Ji-Soo Jang

Mesoporous WO3 Nanofibers with Protein-Templated Nanoscale Catalysts for Detection of Trace Biomarkers in Exhaled Breath

Highly selective detection, rapid response (<20 s), and superior sensitivity (Rair/Rgas> 50) against specific target gases, particularly at the 1 ppm level, still remain considerable challenges in gas sensor applications. We propose a rational design and facile synthesis concept for achieving exceptionally sensitive and selective detection of trace target biomarkers in exhaled human breath using a protein nanocage templating route for sensitizing electrospun nanofibers (NFs). The mesoporous WO3 NFs, functionalized with well-dispersed nanoscale Pt, Pd, and Rh catalytic nanoparticles (NPs), exhibit excellent sensing performance, even at parts per billion level concentrations of gases in a humid atmosphere. Functionalized WO3 NFs with nanoscale catalysts are demonstrated to show great promise for the reliable diagnosis of diseases.

Innovative Nanosensor for Disease Diagnosis

As a futuristic diagnosis platform, breath analysis is gaining much attention because it is a noninvasive, simple, and low cost diagnostic method. Very promising clinical applications have been demonstrated for diagnostic purposes by correlation analysis between exhaled breath components and specific diseases. In addition, diverse breath molecules, which serve as biomarkers for specific diseases, are precisely identified by statistical pattern recognition studies. To further improve the accuracy of breath analysis as a diagnostic tool, breath sampling, biomarker sensing, and data analysis should be optimized. In particular, development of high performance breath sensors, which can detect biomarkers at the ppb-level in exhaled breath, is one of the most critical challenges. Due to the presence of numerous interfering gas species in exhaled breath, selective detection of specific biomarkers is also important. This Account focuses on chemiresistive type breath sensors with exceptionally high sensitivity and selectivity that were developed by combining hollow protein templated nanocatalysts with electrospun metal oxide nanostructures. Nanostructures with high surface areas are advantageous in achieving high sensitivity because the sensing signal is dominated by the surface reaction between the sensing layers and the target biomarkers. Furthermore, macroscale pores between one-dimensional (1D) nanostructures can facilitate fast gas diffusion into the sensing layers. To further enhance the selectivity, catalytic functionalization of the 1D metal oxide nanostructure is essential. However, the majority of conventional techniques for catalytic functionalization have failed to achieve a high degree of dispersion of nanoscale catalysts due to aggregation on the surface of the metal oxide, which severely deteriorates the sensing properties by lowering catalytic activity. This issue has led to extensive studies on monolithically dispersed nanoscale particles on metal oxides to maximize the catalytic performances. As a pioneering technique, a bioinspired templating route using apoferritin, that is, a hollow protein cage, has been proposed to obtain nanoscale (∼2 nm) catalyst particles with high dispersity. Nanocatalysts encapsulated by a protein shell were first used in chemiresistive type breath sensors for catalyst functionalization on 1D metal oxide structures. We discuss the robustness and versatility of the apoferrtin templating route for creating highly dispersive catalytic NPs including single components (Au, Pt, Pd, Rh, Ag, Ru, Cu, and La) and bimetallic catalysts (PtY and PtCo), as well as the core-shell structure of Au-Pd (Au-core@Pd-shell). The use of these catalysts is essential to establish high performance sensors arrays for the pattern recognition of biomarkers. In addition, novel multicomponent catalysts provide unprecedented sensitivity and selectivity. With this in mind, we discuss diverse synthetic routes for nanocatalysts using apoferritin and the formation of various catalyst-1D metal oxide composite nanostructures. Furthermore, we discuss detection capability of a simulated biomarker gas using the breath sensor arrays and principal component analysis. Finally, future prospects with the portable breath analysis platform are presented by demonstrating the potential feasibility of real-time and on-site breath analysis using chemiresistive sensors.

