Innovative Nanosensor for Disease Diagnosis

Supporting Information Innovative Nanosensor for Disease Diagnosis Sang Joon Kim,, Seon Jin Choi,,, Ji Soo Jang, Hee Jin Cho, and Il Doo Kim,* Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology (KAIST), 291 Daehak-ro, Yuseong-gu, Daejeon 34141, Republic of Korea Applied Science Research Institute, Korea Advanced Institute of Science and Technology, 291 Daehak-ro, Yuseong-gu, Daejeon 34141, Republic of Korea These authors contributed equally to this work. *Address correspondence to idkim@kaist.ac.kr

Figure S1 Figure S1. Catalytic NPs synthesized by the apoferritin protein cage. Single component NPs of (a) Ag, (b) Ru, (c) Cu, and (d) La.

Figure S2 Figure S2. Particle size distributions of (a) Au, (b) Pt, (c) Pd, (d) Rh, (e) Ag, (f) Ru, (g) Cu, (h) La, (i) PtY, and (j) PtCo.

Figure S3 Figure S3. (a) Schematic illustration and (b) corresponding camera image of sensor architecture. (c) Schematic illustration of sensor measurement system.

Figure S4 Figure S4. Gas responding properties of Apo-Pt-, Apo-Pd-, Apo-Rh-, and Apo- PtY- toward pure gases such as (a) S (1ppm), (b) acetone (1ppm), and (c) toluene (1ppm), as well as mixture gases such as (d) S (1ppm)-acetone (1ppm), (e) S (1ppm)-toluene (1ppm), and (f) acetone (1ppm)- toluene (1ppm).

Figure S5 Figure S5. Response characteristics of various catalyst-smo composites for detection of acetone molecule under a humidified atmosphere (75 95% RH), as reported in the literature: (a) Response property in log-scale and (b) response property in linear scale.

Figure S6 (a) (b) (c) (d) Figure S6. (a) Portable sensing module integrated with MEMS sensors, (b) MEMS sensor substrate, (c) magnified image of 2 2 MEMS sensor arrays, and (d) MEMS sensor substrate with sensing layers.

Toluene Response (R air /R gas ) S Response (R air /R gas ) Response (R air /R gas ) Acetone Response (R air /R gas ) Response (R air /R gas ) Figure S7 (a) 8 Apo-PtCo Apo-PtY 6 5 4 3 Apo-Pt WO3 Pristine WO3 4 2 2 1 0 5 10 15 20 25 Time (min) 0 0 4 8 12 16 Time (min) (b) 8 6 Apo-PtCo Apo-PtY 5 4 3 Apo-Pt WO3 Pristine WO3 4 2 2 1 (c) Response (R air /R gas ) 0 5 10 15 20 25 Time (min) 8 Apo-PtCo Apo-PtY 6 4 2 0 5 10 15 20 25 Time (min) 0 0 4 8 12 16 Time (min) 5 4 3 2 1 Apo-Pt WO3 Pristine WO3 0 0 4 8 12 16 Time (min) Figure S7. Characteristic sensing property of NF-based sensors functionalized with apoferritin-templated nanocatalysts toward (a) acetone, (b) S, and (c) toluene.

