dataesr/scientific-paragraphs-categorization huggingface dataset:
Adding preferential orientation along a* (1,0,0) improved the profile χ 2 considerably. In 30 simulated annealing runs, the same crystal structure was found 25 times. The profile χ 2 of the best solution was 19. 25, which is about three times the Pawley χ 2 ; this is a good indication that the correct solution has been found. In addition, the structure was very similar to phase I, which made a pressure induced transition likely. For the Rietveld refinement, data out to 15. 9° 2θ were used, which corresponds to 1. 63 Å real-space resolution. The Rietveld refinement was carried out with TOPAS-Academic. 38 Bond lengths, bond angles and planar groups were subjected to suitable restraints, including bonds to H atoms. A global Biso was refined for all non-hydrogen atoms, with the Biso of the hydrogen atoms constrained at 1.
An attempt to obtain form III under ordinary pressure The synchrotron data in Figure  2  lead to the inference that at very low temperatures form III would become stable under its own vapour pressure, i. e. under ordinary conditions. Therefore form I was monitored overnight at 100 K (the lowest possible temperature for the laboratory X-ray equipment) for any visible phase change. None was observed. However, the synchrotron data also indicated that with decreasing temperature, in particular for 293 and 250 K, the transition from form I into form III with increasing pressure became consistently slower. It may therefore be possible that the absence of an observation of form III is due to kinetic reasons, instead of thermodynamic reasons. Therefore in the discussion below only the synchrotron data will be taken into account, where both form I and form III as a function of pressure have been observed; however, in the electronic supplementary information an alternative calculation will demonstrate the effect on the phase diagram if form I is considered to be stable at 100 K.
The PAW calculations performed with the VASP code were carried out as constant volume optimisations and the external pressure was the result of the volume constraint whereas the pob-TZVP computations, effected in the CRYSTAL09 suite, were executed as full geometry optimisations under external pressure defined in the input. Interestingly, all of the models overestimate the As-O bond lengths by ca. 0. 03-0. 05 Å (cf. Fig. 2 ). The discrepancies for As•••O intermolecular distances are a little smaller and the PBE-D2 model has been found to perform better than the B3LYP-D*. The agreement between experimental and calculated As-O-As and O-As-O bond angles is remarkable with most of the calculated values lying within one standard uncertainty (s. u. ) from the experimental values.
, 1963; Yamasaki, 1962; Nyburg, 1964). HalogenÁ Á Áhalogen contacts have two preferred geometries described by the 1 and 2 C-XÁ Á ÁX angles  (Desiraju & Parthasarathy, 1989). Type I geometry is characterized by 1 ' 2 , while in type II 1 ' 180 and 2 ' 90. Notably, a Cambridge Structural Database (CSD, Version 1. 15;  Groom & Allen, 2014 ) statistical analysis of experimentally observed short XÁ Á ÁX halogen contacts (X = F, Cl, Br or I) by  Desiraju & Parthasarathy (1989)  indicated that halogenÁ Á Áhalogen interactions may be understood as specific weak attractive forces. XÁ Á ÁX interactions are of special significance in the design of organic crystal structures, and examples of the utilization of halogen bonding in the production of functional materials are described by  Ding et al. (2012).
The scheme is constructed by partitioning space into regions in which the electron-density sum over the spherical atoms of a molecule dominates the corresponding sum in the crystal  (Spackman & Byrom, 1997; McKinnon et al. , 2004) , i. e. W(r) > 1 2. The CrystalExplorer software  (McKinnon et al. , 2004; Wolff et al. , 2012)  is widely used by the community to display and analyse crystal packings and their resulting intermolecular interactions. A large range of properties can be visualized on the Hirshfeld surface, including the distance of atoms external, d e , and internal, d i , to the surface  (Spackman & Byrom, 1997; Spackman & McKinnon, 2002) , which can be shown in twodimensional fingerprint plots. Normalized contact distances, d norm , have also been defined using van der Waals radii to highlight donors and acceptors and small and larger atoms equally on the surface.
Spectrofluorimetry: Fluorolog Jobin Yvon Horiba equipped with a Xe source. Fluorescence spectra for free ZnPc and conjugate 1a-c were recorded in THF, ethanol or dimethylsulfoxyde. Excitation was performed at 600 nm and emission spectrums were recorded for an absorbance at excitation wavelength between 0. 03 and 0. 07. Fourier Transformed InfraRed spectroscopy (FTIR): measurements were performed on a FTIR Bruker Vertex 70v spectrometer; samples were analyzed on KBr pellets, which were prepared as follows: KBr powder (150 mg) and powder sample (2 mg) were mixed and pressed. TiONts FTIR spectra were recorded and processed by OPUS software: depending on their nature, samples were analyzed as powders into dried KBr or as liquids through an ATR device. MALDI-TOF MS (Matrix-Assisted Laser Desorption/Ionization -Time of Flight Mass Spectroscopy).
