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Nanowire Sensors for Medicine and the Life Sciences For reprint orders, please contact: EVIEW [email protected] R Nanowire sensors for medicine and the life sciences Fernando Patolsky, The interface between nanosystems and biosystems is emerging as one of the broadest and Gengfeng Zheng & most dynamic areas of science and technology, bringing together biology, chemistry, Charles M Lieber† physics and many areas of engineering, biotechnology and medicine. The combination of †Author for correspondence Harvard University, these diverse areas of research promises to yield revolutionary advances in healthcare, Department of Chemistry and medicine and the life sciences through, for example, the creation of new and powerful Chemical Biology, and tools that enable direct, sensitive and rapid analysis of biological and chemical species, Division of Engineering and Applied Sciences, 12 Oxford ranging from the diagnosis and treatment of disease to the discovery and screening of new Street, Cambridge, drug molecules. Devices based on nanowires are emerging as a powerful and general MA 02138, USA platform for ultrasensitive, direct electrical detection of biological and chemical species. Tel.: +1 617 496 3169; Here, representative examples where these new sensors have been used for detection of a Fax: +1 617 496 5442; E-mail: cml@ wide-range of biological and chemical species, from proteins and DNA to drug molecules cmliris.harvard.edu and viruses, down to the ultimate level of a single molecule, are discussed. Moreover, how advances in the integration of nanoelectronic devices enable multiplexed detection and thereby provide a clear pathway for nanotechnology, enabling diverse and exciting applications in medicine and life sciences, are highlighted. Nanotechnology is a broad area of science and The similarity in sizes of synthetic and natu- technology devoted to studies of the synthesis, ral nanostructures makes nanotechnology an properties and applications of structures and obvious choice for creating probes and other materials with at least one critical dimension less tools that can enable detection and treatment than the scale of approximately 100 nm. A of disease in powerful new ways, an intersec- strong motivating force driving interest in nano- tion between nanotechnology and medicine technology in the physical sciences has been the that we and others refer to as nanomedicine. long-standing recognition that the physical and Detection and quantification of biological and chemical properties of synthetic materials can chemical species is central to many areas of significantly improve or radically change as their medicine, ranging from diagnosing disease to size is reduced to the nanometer regime due, for the discovery and screening of new drug mole- example, to the effects of quantum cules. Nanostructures, such as nanowires [3–15] confinement [1,2]. More importantly, it is now and carbon nanotubes [16,17] as well as becoming increasingly well recognized that the nanoparticles [18–39], offer new and some- emerging concepts and applications of nanote- times unique opportunities for this key task. chnology are not limited to the physical sciences Inorganic nanowires, nanocrystals and carbon and, indeed, can be applied to and represent a nanotubes exhibit unique electrical, optical rich area intersecting with the life sciences and and magnetic properties that can be exploited medicine. The natural connection between nan- for sensing and imaging [3–39]. For example, otechnology and the life sciences can be under- colloidal gold and semiconductor nanocrystals stood in many ways, although perhaps the most have been used as labels for the detection of straightforward is to consider the size and organ- disease markers and other biological species ization of common structures, as shown in critical to understanding diseases [18,19,31–39]. In Keywords: biomarkers, biosensors, cancer detection, Figure 1. Here, we see that quantum dots, addition, iron oxide nanocrystals with super- diagnosis, drug discovery, nanowires and proteins, which are built from paramagnetic properties and semiconductor field-effect-transistor, label- atoms, have similar average diameters. These nanocrystals with size-tunable emissive proper- free detection, nanowires, silicon, virus detection basic structures or building blocks can be further ties are being developed as specific contrast organized into large structures, such as viruses agents in magnetic resonance and optical imag- and nanoelectronics circuits, and ultimately fur- ing, respectively, capable of wide-ranging ther elaborated into functional systems, such as applications, including the imaging of cancer cells and computer chips. tumors in live animal models [20–27]. 