dataesr/scientific-paragraphs-categorization huggingface dataset:
Crystal Structure Determinations The structure resolution was accomplished using the SHELXS-97 and SHELXT  [61]  programs, and the refinement was done with the SHELXL program  [62, 63]. The structure solution and the refinement were achieved with the PLATON software  [64]. Pictures of the compound structure were obtained using the MERCURY software. During the refinement steps, all atoms except hydrogen atoms were refined anisotropically. The position of the hydrogen atoms was determined using residual electronic densities. Finally, in order to obtain a complete refinement, a weighting step followed by multiple loops of refinement was done. The structures have been deposited in the CCDC with #1901938 (1) and 1901939 (2).
Preparation of self-assembled surfactant-induced ionic liquid complexes: The n-alkylamines and di-n-alkylamines, which are liquid at room temperature, i. e. Structure simulation: X-ray patterns were indexed using N-TREOR09 in EXPO2014 after manual selection of peaks. [43, 44] Simulated annealing was performed using EXPO2014 with all fragments set up as rigid bodies, except for di-n-nonylamine where secondary amine and adjacent carbons were allowed to move freely between them. All models were then subject to geometry optimization using the Relax function of the DFT package Quantum espresso (method BFGS) with fixed cell parameters. [45, 46] Rietveld refinement was performed in all models using EXPO2014 with all fragments set as rigid bodies. [44, 47, 48] n transport measurement and analysis: Ion transport measurements were carried out using an HF2IS impedance spectroscope (Zurich Instruments).
The samples were first filled in LC cells (Instec Inc. ) at high temperatures allowing easy flow. Parallel ion transport (along the ionic layers) was measured using cells with interdigitated in-plane ITO electrodes on glass substrate. Perpendicular ion transport (across the ionic layers) was measured using cells containing parallel ITO electrodes (sandwich configuration) on glass substrates (schemes shown in Figures  4a-b ). The EIS diagrams were recorded during slow cooling scans (0. 5 °C•min -1 unless noted otherwise) between 5 Hz and 10 MHz using an ac-excitation of 100 mV with a temperature controlled at ±0. 1 °C. The raw data were imported to the Zview software (Scriber Associates Inc. ) for further analyses described in detail in the Supporting Information. The low frequency region of the impedance diagrams in the electrochemistry Nyquist plot showed an inclined straight line and the high frequency region showed a depressed semi-circle.
Acknowledgements P. R. and O. I. conceived the concept. T. C. , P. R. , M. M. , and N. H. made the samples. T. C, M. M. , T. G. D. , N. H. , P. R. , T. M. , J. T. and U. V. made the characterization, D. R. N. and J. J. made the DFT modelling. O. I. and P. R. wrote the first version of the article; all authors contributed to the interpretations and commented on the manuscript. The authors are grateful for financial support by  ERC Advanced Grant ,  Academy of Finland , and the  Centre National de la Recherche Scientifique (CNRS) at the laboratoire des Systèmes Moléculaires et nanoMatériaux pour l'Énergie et la Santé in Grenoble (France)  [ UMR5819-SyMMES (CNRS/CEA/UGA )]. The authors thank Nanomaterials of  Aalto University  for the support. We acknowledge the facilities and technical support by  Aalto University at OtaNano -Nanomicroscopy Centre (Aalto-NMC) , and the technical supports, local contacts and the fruitful helps and discussions on the Large Scale Facilities including  M.
A complete LCI from the cradle to the grave is often quite difficult and heavy to perform. Data are not always available. A gate to gate approach more focused on the process is sometimes adopted (figure  9 ) to facilitate the study. At industrial level, data can be collected directly in the production sites. This approach is useful particularly to compare processes in terms of environmental efficiency. However, in the case of natural extracts, it is recommended to consider also the agricultural step (plant growth and harvest before it use for extraction) and the recycling and treatment of extraction by-products. The next step after LCI is the transformation of data into impacts. For this purpose, there are various LCA software available with implemented databases. Some of them are dedicated to specific sectors of activity.
