SUPPLEMENTARY INFORMATION

Transcription

1 Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A. This journal is The Royal Society of Chemistry 214 SUPPLEMENTARY INFORMATION Polymer chemosensors as solid films and coated fibres for extreme acidity colourimetric sensing Jesús Luis Pablos, 1,* Pedro Estévez, 2 Asunción Muñoz, 1 Saturnino Ibeas, 1 Felipe Serna, 1 Félix Clemente García 1 and José Miguel García 1, * 1 Departamento de Química, Facultad de Ciencias, Universidad de Burgos, Plaza de Misael Bañuelos s/n, 91 Burgos, Spain. Fax: (+) , Tel: (+) jlpablos@ubu.es; jmiguel@ubu.es 2 Departamento de Ciencias de los Materiales, Universidad Simón Bolívar, Apartado 89, Caracas 18-A, Venezuela, mail: pedroestevez@usb.ve Table of contents S1. Experimental. Intermediate and monomer characterisation S2. Experimental. Material characterisation S3. Correlation between the acidity function (H ) and concentration of perchloric acid S4. Titration of perchloric acid... 8 S5. Interference study S6. Reuse and stability of the sensory membranes S7. Response time

2 S1. Experimental part. Intermediate and monomer characterisation a) b) N N 1 N N NH 2 Transmittance (%) Wavenumbers, cm -1 c) d) δ, ppm δ, ppm Figure S1. Characterisation of 4,4'-(2-aminopyrimidine-4,6-diyl)bis(ethene-2,1- diyl))bis(n,n-dimethylaniline) (1): a) chemical structure, b) FT-IR spectrum, c) 1 H NMR spectrum, d) 13 C NMR spectrum (NMR solvent: DMSO-d 6 ). 2

3 a) b) Transmittance (%) Wavenumbers, cm -1 c) d) δ, ppm δ, ppm Figure S2. Characterisation of N-(4,6-bis(4-(dimethylamino)styryl)pyrimidin-2- yl)methacrylamide (M1): a) chemical structure, b) FT-IR spectrum, (c) 1 H NMR spectrum, d) 13 C NMR spectrum (NMR solvent: CDCl 3 ). 3

4 a) b) 1 Transmittance (%) Wavenumbers, cm -1 c) d) δ (ppm) δ (ppm) Figure S3. Characterisation of 4,6-bis(4-methoxystyryl)pyrimidin-2-amine (2): a) chemical structure, b) FT-IR spectrum, c) 1 H NMR spectrum, d) 13 C NMR spectrum (NMR solvent: DMSO-d 6 ). 4

5 a) b) 1 Transmittance (%) Wavenumbers, cm -1 c) d) δ, ppm δ, ppm Figure S4. Characterisation of N-(4,6-bis((E)-4-methoxystyryl)pyrimidin-2- yl)methacrylamide (M2): a) chemical structure, b) FT-IR spectrum, c) 1 H NMR spectrum d) 13 C NMR spectrum (NMR solvent: CDCl 3 ). 5

6 S2. Experimental part. Material characterisation Weigth (%) Temperature (ºC) Msen1a 2 1 Deriv. Weigth (ºC/min) Weigth (%) 1 Msen2a Temperature (ºC) 2 1 Deriv. Weigth (ºC/min) Weigth (%) Temperature (ºC) Msen1b.8.4 Deriv. Weigth (ºC/min) Weigth (%) 1 Msen2b Temperature (ºC).8.4 Deriv. Weigth (ºC/min) Figure S5. Thermogravimetric data for membranes. Measurements from 1ºC to 8ºC at a heating rate of 1ºC/min in nitrogen atmosphere. Table S1. Values obtained by TGA analysis, T 5 (ºC), T 1 (ºC), T onset (ºC) and residue. Membrane T 5 (ºC) T 1 (ºC) T ONSET (ºC) Char yield (%) M M M M

7 S3. Correlation between the acidity function (H ) and the concentration of perchloric acid Table S2. Correlation between the acidity function (H ) and the perchloric acid concentration 1 [HClO 4 ], M H [HClO 4 ], M H K. Yates, H. Wai. J. Am. Chem. Soc. 86, ,

8 S4. Titration of perchloricc acid Figure S6. Titration of perchloric acid with Mem1a in MilliQ water using UV/Vis technique: a) UV/Vis spectra showingg the two protonation processes (low and higher acidity in red and blue, respectively); b) acidity absorbance relationshipp at 375 and 429 nm (continuous lines correspond to the fitting using Eq. 17 and 6, respectively); c) species distribution using Eqs assigning to C T a value of 1; d) ) photographs of the sensory material showing the colour during the titration experiment. e 8

