Thermo-Triggered Catalyst-Free Modification of Glass Surface with An Orthogonal Agent Possessing Nitrile N-oxide and Masked Ketene Functions

Transcription

1 Supporting Information for Thermo-Triggered Catalyst-Free Modification of Glass Surface with An rthogonal Agent Possessing Nitrile N-oxide and Masked Ketene Functions Sumitra Cheawchan, Satoshi Uchida, Hiromitsu Sogawa, Yasuhito Koyama, and Toshikazu Takata*, Department of rganic and Polymeric Materials, Tokyo Institute of Technology, (H-126), okayama, Meguro, Tokyo , Japan Institute for Catalysis, Hokkaido University, N21 W10, Kita, Sapporo , Japan Ø Ø Ø Ø Ø Ø Ø Experimental Section Scheme of Introducing the masked ketene function onto the glass surface Contact angles and surface energy TF-SIM profiles of glass surfaces UV-Visible spectra of spiropyran-, merocyanine-form, SR-GP and MC-GP TGA profiles and calculation of the amount of function moieties on silica nanoparticles surface References S1

2 Ø Experimental Section 1. General methods Equipments. Handy UV lamp 365 nm (LUV-4) was utilized to serve as UV source for observation of photoactive surface. Thermal analysis was carried out on a Shimadzu TGA-50 instrument at N2 atmosphere (flow rate of 50 ml/min) to determine observation of total weight loss. Time of Flight Secondary Ion Mass Spectrometry (TF-SIMS) was measured with TF-SIMS AD from IN-TF GmbH. UV vis absorption spectra were recorded on JASC V-550 spectropolarimeter. The contact angles were measured with DM501-M from Kyowa Kaimen Kagaka Company. XPS profiles were measured with SHIMADZU ESCA-3400 Mgkα. The atomic concentration of the surfaces was calculated by using CMPR11 software. 1,2 2. Materials Nitrile N-oxide-tethering masked ketene agent (1) was prepared according to the literature: Cheawchan, S.; Koyama, Y.; Uchida, S.; Takata, T. Polymer 2013, 54, ther reagents and solvents were commercially available and used without further purification unless otherwise noted. castar size 100 nm, suspended in the water (solid content 50 mg/ml) from Nacalai Tesque Company was used as silica nanoparticle. The slide glass from Matsunami Glass Ind. Ltd. size mm was used for the model of surface modification reaction. Bis-hydroxy perfluoropolyether (Fluorolinker D4000) and fluorine-based solvent R-318, containing perfluorocyclo-butane and 1,2-dichloro octafluorobutane (ratio 9:1) were provided by Solvay Solexis Company. 3. Experimental procedure Preparation of active glass plate The piranha solution was prepared by gradually adding H 2 2 (20.0 ml) to H 2 S 4 (60.0 ml) at low temperature. The glass plates were immersed into prepared piranha solution at rt for overnight in the open-system. The glass plates were washed by sonication with H 2 for 5 min 3 times, and dried in vacuum oven at 70 for 1 h. The obtained surfaces were used in the synthesis of allylfunctionalized surface directly without storage. S2

3 Synthesis of allyl-functionalized surface of the glass plate (Allyl-GP) The dried active glass plates were immersed into CHCl 3 (22.0 ml) and allyltrichlorosilane (0.11 mmol, 15.0 μl) was added into mixture at rt for 4 h under air. The modified glass plates were washed 3 times by sonication 10 min at room temperature with CHCl 3 (50.0 ml), and dried under the vacuum at room temperature to obtain Allyl-GP. Synthesis of masked ketene-functionalized surface of the glass plate (MK-GP) The orthogonal agent (1) (57.3 mg, 0.10 mmol) was smeared on the Allyl-GP and heated at 70 C for 12 h in the open-system. The modified glass plate was cooled down to rt, washed 3 times by sonication 10 min at room temperature with CHCl 3 (50.0 ml), and dried under the vacuum at room temperature to obtain MK-GP. Synthesis of carboxylic acid-functionalized surface of the glass plate (CH-GP) MK-GP was immersed into water in the PTFE petri dish at 160 C in the close-system. When the volume of water decreased, water was refilled into the solution till 12 h. The modified glass plate was cooled down to rt, washed 3 times with acetone (50.0 ml) at room temperature, and dried under the vacuum at room temperature to give the carboxylic acid-functionalized surface (CH- GP). S3

