022). The extent and quality of the dataset used to develop these models directly affect the reliability of their predictions, so that one should strive for a detailed experimental exploration of the largest possible compositional landscape. Unfortunately, there are undeniable experimental challenges related to the viscosity measurements of volcanic melts (or their synthetic analogs), namely: (i) their undercooling-driven tendency to crystallize, which typically limits concentric-cylinder low-viscosity (~10 4 -10 -2 Pa s) determinations (e.
Mössbauer analyses Glass pieces of roughly 2 mm diameter were embedded in epoxy that was cut into disks with thicknesses between 400 and 500 µm, which is close to the optimum thickness for these compositions. Mössbauer spectra were recorded at room temperature (293 K) in transmission mode on a constant acceleration Mössbauer spectrometer with a nominal 370 MBq 57 Co high specific activity (point) source in a 12 µm thick Rh matrix. The velocity scale was calibrated relative to 25 µm thick α-Fe foil and spectra were collected over the range ± 5 mm s -1 for 1 to 3 days each. Spectra were fitted with the full transmission integral using MossA software  (Prescher et al. , 2012). Values of Fe 3+ /Fetot were calculated from relative areas and are listed in Tab. 1.
After reaching the final dwell temperature, the samples were allowed to relax before the load was applied. The indentation depth of the sapphire sphere into the sample was measured as a function of time using a linear variable displacement transducer and viscosity was determined according to the literature  (Douglas et al. , 1965). Viscosity measurements of the standard glass DGG-1 were used to calibrate the vertical dilatometer. The certified viscosity data  (Meerlender, 1974)  were reproduced with a standard deviation of ± 0. 1 in log units.