5 Å). The copper grids were dipped in dilute suspension of samples in ethanol and naturally dried. ThermoGravimetric Analysis (TGA): desorption of TiONts and decomposition of the organic compounds were studied by thermogravimetry (TGA DISCOVERY). This symmetric thermobalance is able to measure weight variations of 0. 1 µg. Heating rate was 5°C up to 800°C N 2 (25 mL/min). Sample weight was 5-10 mg. UV-Visible spectroscopy: ZnPc, TiONts and TiONts-Pc 1a-1b spectra were obtained on a Shimadzu UV-2550 spectrophotometer. Free phthalocyanines 3a-3b and TiONts-Pc conjugate 1a-c spectra were recorded in DMSO in glass cuvettes 1x1x3 cm (1 cm path). Other samples were measured as particle suspensions into ultrapure water (resistivity 18 MΩ) when no otherwise stated. XPS: X-ray Photoelectron Spectroscopy data were recorded on a PHI Versaprobe 5000 device and Al-K α monochromatic radiation (1486.
S11 ). This may be because of the PEG-linker in 1c. Moreover, a satisfactory point in 1c is that click chemistry proceeds well, and only required watersoluble and easily removable copper catalyst and reducing agent, unlike amide bond formation in 1a-b (peptide coupling requires EDC and NHS). Indeed, the synthesis of 1c did not require the use of extra organic reagents, which is an asset for subsequent purification purposes. These reactions proceeded smoothly and each TiONts end-products were well identified and thoroughly characterized by an extensive number of spectroscopic techniques step-by-step. Based on preliminary 8 | J. Name. , 2012, 00, 1--3 This journal is © The Royal Society of Chemistry 2012 data (fluorescence measurements), we are confident on the relevant nature of 1c.
1% formic acid (5 µL/min) and then eluted onto the separation column (Waters nanoAquity UPLC column, C18, 1. 7 µm BEH130, 75 µm × 200 mm, 200 nL/min) with a gradient (A, 0. 1% formic acid; B, 0. 1% formic acid in acetonitrile, 5-50% B in either 60 or 120 min). The spray was done from a silica emitter with a 10 µm tip (PicoTip FS360-20-10, New Objective) at a capillary voltage of 1. 5 kV. For data acquisition, the MSE technique was applied: alternating scans (0. 95 s, 0. 05 s interscan delay) with low (4 eV) and high (ramp from 20 to 35 eV) collision energy was recorded  (Silva et al. , 2005; Li et al. , 2009). The data were evaluated with the software package Protein Lynx Global Server version 2. 5. 2 (Waters, Eschborn, Germany) searching the Uniprot database and Uniprot tremble (Jan 2014 update).
The fragment ions were detected in the linear ion-trap (rapid mode). The LC-ESI-OT-MS data were processed with Proteome Discoverer v1. 4. 1. 14 (Thermo Scientific) using the following parameters: precursor mass tolerance 10 ppm, fragment mass tolerance 0. 2 Da, 1 missed cleavage, carbamidomethylation on Cys as fixed and oxidation on Met and phosphorylation on Ser, The and Tyr as variable modifications. All peptide assignments were verified by manual inspection.
The reason for the incompatibility is not clear but the phos-tag possibly blocks the phosphorylation site for the staining. In any case, to identify detected proteins, spots should be picked and analyzed by MS and/or by Western blot. Other specific staining methods are available for different enzyme activities (e. g. , malate dehydrogenase, lipoxygenase, superoxide dismutase and others)  (Manchenko, 2002). Combination of native two-dimensional gel electrophoresis with the phos-tag technology and the use of specific activity stainings has the benefit that changes of these activities by phosphorylation can be directly monitored. Applications of the method can be the observation of specific activities by phosphorylation under differential stress conditions (Supplemental Data 6). The method itself should not be used as a stand-alone technique but together with Western blot, MS and specific point mutation of phosphorylation sites it can be used for a dynamic analysis of reactions to stress factors.