4 Synthesis of diglyme-functionalized surface of the glass plate (DEG-GP) MK-GP was immersed into 2-(2-methoxyethyoxy)ethanol (26.2 mmol, 3.00 ml) in the PTFE petri dish at 160 ºC for 12 h in the close-system. The modified glass plate was cooled down to rt, washed 3 times at room temperature with MeH (50.0 ml), and dried in the vacuum oven at 50 for overnight to give the diglyme-functionalized surface (DEG-GP). Synthesis of polyethylene glycol-fuctionalized surface of the glass plate (PEG-GP) To mono-hydroxy polyethylene glycol (M w 350, 3.22 g, 9.20 mmol) was added CaS 4 (150 mg) and the mixture was stirred at rt for 1 h to remove the moisture from the polymer. After filtration, MK-GP was immersed into residue in the PTFE petri dish at 160 C in the close-system for 12 h. The modified glass plate was cooled down to rt, washed 3 times at room temperature with MeH (50.0 ml), and dried in vacuum oven at 50 for overnight to give the PEG-functionalized surface (PEG-GP). Synthesis of bis-hydroxy perfluoropolyether-functionalized surface of the glass plate (PolyR f - GP) MK-GP was immersed into bis-hydroxy perfluoropolyether (M w 1090, 5.34 g, 4.90 mmol) in the PTFE petri dish container at 160 ºC for 12 h in the close-system. The modified glass plate was cooled down to rt, washed 3 times at room temperature with fluorine-based solvent R-318 (50.0 ml), and dried in vacuum oven at 50 for overnight to give the perfluoropolyether functionalized surface (PolyR f -GP). S4

5 Synthesis of spiropyran-functionalized surface of the glass plate (SR-GP) 1-(2-Hydroxyethyl)-3,3-dimethylindolino-6'-nitrobenzopyrylospiran (352 mg, 1.00 mmol) was dissolved in DMS (5 ml). The MK-GP was immersed into the prepared solution at 160 ºC for 12 h in the close-system. The modified glass plate was cooled down to rt, washed 3 times at room temperature with CHCl 3 (50.0 ml), and dried under the vacuum at room temperature to obtain the spiropyran-functionalized surface (SR-GP). Allyl-SP Synthesis of allyl-functionalized surface of silica nanoparticle (Allyl-SP) The silica nanoparticle suspended in the water was filtered and dried in the oven at 50 for overnight. The silica powder (100 mg) was stirred in CHCl 3 (1.7 ml) with allyltrichlorosilane (2.40 ml) at rt for 4 h. The mixture was evaporated and purified by decantation with CHCl 3 (5-10 ml) 5 times to remove remaining allyltrichlorosilane from the precipitate. Clean allyl-functionalized silica powder was further dried under vacuum at room temperature to obtain allyl-functionalized silica nanoparticle (Allyl-SP) as white powder (99% yield). S5

6 MK-SP Synthesis of masked ketene-functionalized surface of silica nanoparticle (MK-SP) by utilizing agent 1 Allyl-SP (100 mg) and agent 1 (63.3 mg, 0.11 mmol) are ground and mixed in the mortar with keeping the temperature of its surface at 70 ºC for 12 h. The mixture was cooled down to rt, washed with CHCl 3 (10 ml) 5 times by decantation method, and dried under the vacuum at room temperature to obtain the masked ketene-functionalized surface of silica nanoparticle (MK-SP) (97% yield, 24% conversion). PEG-SP Surface modification of polyethylene glycol-functionalized surface of silica nanoparticle (PEG-SP) To mono-hydroxy polyethylene glycol (M w 350, 1.08 g, 3.10 mmol was added CaS 4 (50.0 mg) and the mixture was stirred at rt for 1 h to remove the water from PEG. The dried PEG was added to MK-SP (30.0 mg) and stirred at 160 ºC for 12 h. The mixture was purified by decantation with water 1 time, MeH 5 times, acetone 1 time, and dried in vacuum oven at 50 for overnight to obtain the PEG-functionalized surface of silica nanoparticle (PEG-SP) (99% yield, 90% conversion). S6