We can cite for example Food'Print v-1 for agri-business or BEE V3. 1 for packaging. Open LCA and SimaPro are examples of more universal software which can be used in extraction field. Databases such as Ecoinvent 2. 1, Agribalyse, ELCD or LCA Food can be implemented by default, but it is generally possible to add the database of its choice in the program used. Therefore, LCA software enables to convert data from LCI into impacts. Actually, depending on the program used, different types of impact can be chosen. The most common are greenhouse effect, euthrophisation, acidification, ozone depleting, eco-toxicity and fossil resources depletion. They correspond to "midpoint" impacts dedicated to scientific or advertised community. It is also possible to express the results into damages, particularly for communicating with non-advertised public.
More recently, Tosta et al. [3]  have used several DFT methods to perform kinetic calculations on the unimolecular gas-phase elimination of primary alkyl acetates including propyl acetate. However, the low levels of theory considered lead to rate constants around one to four orders of magnitude higher than those experimentally obtained earlier  [1, 2]. The aim of this work is two-fold: (i) provide experimental data for propyl acetate kinetics of oxidation and (ii) propose and validate a new kinetic reaction scheme for PA oxidation. To this end, (i) detailed speciation data in the intermediate-to-high temperature range (700 -1250 K) were obtained using a jet-stirred reactor, (ii) rate constants for key reactions were derived from theoretical calculations in order to generate an oxidation kinetic model for PA, and (iii) the proposed kinetic scheme was validated against the present data.
Computational Methodology Quantum chemistry calculations were used to compute the high-pressure rate coefficients of the pericyclic reaction involved in the formation of acetic acid and propene from propyl acetate. Geometry and frequency calculations were performed at the M06-2X/6-311++G(3df,2pd) level of theory from the GAUSSIAN 09 Rev. D01 software  [6]. This density functional method, combined with a large basis set, allows a good estimation of both molecular geometries and harmonic frequencies  [7]. A scaling factor of 0. 983 was used to take into account anharmonicity, in accordance with reference  [8]. The M06-2X method was also considered to perform the one-dimensional relaxed scans needed for the treatment of hindered rotors (see above), but a lower basis set was used in this latter case (6-311+G(d,p)).
,, is the partition function of the torsional mode j, computed in the 1-DHR approximation and qOH,j is the recalculated harmonic partition function for the same torsional mode but treated as a one-dimensional mode (pure 1D harmonic oscillator). This approach was also used to evaluate entropies and heat capacities of the reactants and products. All calculations were performed using the THERMROT software  [10]. In addition, RRKM/master equation analysis was carried out by means of the kinetic code MESS  [11]  in order to investigate the pressure effect in our operating conditions. The interactions between propyl acetate and the bath gas (N2) were modeled with the Lennard-Jones potential (see Supplementary Material). In order to find the lower energy conformer of propyl acetate (Figure  1 ), eighteen conformers were generated by considering the rotations around the C-C and C-O bonds by means of the "ConfGen" module implemented in the MSTor software  [12].
p e m The standard entropy at 298 K and heat capacity of C5H10O2 were computed using the THERMROT software  [10] , while its standard enthalpy of formation at 298 K was obtained from isodesmic reactions (see Supplementary Material). Table  1  summarizes the results obtained and gives comparisons with available experimental results. These results show a good agreement and validates the method chosen for the treatment of hindered rotations as the computed entropy is close to the experimental value (around 0. 5%), whereas the purely harmonic treatment leads to a significantly lower value (91. 41 cal mol -1 K -1 ). Table  1. Thermodynamic properties of propyl acetate. ∆fH°298K is given in kcal mol -1 while S°298K and C°p are expressed in cal mol -1 K -1.
Conclusion New experimental data were obtained for the oxidation of propyl acetate in a JSR at 1 and 10 atm, in the temperature range 700-1250 K, and for equivalence ratios of 0. 5, 1. 0, and 2. 0. They consist of mole fraction profiles of the reactants, final products, and stable intermediates measured by gas chromatography, mass spectrometry, and Fourier transform infrared spectrometry after sonic probe sampling. A detailed kinetic model was proposed and tested against the experimental data obtained in this work. This model was developed based on previous kinetic schemes for the oxidation of other oxygenated fuels and on theoretical calculations at the CCSD(T)-F12/VTZ-F12//M06-2X/6-311++G(3df,2pd) level of theory for the molecular elimination of propene and acetic acid. This new model performs well against the available experimental data.