9 Figure S7. Titration of perchloric acid with Mem2b in MilliQ water using UV/Vis technique: a) UV/Vis spectra showing the first protonation process (inset: photograph of the sensory material inside the cuvette); b) UV/ /Vis spectraa showing the second, third and fourth protonation processes. These processes are shown isolated d as b1), b2) and b3), respectively, and photographs of the sensory materials during d titration are depicted as b4) together with the perchloric acidd concentration. 9

10 nm 43 nm 614 nm H ph Microspecies Distribution % B BH + BH 2+ 2 BH 3+ 3 BH H ph Figure S8. Titration of perchloric acid with Mem2b in MilliQ water using UV/Vis technique: a) acidity absorbance relationship. The process at 43 nm shows the first protonation process and that at 47 shows the concomitant second, third and fourth protonation processed (continuous lines correspond to the fitting using Eq. 18). The absorbance data at 614 nm are useful for determining the acidity of a system taking a single UV/Vis spectrum (the continuous lines correspond to the fitting using Eq. 6); b) species distribution using Eqs assigning to C T a value of 1. 1

11 Figure S9. Expansion of the 1 H NMR spectra (aromatic and a olefinicc region) of M1 (top) and M2 (bottom) in CD 3 CN/D 2 O (1.3/.7 ml) upon graduallyy increasing the acidity by adding deuterated hydrochloric acid. The horizontal red lines indicate the pk 1 calculated for the membranes prepared from M1 and M2 (see main manuscript, Table 1). 11

12 Figure S1. 1 H NMR, COSY 2D and NOESY 2D, from top t to bottom, of monomer M1 under neutral (pd = 6.88) ) and acidic (pd=1.97) conditions, left andd right, respectively. Solvent = CD 3 CN/D 2 O (1.3/.7 ml). 12

13 Figure S11. 1 H NMR, COSY 2D and NOESY 2D, from top to bottom, of monomer M2 under neutral (pd = 6.88) and acidic (pd = 1.97) conditions, left and a right, respectively. Solvent = CD 3 CN/ /D 2 O (1.3/.7 ml). 13

14 S5. Interference study. 1.5 Mem1a Mem1a in HClO 4 1 M in water Mem1a in HClO 4 1M in water + salts 2. Mem1b Mem1b in HClO 4 1 M in water Mem1b in HClO 4 1M in water + salts Wavelength (nm) Wavelength (nm) Mem2a Mem2a in HClO 4 1 M in water Mem2a in HClO 4 1M in water + salts Wavelength (nm) Mem2b Mem2b in HClO 4 1 M in water Mem2b in HClO 4 1M in water + salts Wavelength (nm) Figure S12. Interference study. UV/Vis spectra of the dry membranes and after immersion in 1 M HClO 4 in water and in a solution of salts (NaCl, KCl, CuSO 4.5H 2 O, Co(NO 3 ) 2.6H 2 O, Al(NO 3 ) 3.9H 2 O, Pb(ClO 4 ) 4, FeSO 4.7H 2 O, LiCl, Zn(NO 3 ) 2.6H 2 O, Hg(NO 3 ) 2.H 2 O, Ni(NO 3 ) 2.6H 2 O) in 1 M HClO 4 in water. The concentration of each salt was 1 x 1-3 M. 14

15 S6. Reuse and stability of the sensory membranes 377 nm Time (Hours) Figure S13. Stability study of Mem1a immersed in acidic water (HClO 4 1 M) with time analysed by UV/Vis. 15

16 Mem1a water HClO 4, 4M Wavelenght (nm) 416 nm water HClO 4, 4 M Measuring cycle Mem1b water HClO 4, 4M Wavelength (nm) 416 nm 2.4 water HClO. 4, 4 M Measuring cycle Mem2b HClO 4, 4M water Wavelength (nm) 422 nm.8.4. HClO 4, 4 M water Measuring cycle Figure S14. Reproducibility and reversibility of Mem1a, Mem1b, Mem2b as acidity sensors analysed by UV/Vis spectroscopy (left: UV/Vis spectra; right: absorbance vs. measuring cycle). The measurements were performed by successive cycles of dipping the material in highly acidic water, HClO 4 4 M, followed by washing with pure water. The time of each cycle was approximately 3 min, 1 min in the acid medium and 2 min for washing. 16

17 S7. Response time 429 nm Mem1a 424 nm Mem1b Time (min) Time (min) 43 nm 2 1 Mem2a Time (min) 43 nm Mem2b Time (min) Figure S15. Response time (time vs. absorbance) of sensory membranes after immersion in acidic water (1 M HClO 4 ). 17