7 PolyR f -SP Surface modification of perfluoropolyether-grafting surface of silica nanoparticle (PolyR f -SP) MK-SP (30.0 mg) and bis-hydroxy perfluoropolyether (M w 1090, 1.79g, 1.64 mmol) was stirred at 160 ºC for 12 h. The mixture was washed with decantation method of fluorine-based solvent 5 times to remove the unreacted bis-hydroxy perfluoropolyether, and dried in vacuum oven at 50 for overnight to obtain the PolyR f -functionalized silica nanoparticle (PolyR f -SP) (99% yield, 86% conversion). Ø Scheme of Introducing the masked ketene function onto the glass surface Scheme S1. Introducing the masked ketene function onto the glass surface by coating the agent 1 on the one side of Allyl-GP. S7

8 Ø Contact angles and surface energy Table S1. Contact angles of sample surfaces, and surface energy calculated by Fowkes equation. entry sample θ ( ) of H 2 a θ ( ) of CH 2 I 2 a Surface energy (mj/m 2 ) b 1 Active glass surface Allyl-GP MK-GP CH-GP DEG-GP PEG-GP PolyR f -GP a) Contact Angle measurement (Sessile drop method), volume of droplet = 30 μl. b) The surface energy of substrates was calculated by Fowkes equation. S8

9 Ø TF-SIM profiles of Glass Surfaces Intensity 41.0 Chemical Formula: C 3 H 5-! Exact Mass: Mass (u) Figure S1. TF-SIMS profile of Allyl-GP (Bi3++ species) with positive polarity. Figure S2. TF-SIMS profile of MK-GP (Bi3++ species) with negative polarity. S9

10 Figure S3. TF-SIMS profile of CH-GP (Bi3++ species) with positive polarity. Intensity Chemical Formula: C 34 H 43 7+! Exact Mass: Mass (u) Figure S4. TF-SIMS profile of PEG-GP (Bi3++ species) with positive polarity. S10

11 Intensity Internsity F Chemical Formula: F - Exact Mass: ! 20! 40! 60! 80! 100! Mass (u) Internsity Intensity CF CF CF ! 20! 40! 60! 80! 100! Mass (u) Figure S5. TF-SIMS profile of PolyR f -GP (Bi3++ species) with negative (above) and positive (below) polarity. S11

12 Ø UV-Visible spectroscopy profiles of spiropyran-, merocyanine-form, SR-GP and MC-GP a) 0.8! 0.6! spiropyran form! H N 2 N N 2 Absorbance 0.4! 0.2! Merocyanine form! H N 0! 350$ 450$ 550$ 650$ Wavelenght*(nm) 0.4! Absorbance 0.3! 0.2! SR-GP! MC-GP! 0.1! 0! 350! 450! Wavelenght*(nm) 550! 650! Figure S6. UV vis spectra of SR-GP and MC-GP, together with spiropyran and merocyanine derivatives in CHCl 3 solution at 0.1 µm (298 K). Merocyanine form was monitored after UV light irradiation (λ max = 365 nm) for 3 min. S12

13 Ø TGA profiles and calculation of the amount of function moieties on silica nanoparticles surface 100! TGA-Weight (%)! ! 80! 100! 200! 300! 400! 500! 600! 700! Temperature ( )! Figure S5. Thermogravimetry (TG) profiles of allyl-sp (above) and MK-SP (below) particles at heating rate 10 ºC/min from room temperature to 650 C. Both samples were performed the isothermal degradation at 100 ºC for 20 min to remove water. MK-SP was further performed the isothermal degradation at 190 ºC for 30 min. S13