Table S1 Table S1. Detailed sensing specifications of diverse catalyst-loaded SMO nanostructures. Composites Catalyst concentration Sensitivity (Response) Detection limit Target gas Selectivity Response & recovery time Operating temperature Humidity (RH %) Ref. Pt-SnO 2 NTs 0.16 92 20 ppb acetone toluene, NH 3, S, CO, pentane, NO 40 sec/ 20 sec 350 C 90 1 Au-SnO 2 NTs 0.08 34 30 ppb S toluene, NH 3, acetone, CO, pentane, NO 36 sec/ 44 sec 300 C 90 1 Pt-PS_SnO 2 NTs 0.08 192 10 ppb acetone S, toluene, pentane, CO, NO, NH 3, CH 4, 48 sec/ 88 sec 350 C 90 2 Pt-hollow 0D-1D SnO 2 0.04 93.55 100 ppb acetone S, toluene, pentane, CO, NO, NH 3, CH 4, 48 sec/ 88 sec 350 C 90 3 Pd-hollow 0D-1D SnO 2 0.24 9.25 100 ppb toluene S, acetone, pentane, CO, NO, NH 3, CH 4, 52 sec/ 80 sec 300 C 90 3 Pt-ZnO 0.23 13.07 29 ppb acetone toluene, NO, Co, NH 3 12 sec/ 108 sec 450 C 95 4 La-ZnO 0.07 10.06 35 ppb NO acetone, NH 3, CO, toluene 176 sec/ 244 sec 400 C 95 4 Cu-ZnO 0.12 6.04 55 ppb acetone NH 3, CO, toluene, NO 40 sec/ 160 sec 450 C 95 4 Apo-Pt- 0.022 62 0.54 ppb acetone toluene, ethanol, CO, S, 20.48 sec/ 33.12 sec 350 C 90 5 Apo-Pd- 0.06 11 (@ 1 ppm) 0.17 ppb toluene acetone, ethanol, CO, S, 8.56 sec/ 9.2 sec 350 C 90 5 Apo-Rh- 0.017 21 (@ 1 ppm) 0.98 ppb S acetone, toluene, ethanol, CO, 31.26 sec/ 29.28sec 350 C 90 5 Apof-Au- 18.115 11.1 100 ppb S acetone, toluene, CO, ethanol, NH 3, pentane 44 sec/ 320 sec 350 C 90 6 Apof-Pd- 2.425 43.5 100 ppb S acetone, toluene, CO, ethanol, NH 3, pentane 428 sec/ 36 sec 350 C 90 6 Apof-Pt- 2.628 29.8 100 ppb acetone S, toluene, CO, ethanol, NH 3, pentane 224 sec/ 68 sec 400 C 90 6 Apo-PtY- 0.022 364 5.5 ppb acetone Toluene, Ethanol, CO, S, 34.6 sec/ 13.6 sec 350 C 90 This work Apo-PtCo- 0.022 424 50 ppb acetone Toluene, Ethanol, CO, S, 42.1 sec/ 12 sec 350 C 90 This work

Table S2 Table S2. Sensing performances of conventional acetone sensors. Composites Catalyst concentration Sensitivity (Response) Detectio n limit Target gas Selectivity Response & recovery time Operating temperature Humidity (RH %) Ref. La-doped Fe 2O 3 NTs 7 % 6 (@ 10 ppm) 1 ppm acetone formaldehyde, toluene, NH 3, CO,, butane 3 sec/ 10 sec 240 C 90 7 ZnO-CuO inverse opals 50 at% of CuO 1.8 (@ 1 ppm) 100 ppb acetone toluene, ethanol, CH 4 10 sec/ 15 sec 400 C 90 8 Pt- particles - 3.37 (@ 2 ppm) 120 ppb acetone - -/- 300 C 80 9 ZnO NWloaded ATO-ZnO MP ATO:Zn O=1:9 12.1 1 ppm acetone ethanol, toluene, CO, S, pentane, NH 3, NO <16 sec/ 148 sec 400 C 90 10 Si-doped particles 10 mol% 3.2 (@ 1 ppm) 20 ppb acetone - 78 sec/ 84 sec 400 C 90 11 C-doped - 1.8 (@ 0.9 ppm) 200 ppb acetone NH 3, CH 4, Ethanol 9 sec/ 12 sec 300 C 95 12 ZnO spheres - 4.11 (@ 10 ppm) 0.25 ppm acetone NH 3, methanol, toluene, xylene, benzene, cyclohecane 3 sec/ 230 C 90 13 Rh-loaded 0.5 at% 13.1 (@ 4 ppm) 40 ppb acetone CO, NH 3, S, benzene, toluene, xylene, NO 1 sec/ 100 sec 400 C 80 14 Pt- hemitubes 0.025 4.11 (@ 2 ppm) 120 ppb acetone S, toluene 300 sec/ 300 sec 350 C 85 15 Pt- - 8.7 300 ppb acetone - -/- 350 C 75 16 Thin-wall Assembled SnO 2 5% 2.25 (@ 3 ppm) 120 ppb acetone - 15 sec/ - 400 C 85 17 Graphene- 0.1 graphene 18.5 50 ppb acetone ethanol, NO, toluene, pentane, NH 3, CO 12 sec/ 64 sec 350 C 90 18 Graphite- 0.1 graphite 6.96 500 ppb acetone ethanol, NO, pentane, NH 3, CO 8.5 sec/ 34 sec 300 C 90 19 Reduced graphene oxide-sno 2 5 reduced graphene oxide 10.4 100 ppb acetone S, ethanol, toluene, CO, NH 3, pentane < 3.3 min/ 1.9 min 350 C 90 20 Ir-graphene oxide- Co 3O 4 1 Ir, 1 graphene oxide 2.29 120 ppb acetone acetone, pentane, NO, NH 3, CO, NO 2 22 sec/ 78 sec 300 C 90 21

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