*(Cheol Sang Kim) *(Chan Hee Park)

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1 Supplementary information For ph/nir-responsive Polypyrrole Functionalized Fibrous Localized Drug Delivery Platform for Synergistic Cancer Therapy Arjun Prasad Tiwari 1, Tae In Hwang 1, Jung-Mi Oh 2, Bikendra Maharjan 1, Sungkun Chun 2, Beom Su Kim 3, Mahesh Kumar Joshi 1,4, Chan Hee Park 1,5 *, Cheol Sang Kim 1,5 * 1 Department of Bionanosystem Engineering, Graduate School, Chonbuk National University, Jeonju , Republic of Korea 2 Department of Physiology, Chonbuk National University, Jeonju , Republic of Korea 3 Carbon Nano Convergence Technology Center for Next Generation Engineers, Chonbuk National University, Jeonju , Republic of Korea 4 Department of Chemistry, Tri-Chandra Multiple Campus, Tribhuvan University, Kathmandu, Nepal 5 Division of Mechanical Design Engineering, Chonbuk National University, Jeonju , Republic of Korea *(Cheol Sang Kim) chskim@jbnu.ac.kr, *(Chan Hee Park) biochan@jbnu.ac.kr. Tel.: fax:

2 Supplementary results Figure S1. (A) Cross-section image of the PPy shells after removing core forming PCL-PTX and (B) FT-IR spectrum of PPy. We have removed the core layer (PCL-PTX), using nanofibers (PCL-PTX) as a sacrificial template. PCL-PTX/PPy fiber was subjected to dichloromethane for 12 h, followed by dried in a vacuum to remove the PCL-PTX part. FT-IR spectrum obtained after removal of PCL-PTX shows clearly characteristics peaks of PCL-PTX such as 2945, 2868 cm -1 are disappeared while the major peak of PPy remains at 1540 cm -1 confirming the hollow tubes are consists of only PPy. 2

3 Figure S2. Loading assessment of PPy into different fibrous meshes. 3

4 Figure S3. IR spectra of Polypyrrole (PPy), PCL and PCL-PTX membrane. 4

5 Figure S4. UV-VIS spectra of free PTX and extract of PCL-PTX/PPy. PTX was extracted from composites using methanol as a solvent with extra sonication. The extract in methanol was diluted in PBS (ph 7.4) before evaluation. 5

6 Figure S5. NIR-thermal image of surrounding of PPy coated mat under NIR treatment at 0.5 W/cm 2 laser power intensity. Arrow shows the temperature of PBS solution around irradiating mat. Irradiated mat (white part) shows the temperature around 44 ⁰C. 6

7 Figure S6. Swelling study. (A) Weight of the PCL-PTX and PCL-PTX/PPy mats incubated in PBS buffer of different ph for different time intervals. Significant differences are indicated by *p<0.05, **p<0.01 and ***p<0.001 between PCL-PTX and PCL-PTX/PPy of same day incubation (n=3, mean±sd) and, (B) FE-SEM images of the different mats incubated in PBS of ph 5.5 and 7.4 for 168 h. All mats were incubated in 37 ⁰C. 7

8 PCL/PTX/PPy (before irradiation) PCL/PTX/PPy (after irradiation) Absorbance (a.u.) Wavelength (nm) Figure S7. UV-VIS-NIR spectra of PPy coated mat (PCL-PTX-PPy1) before and after cycles of irradiation. 8

9 PCL-PTX/PPy C1s Counts/s O1s N1s Binding energy (ev) Cl2p Figure S8. XPS spectrum of the PCL-PTX/PPy. Surface state of the samples was checked using X-ray photoelectron spectroscopy (XPS, AXIS-NOVA, Kratos, Inc.) with an Al Kα irradiation source. 9

10 Figure S9. PTX encapsulation efficiency for different mats. 10

11 Figure S10. NIR activatable drug release mechanism was assayed using a PBS with different ph values (7.4 and 5.5). (A) and (B) show the drug release pattern during NIR ON/OFF process at ph 7.4 and 5.5, respectively. PCL-PTX/PPy fibrous mat was irradiated by NIR laser (0.5 W/cm 2 ) for 5 min (NIR-ON), followed by allowing to room temperature without NIR laser irradiation for 20 min (NIR-OFF). This cycle was repeated twice in 1 h period. The released drug was measured using UV-Vis spectrophotometer in a designated time interval. 11

12 Figure S11. (A) Confocal image of NIR treated cells cultured on PPy coated mat with a laser density of 0.5 W/cm 2 for 5 min and (B) cells cultured on PPy coated mat not exposed to NIR laser. 12

13 Table S1. Heating property of different mats under different power intensities when irradiated for 5 min. NIR Laser Density (W/cm 2 ) Temperature C (PCL- PTX) Temperature C (PCL- PTX/PPy1) Temperature C (PCL- PTX/PPy2) Temperature C (PCL-PTX/PPy3) Note: Each sample was evaluated for three times. 13

14 Table S2: Comparison of the photothermal performance of PPy coated PCL-PTX (PCL- PTX/PPy1) mat in PBS with different ph. Power Temperature of the mats under NIR exposure ( C) (W/cm 2 ) 6 h (ph 6 h (ph 48 h 48 h 168 h 168 h 0 h 5.5) 7.4) (ph 5.5) (ph 7.4) (ph 5.5) (ph 7.4) ⁰C Note: Each sample was evaluated for three times. 14