A Nose-Hoover thermostat  44  and barostat  45  with relaxation times of 1. 0 and 2. 0 ps, respectively, were used to constrain temperature and pressure during the equilibration NPT-MD simulations. Tighter conditions, corresponding to relaxation times of 0. 5 and 1. 0 ps, respectively, were used following the equilibration procedure. A cut-off radius rc=9. 0 Å has been applied to the Lennard Jones interactions, and long-range corrections have been considered, while the Ewald summation technique has been used to account for the long-range electrostatic interactions. All simulations were performed using the DL_POLY package  46. The target bcc plastic crystal phase was prepared as follows. First, an initial randomly disordered configuration consisting of Nw=432 water molecules comprised in a cubic box was prepared by using the Packmol tool 47.
Acknowledgements I. S. acknowledges financial support from the group of  Professor Elvira Guardia  at the  Department of Physics of the Technical University of Catalonia (UPC) , which covered the expenses of his visiting scientist position in the same institution during the periods June-July 2016 and April-May 2018. E. G. acknowledges financial support from the  Ministerio de Economía y Competitividad of Spain , Grant  FIS2015-66879-C2-1-P (MINECO/FEDER ).
Acknowledgements This work was funded by the  FWV ALPO Interreg Grant  and the authors thanks the  European Regional Development Fund (FEDER)  and the  University of Lille. Chevreul Institute  ( FR 2638 ),  Ministère de l'Enseignement Supérieur et de la Recherche ,  Région Hauts de France  are also acknowledged for supporting and funding partially this work. The authors are gratefully acknowledged to  Aurélie Malfait  for GPC measurements. The  UMONS laboratory  thanks the  FRS-FNRS (Fonds pour le Recherche Scientifique)  for financial support for the acquisition of the Waters Synapt G2-Si mass spectrometer.
The three main decomposition channels considered were CH3COOH ↔ CO2 + CH4, CH3COOH ↔ CH2CO + H2O, and CH3COOH ↔ CH3 + COOH. H-abstraction reactions by H, OH, OOH, O2, and CH3 from the carboxylic function and from the methyl group were also theoretically determined. Results were found to agree very well with experimental determinations of the rate constants. The updated CRECK model  [18]  provided good predictions in comparison with the limited amount of experimental data on acetic acid pyrolysis and oxidation  [14, 19, 20, 21]. Motivated by the absence of useful data for the development and the validation of butanoic and pentanoic acid gas phase oxidation kinetics in the literature, this work presents the first experimental datasets obtained for the above fuels. Experiments were performed in an atmospheric pressure jet-stirred reactor, over the temperature range 800-1100 K, for 0.
Thermochemistry and bond dissociation energies (BDEs) Thermodynamic properties for butanoic acid, pentanoic acid and their radicals were estimated using software THERGAS  [32]  that implements Benson's group additivity rules  [33]. From the calculated enthalpies of formation, it is possible to estimate the bond dissociation energies (BDEs) reported in Figure  5  for acetic, propanoic, butanoic and pentanoic acids. As recently reported by Pelucchi et al. [5] , the evaluation of BDEs provides useful guidelines for the development of a kinetic model based on analogy rules. This analysis clearly highlights the extent to which the oxygenated functional group influences vicinal bonds. In other words, as also discussed by Heufer et al. [34]  for long chain alcohols oxidation and represented in Figure  5 , it is possible to assume the acid molecule as composed of an acid specific moiety (BDE values in red) and an alkane-like moiety (BDE values in black).
The LIF/CRDS coupling already allowed measuring species with mole fractions as low as a few ppb in the case of NCO  [9]. In the continuation of our previous works carried out for the prompt-NO formation in premixed low-pressure flames  [10] , the present paper reports quantitative measurements of native NH by using LIF and CRDS techniques for the first time. LIF profiles of NH were measured in five lowpressure flames by probing the R 1 (6) transition at 333. 9 nm. The absorption oscillator line strength was calculated with the PGOPHER program  [11]. LIF profiles of NH were converted into mole fraction profiles by using the integrated spectral absorptivity obtained by CRDS in a flame seeded with 2. 2% of N 2 O. The LIF detection limit is significantly improved in the present work by optimizing the collection volume and the LIF signal processing.
