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.

A large amount of work world-wide has been directed towards obtaining an understanding of the fundamental characteristics of porous Si. Much progress has been made following the demonstration in 1990 that highly porous material could emit very efficient visible photoluminescence at room temperature. Since that time, all features of the structural, optical and electronic properties of the material have been subjected to in-depth scrutiny. It is the purpose of the present review to survey the work which has been carried out and to detail the level of understanding which has been attained. The key importance of crystalline Si nanostructures in determining the behaviour of porous Si is highlighted. The fabrication of solid-state electroluminescent devices is a prominent goal of many studies and the impressive progress in this area is described.

The structural and luminescence properties of porous silicon

Nanomaterials, such as metal or semiconductor nanoparticles and nanorods, exhibit similar dimensions to those of biomolecules, such as proteins (enzymes, antigens, antibodies) or DNA. The integration of nanoparticles, which exhibit unique electronic, photonic, and catalytic properties, with biomaterials, which display unique recognition, catalytic, and inhibition properties, yields novel hybrid nanobiomaterials of synergetic properties and functions. This review describes recent advances in the synthesis of biomolecule-nanoparticle/nanorod hybrid systems and the application of such assemblies in the generation of 2D and 3D ordered structures in solutions and on surfaces. Particular emphasis is directed to the use of biomolecule-nanoparticle (metallic or semiconductive) assemblies for bioanalytical applications and for the fabrication of bioelectronic devices.

Integrated Nanoparticle–Biomolecule Hybrid Systems: Synthesis, Properties, and Applications

Based on fundamental chemistry, biotechnology and materials science have developed over the past three decades into today's powerful disciplines which allow the engineering of advanced technical devices and the industrial production of active substances for pharmaceutical and biomedical applications. This review is focused on current approaches emerging at the intersection of materials research, nanosciences, and molecular biotechnology. This novel and highly interdisciplinary field of chemistry is closely associated with both the physical and chemical properties of organic and inorganic nanoparticles, as well as to the various aspects of molecular cloning, recombinant DNA and protein technology, and immunology. Evolutionary optimized biomolecules such as nucleic acids, proteins, and supramolecular complexes of these components, are utilized in the production of nanostructured and mesoscopic architectures from organic and inorganic materials. The highly developed instruments and techniques of today's materials research are used for basic and applied studies of fundamental biological processes.

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Nanoparticles, Proteins, and Nucleic Acids: Biotechnology Meets Materials Science

Recent research in the field of nanometre-scale electronics has focused on two fundamental issues: the operating principles of small-scale devices, and schemes that lead to their realization and eventual integration into useful circuits. Experimental studies on molecular1 to submicrometre2 quantum dots and on the electrical transport in carbon nanotubes3,4,5 have confirmed theoretical predictions6,7,8 of an increasing role for charging effects as the device size diminishes. Nevertheless, the construction of nanometre-scale circuits from such devices remains problematic, largely owing to the difficulties of achieving inter-element wiring and electrical interfacing to macroscopic electrodes. The use of molecular recognition processes and the self-assembly of molecules into supramolecular structures9,10 might help overcome these difficulties. In this context, DNA has the appropriate molecular-recognition11 and mechanical12,13,14,15,16 properties, but poor electrical characteristics prevent its direct use in electrical circuits. Here we describe a two-step procedure that may allow the application of DNA to the construction of functional circuits. In our scheme, hybridization of the DNA molecule with surface-bound oligonucleotides is first used to stretch it between two gold electrodes; the DNA molecule is then used as a template for the vectorial growth of a 12 µm long, 100 nm wide conductive silver wire. The experiment confirms that the recognition capabilities of DNA can be exploited for the targeted attachment of functional wires.

DNA-templated assembly and electrode attachment of a conducting silver wire

We have developed a method of semiconductor nanostructure fabrication relying on the size and shape of a polynucleotide to dictate the overall structure of an assembly of individual nanoparticles. This is exemplified by our use of the 3455‐basepair circular plasmid DNA molecule pUCLeu4 which, when anchored to a suitably derivatized substrate, yields an array of semiconductor nanoparticles matching the shape of the biopolymer stabilizer. The viability of the methodology was confirmed using data from high resolution transmission electron microscopy, selected area electron diffraction, and linear optical absorption spectroscopy. This is a unique demonstration of the self‐assembly of mesoscale semiconductor nanostructures using biological macromolecules as templates.

