dataesr/scientific-paragraphs-categorization huggingface dataset:
e. , where the electronic charge is varying) in an electrochemical reaction. Here, the Fukui function shows changes in electron density around both Ir and O. The shape of the Fukui function around the oxygen atom shows overlapping lobes along the axis joining the O-O pairs with short separations, consistent with the expectation of partially empty antibonding s* orbitals if peroxolike species are formed. By contrast, fig. S9  shows no such orbital overlap in the pristine material. The distortion pattern observed on a local scale was confirmed using the structural refinem e n t so ft h eb u l ks t r u c t u r ef r o mn e u t r o np o wder diffraction (NPD) data for the pristine and fully charged Li-Ir-O samples (included in figs. S5 and S10). The [001] projections of the refined structures are shown overlaid in Fig.
X-ray and Neutron Powder Diffraction X-ray powder diffraction (XRD) patterns of the pristine samples and ex situ samples were recorded using a BRUKER D8 Advance diffractometer using Cu-K radiation. The crystallographic parameters were determined by either Rietveld refinement using the Rietica software (version 2. 1) in cases where stacking faults were minimal, otherwise FAULTS  (32)  was used. The values for a, b, c reported with FAULTS correspond to the monoclinic lattice parameters as used in typical Rietveld refinements and to the interplanar distance between TM layers, respectively, as detailed in  (33). The Li 2 IrO 3 samples (both pristine and ex situ) were also studied using synchrotron X-ray powder diffraction at Argonne National Laboratories' 11-BM beamline. A n i n s i t u X R D experiment was performed on Li 2 IrO 3 u s i n g t h e B r u k e r D 8 d i f f r a c t o m e t e r.
Mössbauer Spectroscopy and Differential Scanning Mass Spectrometry In situ Sn Mössbauer spectroscopy of Li 2 Ir 0. 75 Sn 0. 25 O 3 was performed as described in detail in  (34) (35). 119 Sn Mossbauer spectra were collected with a constant acceleration spectrometer using a Ca 119m SnO 3 source in the transmission geometry. The hyperfine parameters: IS (isomer shift) and QS (quadrupole splitting) were obtained by fitting the data with lorentzian functions. The cell was cycled at a C/30 rate at room temperature. The amount of oxygen and carbon dioxide released during electrochemical cycling was obtained using differential electrochemical mass spectrometr y ( D E M S ). T h e configuration has been described elsewhere  (19)  while the electrode preparation method and experimental details are included in Ref.
Density Functional Theory Density functional theory (DFT) calculations were performed to model the Li y IrO 3 structure as a function of lithium content, y. All calculations were performed using the plane-wave density functional theory (DFT) code from the Vienna Ab initio Simulation Package (VASP, version 5. 3). (37, 38)  Spin-dependent calculations were performed using the generalized gradient approximation of Perdew, Burke, and Ernzerhof (PBE)  (39)  including Hubbard-U corrections following the rotationally invariant formalism of Dudarev. (40)  The electron wavefunctions were described in the projected augmented wave formalism (PAW)  (41, 42) , the plane wave energy cutoff was set to 600 eV and the Brillouin zone integration was done in a k-point grid distributed as uniformly as possible, using Monkhorst-Pack meshes of 6 x 4 x 4.
ACKNOWLEDGMENTS E. M. thanks the  Fonds de Recherche du Québec-Nature et Technologies and ALISTORE-European Research Institute  for funding this work, as well as the European community I3 networks for funding the neutron scattering research trip. This work was also funded by the  Slovenian Research Agency  research program  P2-0148. This work is partially based on experiments performed at the  Institut Laue Langevin. We thank  J. Rodriguez-Carvajal  for help with neutron scattering experiments and for fruitful discussions. We also thank  M. T. Sougrati  for performing the  Sn-Mössbauer measurements. Use of the Advanced Photon Source at Argonne National Laboratory  was supported by the  U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences , under contract no. DE-AC02-06CH11357.
Acknowledgements Authors are in debt to supports from  MINECO  and  FEDER  ( MAT2012-34498 , and  CTQ2013-40855-R ),  Generalitat de Catalunya (XRQTC) ,  CESCA  and  Gobierno de Aragón-FSE  (research group  E40 ). D. J. is indebted to the  European Research Council (ERC)  for support in the framework of the  ERC StG  grant  Marches 278845.
