Resultados de investigación

General methods: Melting points were obtained on a Gallenkamp apparatus in open capillaries and are uncorrected. 1H and 13C-NMR spectra were recorded on a Bruker AV400 at 400 MHz and 100 MHz respectively; δ values are given in ppm (relative to TMS) and J values in Hz. The apparent resonance multiplicity is described as s (singlet), br s (broad singlet), d (doublet), t (triplet), q (quartet) and m (multiplet).1H-1H COSY and 1H-13C-HSQC experiments were recorded in order to establish peaks assignment. Electrospray mass spectra were recorded on a Bruker MicroToF-Q spectrometer and on a Bruker TIMS-TOF; accurate mass measurements were achieved using sodium formate as external reference. UV-Visible spectroscopy was performed with an UV-vis Cary 6000. Also, the quantity of dye adsorbed on the TiO2 anode was estimated by desorption experiments; the desorption solution of was 10-3 M NaOH in H2O/THF (20:80). Cyclic Voltammetry (CV) measurements were performed with a μ-Autolab ECO-Chemie potenciostat, using a glassy carbon working electrode, Pt counter electrode, and Ag/AgCl reference electrode. The experiments were carried out under argon, in CH2Cl2 with Bu4NPF6 as supporting electrolyte (0.1mol L-1). Scan rate was 100 mV s-1.-- Synthetic details: The aldehyde AT-CHO [1] (80 mg, 0.346 mmol), 4-methylpyrimidine (32 μL, 0.346 mmol) and Aliquat 336 (16 μL, 0.035 mmol) was refluxed in 5.2 mL NaOH (5M). The mixture was maintained during 1h, then was cooled and the precipitate was filtered off and washed with water. The aqueous phase was extracted with CH2Cl2 (3x20 mL). The organic phase was dried with MgSO4 and the solvent was removed under reduced pressure. The crude product was purified by flash chromatography increasing the polarity of the eluent hexane/ethyl acetate from 8:2 to 6:4 to obtain the desired product, an orange solid (51 mg, 48%). Molecular weight (g/mol): 307.41 Melting point at 760 mm Hg (˚C): 227.7 IR (KBr) ν (cm-1): 1571 (C=N) Uv-Vis data λmax (CH2Cl2)/nm 428 (ε/mol-1·dm3·cm-1 1.98 ± 0.02·104) 1H-NMR (CDCl3, 400 MHz) δ (ppm): 3.01 (s, 6H), 6.72 (d, J= 8Hz, 2H), 6.75 (d, J=16Hz, 1H), 7.11 (d, J = 4 Hz, 1H), 7.14-7.23 (bs, 2H), 7.51 (d, J = 8 Hz, 2H), 7.99 (d, J = 16 Hz, 1H), 8.62 (bs, 1H), 9.11 (s, 1H) 13C-NMR (CDCl3 , 100 MHz) δ (ppm): 40.5, 112.5, 118.5, 121.5, 123.0, 127.1, 130.8, 131.8, 138.4, 147.7, 150.1, 156.8, 158.5, 162.4. HRMS (ESI)+: Found [M+H]+ 308.1215; molecular formula C18H17N3S requires [M+H]+ 308.1216.-- Under a Creative Commons license CC-BY-NC-ND 4.0, 1. General methods 2. Synthetic details 3. Absorption spectra a. Figure S.1. UV-Vis Absorption spectra in CH2Cl2 and concentration dependence of AT-Pyri dye 4. Electrochemical characterization a. Figure S.2. CV analysis of AT-Pyri in CH2Cl2 b. Table S.1. Optical parameters, transition energy E0-0 and potential values Eox and Eox* 5. NMR spectra 6. References, Financial support from Spanish MICINN/AEI under projects PID2019-104272RB-C51/AEI/10.13039/501100011033 and PID2019-104307GB-I00/AEI/10.13039/501100011033, and the Diputación General de Aragón-European Social Found under projects T03-20R and E47-20R is acknowledged., Peer reviewed

Under the terms and conditions of the Creative Commons Attribution (CC BY) license 4.0, 3.2. Raman analysis of as‐received CNFs and dip‐coated textiles: Figure S1. Example of the deconvolutions performed for parameters shown in Table 1. 3.3. XPS analysis of as‐received CNFs and dip‐coated textiles: Figure S2. XPS survey spectra for CNFs (left) and the CWF@1.6CNF thermoelectric textile (right).Table S1. XPS quantitative information extracted from the survey spectra displayed in Figure S1., Antonio J. Paleo gratefully acknowledges support from the FCT-Foundation for Science and Technology by the “plurianual” 2020–2023 Project UIDB/00264/2020, and European COST Action EsSENce CA19118 for its support with the Short-Term Scientific Mission (STSM) at IPF (Dresden). E. Muñoz acknowledges support from Fondecyt grant number 1230440 and from ANID PIA Anillo ACT/192023., Peer reviewed

Statistical data described in the article and the solfware SPSS and the charts with Prism Graphpad 8.0 (Prism). Repetition of all the experiments (two times eachs), check of the controls, assurance of good and reproducible conditions., Experiment performed in the lab, following details described in the publication: https://doi.org/10.1016/j.biocontrol.2023.105259; http://hdl.handle.net/10261/333898, Ministry of Science and Innovation, grant PID2019-104112RB I00 (MCIN/AEI/10.13039/50110001103). The predoctoral contract FPI-UR 2021 (University of La Rioja) support IVD The Erasmus+ - KA1 Erasmus Mundus Joint Master Degrees Program of the European Commission under the PLANT HEALTH Project supported EC., Peer reviewed