14 lica nanoparticle (SP) Radius of SP r = nm Surface area of SP S = 4πr 2 = 31, nm 2 /particle Density of SP * d SP = 2.00 g/cm 3 Weight of SP Wsp = (4/3)πr 3 d SP = 1.05E 15 g/particle *Data from sicastar[r] plain, 100 nm Allyl silica nanoparticle (allyl-sp) Weight fraction of allyl group ø Al = 6.50 % Weight fraction of SP ø SP = % Weight of allyl group W Al = (ø Al /ø SP )W SP = 7.28E 17 g/particle Molecular weight of allyl group F Al = g/mol Avogadro number N A = 6.02E+23 number/mol Number of allyl group N Al = (W Al /F Al /)N A = 433, number/nm 2 Density of allyl group σ Al = N Al /S = number/nm 2 Masked ketene-silica nanoparticle (MK-SP) Weight fraction of allyl & ø Al+MK = % MK groups Weight fraction of SP ø SP = % Weight of allyl & MK W Al+MK = (ø Al+MK /ø SP )W SP = 1.71E 16 g/particle group Weight of MK W MK = W Al+MK W Al = 9.77E 17 g/particle Weight of C 2 & acetone W bp = W MK (102.09/573.64) = 1.74E 17 g/particle (total M w = ) (after generating the ketene) Molecular weight of MK F MK = g/mol agent Avogadro number N A = 6.02E+23 number/mol Number of MK group N MK = (W MK /F MK )N A = 102, number/particle Density of MK group σ MK = N MK /S = 3.26 number/nm 2 Conversion of MK agent c MK =(N MK /N Al )100 = % on allyl-sp S14

15 Figure S6. Thermogravimetry (TG) profiles of PEG-SP (above) and PolyR f -SP (below) particles at heating rate 10 ºC/min from room temperature to 650 C. Both samples were performed the isothermal degradation at 100 ºC for 20 min to remove water. S15

16 PEG silica nanoparticle (PEG-SP) Weight fraction of allyl, MK & ø Al+MK+PEG = 16.5% PEG groups Weight fraction of SP ø SP = 83.5% Weight of allyl, MK & PEG W Al+MK+PEG = 2.07E 16 g/particle groups (ø Al+MK+PEG /ø SP )W SP = Weight of PEG group W PEG = W Al+MK+PEG W Al+MK +W bp = 5.39E 17 g/particle Molecular weight of PEG F PEG = 350 g/mol Avogadro number N A = 6.02E+23 number/mol Number of PEG N PEG = (W PEG /F PEG )N A = 92, number/particle Density of PEG σ PEG = N PEG /S = 2.95 number/nm 2 Conversion of PEG with MK c PEG =(N PEG /N MK )100 = % R f silica nanoparticle (PolyR f -SP) Weight fraction of allyl, MK & R f ø Al+MK+Rf = % groups Weight fraction of SP ø SP = % Weight of allyl, MK & R f groups W Al+MK+Rf = 3.13E 16 g/particle (ø Al+MK+Rf /ø SP )W SP = Weight of R f group W Rf = W Al+MK+Rf W Al+MK +W bp = 1.60E 16 g/particle Molecular weight of R f F Rf = 1090 g/mol Avogadro number N A = 6.02E+23 number/mol Number of R f N Rf = (W Rf /F Rf )N A = 88, number/particle Density of R f σ Rf = N Rf /S = 2.81 number/nm 2 Conversion of R f with MK c Rf =(N Rf /N MK )100 = % Ø References (1) Tokutaka, H.; bu-cann, K.; Fujimura, K.; Yoshihara, K. Application of Self-rganising Maps (SM) to Chemical Spectra Analysis. Journal of Surface Analysis 2002, 9, (2) Xu, J.; Fukumoto, N.; Azuma, Y.; Kojima, I. Influence of Ion Beam Position Shift on the Depth Profiling in AES. Journal of Surface Analysis 2002, 9, S16