An ocean optic spectrometer connected to the optical microscope was used to measure the transmission spectra. Transmission spectra for glass and graphene on glass were measured as shown in figure  6(c ). The results show that compared to the bare glass substrate, graphene sample transmitted about 75-78% of the incident light. Theoretically, the transmission of 10 layer graphene is given by:. So the measured data is in good agreement with the theoretical calculation. Finally to demonstrate the thinnest possible lens a single layer of graphene was used. Samples consisting of monolayer graphene were patterned lithographically onto 0. 7 mm thick glass using a Microtech Laser writer (LW405, minimum resolution 0. 7 µm) with a 405 nm laser. A positive resist (AZ5214) was used as an etch mask, spin coated at 4000 rpm and dried at 100 o C for 1 minute, resulting in a 1 µm thick resist film which was subsequently patterned with the laser and developed.
Computational Details Calculations are computed by the Gaussian  [26, 27]  packet and recovered by GAUSSVIEW program  [28]. Hartree-Fock (HF) and density functional theory (DFT/B3LYP) methods are used for geometrical optimization. Given the great number of atoms forming the studied compound and in order to keep the calculations time compatible with our machines, basis sets STO-3G of moderate dimension were used. For small compounds, the basis set 6-311G(d,p)  [29]  has also been tested. We checked that all vibrational frequencies are positive, which indicates that each studied structure coincides with a minimum on the potential surface.
thermophilus. After optimization of crystal growth and X-ray data collection conditions, this crystal form was used for the structural determination of the first 30S subunit by laboratories of Venki Ramakrishnan and Ada Yonath. After optimization of crystal growth conditions and X-ray data collection conditions, the crystal form obtained by Ada Yonath laboratory for the 50S ribosomal subunit from H. marismortui was used for X-ray structure determination by the laboratories of Peter Moore and Tomas Steitz. These crystals of individual ribosomal subunits have been used to study complexes with mimics of functional ligands as mRNA and tRNA. High-resolution structures of the T. thermophilus 30S subunit and H. marismortui 50S subunit and experimental electron density maps of the full 70S ribosome containing three tRNAs and mRNA have been used by our group for modeling the full ribosome of T.
Acknowledgments Our own work summarized in this paper was supported by the  French National Research Agency   ANR-11-BSV8-006 01  (to G. Y. ), the  European Research Council  advanced grant  294312  (to M. Y. ), the  Human Frontier Science Program  grant  RGP0062/2012  (to M. Y. ), the  Russian Government Program of Competitive Growth of Kazan Federal University  (to G. Y. and M. Y).
Quantum mechanics Quantum mechanics (QM) calculations were conducted starting from a structure of a methyl-capped guanine and a methyl-capped adenine, as a model system, respectively, for 2 -deoxyguanosine and 2 -deoxyadenine. Density functional theory was employed, according to a previous benchmark against the SCS-MP3/aug-cc-pVTZ//MP2/DZP++ (18) level of theory  (19)  that has stressed out the performance of the range-separated hybrid LC-BLYP. Its performance has been also very recently pinpointed for the singletoxygen attack onto trans-resveratrol  (20). The Gaussian09 software Revision D. 01  (21)  was used for all the QM calculations. Since 2 is an intramolecular charge-separated entity and to better model experimental conditions, an implicit model accounting for solvation in water, polarizable continuum model ((  22 )), was used with a value of the dielectric constant ⑀ r = 78.
Molecular dynamics simulation All classical MD simulations were performed with the Amber12 Molecular Dynamics software package  (23). GAFF  (24)  and ff99bsc0 (25) force fields parameters were used. For the oxidized nucleobase, charges and modified force field parameters have been used. Charges were generated using the Restrained Electrostatic Potential charge model of the Antechamber program (26) from QM calculations for the isolated fragment as prescribed by the usual protocol (see Supplementary Table  S1 ): bonded force field parameters along the C-O-O bonds were assigned against high-level QM calculations at the LC-BLYP/DZP++ level of theory. For the open zwitterionic intermediate, the oxygen--oxygen distance is 1. 504 Å with a harmonic constant force of 306. 30 kcal. mol -. Å-2 (1. 42 Å with a force constant of 343.
In particular, the amount of protein required in SFX experiments is currently rather high even for structure solution based on molecular-replacement techniques (i. e. only native data sets are collected). Moreover, although software for SFX data analysis is rapidly developing  (Sauter et al. , 2013; White et al. , 2012 White et al. , , 2013;; Barty et al. , 2014; Sawaya et al. , 2014) , as the Figure 1 The MeshAndCollect workflow for a multicrystal data-collection method. (a) A mesh scan is performed on the sample. The resulting images are automatically inspected for protein diffraction and scored according to diffraction strength. A heat map is generated that represents the diffraction intensity, where the positions for partial data collections are marked. After the user has selected the settings for the partial data collections, the MxCuBE2 data-collection queue is automatically filled and all partial data sets are collected.
