Innovative Nanosensor for Disease Diagnosis

Transcription

1 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

2 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.

3 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.

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

5 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).

6 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.

7 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.

8 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 Apo-Pt WO3 Pristine WO Time (min) Time (min) (b) 8 6 Apo-PtCo Apo-PtY Apo-Pt WO3 Pristine WO (c) Response (R air /R gas ) Time (min) 8 Apo-PtCo Apo-PtY Time (min) Time (min) Apo-Pt WO3 Pristine WO Time (min) Figure S7. Characteristic sensing property of NF-based sensors functionalized with apoferritin-templated nanocatalysts toward (a) acetone, (b) S, and (c) toluene.

9 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 ppb acetone toluene, NH 3, S, CO, pentane, NO 40 sec/ 20 sec 350 C 90 1 Au-SnO 2 NTs ppb S toluene, NH 3, acetone, CO, pentane, NO 36 sec/ 44 sec 300 C 90 1 Pt-PS_SnO 2 NTs ppb acetone S, toluene, pentane, CO, NO, NH 3, CH 4, 48 sec/ 88 sec 350 C 90 2 Pt-hollow 0D-1D SnO ppb acetone S, toluene, pentane, CO, NO, NH 3, CH 4, 48 sec/ 88 sec 350 C 90 3 Pd-hollow 0D-1D SnO ppb toluene S, acetone, pentane, CO, NO, NH 3, CH 4, 52 sec/ 80 sec 300 C 90 3 Pt-ZnO ppb acetone toluene, NO, Co, NH 3 12 sec/ 108 sec 450 C 95 4 La-ZnO ppb NO acetone, NH 3, CO, toluene 176 sec/ 244 sec 400 C 95 4 Cu-ZnO ppb acetone NH 3, CO, toluene, NO 40 sec/ 160 sec 450 C 95 4 Apo-Pt ppb acetone toluene, ethanol, CO, S, sec/ sec 350 C 90 5 Apo-Pd (@ 1 ppm) 0.17 ppb toluene acetone, ethanol, CO, S, 8.56 sec/ 9.2 sec 350 C 90 5 Apo-Rh (@ 1 ppm) 0.98 ppb S acetone, toluene, ethanol, CO, sec/ 29.28sec 350 C 90 5 Apof-Au ppb S acetone, toluene, CO, ethanol, NH 3, pentane 44 sec/ 320 sec 350 C 90 6 Apof-Pd ppb S acetone, toluene, CO, ethanol, NH 3, pentane 428 sec/ 36 sec 350 C 90 6 Apof-Pt ppb acetone S, toluene, CO, ethanol, NH 3, pentane 224 sec/ 68 sec 400 C 90 6 Apo-PtY ppb acetone Toluene, Ethanol, CO, S, 34.6 sec/ 13.6 sec 350 C 90 This work Apo-PtCo ppb acetone Toluene, Ethanol, CO, S, 42.1 sec/ 12 sec 350 C 90 This work

10 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 (@ 2 ppm) 120 ppb acetone - -/- 300 C 80 9 ZnO NWloaded ATO-ZnO MP ATO:Zn O=1: ppm acetone ethanol, toluene, CO, S, pentane, NH 3, NO <16 sec/ 148 sec 400 C Si-doped particles 10 mol% 3.2 (@ 1 ppm) 20 ppb acetone - 78 sec/ 84 sec 400 C C-doped (@ 0.9 ppm) 200 ppb acetone NH 3, CH 4, Ethanol 9 sec/ 12 sec 300 C ZnO spheres (@ 10 ppm) 0.25 ppm acetone NH 3, methanol, toluene, xylene, benzene, cyclohecane 3 sec/ 230 C 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 Pt- hemitubes (@ 2 ppm) 120 ppb acetone S, toluene 300 sec/ 300 sec 350 C Pt ppb acetone - -/- 350 C Thin-wall Assembled SnO 2 5% 2.25 (@ 3 ppm) 120 ppb acetone - 15 sec/ C Graphene- 0.1 graphene ppb acetone ethanol, NO, toluene, pentane, NH 3, CO 12 sec/ 64 sec 350 C Graphite- 0.1 graphite ppb acetone ethanol, NO, pentane, NH 3, CO 8.5 sec/ 34 sec 300 C Reduced graphene oxide-sno 2 5 reduced graphene oxide ppb acetone S, ethanol, toluene, CO, NH 3, pentane < 3.3 min/ 1.9 min 350 C Ir-graphene oxide- Co 3O 4 1 Ir, 1 graphene oxide ppb acetone acetone, pentane, NO, NH 3, CO, NO 2 22 sec/ 78 sec 300 C 90 21

