dataesr/scientific-paragraphs-categorization huggingface dataset:
Conversely, the FF terms concerning with the solute-solvent interaction and the chrompohore's intramolecular term were refined specifically for the target system: the former intermolecular term, ! *: 6#7;'6#78 , was refined by deriving through the RESP scheme the solute point charges entering in eq. (S4) from QM calculations, purposely carried out on the solute's optimized geometries in either their ground or excited state. Concretely, all CYC or PYR atomic charges were derived from CAM-B3LYP/6-311++G** electronic density computed at DFT (for the ground state) or TD-DFT (for S1), accounting for the solvent by means of the C-PCM method. Finally, the LJ terms entering eq. (S4) were transferred for both states from the OPLS FF. The intramolecular term ! 121/425 $%&'(( was derived through the JOYCE protocol from the QM database consisting in the gas phase optimized geometry, its Hessian matrix and the relaxed torsional energy scans.
Acknowledgements Raúl Losantos  is grateful to  Universidad de La Rioja  and  Ministerio de Universidades  for the " Margarita Salas " grant. G. P. gratefully acknowledges ICSC- Centro Nazionale di Ricerca in High Performance Computing , Big Data and Quantum Computing, funded by  European Union-NextGenerationEU PNRR ,  Missione 4 Componente   2 Investimento 1. 4  for fundings. A. M. thanks  ANR  and  CGI  for their financial support of this work through  Labex SEAM   ANR 11 LABX 086 ,  ANR 11 IDEX 05 02. The support of the  IdEx "Université Paris 2019 "  ANR-18-IDEX-0001  and of the Platform P3MB is gratefully acknowledged. Keywords:  Cyclocurcumin derivatives • Molecular Photoswitches • Solvent reorganization • Quantum Derived Force Field • Molecular dynamics.
The phase proportions (tetragonal/monoclinic) of the ceramics have been determined from room temperature X-ray diffraction patterns using the methodology developed by R. C. Garvie et al. and Toraya et al. [17, 18]. It consists in measuring the integrated areas of three peaks: (11-1) et (111) corresponding to the monoclinic phase (28. High Resolution Scanning Electron Microscopy (HRSEM) analysis of the fracture surfaces of the samples was carried out on SEM-JEOL-6700 equipment at the PLACAMAT platform (University of Bordeaux, France). To optimize charge evacuation during analysis, samples are metallized by PVD deposition of a 1. 5 nm-thick layer of platinum. Thermogravimetric analyses data of the materials were recorded under an N 2 /O 2 (80%/20%) flow between 30 and 900 • C. The experiments were performed on a thermogravimeter NETZSCH STA 449 F5 Jupiter coupled with QMS 403 D Aeolos Quadro simultaneous analyzer (Netzsch, Germany).
The sample holder was directly placed into vacuum and transferred into the analysis chamber when the pressure reached 10 -5 Pa. The full spectra (0-1150 eV) were acquired with a constant pass energy of 200 eV and high-resolution spectra with a constant pass energy of 40 eV. Charge neutralization was applied during analysis. Slight sputtering was performed with low energy Ar + ions (i. e. 480s sputtering corresponding to about 60 nm in depth). High resolution spectra (i. e. C1s, O1s, Zr3d, Y3d) were quantified (Scofield sensitivity factors applied) and fitted using the AVANTAGE software provided by ThermoFisher Scientific. Concerning O1s, a model with 3 Lorentzian/ Gaussian components of similar Full Width at Half Maximum (FWHM) was applied. Electron Paramagnetic Resonance (EPR) experiments were performed using a Bruker ESP300E X-band spectrometer equipped with an Oxford Instruments ESR900 He-flow cryostat.
A two contacts sample holder was used with gold grids as current collectors. The set-up allows performing measurements from 25 • C to 900 • C under controlled gas (air, nitrogen, argon). The frequency range extends from 1 Hz to 1 MHz. The dimensions of the studied samples were around 10 mm in diameter and 2 mm in thickness. Highly homogeneous platinum of electrodes of 300 nm thickness were deposited on both sample surfaces by Plasma Vapour Deposition. Measurements were then carried out at 50 • C intervals in the temperature range from 200 to 800 • C. Data were modelled using ZView® software program to determine the electrical characteristics using equivalent circuits.
Funding This work was supported by the  European Research Council (ERC)  (European Community's  Seventh Framework Programme  ( FP7/2007-2013 )/ERC Grant Agreement No. 258782 ) and the  French National Research Agency ANR  through contracts  DYOR  ( ANR-18-CE06-0019 ) and  SCDiag  ( ANR-21-CE18-0051 ).