Methods In the experiments described here, the best results were obtained from crystals mounted in a flat sample holder (i. e. MiTeGen MicroMeshes; MiTeGen, USA; Fig. 1a ), avoiding stacking of crystals and an excess of surrounding mother liquor, before either flash-cooling in liquid nitrogen or directly on the beamline. When mounted on a goniometer, the plane of the sample holder should be perpendicular to the direction of the X-ray beam. This ensures that any crystal brought into the X-ray beam will remain illuminated over a relatively small rotation range (AE5 in the experiments described here 1  ). To make this adjustment, we usually exploit the mini-kappa Multi-crystal data collection and structure solution from larger crystals of bacteriorhodopsin. (a) Crystals of bacteriorhodopsin obtained from crystallization in lipidic mesophase  (Borshchevskiy et al.
Ideally, this should correspond to, or be smaller than, the minimum dimension of the crystals contained in the sample holder. The area over which the initial two-dimensional mesh scan is performed (Fig. 1a ) is drawn by the user, with the dimensions of the grid and the X-ray beam size defining the number of points in the mesh scan. Diffraction images collected at each of these points are analysed on the fly for protein diffraction using the software DOZOR (x2. 1). The user receives a heat map (Fig. 1 ), also stored in the ISPyB database  (Delageniere et al. , 2011) , showing the grid points at which diffraction has been observed. The user then has the possibility of adjusting the contrast level to include or exclude points for subsequent data collection. In the last experimental step partial data sets (AE5 total rotation range, 100 images per partial data set) are collected sequentially at each grid point with a DOZOR score above the threshold.
DOZOR One of the core features of the protocol described here is the ability to automatically recognize and rank the series of single diffraction patterns collected during the low-dose mesh scan of the sample holder. This is carried out using the program DOZOR. As the algorithm used will be illustrated in more detail elsewhere, it will be only briefly described here. In a first step, DOZOR determines the distribution of background intensity on a diffraction image as a function of the diffraction vector length h. This is accomplished by the iterative summation of pixel intensities and the sequential rejection of outliers. After azimuthal averaging this produces the one-dimensional background function Î I background ðhÞ. This    function should be smooth: any sharp peaks are an indication of ice rings or salt diffraction, and such areas are not used in further calculations.
The program also identifies individual Bragg spots and makes a few simple geometrical checks which additionally validate the presence of diffraction from macromolecular crystals and allow the rejection of ice or salt contamination. Finally, a score of diffraction strength is estimated as the total averaged diffraction intensity multiplied by CC powder , where V(h) is the reciprocal volume of the resolution shell, score ¼ CC powder P h VðhÞ scale Ĵ J u ðhÞ expðÀBh=2Þ= P h VðhÞ: ð3Þ In the case where DOZOR cannot find any Bragg spots, the score is determined as zero.
3 A (Table  1 ; Wilson plot shown in Fig. 2d ). For BR2, the initial mesh scan (X-ray beam of 10 mm in diameter with a flux of 1. 5 Â 10 11 photons s À1 ) produced a heat map (Fig. 3b ) showing 59 diffracting positions in the sample holder from which partial data sets were collected. 38 partial data sets could be automatically processed and, after   HCA (Fig. 3c ), ten were merged to produce a final data set to d min = 2. 6 A ˚; Table  1 ; Wilson plot shown in Fig. 3d ). For both BR1 (twinning fraction 0. 06) and BR2 (twinning fraction 0. 39) structure solution was carried out by molecular replacement using MOLREP  (Vagin & Teplyakov, 2010)  with PDB entry 3ns0  (Borshchevskiy et al. , 2011)  stripped of water molecules and ligands as a search model. Structure refinement (Table  2 ) was carried out using the twinning refinement option in REFMAC5  (Murshudov et al.
