BUSCADOR RECOLECTA

Additional information on the synthesis of graphene oxide, stability of water dispersions of P3HTNPs–GO using different GO sheet sizes, UV–vis and Raman spectra, AFM/KPFM images of P3HTNPs and P3HT–GO nanohybrids, and cyclic voltammetry results of films of P3HTNPs and P3HTNPs–GO as a function of the scan rate., Peer reviewed

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

Chemical structure of the nanostructured biopolymers: Figure S1. Chemical structure of cellulose nanocrystals (A) and chitin nanocrystals (B).-- Polydispersity results of nanostructured biopolymers: Figure S2. Polydispersity indexes of the NBs (CNCs I, CNCs II and ChNCs) in water with different NaCl concentrations.-- Evolution of the visual appearance of PEs: Figure S3. Evolution over time of the PEs made with CNCs I. The images were used to determine the creaming index. Figure S4. Evolution over time of the PEs made with CNCs II. The images were used to determine the creaming index. Figure S5. Evolution over time of the PEs made with ChNCs. The images were used to determine the creaming index.-- BNC production with ChNCs without PEs: Figure S6. BNC culture media without ChNCs (left) and two different ChNCs concentrations (center and right) after 14 days since inoculation. It can be observed that ChNCs precipitate, what reduces the ChNCs incorporation in the BNC composites.-- BNC hydrogels prepared with emulsified culture media: Figure S7. BNC hydrogels prepared with emulsified culture media after cleaning.-- Under Creative Commons Attribution (CC BY) license., Chemical structure of the nanostructured biopolymers. Polydispersity results of nanostructured biopolymers. Evolution of the visual appearance of PEs. BNC production with ChNCs without PEs. BNC hydrogels prepared with emulsified culture media., This research was funded by Spanish MICINN/AEI under projects PID2019-104272RB-C51/AEI/10.13039/501100011033 and PID2020-120439RA-I00, from Spanish CSIC (PIE iniciación ref. 202280I007), and support from Gobierno de Aragón (DGA, Grupo Reconocido DGA-T03_23R) is acknowledged. Víctor Calvo thanks the DGA for funding their Ph.D. contracts (Ref. CUS/581/2020)., Peer reviewed