Synchrotron μCT data collection and reconstruction X-ray phase contrast microtomography was performed at the beamline ANATOMIX of Synchrotron SOLEIL (Saint-Aubin, France)  [27, 28]. The central photon energy in the filtered white X-ray beam spectrum was around 40 keV; the voxel size was (3. 07 μm) 3. For each scan, 1800 projections were collected at sample orientation angles equally distributed over 180 • ; the acquisition time for each projection was 35 ms. The resulting reconstructed volume from each scan had a diameter and height of 2048 pixels, i. e. , 6. 3 mm. Three or four CT scans with approximately 750 μm overlap in the vertical direction were performed on each stent to cover the entire sample. Tomographic reconstruction was performed using the standard data processing pipeline of the ANATOMIX beamline, with a Python-based configuration tool written at SOLEIL and calling the reconstruction program PyHST2 developed at the European Synchrotron Radiation Facility (ESRF)  [29].
Synchrotron μCT data analysis To evaluate the degradation volume of the Resoloy scaffolds, each volume was segmented into three different material compartments, namely into the metallic Mg phase, degraded Mg, and severely degraded Mg phase. The computer code for the segmentation was developed inhouse in the Python programming language, using the U-Net convolutional network (Fig. 2 )  [18]. A 2D U-Net with three encoding stages and two convolutions in each stage was used. The number of feature maps in the initial encoding stage was 16 and was doubled after each encoding stage. In total, this resulted in 186,409 trainable parameters for the network. A non-linear ReLU activation was applied after each convolution and max-pooling was used to down-sample the feature maps after each encoding stage.
Upsampling in the symmetric decoding path was achieved by upconvolution and the skip-connections between the corresponding encoding and decoding stages by concatenations. Finally, a 1 × 1 convolution reshaped the output to the same shape as the input. The network architecture is illustrated in Fig. 2. The 3D information of the μCT volumes was partially preserved by extracting 2D patches from three orthogonal planes, namely the x-y, y-z and x-z planes. This resulted in 2400 training data pairs for one volume of size 800 × 800 x 800 when a patch size of 800 × 800 with zero overlap was used. In total, six of these volume pairs were used, resulting in 14,400 2D training data pairs. Training was carried out on an NVIDIA RTX A6000 graphics card with 48 GB GPU memory. After segmentation, the 3D morphology of corroded and metallic Mg was quantified using Python.
The surface area was computed in the software IPSDK (Reactiv IP, Grenoble France) which sums up the areas of the triangles forming the shape mesh of the segmented stents (Fig. 8 , Appendix). This resulted in 4 labels for each sample (Fig. 3 ). • Label 0 for a background/soft tissue voxel • Label 1 for metallic Mg (grey) • Label 2 for degraded Mg (red) • Label 3 for severely degraded Mg (blue) The visualization of the renderings (Fig. 6 ) were obtained with the AVIZO software (Thermo Fisher Scientific, Waltham, Massachusetts, USA).
Statistical analysis All statistical analyses were performed using the statistics toolbox in MATLAB (MathWorks, Natick, Massachusetts, USA). Differences between four groups were assessed by analyses of variance (ANOVA), followed by post hoc multiple comparison Tukey-Kramer tests. The small number of samples per group analyzed by synchrotron μCT (N = 3) limits the power of the statistical evaluation. All statistical results were considered significant for p < 0. 05.
Acknowledgment ANATOMIX is an Equipment of Excellence ( EQUIPEX ) funded by the  Investments for the Future program  of the  French National Research Agency (ANR) , project  NanoimagesX , grant no. ANR-11-EQPX-0031. The authors thank  Jussi-Petteri Suuronen  from  Xploraytion GmbH  for his conception of the DL-based segmentation approach for degradable materials and discussions related to the data analysis strategy.
X-ray absorption spectroscopy The in situ XAS data were collected at the BM23 beamline  [33]  of the European Synchrotron Radiation Facility (ESRF), under the beamtime awarded through the CH-6264 proposal  [34]. The Microtomo  [35]  reactor cell, developed by the ESRF sample environment group, was chosen as sample environment. The powdered Cu-zeolites were prepared in the form of self-supporting pellets of 1. 3 cm diameter with masses optimized for transmission-mode XAS measurements (ca. 40 mg, resulting in Δμx= in the range 0. 6-1. 0 with total absorption after the edge of less than μx=2. 5 for all samples) and placed inside the reactor cell. The temperature of the sample was controlled by the heating system integrated in the Microtomo cell. The total gas flow rate and the composition of the feed were adjusted by a set of mass flow controllers controlled by a remote terminal.