Dictation of the shape of mesoscale semiconductor nanoparticle assemblies by plasmid DNA

Intermetallic phases formed along a Sn-Ag eutectic solder/Cu interface during solid-state aging have been characterized and the activation energies of Cu3Sn and Cu6Sn5 growth have been calculated. Diffusion couples consisting of Cu/ 96.5Sn-3.5Ag/Cu were aged at 110 to 208°C for 0 to 32 days. After aging, the Cu/ solder interfaces were examined using scanning electron microscopy and energy dispersive x-ray spectroscopy. The growth rate constants for each intermetallic layer were calculated assuming a simple parabolic diffusion-controlled growth model. The activation energy for Cu3Sn growth is 0.73 eV/atom and the activa-tion energy for Cu6Sn5 growth is 1.11 eV/atom.

Activation energies of intermetallic growth of Sn-Ag eutectic solder on copper substrates

The formation and growth of intermetallics at the solder/substrate interface are factors affecting the solderability and reliability of electronic solder joints. This study was performed to better understand the diffusion behavior and microstructural evolution of Cu−Sn intermetallics at the composite solder/copper substrate interface for eutectic solder and solder alloys containing particle additions of Cu, Cu3Sn, Cu6Sn5, Ag, Au, and Ni. Annealing temperatures of 110 to 160°C were used with aging times of 0 to 64 days. The copper-containing composite solders generally formed thinner Cu6Sn5 layers, but thicker Cu3Sn layers than were formed by the eutectic solder alone. These copper-containing additions, therefore, resulted in increased activation energies for Cu6Sn5 formation and decreased activation energies for Cu3Sn formation as compared to the eutectic solder. The activation energy for Cu3Sn formation decreased relative to eutectic solder for silver and gold composite solders even though less Cu3Sn was formed at the substrate interface. Nickel and palladium drastically reduced the Cu3Sn thickness and increased the Cu6Sn5 thickness. However, the Cu6Sn5 contained a substantial volume fraction of voids close to the copper substrate. We propose two mechanisms to explain the effects of the copper-containing and silver particles on the kinetics of intermetallic formation. First, the particles act as tin-sinks which remove tin from the solder and decrease the amount of tin available for reaction at the solder/substrate interface. Second, the particles reduce the cross-sectional area available for tin diffusion, which also reduces the amount of tin available at the interface for reaction.

The formation and growth of intermetallics in composite solder

The preparation of discrete erbium-doped silicon nanoparticles prepared by the co-pyrolysis of disilane and the volatile complex Er(tmhd)3 (tmhd = 2,2,6,6-tetramethyl-3,5-heptanedionato) is described. The nanoparticles were characterized by transmission electron microscopy, selected area electron diffraction, X-ray dispersive spectroscopy, photoluminescence, and UV−visible absorption spectroscopies. Erbium-doped silicon nanoparticles possess a distinctive dark contrast in the transmission electron microscope, and the presence of erbium is confirmed by X-ray energy dispersive spectroscopy. The mean diameter of the nanoparticle aggregates can be shifted by altering the length of the pyrolysis oven employed. Chacteristic Er3+ near-infrared photoluminescence at 1540 nm is detected in these doped nanoparticles; preliminary excitation and power dependence measurements of this luminescence suggest a carrier-mediated emission mechanism.

Synthesis and characterization of discrete luminescent erbium-doped silicon nanocrystals

In this work, the incorporation and characterization of cis-platin (cis-diammine dichloroplatinum(II)), carbo-platin [cis-diammine(cyclobutane-1,1-dicarboxylato] platinum(II)), and Pt(en)Cl2 (ethylenediamminedichloro platinum(II)) within layers of calcium phosphate on porous Si/Si substrates are described. These materials have been characterized by scanning electron microscopy, secondary ion mass spectrometry, and X-ray energy dispersive spectroscopy. The diffusion of platinum species from the doped calcium phosphate layers has also been investigated by UV-visible absorption spectrometry and inductively-coupled plasma spectroscopy. The influence of initial platinum concentration, the impact of thermal annealing of the calcium phosphate/porous Si/Si matrix, as well as the effect of varying the ligand coordination sphere of the Pt complex on its ability to be delivered to the surroundings have also been analyzed. For the case of cis-platin, it is found that increasing the concentration of platinum complex in the electrolyte during cathodic growth of calcium phosphate results in a relatively greater concentration of Pt incorporated into the calcium phosphate layers and a larger amount of Pt which subsequently can be delivered to the surrounding medium upon exposure to solvent.

Russell F. Pinizzotto

Papers

Dictation of the shape of mesoscale semiconductor nanoparticle assemblies by plasmid DNA

Activation energies of intermetallic growth of Sn-Ag eutectic solder on copper substrates

The formation and growth of intermetallics in composite solder

Synthesis and characterization of discrete luminescent erbium-doped silicon nanocrystals

Porosified Silicon Wafer Structures Impregnated With Platinum Anti-Tumor Compounds: Fabrication, Characterization, and Diffusion Studies