Thaumatin Thaumatin (Sigma-Aldrich catalogue No. T7638) was dissolved in double-distilled water to a concentration of 20 mg ml À1. Crystals of approximate dimensions 40 Â 40 Â 60 mm were obtained in 2 ml (1:1 ratio) hanging drops using 0. 1 M HEPES pH 7. 5, 0. 7 M potassium/sodium tartrate, 20% glycerol as a reservoir. Crystals were mounted as described in x2 without further cryoprotection. Data were collected on ESRF beamline ID29. The initial mesh scan was performed with an X-ray beam of 10 mm in diameter with a flux of 8. 7 Â 10 11 photons s À1. From the resulting heat map (Fig. 4a ), 100 well diffracting points were chosen for the collection of partial data sets, of which 78 could be automatically integrated. After HCA (Fig. 4b ) 74 were merged to produce a final data set to d min = 1.
2 A ˚(Table  1 ; Wilson plot shown in Fig. 4c ). Structure solution was carried out by molecular replacement using MOLREP with PDB entry 4axu  (Cipriani et al. , 2012)  stripped of water molecules and ligands as a search model. Structure refinement (Table  2 , Fig. 4d ), during which analysis of difference electron-density maps clearly allowed the assignment of tartrate (one molecule; Figs. 4e  and 4f ) and glycerol (one molecule) moieties bound to the protein, was carried out in REFMAC5 alternated with manual rebuilding in Coot.
After HCA (Fig. 5c ) 21 partial data sets were merged to produce a final data set to d min = 1. 6 A ˚(Table  1 ; Wilson plot shown in Fig. 5d ). Structure solution and refinement (Table  2 , Fig. 5d ) were then carried out as described above for thaumatin (using PDB entry 4axt stripped of water molecules and ligands as the search model for molecular replacement;  Cipriani et al. , 2012) , during which analysis of electron-density and difference electron density maps allowed the assignment of a nitrate (NO 3 À ) ion bound to one of the lysozyme molecules in the asymmetric unit (Fig. 5f  ).
, 2006)  generally used in diffraction data collection from cryocooled single crystals of macromolecules. In future versions of the pipeline presented here, following the low-dose twodimensional mesh scan the optimum total exposure time per crystal (partial data set) will be calculated before the datacollection step using the EDNA characterization software  (Bourenkov & Popov, 2010; Incardona et al. , 2009) , the result being better quality and/or higher resolution data collected per crystal. For crystals that are highly radiation-sensitive one might even imagine the use of a 'Burn Strategy' workflow  (Leal et al. , 2011)  to provide a precise estimation of the maximum allowable total absorbed dose per crystal. As the EDNA procedure implies the indexing of diffraction patterns  (Incardona et al.
Release Kinetics-Model Dependent Method The release kinetic study was assessed by model dependent method. Based on number of kinetic models available in literature, which described the overall release of drug from the dosage forms, were carefully selected and used to fit the release data  [11] [12] [13] [14]. Finally, data were fitted to seven different models: Zero order, 1st Order, Higuchi, Hixson-Crowell, Korsmeyer-Peppas and Reciprocal powered time. The correlation coefficients (r 2 ) indicate that drug release kinetic of PLAGM and PLAHApGM fitted with the power law model described by Korsmeyer-Peppas (Table  1 ). If this semi-empirical equation doesn't allow for the determination of all of the mechanisms involved in the release, it is still possible to determine the mechanisms of transport by considering two borderline cases, which correspond to distinct physical realities (when n = 0.
The assumptions were sampling time were equally spaced, release were normally distributed and data were complete with no missing observations. Statistical software, SPSS 21. 0 for Windows was employed. Multivariate tests were conducted on Pillai's Trace, Wilks' Lambda Hotelling's Trace and Roy's Largest Root. The results show that release differences between PLAGM and PLAHApGM were very significant with ** p ≤ 0. 01 while the effect of time on their release was highly significant with *** p ≤ 0. 001.
The mathematical modelling was carried out using GraphPad Prism software (GraphPad software Inc. , La Jolla, CA, USA). The comparison of the release profiles between PLAGM and PLAHApGM was evaluated using t50% determined from the reciprocal powered time equation (i. e. , the time necessary to release 50% of the drug substance) and the difference (f1) and similarity (f2) factors  [13]. Two dissolution profiles are considered similar when f1 is not greater than 15 and f2 varies from 50 to 100.
Even if the error only involves the mass loss rates, the fitting procedure is performed using mainly the mass loss rate curves but also the mass loss curve for the choice of the initial guess of the values of the kinetic constants. Choosing another expression for the error does not change so much the results. The numerical resolution of system (2) of ODEs has been performed using the routine 'ode' of the SCILAB software  [17]. The determination of the best kinetic constants has been performed using the routine 'datafit' of the SCILAB software. As already mentioned, we first consider a  heating rate of 5 °C/min. The set of kinetic constants which are obtained here are then tested for higher temperature ramps, namely 10 °C/min, 20 °C/min and 50 °C/min. Table  3  presents the results obtained for the different parts of the grape marc at the heating rate of 5 °C/min.