Nanoscale PdO Catalyst Functionalized Co3O4 Hollow Nanocages Using MOF Templates for Selective Detection of Acetone Molecules in Exhaled Breath

The increase of surface area and the functionalization of catalyst are crucial to development of high-performance semiconductor metal oxide (SMO) based chemiresistive gas sensors. Herein, nanoscale catalyst loaded Co3O4 hollow nanocages (HNCs) by using metal-organic framework (MOF) templates have been developed as a new sensing platform. Nanoscale Pd nanoparticles (NPs) were easily loaded on the cavity of Co based zeolite imidazole framework (ZIF-67). The porous structure of ZIF-67 can restrict the size of Pd NPs (2-3 nm) and separate Pd NPs from each other. Subsequently, the calcination of Pd loaded ZIF-67 produced the catalytic PdO NPs functionalized Co3O4 HNCs (PdO-Co3O4 HNCs). The ultrasmall PdO NPs (3-4 nm) are well-distributed in the wall of Co3O4 HNCs, the unique structure of which can provide high surface area and high catalytic activity. As a result, the PdO-Co3O4 HNCs exhibited improved acetone sensing response (Rgas/Rair = 2.51-5 ppm) compared to PdO-Co3O4 powders (Rgas/Rair = 1.98), Co3O4 HNCs (Rgas/Rair = 1.96), and Co3O4 powders (Rgas/Rair = 1.45). In addition, the PdO-Co3O4 HNCs showed high acetone selectivity against other interfering gases. Moreover, the sensor array clearly distinguished simulated exhaled breath of diabetics from healthy peoples breath. These results confirmed the novel synthesis of MOF templated nanoscale catalyst loaded SMO HNCs for high performance gas sensors.

WO3 Nanofiber‐Based Biomarker Detectors Enabled by Protein‐Encapsulated Catalyst Self‐Assembled on Polystyrene Colloid Templates

A novel catalyst functionalization method, based on protein-encapsulated metallic nanoparticles (NPs) and their self-assembly on polystyrene (PS) colloid templates, is used to form catalyst-loaded porous WO3 nanofibers (NFs). The metallic NPs, composed of Au, Pd, or Pt, are encapsulated within a protein cage, i.e., apoferritin, to form unagglomerated monodispersed particles with diameters of less than 5 nm. The catalytic NPs maintain their nanoscale size, even following high-temperature heat-treatment during synthesis, which is attributed to the discrete self-assembly of NPs on PS colloid templates. In addition, the PS templates generate open pores on the electrospun WO3 NFs, facilitating gas molecule transport into the sensing layers and promoting active surface reactions. As a result, the Au and Pd NP-loaded porous WO3 NFs show superior sensitivity toward hydrogen sulfide, as evidenced by responses (R(air)/R(gas)) of 11.1 and 43.5 at 350 °C, respectively. These responses represent 1.8- and 7.1-fold improvements compared to that of dense WO3 NFs (R(air)/R(gas) = 6.1). Moreover, Pt NP-loaded porous WO3 NFs exhibit high acetone sensitivity with response of 28.9. These results demonstrate a novel catalyst loading method, in which small NPs are well-dispersed within the pores of WO3 NFs, that is applicable to high sensitivity breath sensors.

Metal-Organic Framework Templated Synthesis of Ultrasmall Catalyst Loaded ZnO/ZnCo 2 O 4 Hollow Spheres for Enhanced Gas Sensing Properties

To achieve the rational design of nanostructures for superior gas sensors, the ultrasmall nanoparticles (NPs) loaded on ternary metal oxide (TMO) hollow spheres (HS) were synthesized by using the polystyrene (PS) sphere template and bimetallic metal-organic framework (BM-MOFs) mold. The zinc and cobalt based zeolite imidazole frameworks (BM-ZIFs) encapsulating ultrasmall Pd NPs (2–3 nm) were assembled on PS spheres at room temperature. After calcination at 450 °C, these nanoscale Pd particles were effectively infiltrated on the surface of ZnO/ZnCo2O4 HSs. In addition, the heterojunctions of Pd-ZnO, Pd-ZnCo2O4, and ZnO-ZnCo2O4 were formed on each phase. The synthesized Pd-ZnO/ZnCo2O4 HSs exhibited extremely high selectivity toward acetone gas with notable sensitivity (S = 69% to 5 ppm at 250 °C). The results demonstrate that MOF driven ultrasmall catalyst loaded TMO HSs were highly effective platform for high performance chemical gas sensors.