XANES statistical analysis and multivariate curve resolution All the analysed XANES datasets comprised a range of spectra in the range 8070-9020 eV, with the number of spectra depending on the considered treatment step (vide infra). The XANES spectra collected throughout this work were analysed sample-wise via a Multivariate Curve Resolution (MCR) approach. [22, 39, 40]  This technique involves the decomposition of experimental data in a set of pure spectra and concentration profiles, which can be used as qualitative and quantitative descriptive tools when a mixture of several species is present. An initial guess was generated via a Principal Component Analysis (PCA) of the experimental data, which provides a set of pure spectra based on the selected number of Principal Components (PC); the PCs are then used to initialize the Alternating Least Squares (ALS) algorithm, an iterative process that provides the spectra and concentration profiles upon convergence.
[41]  Indeed, in all cases convergence was achieved in less than 25 iterations, with final LOF values < 0. 5%. Quality of reproduction of the experimental data was evaluated through the %R Factor , defined as: %R Factor = ∑ i,j ⃒ ⃒ D -D PCA ⃒ ⃒ ∑ i,j |D| where D and D PCA are the original and the PCA reconstructed dataset, while the subscripts i and j are the respective rows and columns. For every dataset, the %R Factor was > 99. 999%.
Computational details The adsorption of CO on the different Cu-zeolites studied experimentally was simulated at DFT level of theory by means of the CRYS-TAL17 periodic code  [43]. For each framework, Cu + substitution was studied at different positions, aiming at accounting for the possible heterogeneity of the CO adsorption sites as a function of the ring system hosting the cation. In detail, two sites, placed respectively in a large and a small ring, were investigated herein. Nomenclature and sites labelling used hereafter for defining the ring-systems refers to that proposed by the International Zeolites Association on the Database of Zeolite Structures  [44]. For CHA, Cu + was positioned in the 6-membered ring (-MR) of the d6r cage or within the 8-MR window of the cha cage, maintaining the same position for the framework Al that is charge-balanced by the extraframework ion.
Acknowledgements The work is financially supported by the  European Research Council (ERC) , under the  Horizon 2020 research and innovation program :  CuBE ERC-Synergy project  (Grant agreement n •  856446 ). The authors acknowledge the  European Synchrotron Radiation Facility (ESRF)  for the provision of beamtime at the X-ray Absorption Spectroscopy beamline BM23. GD, MS, EB, VC and SB acknowledges support from the Project CH4. 0 under the  MUR program "Dipartimenti di Eccellenza 2023 -2027 " (CUP:  D13C22003520001 ). This work has been partially supported by the  Spoke 7 "Materials and Molecular Sciences" of ICSC -Centro Nazionale di Ricerca   in High-Performance Computing, Big Data and Quantum Computing , funded by  European Union -NextGenerationEU.
Source of support Any grants/equipment/drugs, and/or other support that facilitated the conduct of research/writing of the manuscript including AFMRC project details, if applicable): -Financial support from Agence Nationale de la Recherche, project BIORESORB ANR-21-CE18-0012, coordinator: Yun Luo. -Scholarship granted to Yang Zhang from China Scholarship Council, grant's number: CSC 202106340022.
The experiment was performed at the extreme conditions beamline I15 at Diamond Light Source  (51). The beamline's polychromatic beam was tuned to 29. 5 keV and focused down to 9×6 µm (Full Width at Half Maximum -FWHM) using two pairs of KB-mirrors. A Si Pilatus 2M detector was used to rapidly collect diffraction data from the sample while keeping a good signal-to-noise ratio. The sample-to-detector distance was determined from the diffraction rings of a CeO 2 standard using the calibration routine of the DIOPTAS software suite  (52). The HP -HT experiment was performed using the laser-heating system mounted on the beamline and following the procedure described in Anzellini and Boccato  (48). Before each heating ramp, the sample was brought to the target P evaluated according to the KCl equation of state following the calibration of Dewaele et al.
During the data analysis, great care was taken to investigate the different aspects of the experiment. The reliability of T measurements was double checked following the procedure described in Benedetti and Loubeyre  (54). An accurate analysis of the diffraction patterns was performed to detect the onset of melting and to obtain structural and textural information about the sample and the insulating material. Masks were applied on a per-image basis and the images azimuthally integrated using the DIOPTAS suite  (52). Both Co and KCl data were treated as powder data and a Pawley analysis was performed with the TOPAS suite (55) using previously reported parameters as starting values. Finally, the outcome of the analysis of the in situ XRD measurements were associated to the corresponding T , so to obtain a precise structural evolution of the sample as a function of P and T.