S2. Redox charge density & thickness: Figure S2. Cyclic voltamogramms of the different P3HT film series with different film thicknesses (indicated by different colors) taken at a scan rate of 20 mV/s. A) P3HT-CHCl3 B) P3HT-THF C) P3HT-CHCl3(NP) D) P3HT-THF(NP). Respective figures E), F) ,G) and H) represent the linear relations found between resulting redox charge densities and measured thicknesses (colors of each film thickness according to the corresponding cyclic voltammogram). Redox charge density values in units of mCcm-2 are calculated by the integration of the anodic and cathodic CV curves for each thickness followed by dividing the obtained values by the scan rate and the probed surface area.-- Figure S3. Transmittance values at 520 nm for the P3HT film series taken in their A) oxidized transparent states and B) neutral colored states as a function of the calculated redox charge density. Symbols represent experimental data points. Lines represent the fitted curves according to exponential decay functions. Regression coefficients r2 are indicated for all the film series. The transmittance curve for P3HT-CHCl3 in the neutral state not only shows overall higher transmittance values but also its exponential fitting curve with lowest regression coefficient strongly deviates from the behavior of all the other films. The different and rather poor transmittance behavior reflects the non-continuous island-like coating of the ITO substrate obtained for this sample by the employed spray-coating process, as demonstrated by the SEM and profilometry results in the main manuscript (Figure 5D and 6D, respectively). The poor transmittance behavior of the spray-coated P3HT-CHCl3 sample in the neutral state thus accounts for the largely different contrast behavior compared to the other P3HT samples, with an apparent shift of the optimum contrast range towards rather high, i.e. out-of-range redox charge density values, as a consequence of unsatisfying fitting results.--, Figure S4. Transmittance spectra of a P3HT film in its neutral and oxidized states.-- Figure S5. A) Transmittance vs. time plot a P3HT-THF film. B) Contrast vs. pulse length extracted from the previous data and corresponding fitting function from which τ values can be obtained.-- Figure S6. A) Transmittance vs. time plot for a P3HT-THF film. B) Contrast vs. number of cycles extracted from the previous data and corresponding fitting function from which N80 values can be obtained.-- Figure S7. Characterization of spin-coated P3HT films deposited from chloroform. A) SEM image obtained at 30 kX magnification (scale bar 200 nm). B) Profilometry of a representative film with average thickness of 77 nm. C) Transmittance in transparent and colored states, together with resulting contrast, versus redox charge density. D) Switching speeds, represented by t90 values versus redox charge density. E) Cycling stability, represented by the number of cycles corresponding to a 20 % loss of the initial contrast value, i.e. N80 value. F) Images of delaminated films after cycling stability tests. Table S1. Electrochromic performance parameters for spin-coated P3HT-CHCl3 series.--, Under a Creative Commons license BY-NC-ND 4.0., S1. UV-vis absorption spectra. S2. Redox charge density & thickness. S3. Stationary transmittance at 520 nm. S4. Transmittance spectra. S5. Switching speed. S6. Stability test. S7. Spin-coated P3HT-CHCl3 film. References., S1. UV-vis absorption spectra: The UV-vis spectra (Figure S1) of P3HT-THF and CHCl3 solutions show a featureless broad π-π* transition absorption band with its maximum at 445 nm, typical for amorphous P3HT. This band is red-shifted to 510 nm for the nanoparticle polymer P3HT (NP) dispersions. The spectra for these dispersions also show the appearance of peaks at 520 nm, 560 nm, and 620 nm, which indicate the existence of vibronic transitions caused by the internal aggregation of the P3HT chains inside the nanoparticles.[1,2] The acquired aggregate structure with its electronic transitions of the P3HT (NPs) in dispersion is maintained when deposited in the form of films onto substrates.-- S2. Redox charge density & thickness: Figure S2 shows the cyclic voltammograms of the different P3HT film probed for different film thicknesses at a scan rate of 20 mV/s in the potential window from -0.3 to 1.1 V vs. Ag/AgCl reference electrode (RE), calibrated at 0.45 V vs. ferrocene. The surface area exposed to the electrolyte is about 1 cm2.-- S3. Stationary Transmittance: Figure S4 show the stationary transmittance curves of the P3HT film series taken at 520 nm in the oxidized and neutral state as a function of the calculated redox charge densities. Experimental data points are fitted by exponential decay functions. The P3HT film series show similar transmittance curves in the oxidized state (Figure S3A), while those in the neutral state (Figure S3B) exhibit larger deviations. The difference between transmittance values in the oxidized and neutral state then provides the contrast curve as a function of the redox charge density as shown in Figure 2 of the main manuscript.--, S4. Transmittance spectra: Figure S4 shows the transmittance spectra of P3HT-THF film acquired in its neutral and oxidized states, reflecting its magenta and transparent pale blue colors, respectively. The transmittance minimum is obtained at 520 nm for the neutral state and provides the reference value at which maximum contrast, i.e. transmittance differences between the oxidized and neutral state is calculated for the different P3HT film series.-- S5. Switching speed: The switching speed of the P3HT films has been determined following the experimental procedure described in the experimental section of the main manuscript. Here the films are submitted to potential steps of variable pulse lengths of 15, 10, 5, 2, 1, 0.5 and 0.25 s between -0.3 and 1.1 V. A representative case study for a P3HT-THF film is depicted in Figure S5.-- S6. Cycling stability: The cycling stability of the P3HT films has been determined following the experimental procedure described in the experimental section of the main manuscript. Here the films are submitted to a number of potential steps between -0.3 and 1.1 V: 300 cycles of 10 s for each step were applied. A representative case study for a P3HT-THF film is depicted in Figure S6.-- S7. Spin-coated P3HT-CHCl3 film: Spin-coating of non-nanostructured P3HT-CHCl3 dispersions, provides a continuous film coverage of the ITO substrate, as can be seen by SEM (Figure S7A) and the profilometry curve of a representative film with average film thickness of 77 nm (Figure S7B). Therefore, the electrochromic transmittance and contrast behavior at 520 nm (Figure S7C) now shows more consistent results, comparable to those of the spray-coated films of the other P3HT series. This especially refers to the optimum redox charge density and maximum contrast being achieved. Equally, t90 switching speed (Figure S7D), as well as the cycling stability (Figure S7E) in the optimum redox window reveal a behavior close to the ones of the other spray-coated film series. However, the spin-coated P3HT-CHCl3 film is prone to delamination issues (Figure S7F), compromising the mechanical integrity of the film, and thus as well the contact to the underlying substrate. This results in the non-linear enhancement of the t90 switching and the decrease of the cycle stability, beyond the established optimum redox charge densities window, as can be seen in Figure S7D and S7E, respectively. The overall electrochromic performance parameters for the spin-coated P3HT-CHCl3 series are summarized in Table S1., This work was funded by Ministerio de Ciencia e Innovación-Agencia Estatal de Investigación (MCIN-AEI, Spain) under Grant numbers PID2019-104272RB-C55/AEI/10.13039/501100011033, PID2019-104272RB-C51/AEI/10.13039/501100011033 and TED2021-129609B-I00/MCIN/AEI/10.13039/501100011033 (co-funded by European Union NextGenerationEU/PRTR). A.C-S acknowledges financial support from UPCT-Banco Santander through a research grant (“Iniciación en investigacion” Program 2021). W.M. and A.M.B acknowledge financial support from Gobierno de Aragon (DGA) under project “Grupos de Investigación Reconocidos” T03_23R. E.C. is grateful for his PhD grant from MINECO (FPI BES2017-080020) and associated European Social Funds (ESF)., Peer reviewed