Under a Creative Commons license CC-BY 4.0, S1. S-Type thermocouples with roughly equal fine wire diameter (75 µm in the left-most, 70 µm in the others) and different bead sizes, as seen with a binocular microscope (~40x)., Peer reviewed

Experimental section Materials for synthesis and analysis Instrumentation Nuclear magnetic resonance (NMR) spectroscopy Elemental analysis (EA) Mass spectrometry (MS) Gel permeation chromatography (GPC) Experimental details for chemical synthesis Solution studies Stability of Pt-TARF compounds Photoactivation of Pt-TARF compounds Computational details In vitro cell studies Cell culture Exposure to metal and organic compounds Cell viability Statistical analysis Synthesis and characterization Synthesis of the TARF ligand Synthesis of Pt precursors Figures Figure S1-14, Characterization of compounds Figure S15-18, Stability studies Figure S19-27, Activation studies with bioreductants Figure S28, DFT calculations, Peer reviewed

Comprehensive characterizing information about the series of materials; crystal, composition, and hyperfine parameters of the 57Fe Mössbauer spectra of samples K2−δMn1–xCox[Fe(CN)6]; SAED and TGA patterns, HAADF-STEM images, ATR–FTIR, 57Fe Mössbauer spectra, and electrochemical galvanostatic profiles of the mentioned series of samples; calculated fit of XAS experiments; and plots of KCMF50 and KCF operando SXRD in a 10–54° 2Θ range (λ = 1.0332 Å)., Peer reviewed

Case scenarios or vignettes (answers in bold will be considered suboptimal treatment decisions)., Peer reviewed

Experimental details, crystallographic data, theoretical studies, and NMR and IR spectra (PDF) Cartesian coordinates of the optimized structures (XYZ), Peer reviewed

The study was conducted in accordance with the Declaration of Helsinki, and approved by the Human Research Review Committee of the Research Ethics Committee of the Community of Aragon (Comité de Ética de la Investigación de la Comunidad de Aragón, CEICA) ((PI18/198), 04/07/2018).-- Licensed under the terms and conditions of the Creative Commons Attribution (CC BY) license., Table S1: Atomic percentage of EVs isolated from cell cultures. Mean ± SD; Table S2: Nitrogen chemical environmental analysis of EVs isolated from cell cultures. Mean ± SD; Table S3: Percentage atomic composition of EVs isolated from female control donors (n = 6) and ovarian tumor patients of different tumor grades: I (n = 8), II (n = 1), III (n = 2) and IV (n = 7). Mean ± SD; Table S4: Nitrogen composition of EVs isolated from female control donors (n = 6) and ovarian tumor patients of different tumor grades: I (n = 8), II (n = 1), III (n = 2) and IV (n = 7). Mean ± SD; Table S5: Atomic composition of EVs isolated from healthy donors (n = 10) and pancreatic tumor patients (n = 10) at diagnosis. Mean ± SD; Table S6: Nitrogen composition of EVs isolated from healthy donors (n = 10) and pancreatic tumor patients (n = 10) at diagnosis. Mean ± SD., This research was funded by ERC Advanced Grant CADENCE, grant number ERC-2016-ADG-742684”. The research was supported by Instituto de Salud Carlos III (ISCIII) (PI19/01007 and DTS21/00130) and by Fondo Europeo de Desarrollo Regional (Feder) “Una manera de hacer Europa”. We also thank CIBER-BBN, an initiative funded by the VI National R&D&i Plan 2008–2011 financed by the Instituto de Salud Carlos III (ISCIII) with the assistance of the European Regional Development Fund. This study was also partially funded by the Aragon Government (Ph.D. Grant No.r B054/12) and co-funded by Aragon/FEDER 2014–2020 “Building Europe from Aragon”., Peer reviewed

Energy Dispersive X-ray Spectroscopy (EDS) was used to obtain information about the chemical nature of the Co-B and Co-Zn-B samples. As observed in Supplementary Figure S1A, the EDS profiles show the presence of cobalt, oxygen and boron in the Co-B sample. If the material is prepared with the addition of Zn(NO3)2, a new intense peak is observed in the EDS profile (Supplementary Figure S1B), which is attributed to the presence of Zn in the material composition Moreover, EDS mapping was performed to further check the distribution of Co and Zn atoms in HRTEM images.The particle size distributions of the two samples are shown in Supplementary Figure S2. To assess whether the HER performance damaged the chemical nature of the Co-Zn-B material, CV before and after the HER measurements were performed. Supplementary Figure S3 shows that the CV-profile does not exhibit any significant change in the electrochemical behavior of Co-Zn-B, suggesting strong stability under HER working conditions. Furthermore, to confirm the high stability of the Co-Zn-B sample, chronopotentiometric (CP) measurements were performed at a fixed current density of −5 mA cm−2 (Supplementary Figure S4).-- Creative Commons Attribution License (CC BY)., Figure S1: EDS of (a) Co-B and (b) Co-Zn-B. Figure S2 : Particle size distribution of Co-B and Co-Zn-B. Figure S3 : CV pre and post HER of Co-Zn-B at a scan rate of 50 mV·s-1 in a N2-saturated 0.1 M KOH solution. Figure S4: Chronopotentiometric analysis of Co-Zn-B sample at a fixed current density of -5 mA·cm-2., JQ-B thanks the Ministerio de Universidades, the European Union and the University of Alicante for the financial support (MARSALAS21-21). SG-D thanks the Ministerio de Universidades, the European Union and the University of Oviedo for the financial support (MU-21-UP2021-030 30267158)., This study was partly supported by the French PIA project “Lorraine Université d’Excellence,” reference ANR-15-IDEX-04-LUE and the TALiSMAN project funded by ERDF (2019-000214)., Peer reviewed