S-1

Electronic Supplementary Information

Boronic acids as molecular inks for surface functionalization of polyvinyl alcohol

substrates

Ryuhei Nishiyabu,* Miku Tomura, Tomo Okade, and Yuji Kubo*

Department of Applied Chemistry, Graduate School of Urban Environmental Sciences, Tokyo

Metropolitan University, Minami-ohsawa, Hachioji, Tokyo 192-0397, Japan. Tel: +81-42-677-1111,

Fax: +81-42-677-2821, E-mail: ryuhei@tmu.ac.jp

*Corresponding authors: Dr. Ryuhei Nishiyabu and Prof. Dr. Yuji Kubo

Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2018

S-2

Scheme S1 Synthetic route for a boronic acid-appended dimethylaminoazobenzene (4).

Scheme S2 Synthetic route for a boronic acid-appended fluoroalkane (6).

Fig. S1 1H NMR spectrum of 4 in DMSO-d6.

S-3

Fig. S2 13C NMR spectrum of 4 in DMSO-d6.

Fig. S3 11B NMR spectrum of 4 in DMSO-d6.

S-4

Fig. S4 HRMS (ESI) of the isolated product (top and middle) and simulated (bottom) isotope

patterns of [4 + H]+.

S-5

Fig. S5 1H NMR spectrum of 6 in DMSO-d6.

Fig. S6 13C NMR spectrum of 6 in DMSO-d6.

S-6

Fig. S7 11B NMR spectrum of 6 in DMSO-d6.

Fig. S8 19F NMR spectrum of 6 in DMSO-d6.

S-7

Fig. S9 HRMS (ESI) of the product (top and middle) and simulated (bottom) isotope patterns of [6

+ Na]+.

Fig. S10 SEM image of the cross-section of the PVA film.

Film

S-8

200 150 100 50 0 -50

(ppm)

Fig. S11 Solid state 13C CP/MAS NMR spectrum of the PVA film.

Fig. S12 Photograph of the PVA-GA film on the glass slide (left) and SEM image of the cross-section

of the PVA-GA film (right).

200 150 100 50 0 -50

(ppm)

Fig. S13 Solid state 13C CP/MAS NMR spectrum of a PVA-GA film.

Film

S-9

Fig. S14 Photograph of the PVA-BA film on the glass slide (left) and SEM image of the cross-section

of the PVA-BA film (right).

200 150 100 50 0 -50

(ppm)

Fig. S15 Solid state 13C CP/MAS NMR spectrum of the PVA-BA film.

(a) (b)

Fig. S16 Photographs of (a) the empty marker pen and (b) the marker pen filled with methanol

solution containing 1a.

Film

S-10

Fig. S17 Photographs of the 1a/PVA film on the glass slide (a) before and (b) after washing with

methanol.

500 550 600 6500.0

0.1

0.2

0.3

Ab

sorb

an

ce

Wavelength (nm)

Fig. S18 UV-vis absorption spectra of the 1a/PVA film before (circle) and after (square) washing

with methanol.

S-11

Fig. S19 Photographs of the 1b/PVA film on a glass slide (a) before and (b) after washing with

methanol.

EVOH

CH/P

VA

CE/P

VA

CS

CE

0.0

2.0x1014

4.0x1014

6.0x1014

Am

ou

nt

of

imm

ob

ilize

d 1

a (

mo

lecule

/cm

-2)

Film

Fig. S20 The amounts of 1a immobilized on the surface of EVOH, CH/PVA, CE/PVA, CH and

CE films.

S-12

500 400 300 200 100

404 402 400 398 396 194 192 190 188

C1s

B1s

N1s

Co

unt

(arb

. u

nit)

Binding energy (eV)

O1s

Co

unt (a

rb. unit)

Binding energy (eV)

Co

unt (a

rb. unit)

Binding energy (eV)

Fig. S21 X-ray photoelectron spectrum of the 1a/PVA film.

Fig. S22 Fluorescence microscopic image of the cross-section of the 1/PVA film.

Film

Glass slide

S-13

450 500 5500.00

0.05

0.10

0.15

Ab

sorb

an

ce

Wavelength (nm)

Fig. S23 UV-vis absorption spectra of the 2/PVA film before (circle) and after (square) washing with

methanol.

360 380 400 420 4400.000

0.005

0.010

0.015

0.020

0.025

Ab

sorb

an

ce

Wavelength (nm)

Fig. S24 UV-vis absorption spectra of the 3/PVA film before (circle) and after (square) washing with

methanol.

S-14

500 550 600 6500.00

0.05

0.10

0.15A

bsorb

an

ce

Wavelength (nm)

Fig. S25 UV-vis absorption spectra of the 1a/PVA-GA film before (circle) and after (square) washing

with methanol. The amount of immobilized 1a was determined to be 8.1 × 1014 molecule/cm2.

500 550 600 6500.0

0.1

0.2

0.3

Ab

sorb

an

ce

Wavelength (nm)

Fig. 26 UV-vis absorption spectra of 1a/PVA-BA film before (circle) and after (square) washing with

methanol. The amount of immobilized 1a was determined to be 1.4 × 1015 molecule/cm2.