10.2217/17435889.1.1.51 © 2006 Future Medicine Ltd ISSN 1743-5889 Nanomedicine (2006) 1(1), 51–65 51 REVIEW – Patolsky, Zheng & Lieber Figure 1. Comparison of the sizes of biological, chemical and (p-Si), is connected to metal source and drain nanoscale structures, assemblies and systems. electrodes, through which a current is injected and collected, respectively. The conductance of the semiconductor between source and drain is switched on and off by a third gate electrode capacitively coupled through a thin dielectric Cells layer [46]. The gate voltage can be applied in a conventional manner using the degeneratively doped silicon substrate as a back-gate or by an external electrode immersed in the aqueous solu- tion as a water gate. In the case of a p-Si or other Integrated systems Nanowires Atoms Molecules Quantum dots Viruses Proteins p-type semiconductor, applying a negative gate voltage, which leads to negative charges at the 0.1 1 10 100 1 10 100 1000 interface between the gate electrode and dielec- Nanometers Microns tric, leads to an accumulation of carriers (positive holes) and a corresponding increase in conduct- ance, as shown in Figure 2A. However, applying a positive gate voltage to a p-type device, which The reproducible and tunable conducting leads to positive charges at the interface between properties of semiconducting nanowires com- the gate electrode and dielectric, will deplete car- bined with surface binding provide a very dif- riers in the device and lead to a decrease in ferent and powerful approach to nanomedicine. the conductance. Specifically, nanowires enable a detection and The dependence of the conductance on gate sensing modality – direct and label-free electri- voltage and corresponding charge at the gate cal readout – that is exceptionally attractive for electrode–dielectric interface makes FETs natu- many applications in medicine and the life sci- ral candidates for electrically based sensing ences [40–45]. Electronic nanowire devices are because the binding of a charged or polar biolog- readily integrated into miniaturized systems ical or chemical species to the gate dielectric is and, moreover, direct electrical detection dis- analogous to applying a voltage using a gate elec- penses with time-consuming labeling chemis- trode. For example, binding of a protein with net try. These characteristics, together with negative charge to the surface of a p-Si FET will ultrahigh sensitivity, suggest that nanowire lead to an accumulation of positive hole carriers devices could revolutionize many aspects of and an increase in device conductance sensing and detection medicine, ranging from (Figures 2B,2C). This idea for sensing with FETs the diagnosis and monitoring of disease treat- was introduced several decades ago [47,48], ment to the discovery and screening of new although the limited sensitivity, which usually drug molecules. While similar concepts are pos- does not allow sensing of a biological analyte sible with carbon nanotubes, the lack of control with planar FET sensors of previous planar of the electronic properties of this nanomaterial devices, has precluded them from having a large make it much less attractive for the develop- impact as chemical or biological sensors. ment of electronic nanosensors compared with Semiconductor nanowires composed of silicon semiconducting nanowires. Here, the authors and other materials can also function as FET provide an introduction to the underlying devices [5,9,11–15]. The structure of one of the best nanowire nanotechnology and then illustrate characterized examples of semiconducting the diverse and exciting applications of this nanowires, silicon nanowires, can be prepared as technology in nanomedicine. single-crystal structures with diameters as small as 2–3 nm [49,50]. The Si nanowires can be prepared Nanowire field-effect sensors as both p- and n-type materials and configured as Underlying detection using semiconductor FETs that exhibit performance characteristics nanowires is their configuration as field-effect comparable to or better than the best achieved in transistors (FETs), which will exhibit a conduc- the microelectronics industry for planar silicon tivity change in response to variations in the elec- devices [11,13,14]. These attractive performance tric field or potential at the surface of the characteristics are also achieved with high repro- nanowire FET [5,40]. In a standard FET ducibility [13]; that is, the electronic characteris- (Figure 2A), a semiconductor, such as p-type silicon tics of the nanowire are well controlled during 52 Nanomedicine (2006) 1(1) Nanowire sensors for medicine and the life sciences – REVIEW Figure 2. Nanowire field-effect transistor sensors. A Metal gate Oxide Source Drain G G VG<0 S D S p-Si p-Si Accumulation of carriers Conductance increase - Molecular n - Surface
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