CRDS CRDS measurements for NH were performed by using an experimental set-up and data processing similar to the one described for CH measurements in  [14, 15]. The 420 mm length cavity is ended by two highly reflective mirrors (LaserOptik, 25 mm diameter, 250 mm radius of curvature, reflectivity>0. 997). The laser beam was shaped with a system consisting of a 100 µm pinhole aperture and two lenses (100 and 175 mm focal lengths) in order to match approximately the TEM 00 transverse mode of the optical cavity. The CRD signal was collected by the PMT in front of which was placed a UG11 filter. Cavity decaytimes were determined from an exponential fitting over 1. 6 µs. The ringdown decaytime in the burned gases (in absence of NH absorption) was typically equal to 475 ns. The concentration of the absorbing species is determined from the measurement of the decaytime on-and off-resonance with the transition as detailed in  [16, 17].
NH spectroscopy The PGOPHER program (version 9. 1. 100) [11]  allows calculating the absorption spectrum in absolute intensity, and also extracting the rotational terms of energy (E J" ), the rotational Einstein A coefficients (A J'J" ), or the rotational oscillator strength (f J"J' ). The revised spectroscopic constant values of NH in the A 3 Π-X 3 Σ -system proposed by Ram and Bernath  [18]  were introduced in PGOPHER. The vibrational and rotational partition functions in the ground state X 3 Σ -were calculated by using the equilibrium molecular constants reported by Brooke et al. [19]. The Boltzmann factors were determined as function of the temperature by using E J" calculated by PGOPHER. In order to calculate the values of A J'J" and f J"J' , the electronic transition moment ( ′ " ) that is required, was calculated (in D) from the vibronic Einstein A coefficient (A v'v" in unit s -1 ) according to Eq.
Modeling and discussions Modeling was performed using either the GDFkin ® 3. 0 model  [12]  for CH 4 oxidation or the Lindstedt and Skevis model  [13]  for C 2 H 2 oxidation (named LS hereafter). These models were completed with the NOMecha2. 0 submechanism  [10]. NOMecha2. 0 was fully validated in low-pressure flames for the prompt-NO formation against a large experimental database gathering species such as NCN, NCO, HCN, CN, CH and NO. NH was one of the missing intermediate species involved in the prompt-NO scheme. Calculations were done with the Chemkin/Premix-II package, using the experimental temperature profiles previously reported in  [10, 14]. The NH profiles were simulated in all flames. The acetylene oxidation mechanism proposed by Lindstedt and Skevis  [13]  was previously adopted to simulate prompt-NO and intermediate species in the acetylene flames as reported in  [10, 14].
Acknowledgments This work is a contribution to the CPER research project CLIMIBIO. The authors thank the  French Ministère de l'Enseignement Supérieur et de la Recherche , the  Hauts-de-France Region  and the  European Funds for Regional Economical Development  for their financial support to this project. SMM. pdf file containing additional information concerning dispersed fluorescence spectra, temporal fluorescence decays, and species profiles (experimental and simulated obtained in the acetylene flames).
ACKNOWLEDGMENTS PFL would like to thank Eric Neuscamman for valuable discussions. Funding from Projet International de Coopération Scienti que (PICS08310) is acknowledged. is work was performed using HPC resources from CALMIP (Toulouse) under allocation 2019-18005 and from GENCI-TGCC (Grant 2018-A0040801738). AB was supported by the U. S. Department of Energy, O ce of Science, Basic Energy Sciences, Materials Sciences and Engineering Division, as part of the Computational Materials Sciences Program and Center for Predictive Simulation of Functional Materials.
Instantaneous and mean nitric oxide (NO) concentrations are measured in a turbulent, lifted, -heptane jet spray flame at an atmospheric pressure using planar laser-induced fluorescence (PLIF). The flame-front is simultaneously located using OH-PLIF. The NO excitation line with the least temperature-quenching dependence is selected, and the associated NO-LIF dependence is corrected. LIF optimization and data reduction are based on previous work [Mulla et al. Combust. Flame 203 (2019) 217-229] where the NO-LIF signal was simulated at the spray flame condition (temperature and gas composition from LES) using a spectroscopic model. In the present work, to reduce interferences from polycyclic aromatic hydrocarbons (PAH) and soot, the detection bandwidth is progressively reduced from broadband (F6), intermediate (F3), to narrowband (F1).