Conclusions In this contribution, a thermogravimetric analyzer has been used for the investigation of the pyrolysis and combustion processes of grape marc. The experimental results are modeled using a biomass lignocellulosic representation and an extended independent parallel reaction model. Optimal sets of kinetic parameters have been obtained for the three constituents of the grape marc (seed, skin, stalk) using the SCILAB software, first at a heating rate of 5 °C/min. These sets of kinetic constants have finally been tested at different other heating rates.
Acknowledgments Part of the work described in this review was funded by the  University of Rouen , GRR-VASI, GRR-IRIB as well as the  Institut Universitaire de France , (B. G. ; C. B. ; P. L. and M. B. ). T. L. C. and W. H. received funding from the  European Community Seventh Framework Programme  ( FP7)  under grant agreement No. 286354. The authors would like to thank  Azzedine Driouich  for critical reading and valuable advice on this manuscript.
The Xray photoelectron spectroscopy (XPS) measurements were performed using a VG ESCA 3 MK II XPS installation ( = 1486. 7 eV). The vacuum analysis chamber pressure was  ∼ 3 × 10 -8 torr. The XPS recorded spectrum involved an energy window  = 20 eV with the resolution  = 50 eV with 256 recording channels. The XPS spectra were processed using Spectral Data Processor v 2. 3 (SDP) software. After Shirley background subtraction, the deconvolution of the XPS curves was conducted by using a fitting procedure based on the summation of Gaussian functions. When irradiated with Xrays, electrons from the inner shells cause the apparition of several peaks with different shapes in the analyzed spectra. Due to the characteristics of the measurement device that can lead to distortions and the ionization process, the peaks can be considered a convolution of Lorentz and Gaussian functions.
Acknowledgements This work was supported by the  French ANR  within the  program ''Nanocrisnet''  under Contract  ANR-11-BS10-018  and by the  LabEx MiChem part of French  state funds managed by the  ANR  within the  "Investissements d'Avenir" program  under reference  ANR-11-IDEX-0004-02. We thank SOLEIL for having provided the installations in synchrotron as well as  Dr Franck Meneau  for the help brought for the use of the line of light "SWING". Calculations were performed using HPC resources from  GENCI-CINES/IDRIS  (grants x2011082131, x2012082131, and x2013082131 for 2011-2013) and the  CCRE-DSI  of the University P. M. Curie. Thanks to  SMART-IP2CT  ( FR UPMC-CNRS 2622 ) for nancial support.
Acknowledgements The author is indebted to  O. Cretu ,  A. La Torre ,  C. Pham-Huu ,  A. Botello-Mendez , and  J. -C. Charlier  for fruitful collaboration in the field of carbon chains. Financial support from the  Agence Nationale de Recherche  (grants  NANOCONTACTS NT09 507527  and  NANOCELLS ANR12 BS1000401 ) is gratefully acknowledged.
Structural characterization was performed at room temperature by X-ray powder diffraction (XRD) using (h-2h) Panalytical X'Pert Pro MPD diffractometer with a copper anti-cathode (kCu Ka1 = 1. 54060 A ˚, kCu Ka2 = 1. 54443 A ˚, ratio = 0. 5). The patterns were recorded over the range 10°-110°in 2h by step of 0. 04°. Phase analysis and structural determination were performed using Fullprof software  [21]  based on the Rietveld method  [22, 23]. The background contribution was refined in the final fit. The refined parameters were, respectively, the following: zero shift, cell parameters, occupancies, z position of La and Mg in the 6c sites, Lorentzian constant Y and Gaussian constant U, and finally the background. At the last cycle, all the parameters were refined simultaneously. The morphology of the S30 mechanically alloyed sample was studied by scanning electron microscopy using a SEM-FEG LEO 1530 device.
Acknowledgments The authors are thankful to  Dr E. Leroy  for technical assistance in the TEM analysis. Financial support was guaranteed by the  CMCU  project ( CMCU PHC Utique N 10G1208 ). Open Access This article is distributed under the terms of the Creative Commons Attribution 4. 0 International License (http:// creativecommons. org/licenses/by/4. 0/),which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.