In the last 10 years the field of molecular diagnostics has witnessed an explosion of interest in the use of nanomaterials in assays for gases, metal ions, and DNA and protein markers for many diseases. Intense research has been fueled by the need for practical, robust, and highly sensitive and selective detection agents that can address the deficiencies of conventional technologies. Chemists are playing an important role in designing and fabricating new materials for application in diagnostic assays. In certain cases assays based upon nanomaterials have offered significant advantages over conventional diagnostic systems with regard to assay sensitivity, selectivity, and practicality. Some of these new methods have recently been reviewed elsewhere with a focus on the materials themselves or as subclassifications in more generalized overviews of biological applications of nanomaterials.1-7 We intend to review some of the major advances and milestones in the field of detection systems based upon nanomaterials and their roles in biodiagnostic screening for nucleic acids, * To whom correspondence should be addressed. Phone: 847-4913907. Fax: 847-467-5123. E-mail: chadnano@northwestern.edu. Nathaniel L. Rosi earned his B.A. degree at Grinnell College (1999) and his Ph.D. degree from the University of Michigan (2003), where he studied the design, synthesis, and gas storage applications of metal−organic frameworks under the guidance of Professor Omar M. Yaghi. In 2003 he began postdoctoral studies as a member of Professor Mirkin’s group at Northwestern University. His current research focuses on the rational assembly of DNA-modified nanostructures into larger-scale materials.

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Nanostructures in Biodiagnostics

Nanotechnology is a multidisciplinary field, which covers a vast and diverse array of devices derived from engineering, biology, physics and chemistry. These devices include nanovectors for the targeted delivery of anticancer drugs and imaging contrast agents. Nanowires and nanocantilever arrays are among the leading approaches under development for the early detection of precancerous and malignant lesions from biological fluids. These and other nanodevices can provide essential breakthroughs in the fight against cancer.

Cancer nanotechnology: opportunities and challenges.

Department of Materials Science, University of Patras, 26504 Rio Patras, Greece, Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vass. Constantinou Avenue, 116 35 Athens, Greece, Institut de Biologie Moleculaire et Cellulaire, UPR9021 CNRS, Immunologie et Chimie Therapeutiques, 67084 Strasbourg, France, and Dipartimento di Scienze Farmaceutiche, Universita di Trieste, Piazzale Europa 1, 34127 Trieste, Italy

Chemistry of Carbon Nanotubes

3.6.1. Polishing and Cleaning 2663 3.6.2. Vacuum and Heat Treatments 2664 3.6.3. Carbon Electrode Activation 2665 3.7. Summary and Generalizations 2666 4. Advanced Carbon Electrode Materials 2666 4.1. Microfabricated Carbon Thin Films 2666 4.2. Boron-Doped Diamond for Electrochemistry 2668 4.3. Fibers and Nanotubes 2669 4.4. Carbon Composite Electrodes 2674 5. Carbon Surface Modification 2675 5.1. Diazonium Ion Reduction 2675 5.2. Thermal and Photochemical Modifications 2679 5.3. Amine and Carboxylate Oxidation 2680 5.4. Modification by “Click” Chemistry 2681 6. Synopsis and Outlook 2681 7. Acknowledgments 2682 8. References 2682

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Advanced carbon electrode materials for molecular electrochemistry.

From diagnosis of life-threatening diseases to detection of biological agents in warfare or terrorist attacks, biosensors are becoming a critical part of modern life. Many recent biosensors have incorporated carbon nanotubes as sensing elements, while a growing body of work has begun to do the same with the emergent nanomaterial graphene, which is effectively an unrolled nanotube. With this widespread use of carbon nanomaterials in biosensors, it is timely to assess how this trend is contributing to the science and applications of biosensors. This Review explores these issues by presenting the latest advances in electrochemical, electrical, and optical biosensors that use carbon nanotubes and graphene, and critically compares the performance of the two carbon allotropes in this application. Ultimately, carbon nanomaterials, although still to meet key challenges in fabrication and handling, have a bright future as biosensors.

