†Electronic Supplementary Information (ESI) Nano thick poly (ε-caprolactone)-poly (ethylene glycol) coatings developed by catalyst free plasma assisted copolymerization process for biomedical applications

Sudhir Bhatt*, Jérome Pulpytel, Massoud Mirshahi and Farzaneh Arefi-Khonsari*

Fig S1 Experimental Set up for plasma copolymerization

Fig S2 Flow rates of ε-CL and DEGME precursor molecules in the plasma reactor as a

function of carrier gas (Ar) flow rate at 0.5 mbar pressure.

Fig S3 FTIR-ATR spectra of ε-CL and DEGME liquid monomer (measurement volume was

40μL each)

Fig S4 FTIR-ATR spectra of PCL-co-PEG (1:4) coatings deposited at (a) 50W CW (b) 20W

CW (c) 0.25W PW and (d) 1W PW

Fig S5 FTIR-ATR spectra of pulsed plasma polymerized PCL, pDEGME and PCL-co-PEG

coatings deposited at Peff = 1W.

Fig S6 Enlargement of the MALDI-ToF mass spectrum (210-370 Da) of plasma polymerized

PCL-co-PEG coating prepared in alpha-matrix.

Fig S7 Enlargement of the MALDI-ToF mass spectrum (370-550 Da) of plasma polymerized

PCL-co-PEG coating prepared in alpha-matrix.

Fig S8 Microscopic images of HBMEC cell adhesion and proliferation on plasma

polymerized coatings for 24, 48 and 72 hrs of cell culture. Bare glass and PS plate were taken

positive control.

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Experimental set up for plasma copolymerization

Fig S1 Schematic diagram of the low pressure inductively excited RF tubular plasma reactor set-up for copolymerization.

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5 10 15 200,4

0,6

0,8

1,0

1,2

1,4

1,6

1,8

2,0

Pre

curs

sor

flo

w r

ate

at 0

.5 m

bar

pre

ssu

re (

sccm

)

Ar flow rate (sccm)

ε-CL flow rate (sccm) DEGME flow rate (sccm)

Fig S2 Flow rates of ε-CL and DEGME precursor molecules in the plasma reactor as a function of carrier gas (Ar) flow rate at 0.5 mbar pressure.

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FTIR-ATR spectra of ε-CL and DEGME liquid monomer

600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800

0,7

0,8

0,9

1,0

1,1

1,2

2867cm-1

1107 cm-1

2946 cm-1

1729 cm-1

DEGME

ε-CL

Wavenumber (cm-1)

Tra

nsm

itta

nce

(a.

u)

Fig S3 FTIR-ATR spectra of ε-CL and DEGME monomer (measurement volume was

40μL each)

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FTIR Spectra of plasma polymerized PCL-co-PEG coatings at different effective power

600 900 1200 1500 1800 2100 2400 2700 3000 3300 3600

PCL-co-PEG(1:4) Peff

=50W CW

Tra

nsm

issi

on (

arb.

unit)

Wavenumber (cm-1)

2946 cm-1

2867 cm-1

600 900 1200 1500 1800 2100 2400 2700 3000 3300 3600

2946 cm-1

2867 cm-1

PCL-co-PEG(1:4) Peff

=20W CW

Tra

nsm

issi

on (

arb.

unit)

Wavenumber (cm-1)

600 900 1200 1500 1800 2100 2400 2700 3000 3300 3600

2946 cm-1

2867 cm-1

1724 cm-1

PCL-co-PEG(1:4) Peff

=0.25W PW

Tra

nsm

issi

on (

arb.

unit)

Wavenumber (cm-1)600 900 1200 1500 1800 2100 2400 2700 3000 3300 3600

2867 cm-1 2946 cm-1

1724 cm-1

1107 cm-1

PCL-co-PEG(1:4) Peff

=1W PWT

rans

mis

sio

n (a

rb.u

nit)

Wavenumber (cm-1)

(a) (b)

(c) (d)

1246 cm-1

Fig S4 FTIR-ATR spectra of PCL-co-PEG (1:4) coatings deposited at (a) 50W CW (b) 20W CW (c) 0.25W PW and (d) 1W PW

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Detailed FTIR-ATR Spectra of plasma polymerized coatings deposited at Peff=1W for different ε-CL:DEGME ratio

600 800 1000 1200 1400 1600 1800 2600 2800 3000 3200 3400 3600 380

0,95

1,00

1,05

1,10

1,15

1,20

Tra

nsm

issi

on

(au

)

Wavenumber (cm-1)

PCL

pDEGME

PCL-co-PEG (1:1)

PCL-co-PEG(1:2)

PCL-co-PEG(1:3)

PCL-co-PEG(1:4)

Fig S5 FTIR-ATR spectra of pulsed plasma polymerized PCL, pDEGME and PCL-co-PEG coatings deposited at Peff = 1W.

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210 220 230 240 250 260 270 280 290 300 310 320 330 340 350 360 370

0

10

20

30

40

50

60

70

δm=32,1

δm=32

δm=32δm=44,1

δm=114δm=88

δm=88

260,2

273,3

270,2

300,2

307288,5

304,3

272,2

228,2

354,5

242,2 248,5

256,5

230,2

240,2219

No

rmal

ized

Inte

nsi

ty (

%)

Mass (m/z)

212,2

δm=44,3

Fig S6 Enlargement of the MALDI-ToF mass spectrum (210-370 Da) of plasma polymerized PCL-co-PEG coating prepared in alpha-matrix.

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370 380 390 400 410 420 430 440 450 460 470 480 490 500 510 520 530 540 550

0

20

40

60

80

100

δm=44

443 488,7

Nor

mal

ized

Inte

nsity

(%

)

Mass (m/z)

379,1

456,3

457,3

442,3

434,3 458,3470,3 501,3

518,3 538,2

Fig S7 Enlargement of the MALDI-ToF mass spectrum (370-550 Da) of plasma polymerized PCL-co-PEG coating prepared in alpha-matrix.

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HBMEC cell adhesion and proliferation on plasma polymerized coatings

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Fig S8 Microscopic images of HBMEC cell adhesion and proliferation on plasma polymerized coatings for 24, 48 and 72 hrs of cell culture. Bare glass and PS plate were taken as positive control (Optical Magnification: 10X)

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