Metal–Organic Framework Templated Catalysts: Dual Sensitization of PdO–ZnO Composite on Hollow SnO2 Nanotubes for Selective Acetone Sensors

Metal-organic framework (MOF)-derived synergistic catalysts were easily functionalized on hollow SnO2 nanotubes (NTs) via electrospinning and subsequent calcination. Nanoscale Pd NPs (∼2 nm) loaded Zn-based zeolite imidazole framework (Pd@ZIF-8, ∼80 nm) was used as a new catalyst-loading platform for the effective functionalization of a PdO@ZnO complex catalyst onto the thin wall of one-dimensional metal oxide NTs. The well-dispersed nanoscale PdO catalysts (3-4 nm) and multiheterojunctions (PdO/ZnO and ZnO/SnO2) on hollow structures are essential for the development of high-performance gas sensors. As a result, the PdO@ZnO dual catalysts-loaded hollow SnO2 NTs (PdO@ZnO-SnO2 NTs) exhibited high acetone response (Rair/Rgas = 5.06 at 400 °C @ 1 ppm), superior acetone selectivity against other interfering gases, and fast response (20 s) and recovery (64 s) time under highly humid atmosphere (95% RH). In this work, the advantages of hollow SnO2 NT structures with high surface area and open porosity were clearly demonstrated by the comparison to SnO2 nanofibers (NFs). Moreover, the sensor arrays composed of SnO2 NFs, SnO2 NTs, PdO@ZnO-SnO2 NFs, and PdO@ZnO-SnO2 NTs successfully identified the patterns of the exhaled breath of normal people and simulated diabetics by using a principal component analysis.

Metal Chelation Assisted In Situ Migration and Functionalization of Catalysts on Peapod-Like Hollow SnO2 toward a Superior Chemical Sensor.

Rational design of nanostructures and efficient catalyst functionalization methods are critical to the realization of highly sensitive gas sensors. In order to solve these issues, two types of strategies are reported, i.e., (i) synthesis of peapod-like hollow SnO2 nanostructures (hollow 0D-1D SnO2 ) by using fluid dynamics of liquid Sn metal and (ii) metal-protein chelate driven uniform catalyst functionalization. The hollow 0D-1D SnO2 nanostructures have advantages in enhanced gas accessibility and higher surface areas. In addition to structural benefits, protein encapsulated catalytic nanoparticles result in the uniform catalyst functionalization on both hollow SnO2 spheres and SnO2 nanotubes due to their dynamic migration properties. The migration of catalysts with liquid Sn metal is induced by selective location of catalysts around Sn. On the basis of these structural and uniform functionalization of catalyst benefits, biomarker chemical sensors are developed, which deliver highly selective detection capability toward acetone and toluene, respectively. Pt or Pd loaded multidimensional SnO2 nanostructures exhibit outstanding acetone (R air /R gas = 93.55 @ 350 °C, 5 ppm) and toluene (R air /R gas = 9.25 @ 350 °C, 5 ppm) sensing properties, respectively. These results demonstrate that unique nanostructuring and novel catalyst loading method enable sensors to selectively detect biomarkers for exhaled breath sensors.

Silver Nanowire Embedded Colorless Polyimide Heater for Wearable Chemical Sensors: Improved Reversible Reaction Kinetics of Optically Reduced Graphene Oxide.