Calculations Theoretical calculations were performed based on a DFT approach, with the projector-augmented-wave (PAW)  (56)  implementation and the generalized gradient approximation (GGA) for exchange-correlation energy, in the form known as Perdew-Burke-Ernzerhof (PBE)  (57). For these calculations the Vienna Ab initio Simulation Package (VASP) was used. GGA was preferred to local density approximation (LDA), because, in spite of the case of hcp-Co, where LDA calculations yields to single crystalline elastic moduli in closer agreement with experimental results than GGA calculations  (27) , GGA well account for the compressibility curve  (37). Furthermore, it is known that LDA does not accurately describe the properties of other 3d transition metals e. g. chromium for which its predictions are in drastic disagreement with experiment (58; 59), and iron for which it produces a wrong ground state  (60; 61; 62; 63).
Phase diagram Ten HT ramps were performed at selected P following the procedure described in the method section. The data were collected in a P -T range between 15 GPa and 98 GPa and from ambient T up to 4200 K. In this investigated range it was possible to index Co hcp and f cc solid phases and the B2 phase of KCl (used as PTM and standard). Only the ramp performed around 40 GPa showed some formation of CoO(69) above 2600 K, therefore the data obtained in this run above this T were discarded. The analysis of XRD patterns also excludes the formation of cobalt carbide and dicobalt carbide  (70) , thus if any reaction occurred, the amount of unwanted phases is below the detection limits of the XRD technique. An overall similar T -induced textural evolution was observed in each of the performed ramps (Fig.
The ambient T data are those obtained before each heating ramps and do not necessarily represent the thermodynamic equilibrium (as some point are obtained from cold compression and others from the sample quenched from HT ). We note however that the observed f cc-hcp transition pressure at 300 K is in agreement with those obtained from nonhydrostatic compression  (73) , and lower than what expected on the basis of quasi-hydrostatic data  (30; 37). We also note a good agreement between the HP -HT stability of the f cc phase observed in this study and the f cc-hcp phase boundary reported in previous studies  (30). However, because of the minimal temperatures that can be generated and measured in LH-DAC experiments it was only possible to obtain an in situ characterization of the HP -HT f cc-hcp phase boundary of Co for the ramp around 47 GPa.
Thermal equation of state Fig. 4  shows the volumes measured for f cc-Co at HP -HT and the resulting compression curves along different isotherms. Starting from the presented data it was possible to establish the P -V -T equation of state (EoS) for f cc-Co using the EOSfit software suite  (78). According to the formalism described in Angel et al. (78) P at HT can be described as the sum of P at a reference T condition (typically 300 K) and the thermal P with increasing T evaluated along isochors, and hence it can be expressed as: P (V, T ) = P (V, 300K) + P T h (T ) (2) where the P (V , 300 K) is the isothermal EoS of the material at ambient T and P T h (T ) the thermal pressure. In the present work, P (V , 300 K) was calculated from the data reported by Armentrout and Kavner (41), while (P T h ) was modelled fallowing Holland and Powell: Where Θ E is the Einstein T of the material (299 K for Co), K 0 is the bulk modulus obtained from the isothermal EoS at ambient T , α 0 is the thermal expansion coefficient at 300 K and ζ 0 is expressed as: P T h (T ) = α 0 K 0 Θ E ζ 0 ( 1 exp(Θ E /T ) -1 - 1 exp(Θ E /300) -1 ) (3) ζ 0 = (Θ E /300) 2 exp(Θ E /300) (exp(Θ E /300) -1) 2 (4) As shown in Fig.
Conclusions The P -T phase diagram of cobalt was determined up to 100 GPa and 4000 K by LH-DAC and synchrotron-based XRD measurements. QMD simulation for both non magnetic and paramagnetic phases of fcc-Co were also performed up to 1 TPa and 14000 K to characterize its melting curve. The agreement between the experiment and the calculation is excellent in the P -T range experimentally explored, with the computed melting for the paramagnetic phase in slightly better agreement with the experimental data. Unit-cell volumes of the f cc phase measured at high pressures and high temperatures were used to obtain the thermal equation of state of f cc-Co. Data can be well fit by a combination of a 3rd order Birch-Murnaghan EoS describing the P -V compression curve at ambient T with a Holland and Powell expression for the thermal pressure with the following parameters: V 0 =44.