F6 results in a significant interference, while F1 contains the least interference. Instantaneous NO mole fraction (   ) is deduced from F1 dataset using a novel instant-wise mapped interference subtraction approach (F1-Inst). The conditional mean NO concentrations derived from F6, F3, F1, and F1-Inst are in agreement (within uncertainty limits); however, F1-Inst appears to be the most reliable. Instantaneous flame-structure (OH) and NO concentration fields are analyzed. The spray flame structure consists of the inner (B1) and outer (B2) flame branches. Local extinctions are observed along B1. Small-scale.
Introduction Spray flames exhibit a complex interaction between droplets, turbulence, and combustion. A large spatial variation of droplet size, flow velocity, and fuel concentration exists in spray flames  [1]. This leads to the formation of a hybrid structure containing premixed, partially premixed, and diffusion flame branches  [2]. The droplet-flame interaction also leads to local extinctions and heat release rate perturbations. These complex phenomena affect the formation of nitric oxide (NO) which is highly sensitive to the mode of combustion, residence time, and temperature. Therefore, to accurately predict the NO concentration, it is necessary to develop and validate thermochemical (and turbulence) models against an experimental database. Thus, physical insights and measurements derived from well-defined target flames are of great interest to the modeling community.
The      (TCS) network  [3]  has been facilitating collaborations between experimental and computational communities. Since its inception (in 2009), TCS has evolved from identifying target flames to establishing comprehensive databases in select flames. The target flames include a Sydney piloted dilute spray burner  [4]  and a Cambridge swirl spray burner  [5]. The contribution by CORIA Rouen Spray Burner (CRSB) group has also been recognized. The CRSB database  [1-3, 6, 7]  includes spray shadowgraphy, droplet size and temperature, flow and droplet velocities, flame-front, ignition probability map, and mean NO concentration. So far, the TCS databases has primarily provided spray characterization, flow-field, and flame-structure information. There is a need to strengthen the database by measuring species concentrations, especially the pollutants such as NO and soot.
05 / 2 ) leads to a strong LII interference from soot. The distinction between LII and PAH-LIF signatures is discussed subsequently in Sec. 3. 3. 6 using instantaneous detuned images. The soot interference is not significant with F6 due to lower fluence (0. 02 / 2 ). Nevertheless, appreciable detuned signal (attributed to PAH-LIF and weak LII) exists between c = 0. 9 and c = 0. 3 in a region of  > 60. This comparison demonstrates that in a non-sooting, PAH-containing region, F1 strategy provides the least interference. To evaluate NO concentration, the detuned signal (interference) is subtracted from the tuned signal. Since the detuned signal in a region of  > 60  spreads outside of the mean flame-front, we retain the data only till  = 60. In a sooting environment, laser fluence cannot be increased beyond a certain threshold due to LII interference.
along with the additional result from the F1-Inst dataset. The observations/discussion in the present section and the Sec. 3. 1 lead to the following preliminary conclusions from the diagnostics point of view. The use of high fluence is necessary to increase the NO-LIF signal intensity relative to the camera dark-noise and photon shot-noise. In non-sooting and aromaticfree regions, all three strategies F6, F3, and F1 can be employed with high laser fluence. However, in the PAH-containing regions, the use of the F1 strategy is recommended due to the least interference. F3 is a compromise between the NO-LIF signal and PAH interference. For practical (aromatics-containing) fuels, F3 or F1 detection can be employed instead of broadband F6 to mitigate the fluorescence interference from non-reacting fuel.
Conditional mean NO based on instant-wise PAH subtraction The instant-wise PAH subtracted instantaneous NO concentration images (e. g. , Fig. 10  and 13 ) deduced from F1 dataset are conditionally averaged over 1500 realizations to provide a mean NO field. This data reduction strategy is denoted as F1-Inst. The mean NO concentration from F1-Inst is shown in Fig. 14. The composite image is obtained from H1 and H2 data. The data beyond 60  height is not retained due to higher LII noise. The mean    from F1 (Fig. 5c ) and F1-Inst are almost identical, as expected since the LII noise is not significant below  = 60. However, there are subtle differences between F1 and F1-Inst. As noted earlier, with F1 a very low    patch is observed around  = 40-60 ,  = 16-20  region, while with F1-Inst (Fig. 10 ) the    at this location is slightly higher (∼20 ).