Carbon Nanomaterials in Biosensors: Should You Use Nanotubes or Graphene?

A nanoelectrode array based on vertically aligned multiwalled carbon nanotubes (MWNTs) embedded in SiO2 is used for ultrasensitive DNA detection. Characteristic electrochemical behaviors are observed for measuring bulk and surface-immobilized redox species. Sensitivity is dramatically improved by lowering the nanotube density. Oligonucleotide probes are selectively functionalized to the open ends of nanotubes. The hybridization of subattomole DNA targets can be detected by combining such electrodes with Ru(bpy)32+ mediated guanine oxidation.

Carbon Nanotube Nanoelectrode Array for Ultrasensitive DNA Detection

Multilevel molecular memory devices were proposed and demonstrated for nonvolatile data storage up to three bits (eight levels) per cell, in contrast to the standard one-bit-per-cell (two levels) technology. In the demonstration, charges were precisely placed at up to eight discrete levels in redox active molecules self-assembled on single-crystal semiconducting nanowire field-effect transistors. Gate voltage pulses and current sensing were used for writing and reading operations, respectively. Charge storage stability was tested up to retention of 600 h, as compared to the longest retention of a few hours previously reported for one-bit-per-cell molecular memories.

Multilevel memory based on molecular devices

We present an approach to tackle long-standing problems in contacts, thermal damage, pinhole induced short circuits and interconnects in molecular electronic device fabrication and integration. Our approach uses metallic nanowires as top electrodes to connect and interconnect molecular wires assembled on electrode arrays in crossbar architectures. Using this simple and reliable approach, we have revealed intriguing memory effects for several different molecular wires, and demonstrated their applications in molecular memory arrays. Our approach has great potential to be used for fast screening of molecular wire candidates and construction of molecular devices.

Fabrication approach for molecular memory arrays

The rapid development in nanomaterials and nanotechnologies has provided many new opportunities for electroanalysis. We review our recent results on the fabrication and electroanalytical applications of nanoelectrode arrays based on vertically aligned multi-walled carbon nanotubes (MWCNTs). A bottom-up approach is demonstrated, which is compatible with Si microfabrication processes. MWCNTs are encapsulated in SiO2 matrix leaving only the very end exposed to form inlaid nanoelectrode arrays. The electrical and electrochemical properties have been characterized, showing well-defined quasireversible nanoelectrode behavior. Ultrasensitive detection of small redox molecules in bulk solutions as well as immobilized at the MWCNT ends is demonstrated. A label-free affinity-based DNA sensor has shown extremely high sensitivity approaching that of fluorescence techniques. This platform can be integrated with microelectronics and microfluidics for fully automated microchips.

Inlaid Multi-Walled Carbon Nanotube Nanoelectrode Arrays for Electroanalysis

Detailed memory studies have been carried out based on In2O3 nanowires coated with self-assembled monolayers of porphyrins. Devices with redox-active Co-chelated porphyrin coatings exhibited prominent memory effects, where the bit was represented by the charge stored in the molecules and the nanowire conductance was used as the readout. These devices exhibited reliable operation with on/off ratios of ∼104 and were electronically programmable and erasable. Temperature-dependent retention measurements revealed a thermal activation behavior with a barrier of 264 meV. While devices with Co-porphyrin coatings showed efficient memory operation, analogous protio porphyrin coated nanowire devices exhibited no memory effects. A largely metal-centered oxidation (e.g., Co2+/3+) appears to be important for achieving a memory effect in these devices. Our results have convincingly established a direct correlation between the molecular structure and the observed memory effect, and further in-depth studies may eventually...

Wendy Fan

Papers

Carbon Nanotube Nanoelectrode Array for Ultrasensitive DNA Detection

Multilevel memory based on molecular devices

Fabrication approach for molecular memory arrays

Inlaid Multi-Walled Carbon Nanotube Nanoelectrode Arrays for Electroanalysis

Data Storage Studies on Nanowire Transistors with Self-Assembled Porphyrin Molecules