Identified Proteins. Protein spots picked from the second dimension hrCNE and phos-tag hrCNE (Figure4) were digested by trypsin and analyzed by MS. Protein names listed in UniProt are used in the table. No. , spot number; ID, accession number in UniProt (http://www. uniprot. org/); Shift, difference in the separation distance of the spot on phos-tag hrCNE and hrCNE in % (?, if unclear). Significant changes (student's T-test) were indicated by * ≤ 0. 01 and ** ≤ 0. 001 for n = 3 technical replicates; P, phosphorylated form detected (+, positive; -, negative); Pept, number of identified peptides-manual sequencing was marked with an asterisk; pI, theoretical isoelectrical point; MW, theoretical molecular weight in kD; NetPhos, theoretical phosphorylation sites calculated with NetPhos 2. 0 (http://www.
Acknowledgements B. L. and A. F. thank the  European Research Council  ( ERC, Marches -278845 ) for supporting his stays in Nantes and for his post-doctoral grant, respectively. D. J. acknowledges the  ERC  and the  Région des Pays de la Loire  for nancial support in the framework of a  Starting Grant  ( Marches -278845 ) and a recrutement sur poste stratégique, respectively. This research used resources of: 1) the  GENCI-CINES/IDRIS, 2) CCIPL (Centre de Calcul Intensif des Pays de Loire ) and 3) a local Troy cluster.
Changes in the absorption intensity of 1 at 321 nm in the presence of increasing concentrations of TM-βCD or TM-γCD provides the values of K s , Figures  S1  and S2  in Supporting Information File 1. The analysis data shows that K s could be approximately around 580 ± 100 and 160 ± 30 M -1 for 1•TM-βCD and 1•TM-γCD, respectively. K s values of TM-βCD encapsulation were higher than that of TM-γCD, due to its more favorable dimensional compatibility. Characterization of these compounds has been performed using FTIR and NMR spectroscopy. Figure  S3  in Supporting Information File 1 gives the FTIR spectra of both polyrotaxanes and the reference 3. FTIR of encapsulated compounds 3•TM-βCD and 3•TM-γCD reveals a distinct vibration peaks located in 1159-1042 cm -1 region due to the presence of TM-βCD or TM-γCD, whereas the reference 3 does not show any absorption peaks in this interval.
The PLQE was estimated by comparison with a solution of quinine sulfate dehydrate in 0. 5 M sulfuric acid of known quantum efficiency, 56 ± 5%. CVs were carried out in a three-electrode cell in which Pt (1 mm diameter) was used as a working electrode, a Pt wire as counter-electrode and an Ag wire as pseudo-reference electrode. A TBAClO 4 solution (0. 1 M) in anhydrous ACN was used as the supporting electrolyte. The set-up was introduced into a glove box and controlled by AUTOLAB PGSTAT 101 (Ecochemie) using NOVA software. The pseudo-reference was calibrated with a 10 -3 M of Fc solution in ACN. The polymer samples were drop-casted onto the working electrode from a concentrated DCM solution and studied in the interval -2. 5 and +2. 0 V vs Ag wire. Cathodic and anodic scans were performed independently.
Acknowledgements This research was supported by a grant of the  Romanian National Authority for Scientific Research, CNCS -UEFISCDI , project number  PN-II-ID-PCE-2011-3-0035. A. F. acknowledges financial support from  Institute d`Etude Avancees (IEA), University of Cergy-Pontoise, France. Also, we are grateful to  Prof. Sophie Cantin  for advancing contact angles of water and diiodomethane measurements. We also thank the  EC Seventh Framework Programme  ( FP7/2007-2013 ) under Grant Agreement No. 264694  (GENIUS), the  EU   Horizon 2020 Research and Innovation Programme  under Grant Agreement N. 643238 (SYNCHRONICS), as well as the  Royal Society  and the  EPSRC. FC is a  Royal Society Wolfson Research Merit Award  holder.
This is expected to yield allosteric control of substrate binding and tunable coupling interactions through variation of the bridging ligand. BD thanks the Ecole Normale Superieure de Cachan for a PhD Fellowship. Dr Sebastien Blanchard is warmly acknowledged for fruitful discussions. Geoffrey Gontard is thanked for the XRD measurements. Financial support from the ANR Switch (2010-Blan-712) and ANR E-storic (14-CE05-0002) are acknowledged.
29 ± 0. 1 nm À1 for HNS fibers and 0. 18 ± 0. 1 nm À1 for TSA3 fibers. It has been determined by counting the number of stripes per unit length in the perpendicular direction using ImageJ  [4]  image analysis software. Also, mean maximum and minimum Feret diameterswhich correspond to the shortest and the longest distances between any two points along the grain boundary (GB)were determined. These values yield, respectively, 26 and 36 nm for the HNS fibers and 141 and 210 nm for the TSA3 fibers  [5].
