Core-Shell Assisted Bimetallic Assembly of Pt and Ru Nanoparticles by DNA Hybridization

We have discovered that the current protocols to assemble Au nanoparticles based on DNA hybridization do not work well with the small metal nanoparticles (e.g. 5 nm Au, 3.6 nm Pt and 3.2 nm Ru particles). Further investigations revealed the presence of strong interaction between the oligonucleotide backbone and the surface of the small metal nanoparticles. The oligonucleotides in this case are recumbent on the particle surface and are therefore not optimally oriented for hybridization. The nonspecific adsorption of oligonucleotides on small metal nanoparticles must be overcome before DNA hybridization can be accepted as a general assembly method. Two methods have been suggested as possible solutions to this problem. One is based on the use of stabilizer molecules which compete with the oligonucleotides for adsorption on the metal nanoparticle surface. Unfortunately, the reported success of this approach in small Au nanoparticles (using K₂BSPP) and Au films (using 6-mercapto-1-hexanol) could not be extended to the assembly of Pt and Ru nanoparticles by DNA hybridization. The second approach is to simply use larger metal particles. Indeed most reports on the DNA hybridization induced assembly of Au nanoparticles have made use of relatively large particles (>10 nm), hinting at a weaker non-specific interaction between the oligonucleotides and large Au nanoparticles. However, most current methods of nanoparticle synthesis are optimized to produce metal nanoparticles only within a narrow size range. We find that core-shell nanoparticles formed by the seeded growth method may be used to artificially enlarge the size of the metal particles to reduce the nonspecific binding of oligonucleotides. We demonstrate herein a core-shell assisted growth method to assemble Pt and Ru nanoparticles by DNA hybridization. This method involves firstly synthesizing approximately 16 nm core-shell Ag-Pt and 21 nm core-shell Au-Ru nanoparticles from 9.6 nm Ag seeds and 17.2 nm Au seeds respectively by the seed-mediated growth method. The core-shell nanoparticles were then functionalized by complementary thiolated oligonucleotides followed by aging in 0.2 M PBS buffer for 6 hours. The DNA hybridization induced bimetallic assembly of Pt and Ru nanoparticles could then be carried out in 0.3 M PBS buffer for 10 hours.

Reflectance Map Techniques for Analyzing Surface Defects in Metal Castings

This report explores the relation between image intensity and object shape. It is shown that image intensity is related to surface orientation and that a variation in image intensity is related to surface curvature. Computational methods are developed which use the measured intensity variation across surfaces of smooth objects to determine surface orientation. In general, surface orientation is not determined locally by the intensity value recorded at each image point. Tools are needed to explore the problem of determining surface orientation from image intensity. The notion of gradient space , popularized by Huffman and Mackworth, is used to represent surface orientation. The notion of a reflectance map, originated by Horn, is used to represent the relation between surface orientation image intensity. The image Hessian is defined and used to represent surface curvature. Properties of surface curvature are expressed as constraints on possible surface orientations corresponding to a given image point. Methods are presented which embed assumptions about surface curvature in algorithms for determining surface orientation from the intensities recorded in a single view. If additional images of the same object are obtained by varying the direction of incident illumination, then surface orientation is determined locally by the intensity values recorded at each image point. This fact is exploited in a new technique called photometric stereo. The visual inspection of surface defects in metal castings is considered. Two casting applications are discussed. The first is the precision investment casting of turbine blades and vanes for aircraft jet engines. In this application, grain size is an important process variable. The existing industry standard for estimating the average grain size of metals is implemented and demonstrated on a sample turbine vane. Grain size can be computed form the measurements obtained in an image, once the foreshortening effects of surface curvature are accounted for. The second is the green sand mold casting of shuttle eyes for textile looms. Here, physical constraints inherent to the casting process translate into these constraints, it is necessary to interpret features of intensity as features of object shape. Both applications demonstrate that successful visual inspection requires the ability to interpret observed changes in intensity in the context of surface topography. The theoretical tools developed in this report provide a framework for this interpretation.