11 References (1) Jang, J. S.; Kim, S. J.; Choi, S. J.; Kim, N. H.; Hakim, M.; Rothschild, A.; Kim, I. D. Thin-walled SnO 2 nanotubes functionalized with Pt and Au catalysts via the protein templating route and their selective detection of acetone and hydrogen sulfide molecules. Nanoscale 2015, 7, (2) Jang, J. S.; Choi, S. J.; Kim, S. J.; Hakim, M.; Kim, I. D. Rational Design of Highly Porous SnO 2 Nanotubes Functionalized with Biomimetic Nanocatalysts for Direct Observation of Simulated Diabetes. Adv. Funct. Mater. 2016, 26, (3) Jang, J. S.; Yu, S.; Choi, S. J.; Kim, S. J.; Koo, W. T.; Kim, I. D. Metal Chelation Assisted In Situ Migration and Functionalization of Catalysts on Peapod-Like Hollow SnO 2 toward a Superior Chemical Sensor. Small 2016, 12, (4) Cho, H.-J.; Kim, S.-J.; Choi, S.-J.; Jang, J.-S.; Kim, I.-D. Facile synthetic method of catalyst-loaded ZnO nanofibers composite sensor arrays using bio-inspired protein cages for pattern recognition of exhaled breath. Sens. Actuators B 2017, 243, (5) Kim, S. J.; Choi, S. J.; Jang, J. S.; Kim, N. H.; Hakim, M.; Tuller, H. L.; Kim, I. D. Mesoporous Nanofibers with Protein-Templated Nanoscale Catalysts for Detection of Trace Biomarkers in Exhaled Breath. ACS Nano 2016, 10, (6) Choi, S. J.; Kim, S. J.; Cho, H. J.; Jang, J. S.; Lin, Y. M.; Tuller, H. L.; Rutledge, G. C.; Kim, I. D. Nanofiber-Based Biomarker Detectors Enabled by Protein-Encapsulated Catalyst Self-Assembled on Polystyrene Colloid Templates. Small 2016, 12, (7) Shan, H.; Liu, C. B.; Liu, L.; Li, S. C.; Wang, L. Y.; Zhang, X. B.; Bo, X. Q.; Chi, X. Highly sensitive acetone sensors based on La-doped α-fe 2 O 3 nanotubes. Sens. Actuators B 2013, 184, (8) Xie, Y.; Xing, R. Q.; Li, Q. L.; Xu, L.; Song, H. W. Three-dimensional ordered ZnO- CuO inverse opals toward low concentration acetone detection for exhaled breath sensing. Sens. Actuators B 2015, 211, (9) Lee, I.; Choi, S. J.; Park, K. M.; Lee, S. S.; Choi, S.; Kim, I. D.; Park, C. O. The stability, sensitivity and response transients of ZnO, SnO 2 and sensors under acetone, toluene and H2S environments. Sens. Actuators B 2014, 197, (10) Choi, H. J.; Choi, S. J.; Choo, S.; Kim, I. D.; Lee, H. Hierarchical ZnO Nanowiresloaded Sb-doped SnO 2 -ZnO Micrograting Pattern via Direct Imprinting-assisted Hydrothermal Growth and Its Selective Detection of Acetone Molecules. Sci. Rep. 2016, 6, (11) Righettoni, M.; Tricoli, A.; Pratsinis, S. E. Si: Sensors for Highly Selective Detection of Acetone for Easy Diagnosis of Diabetes by Breath Analysis. Anal. Chem. 2010, 82, (12) Xiao, T.; Wang, X. Y.; Zhao, Z. H.; Li, L.; Zhang, L.; Yao, H. C.; Wang, J. S.; Li, Z. J. Highly sensitive and selective acetone sensor based on C-doped for potential

12 diagnosis of diabetes mellitus. Sens. Actuators B 2014, 199, (13) Jia, Q. Q.; Ji, H. M.; Zhang, Y.; Chen, Y. L.; Sun, X. H.; Jin, Z. G. Rapid and selective detection of acetone using hierarchical ZnO gas sensor for hazardous odor markers application. J. Hazard Mater. 2014, 276, (14) Choi, K. I.; Hwang, S. J.; Dai, Z. F.; Kang, Y. C.; Lee, J. H. Rh-catalyzed with anomalous humidity dependence of gas sensing characteristics. RSC Adv. 2014, 4, (15) Choi, S. J.; Lee, I.; Jang, B. H.; Youn, D. Y.; Ryu, W. H.; Park, C. O.; Kim, I. D. Selective Diagnosis of Diabetes Using Pt-Functionalized Hemitube Networks As a Sensing Layer of Acetone in Exhaled Breath. Anal. Chem. 2013, 85, (16) Shin, J.; Choi, S. J.; Youn, D. Y.; Kim, I. D. Exhaled VOCs sensing properties of nanofibers functionalized by Pt and IrO 2 nanoparticles for diagnosis of diabetes and halitosis. J. Electroceram. 2012, 29, (17) Shin, J.; Choi, S. J.; Lee, I.; Youn, D. Y.; Park, C. O.; Lee, J. H.; Tuller, H. L.; Kim, I. D. Thin-Wall Assembled SnO 2 Fibers Functionalized by Catalytic Pt Nanoparticles and their Superior Exhaled-Breath-Sensing Properties for the Diagnosis of Diabetes. Adv. Funct. Mater. 2013, 23, (18) Choi, S. J.; Choi, C.; Kim, S. J.; Cho, H. J.; Jeon, S.; Kim, I. D. Facile synthesis of hierarchical porous nanofibers having 1D nanoneedles and their functionalization with non-oxidized graphene flakes for selective detection of acetone molecules. RSC Adv. 2015, 5, (19) Choi, S. J.; Fuchs, F.; Demadrille, R.; Grevin, B.; Jang, B. H.; Lee, S. J.; Lee, J. H.; Tuller, H. L.; Kim, I. D. Fast Responding Exhaled-Breath Sensors Using Hemitubes Functionalized by Graphene-Based Electronic Sensitizers for Diagnosis of Diseases. ACS Appl. Mater. & Interfaces 2014, 6, (20) Choi, S. J.; Jang, B. H.; Lee, S. J.; Min, B. K.; Rothschild, A.; Kim, I. D. Selective Detection of Acetone and Hydrogen Sulfide for the Diagnosis of Diabetes and Halitosis Using SnO 2 Nanofibers Functionalized with Reduced Graphene Oxide Nanosheets. ACS Appl. Mater. & Interfaces 2014, 6, (21) Choi, S. J.; Ryu, W. H.; Kim, S. J.; Cho, H. J.; Kim, I. D. Bi-functional co-sensitization of graphene oxide sheets and Ir nanoparticles on p-type Co 3 O 4 nanofibers for selective acetone detection. J. Mater. Chem. B 2014, 2,