Under a Creative Commons license BY-NC-ND 4.0 Deed., Synthesis of cellulose nanocrystals: Cellulose nanocrystals (CNCs) were synthesized following the protocol described in two previous publications.[1,2] 10 g of microcrystalline cellulose (MCC) (Sigma-Aldrich, ref 310697) were dispersed in 45 ml of ultrapure water using an ultrasound bath (45 kHz) for 5 min. Then, 45 ml of H2SO4 98 wt% (Labkem, ref SUAC-00A) were added dropwise to the mixture (externally cooled in an ice/water bath at 0 °C) reaching a final H2SO4 concentration of 64 wt%. This addition was performed fast (less than 5 min) and with magnetic stirring to obtain type I CNCs or slow (longer than 100 min) and with high shear mixing to obtain type II CNCs.[1] After that, the mixture was put in a heating plate at 70°C for 10 minutes for type I CNCs or at ambient temperature for 1 hour for type II CNCs. The reaction was stopped by diluting in 1 liter of ultrapure water at 4°C, also to increase the pH, and the mixture was left decanting overnight at 4°C. The bottom sediment was dialyzed against ultrapure water until a neutral pH was achieved, using specific dialysis membranes (Merck, average flat width 33 mm, ref D9652-100FT). The neutralized dispersions were subjected to centrifugation/re-dispersion cycles at 9000 rpm (9327 rcf) for 1 min to keep only the nanocrystals. The average mass yield and the concentration (Table S1) were determined by lyophilization of 3 aliquots of 30 mL of the CNCs dispersions. The hydrodynamic radii, polydispersity, and ζ-potential were measured using a Malvern Nano ZS instrument, and the mean values of these parameters are presented in Table S1. The CNCs in solid were measured by a Bruker D8 Advance X-Ray diffractometer using a Cu tube as the X-ray source (λ Cu Kα = 1.54 Å), a tube voltage of 40 kV, and a current of 40 mA. The X-Ray diffraction patterns of the prepared CNCs (Fig. S1) confirmed the different presence of the characteristic planes of type I or type II cellulose.--, Synthesis of cellulose nanocrystals: Table S1. Mean values of the characterization results of type I and type II CNCs dispersions. Fig. S1. X-ray diffraction profiles of type I (red) and type II (blue) CNCs. Surface resistivity of n-type thermoelectric cotton textiles as a function of the number of dip-coating cycles: Fig. S2. Surface resistivity (Rsh) of nanocomposite textiles from 1 to 10 immersion cycles with equivalent inks, but different immersion methodology: regular (red) and using a complementary ultrasounds bath treatment for 5 min (black). Measured with an in-line 4-point probe configuration. Error bars show standard deviation of at least 3 repetitions. SEM images of the surface of original and washed CWF@CNF textile samples: Fig. S3. SEM images of the surface of original and washed CWF@CNF textile samples at different magnifications (a) CWF@CNF, (b) CWF@CNF W30 and (c) CWF@CNF W45. Model proposed for describing the nonlinear Seebeck of CNFs and CWF@CNF: The model presented in this work represents the combination of two physical mechanisms occurring in parallel: S(T)=S_met (T)+S_imp (T) (1). Power factor and estimative figure of merit of unwashed and washed samples and CNFs: Table S2. Thermoelectrical properties of dip-coated textiles and carbon nanofibers. References., Financial support from Spanish MCIN/AEI under projects PID2019-104272RB-C51/AEI/10.13039/501100011033 and PID2020-120439RA-I00, from Spanish CSIC (PIE iniciación ref. 202280I007), as well as from Gobierno de Aragón (DGA, Grupo Reconocido DGA-T03_23R) is acknowledged. Vícto Calvo thanks the DGA for funding his PhD contract (Ref. CUS/581/2020). Antonio J. Paleo gratefully acknowledges support from 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) grant E-COST-GRANT-CA19118-0ed3a197 at IPF (Dresden). E. Muñoz acknowledges funding from ANID ANILLO ACT/192023 and Fondecyt No 1230440., Peer reviewed