S-15

350 400 450 500 550 600 6500.00

0.02

0.04

0.06

0.08

0.10

0.12

Absorb

ance

Wavelength (nm)

(a)

350 400 450 500 550 600 6500.00

0.02

0.04

0.06

0.08

0.10

0.12

Absorb

ance

Wavelength (nm)

(b)

350 400 450 500 550 600 6500.00

0.02

0.04

0.06

0.08

0.10

0.12

Ab

sorb

an

ce

Wavelength (nm)

(c)

350 400 450 500 550 600 6500.00

0.02

0.04

0.06

0.08

0.10

0.12

Ab

sorb

an

ce

Wavelength (nm)

(d)

350 400 450 500 550 600 6500.00

0.02

0.04

0.06

0.08

0.10

0.12

Absorb

ance

Wavelength (nm)

(e)

Fig. S27 Absorption spectral changes of the 4/PVA-BA film after repetitive immersion (5 min) in

acidic (solid line) and basic (dashed line) aqueous solutions. (a) First, (b) second, (c) third, (d) fourth

and (e) fifth cycles.

S-16

400 450 500 550 600 6500

50

100

150

200

250

30 min

Flu

ore

scence inte

nsity (

arb

. unit)

Wavelength (nm)

0 min

(a)

0 5 10 15 20 25 300

50

100

150

200

250

(b)

Flu

ore

scence inte

nsity (

arb

. unit)

Time (min)

Fig. S28 (a) Fluorescence spectra and (b) intensity (λem = 502 nm) of the 5/PVA-BA film at different

immersion time in aqueous solution containing Cu2+ ions (2.0 × 10−5 M). Conditions: 5 mM HEPES

buffer (30 mL, pH 7.0), λex = 340 nm. Stock solution of copper perchlorate (1.0 × 10−2 M, 60 μL)

dissolved in distilled water were added to 5 mM HEPES buffer solutions (30 mL, pH 7.0) in the

presence of the 5/PVA-BA film.

400 450 500 550 6000

50

100

150

200

250

Flu

ore

sce

nce

inte

nsity (

arb

. u

nit)

Wavelength (nm)

(a)

400 450 500 550 6000

50

100

150

200

250

(b)

Flu

ore

sce

nce

inte

nsity (

arb

. u

nit)

Wavelength (nm)

400 450 500 550 6000

50

100

150

200

250

(c)

Flu

ore

sce

nce

inte

nsity (

arb

. u

nit)

Wavelength (nm)

400 450 500 550 6000

50

100

150

200

250

(d)

Flu

ore

sce

nce

inte

nsity (

arb

. u

nit)

Wavelength (nm)

S-17

400 450 500 550 6000

50

100

150

200

250

(e)

Flu

ore

sce

nce

inte

nsity (

arb

. u

nit)

Wavelength (nm)

400 450 500 550 6000

50

100

150

200

250

(f)

Flu

ore

sce

nce

inte

nsity (

arb

. u

nit)

Wavelength (nm)

400 450 500 550 6000

50

100

150

200

250

(g)

Flu

ore

sce

nce

inte

nsity (

arb

. u

nit)

Wavelength (nm)

400 450 500 550 6000

50

100

150

200

250

(h)

Flu

ore

sce

nce

inte

nsity (

arb

. u

nit)

Wavelength (nm)

400 450 500 550 6000

50

100

150

200

250

(i)

Flu

ore

sce

nce

inte

nsity (

arb

. u

nit)

Wavelength (nm)

400 450 500 550 6000

50

100

150

200

250

(j)

Flu

ore

sce

nce

inte

nsity (

arb

. u

nit)

Wavelength (nm)

400 450 500 550 6000

50

100

150

200

250

(k)

Flu

ore

sce

nce

inte

nsity (

arb

. u

nit)

Wavelength (nm)

400 450 500 550 6000

50

100

150

200

250

(l)

Flu

ore

sce

nce

inte

nsity (

arb

. u

nit)

Wavelength (nm)

S-18

400 450 500 550 6000

50

100

150

200

250

(m)

Flu

ore

sce

nce

inte

nsity (

arb

. u

nit)

Wavelength (nm)

Fig. S29 Fluorescence spectra of 5/PVA-BA films after immersion in aqueous solution in the absence

(solid line) and the presence (dashed line) of (a) Na+, (b) K+, (c) Mg2+, (d) Ca2+, (e) Fe3+, (f) Co2+, (g)

Ni2+, (h) Cu2+, (i) Zn2+, (j) Cd2+, (k) Hg2+, (l) Al3+, and (m) Pb2+ ions. Conditions: 5 mM HEPES

buffer (30 mL, pH 7.0), [Mn+] = 2.0 × 10−5 M, λex = 340 nm. Solutions of metal perchlorates dissolved

in distilled water (1.0 × 10−2 M, 60 μL) were added to 5 mM HEPES buffer solutions (30 mL, pH

7.0) in the presence of the 5/PVA-BA films.

800 700 600 500 400 300 200 100

404 402 400 398 396 194 192 190 188

F1s

C1s

B1sN

1s

Co

unt

(arb

. u

nit)

Binding energy (eV)

O1s

Co

unt (a

rb. unit)

Binding energy (eV)

Co

unt (a

rb. unit)

Binding energy (eV)

Fig. S30 X-ray photoelectron spectrum of the 6/PVA film.