The field of sensors encompasses a wide variety of materials and devices used for capturing physical, chemical or biological stimuli converting them to measurable output signals. Nanomaterials may be used as active sensing elements or receptors, as transducing components (e.g. electro- or chemo-mechanical actuators), and even as electrodes in electronic circuitry and power systems (e.g. nanowires)1,2.
The Center for Nanomaterials and Sensor Development at the State University of New York at Stony Brook which the author established in 2003 and she still directs, specializes on the synthesis and use of nanomaterials: metal oxides, electro-active polymers, their composites, and their hybrids with biomolecules (enzymes, peptides), primarily as active elements of bio-/chemical sensor systems. Nanomaterials are very important to resistive chemosensing2, a key transduction mode in which chemical or biochemical signal inputs induce changes in the electrical resistance of the active element.
Since gas adsorption on the sensor materials' surfaces is fundamental to the resistive gas detection process, reducing the dimensionality of the sensor materials to the nanoscale, thus increasing their surface to volume ratio, has the obvious effect of improving gas sensitivitya. Numerous reports in the literature have documented several orders of magnitude increases in the gas response of nanomaterials compared to their bulk(ier) counterparts1,3. The response and recovery time of nanomaterials-based chemiresistors may be impressively as low as milliseconds1-3.
a increasing the amplitude of change of the electrical resistance of the active element in the presence of the same concentration of the gas
bsingle crystal metal oxide nanowires of "extreme" aspect ratio were synthesized by Professor Gouma's research group by means of electrospinning
c the use of nanotechnology for the early detection, prevention and cure of diseases
Professor Gouma's research group has made unique contributions to establishing and explaining the gas specificity observed in functional metal oxide nanomaterials, such as TiO2, MoO3 and WO3. Using a crystallo-chemical approach, it is shown that the phase of the nanomaterial (crystallographic polymorph) rather than it's chemical composition, is the critical parameter controlling the affinity of a stoichiometric metal oxide to a specific gaseous analyte4,5. For example, both the â-phase of MoO3 and the ã-phase of WO3 are selective to nitric oxide (NO), because both share the cubic rhenium trioxide structure6. This is not the case with the a-phase of MoO3- having a unique, open orthorhombic crystal structure- that serves as a highly selective ammonia detector7.
Interestingly, there is a little-known phase of the WO3 material that is ferroelectric and makes an excellent acetone detector8. This phase is thermodynamically stable below -40°C9. Thanks to the availability of nanomanufacturing processes10, Professor Gouma's research group was able to stabilize this nanophase to RT and to use it for sensing11. This "novel" nanomaterial, å-phase WO3, interacts with polar gases through a dielectric poling sensing mechanism8,11, a true breakthrough in gas sensing.
As nanoscale synthesis of metal oxides favors metastability12, there is a toolbox of "rare" phases now available to gas detection and monitoring, including hexagonal WO3, anatase and brookite TiO2, to name a few. Furthemore, processing these "gas-selective" oxide phases in 1D nanowire configurationsb adds improved sensitivity to gas specificity13, thus detection limits of only a few gas molecules (ppb levels) of signaling metabolites have been achieved recently1-3. This finding has important implications for nanomedicinec applications of nanomaterials.
Among the successful nanotechnologies that The Center for Nanomaterials and Sensor Development at the State University of New York at Stony Brook has pioneered, single breath analysis diagnostics stand out. Electronic Olfaction14 (whether it is electronic nose or tongue technologies), has been limited by the lack of selective sensors to discriminate gases in a complex gas environment (such as breath odor).
Figure 1. Ceramic oxide nanoparticles that are used as sensing elements in a breathanalysis device prototype (shown above) that monitors selectively the concentration of a gaseous biomarker for diabetes monitoring in a non-invasive manner (copyright: P. Gouma, CNSD).
The nanomaterials-based sensors described above offer inexpensive alternatives to costly and bulky optical detectors, the main competing selective gas sensing technology under development15. On/off nanosensor devices have been demonstrated that may detect from bacterial infection to diabetes, and even lung cancer16. Using bio-doped nanostructured oxides (urease in MoO3)17 or bio-nanocomposites (PANI/CAionophores/ peptides)18 as sensing elements, further expands the scope of using nanomaterials as resistive biosensors in non-invasive diagnostic tools.