Preparation procedures and physical and spectroscopic data for compounds 17−43 and crystallographic data in CIF format and ORTEP diagrams of 28 and 30., Peer reviewed

Analytical and spectral characterization data of all new compounds, NMR/NOESY interprotonic distances, and crystallographic data (CIF)., Peer reviewed

Preparation procedures, physical and spectroscopic data for compounds 5a−f, 7a−f, and 8, HPLC chromatograms for ee determination, NMR spectra of complexation and diffusion studies, Cartesian coordinates of all computed stationary points, relative and absolute activation energies for all reactions, and complete ref 22., Peer reviewed

Supporting Information: Preparation Details and Physical and Spectroscopic Data of Compounds 12, 16-36; Computational Data: Cartesian Coordinates and Total Energies., Peer reviewed

9 figures, 6 tables.-- S.3.1. Linear sweep voltammetry: The LSV experiments were performed at a scan rate of 50 mV·s-1 in oxygen-saturated 0.1 M KOH. The scan in the nitrogen-saturated electrolyte is also presented. Apart from the 5 electrodes with the CNT inks, a reference catalyst Pt/C (60%) was tested. S.4. Specific capacitance: We calculated the double-layer capacitance (DLC) from CV at scan rates ranging from 0 to 150 mV·s-1 on a GC electrode of 4 mm diameter and 0.06 μF·cm-2 specific capacitance. The capacitive current was determined as the difference between the cathodic and anodic current at a given potential. Capacitive currents were plotted vs. the scan rate (Figure 4.b) and the calculated slope was divided by 2 to obtain the electrode capacitance. Next, the specific capacitance was calculated dividing the electrode capacitance by the real specific surface area from AFM (Table S.6). The area of vertical nano-crevices is not considered because of the cantilever tip size, resulting in an underestimated surface. Nonetheless, the use of AFM to obtain the specific capacitance has been recommended in the case of low RF surfaces [13].-- S.5. Stability tests: The stability of the carbon-based catalysts was assessed on the GC electrode by CV. Up to 1,600 cycles were performed in the O2 saturated electrolyte without rotating the electrode. Two control measurements, before and after the series in static, were performed with a rotation speed of 1,600 rpm.-- Under a Creative Commons license CC-BY 4.0, S.1. Experimental details S.2. Characterization of the carbon materials S.2.1. Raman spectroscopy and sheet resistivity S.2.2. X-ray photoelectron spectroscopy (XPS) S.2.3. AFM measurements S.3. The full set of LSV curves in the RRDE S.3.1. Linear sweep voltammetry S.3.2. Koutecky-Levich (KL) analysis S.4. Specific capacitance S.5. Stability tests, Peer reviewed