The pressure variations due to both gas expansion and hydrogen sorption are measured after reaching thermodynamic equilibrium, usually in the range of minutes. Real equation of state for hydrogen gas is used from the program GASPAK V3. 32. The PCI curves were measured twice (i. e. , two full adsorption-desorption cycles) in order to check the hysteresis effect and the measurement repeatability. Good repeatability has been obtained for all samples. All capacities reported are excess hydrogen sorption quantities and refer to the sample dry mass (i. e. , degassed mass). Sample volume correction is derived from skeletal density measurements and data correspond to the excess values obtained by He pycnometry (Utrapyc 1200 Quantachrome, Hartley Wintney, UK).
Schenk et al. 6  investigated the structure of premixed flat flames of the isomers of butene (C 4 H 8 /O 2 /Ar) at low pressure. Concentrations of stable species and radicals in the flames were measured by molecular-beam mass spectrometry. More recently, Fenard et al. 7  studied the oxidation of trans-2-butene in a jet-stirred reactor and in a combustion vessel. Stable species were quantified by GC and FTIR. The focus of this paper is on the oxidation of 1-butene and cis-2-butene. New experimental data for the oxidation of 1butene and cis-2-butene in a JSR and a combustion vessel are presented. Also, the validation of the oxidation mechanisms for three linear butene isomers was achieved.
We used in a previous work  7  Schenk's experimental data to validate our model on the oxidation of trans-2-butene. In this work, we compared the experimental data provided by Schenk et al. for a 1-butene flame (16. 5% 1-C 4 H 8 /58. 5% O 2 /25% Ar) to the results obtained by computation with our model. We focused on stable intermediates concentration profiles experimentally measured by molecular-beam mass spectrometry (MBMS). Comparisons are presented in Figure  18. The simulations exhibit a reliable prediction of experimental data for reactants (1-C 4 H 8 and O 2 ) as well as for combustion products (CO, CO 2 , and H 2 O). 1-Butene is consumed for a distance to the burner of 0. 3 cm, and the mole fraction of final combustion products reaches a plateau of concentration above 0. 6 cm. Predicted concentration profiles of abundant intermediates such as ethylene, propene, methane, or formaldehyde are in a good agreement with experimental data.
A simple and efficient organic synthesis approach is employed in order to yield balanced azo-polymer structures. The SHG efficiency of poled azo-polymer thin films is investigated by the SHG Maker Fringes technique. A necessary comparison is carried out between the azobenzene containing poly(methyl methacrylate)s and some poly(styrene)s  [31]  containing the same type of azo-moieties, that we have recently synthesized by another approach. The overall impact of the polymer matrix type and various chromophore loads is debated. We obtained two dimensional SHG images of the samples by employing SHG microscopy and we show that optical data storage can be successfully achieved in these structures.
The SHG beam has been detected by means of an appropriate photomultiplier (after being attenuated with sufficient neutral density filters), then smoothed by a boxcar average. The averaged values of the SHG have been stored as a function of the incident angle by means of a homemade Labview program, which was also controlling the position of the rotation stage. The obtained data have been examined using the model of HermaneHayden  [36]  in order to find the effective values of the second order nonlinear susceptibility ðc ð2Þ eff Þ. The advantage of this model is that it takes into account the linear absorption of the material under investigation. The second harmonic generation intensity is given by the following equation: I sÀp 2u ðqÞ ¼ 128p 5 cl 2 h t 1s af i 4 h t 2p fs i 2 h t 2p sa i 2 n 2 2u cos 2 q 2u I 2 u Lc ð2Þ eff 2 Â exp½À2ðd 1 þ d 2 Þ sin 2 F þ sinh 2 J F 2 þ J 2 (9) where I 2u and I u are is the SHG and fundamental intensities, l is the laser excitation wavelength, t 1s af , t 2p fs , t 2p sa are the transmission coefficients for the air/film, film/substrate and substrate/air interfaces L is the thickness of the investigated film.
SHG microscopy technique setup Two-dimensional SHG images over the investigated samples have been obtained by means of a SHG microscopy setup. The same setup has been utilized in order to perform optical data storage in the thin azobenzene containing polymer films. A Ti:Sapphire laser (Tsunami, Spectra Physics) has been employed, which is tunable in the range 700e1080 nm and can provide 120 fs laser pulses with a repetition rate of 80 MHz. The laser beam has been focused by an objective lens (Â20 or Â50 magnification) of an inverted modified microscope (IX 71, Olympus), while the laser power could be adjusted by an electro optic modulator. The angular deviation of the laser beam has been achieved by means of two galvanometric mirrors allowing a rapid scanning of the SHG efficiency over the material.