In summary, nanomaterials are having a tremendous impact in sensing applications as they offer improved selectivity, sensitivity, and rapid response to the bio-/chemical analytes of interest. Resistive chemosensors using nanomaterials have enabled novel inexpensive and non-invasive applications for health and safety, such as breath analyzers, sweat test diagnostics, and other personalized medicine and protection tools. Selfpowered nanosensor devices relying completely on hybrid nanowire technology are envisioned for the near future.
1. P. Gouma, Nanomaterials for Chemical Sensors and Biotechnology, Pan Stanford Publishing, 2009.
2. P. Gouma, D. Kubinski, E. Comini, and V. Guidi, eds, "Nanostructured Materials and Hybrid Composites for Gas Sensors and Biomedical Applications", Materials Research Society, Warrendale, PA, Spring 2006.
3. G. Shen, P-C. Chen, K. Ryu, and C. Zhou, "Devices and Chemical Sensing Applications of Metal Oxide Nanowires, Journal of Materials Chemistry, 19, pp. 828-839, 2009.
4. P.I. Gouma, A. K. Prasad, and K.K. Iyer, "Selective Nanoprobes for Signaling Gases", Nanotechnology, 17, pp. S48-S53, 2006.
5. P. I. Gouma, "Nanostructured Polymorphic Oxides for Advanced Chemosensors", Rev.Adv. Mater. Sci., 5, pp. 123-138, 2003.
6. P.I Gouma and K. Kalyanasundaram, "A Selective Nanosensing Probe for Nitric Oxide", Appl. Phys. Lett., 93, 244102, 2008.
7. A.K. Prasad, D. Kubinski, and P. I. Gouma, "Comparison of Sol-Gel and RF Sputtered MoO3 Thin Film Gas Sensors for Selective Ammonia Detection", Sensors & Actuators B, 9, pp.25-30, 2003.
8. Lisheng Wang, "Tailored Synthesis and Characterization of Selective Metabolitedetecting Nanoprobes for Handheld Breath Analysis", Ph.D. thesis, SUNY Stony Brook, Dec 2008.
9. B.T. Matthias and E.A. Wood, "Low temperature polymorphic transformation in WO3". Phys. Rev., 84(6), pp. 1255-1255, 1951.
10. K. Wegner and S.E. Pratsinis, "Nozzle-quenching process for controlled flame synthesis of titania nanoparticles", AICHE J., 15, pp. 432-436, 2003.
11. L. Wang, A. Teleki, S.E. Pratsinis, and P.I. Gouma, "Ferroelectric WO3 Nanoparticles for Acetone Selective Detection", Chem. Mater., 20(15), pp. 4794- 4796, 2008.
12. H. Zhang, H. and J.F. Banfield, "Understanding polymorphic phase transformation behavior during growth of nanocrystalline aggregates: Insights from TiO2", Journal of Physical Chemistry B, 104, pp. 3481-3487 2000.
13. P. Gouma, K. Kalyanasundaram, and A. Bishop, "Electrospun Single Crystal MoO3 Nanowires for Bio-Chem sensing probes", Journal of Materials Research, Nanowires and Nanotubes special issue, 21(11), pp. 2904-2910, 2006.
14. P. Gouma and G. Sberveglieri, "Novel Materials and Applications of Electronic Noses and Tongues", MRS Bulletin, 29 (10), pp. 697-700, 2004.
15. M.R. McCurdy, Y. Bakhirkin, G. Wysocki, R. Lewicki, and F.K. Tittel, "Recent Advances in Laser-spectroscopy-based Techniques for Applications in Breath Analysis", J. Breath Res., 1, 014001, pp. R1-R12, 2007.
16. P. Gouma, K. Kalyanasundaram, X. Yun, M. Stanacevic and L. Wang, "Chemical Sensor and Breath Analyzer for Ammonia Detection in Exhaled Human Breath", IEEE Sensors, Special Issue on Breath Analysis, 10 (1), pp. 49-53, 2010.
17. S.Y. Gadre and P. Gouma, "Biodoped Ceramics: Synthesis, Properties And Applications", J. Amer. Ceram. Soc. - Invited Feature Article, 89 (10), pp. 2987- 3002, 2006.
18. A. S. Haynes and P.I. Gouma, "Electrospun Conducting Polymer-based Sensors for Advanced Pathogen Detection", IEEE Sensors Journal, 8(6), pp. 701-70, June 2008.
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