88(5) Å3 ; K 0 =194(2) GPa; K I 0 =3. 75(3) and α 0 =2. 897(8)×10 -5 K -1. Finally, the value of 37. 5 K/GPa of the slope of Co melting line at 0 GPa obtained from the calculations performed for NM-f cc Co can be compare to the values reported for Fe (30. 5 K/GPa, (  14 )) and Ni (38 K/GPa,  (22) ). Although, we note an increase in the values of the melting slope as a function of the d electron occupation, this increase is relatively small and can be considered within the experimental error. Therefore, the obtained results do not necessarily support the hypothesis that the behavior of the melting curve of 3d transition metals depends on the d-electron occupation as proposed in Japel et al. (12). programme (Grant agreement No. 724690). This work was supported by the Generalitat Valenciana under grants PROMETEO CIPROM/2021/075-GREENMAT and MFA/2022/007, and by the Spanish Ministerio de Ciencia e Innovación, Agencia Estatal de Investigación, and the European Union (MCIN/AEI/10.
13039/501100011033) under grants PID2019-106383GB-41 and RED2018-102612-T (MALTA Consolider Team). This study forms part of the Advanced Materials program and is supported by MCIN with funding from European Union Next Generation EU (PRTR-C17. I1) and by the Generalitat Valenciana. S. A. thanks the Generalitat Valenciana for the CIDE-GENT grant no. CIDEXG/2022/6.
Data Availability The datasets generated during and/or analysed during the current study are available from the corresponding author upon request. Figure  2 : a) Integrated XRD patterns for increasing T around 47 GPa. The onset of melting, characterized by the first appearance of the diffuse signal, is observed at 2951 K (blue pattern). The diffuse scattering increases with the rising T , showing its maximum at 3256 K (red pattern). b) Evolution of T (black points) and sample's volume (green empty points) during the heating ramp performed at 47 GPa. It is possible to observe a plateau in the volumetric expansion starting between the measurement at 2860 K and 2951 K, independently confirming the onset of melting. Concerning the T evolution, it is possible to observe a first plateau after 2500 K ascribed for this particular ramp to the onset of fast re-crystallization.
Acknowledgement(s) The authors acknowledge the  DLS synchrotron facility  for provision of beamtime at the beamlines I15 (exp. CY21943). The authors are also grateful to  Francesca Miozzi ,  Ruggero Giampaoli ,  Annette Kleppe  and  Allan Ross  for their support in the experimental preparation. Femtosecond laser micro-machining at IMPMC has been developed and realized by the " Cellule Project " with the financial support of  ANR 2010-JCJC-604-01. D. A. and S. B. have received funding from the  European Research Council (ERC)  under the  European Union 's  Horizon 2020 research and innovation.
02 • 2θ; time per step = 1 s). Lattice parameters and cell volumes were determined by UnitCell Software, while the crystallite size (L) has been calculated by Scherrer formula: = kλ βcosθ , k is a constant equal to 0. 90, λ is the X-ray wavelength equal to 0. 154 nm, β is the full width at half maximum, and θ is the half diffraction angle. The optical properties of the powders were recorded on a UV -Vis Varian Cary 5000 spectrophotometer equipped with a DR integration sphere in the 200-600 nm range. The indirect band gap values are obtained by applying the Tauc plot method referring to the formula (F(R)hv ) 1 2 = f(hν). The vibrational properties of the samples have been analysed with Raman spectroscopy. Spectra were collected and recorded at room temperature with a LabRAM HR spectrometer (Jobin Yvon-Horiba), using a X50 confocal microscope and an excitation wavelength of nm.
The excitation power was kept low to ensure no photodegradation of the samples. The spectra were dispersed with 1800 gr/mm grating, leading to a 1 cm -1 accuracy. Transmission Electron Microscopy characterization was carried out with a Thalos F200X instrument (ThermoFisher) and Energy Dispersive X-ray spectroscopy (EDX) spectra were acquired with four Silicon drift detectors (SDD). The catalysts as dry powders were dispersed in isopropyl alcohol and subsequently drop-casted onto Cu holey carbon grids. Before insertion in the TEM column, the samples were plasmacleaned in Ar atmosphere. Thermo Scientific Velox software was used for the analysis of TEM and EDX data. The crystallographic model for cubic CeO 2 (Fm-3 m space group) is provided in the Crystallography Open Database (COD ID: 4343161).