A home-made Labview program provided the possibility to precisely adjust the polarization and the intensity of the laser beam and to control the amplitude of the galvanometric mirrors, which is related with the size of the scanned area. With the same program the number of pixels of each 2-D SHG image, the exposure time for each pixel and the position of the thin film have been controlled. The latter has been achieved by placing the thin films on XYZ motorized stages (Newport) controlled by an 8 axes Motion Controller/Driver (XPS, Newport). The SHG signal has been detected by means of a photon counter after blocking the residual incident laser beam by a short-pass filter (BG39, Schott). The SHG signal has been stored for each position of the laser beam with respect to the sample, providing the 2-D images.
The impact on the NLO response that dictates the trade-off in choosing a poly(methyl methacrylate) or a poly(styrene) matrix, different molecular weights of these matrices, the sequence distribution in copolymers and various chromophore loads is debated in comparison with other reported studies. Additionally, we obtained two dimensional SHG images of the samples by employing SHG microscopy and we show that optical data storage can be successfully achieved in these structures.
Copolymer composition and monomer reactivity ratios The microstructure of a polymeric material plays an important role in the behavior of the material toward a variety of external stimuli (light, pH) systems, and could be especially important in copolymerizations with monomers of different reactivities. Monomer reactivity ratios provide a tool for estimating the average compositions of copolymers and the relative placement of reactive or functional monomers along the polymer chain. In order to determine the reactivity ratios, we have used an integral method and the corresponding software, the OptPex2 program  [39]  provided by Hagiopol and coworkers. Taking into account the obtained values, r MMA ¼ 1. 95 and r D1-IPRO ¼ 0. 94, it can be said that D1-IPRO favors cross-propagation as opposed to homopropagation and MMA favors homopropagation over crosspropagation.
First-order hyperpolarizability A complete insight into the NLO properties of a model azocompound (D1-EtOxa  [31] ) that has the same structure with the azo-moieties after chemical attachment is further presented. These data are of interest since it would reveal the efficiency in the translation of the microscopic optical nonlinearity to the macroscopic optical nonlinearity. We employ a crude technique for the determination of the first-order molecular hyperpolarizability tensor (b) using the solvatochromic response of the model compound, and DR1 as standard. The ground state dipole moments of the azo dyes were determined by quantum chemical calculations. All the computations were carried out using GAMESS  [43]  program and the basic set level used was M11/KTZVP  [44]. The experimental values of D1-EtOxa and DR1 are summarized in Table  2 , where DR1 data were measured under identical experimental conditions.
[47]  Two-dimensional SHG images have been obtained for all the investigated samples. The sample M1 combined at the same time high SHG efficiency and very good homogeneity over the surface of the film as it can be seen by examining Fig. S5. For this reason, we have chosen this sample to perform optical data storage. The optical data storage has been achieved through successive isomerization cycles induced through two-photon absorption processes  [13]. During these studies, the laser excitation wavelength has been adjusted to be 800 nm and the laser beam has been focused into the sample by means of a Â50 objective lens. In order to demonstrate the possibility to perform optical data storage in these samples we have recorded the image of the filmmaker Georges M eli es (Fig. S6 ). The size of this image is 125 Â 125 pixels and prior to the recording it had been converted into a 2D matrix.
Acknowledgment The authors acknowledge the contribution of  Konstantinos Iliopoulos ,  Florica Adriana Jerca ,  Valentin Victor Jerca  and  Dumitru Mircea Vuluga  being equal to that of the first and reprint author. K. I. acknowledges the support from the  European Commission  and the  General Secretariat for Research and Technology (Greece)  for a National Strategic Reference Framework (NSRF) Project ( PE3-(1612 )). M. C. S. acknowledges the financial support offered by the  Sectorial Operational Program e Human Resources Development 2007-2013  of  Romanian Ministry of Labor, Family and Social Protection  through the  Financial Agreement   POSDRU/107/1. 5/S/76903. V. V. J. acknowledges the financial support offered by the  Sectorial Operational Program Human Resources Development 2007-2013  of the Ministry of European Funds through the  Financial Agreement   POSDRU/159/1.
■ ACKNOWLEDGMENTS This work was supported by the U. K. EPSRC grant EP/ G060649/1 and EPSRC grant EP/L027151/1, Defence Science and Technology Laboratory (DSTL), a Marie Curie Intra-European Fellowship (FP7-PEOPLE-2011-IEF 298012 to L. Z. ) and ERC grant 320503 LINASS. (2) Hisatomi, T. ; Kubota, J. ; Domen, K. Recent Advances in Semiconductors for Photocatalytic and Photoelectrochemical Water Splitting. Chem. Soc. Rev. 2014, 43, 7520-7535.