Optically reduced graphene oxide (ORGO) sheets are successfully integrated on silver nanowire (Ag NW)-embedded transparent and flexible substrate. As a heating element, Ag NWs are embedded in a colorless polyimide (CPI) film by covering Ag NW networks using polyamic acid and subsequent imidization. Graphene oxide dispersed aqueous solution is drop-coated on the Ag NW-embedded CPI (Ag NW-CPI) film and directly irradiated by intense pulsed light to obtain ORGO sheets. The heat generation property of Ag NW-CPI film is investigated by applying DC voltage, which demonstrates unprecedentedly reliable and stable characteristics even in dynamic bending condition. To demonstrate the potential application in wearable chemical sensors, NO2 sensing characteristic of ORGO is investigated with respect to the different heating temperature (22.7-71.7 °C) of Ag NW-CPI film. The result reveals that the ORGO sheets exhibit high sensitivity of 2.69% with reversible response/recovery sensing properties and minimal deviation of baseline resistance of around 1% toward NO2 molecules when the temperature of Ag NW-CPI film is 71.7 °C. This work first demonstrates the improved reversible NO2 sensing properties of ORGO sheets on flexible and transparent Ag NW-CPI film assisted by Ag NW heating networks.

Metal Organic Framework-Templated Chemiresistor: Sensing Type Transition from P-to-N Using Hollow Metal Oxide Polyhedron via Galvanic Replacement

Facile synthesis of porous nanobuilding blocks with high surface area and uniform catalyst functionalization has always been regarded as an essential requirement for the development of highly sensitive and selective chemical sensors. Metal-organic frameworks (MOFs) are considered as one of the most ideal templates due to their ability to encapsulate ultrasmall catalytic nanoparticles (NPs) in microporous MOF structures in addition to easy removal of the sacrificial MOF scaffold by calcination. Here, we introduce a MOFs derived n-type SnO2 (n-SnO2) sensing layer with hollow polyhedron structures, obtained from p-n transition of MOF-templated p-type Co3O4 (p-Co3O4) hollow cubes during galvanic replacement reaction (GRR). In addition, the Pd NPs encapsulated in MOF and residual Co3O4 clusters partially remained after GRR led to uniform functionalization of efficient cocatalysts (PdO NPs and p-Co3O4 islands) on the porous and hollow polyhedron SnO2 structures. Due to high gas accessibility through the meso- and macrosized pores in MOF-templated oxides and effective modulation of electron depletion layer assisted by the creation of numerous p-n junctions, the GRR-treated SnO2 structures exhibited 21.9-fold higher acetone response (Rair/Rgas = 22.8 @ 5 ppm acetone, 90%RH) compared to MOF-templated p-Co3O4 hollow structures. To the best of our knowledge, the selectivity and response amplitudes reported here for the detection of acetone are superior to those MOF derived metal oxide sensing layers reported so far. Our results demonstrate that highly active MOF-derived sensing layers can be achieved via p-n semiconducting phase transition, driven by a simple and versatile GRR process combined with MOF templating route.

Exceptional High‐Performance of Pt‐Based Bimetallic Catalysts for Exclusive Detection of Exhaled Biomarkers

Achieving an improved understanding of catalyst properties, with ability to predict new catalytic materials, is key to overcoming the inherent limitations of metal oxide based gas sensors associated with rather low sensitivity and selectivity, particularly under highly humid conditions. This study introduces newly designed bimetallic nanoparticles (NPs) employing bimetallic Pt-based NPs (PtM, where M = Pd, Rh, and Ni) via a protein encapsulating route supported on mesoporous WO3 nanofibers. These structures demonstrate unprecedented sensing performance for detecting target biomarkers (even at p.p.b. levels) in highly humid exhaled breath. Sensor arrays are further employed to enable pattern recognition capable of discriminating between simulated biomarkers and controlled breath. The results provide a new class of multicomponent catalytic materials, demonstrating potential for achieving reliable breath analysis sensing.