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.

Structure and Interpretation of Computer Programs

"The Structure and Interpretation of Computer Programs" is the entry-level subject in Computer Science at the Massachusetts Institute of Technology. It is required of all students at MIT who major in Electrical Engineering or in Computer Science, as one fourth of the "common core curriculum," which also includes two subjects on circuits and linear systems and a subject on the design of digital systems. We have been involved in the development of this subject since 1978, and we have taught this material in its present form since the fall of 1980 to approximately 600 students each year. Most of these students have had little or no prior formal training in computation, although most have played with computers a bit and a few have had extensive programming or hardware design experience. Our design of this introductory Computer Science subject reflects two major concerns. First we want to establish the idea that a computer language is not just a way of getting a computer to perform operations, but rather that it is a novel formal medium for expressing ideas about methodology. Thus, programs must be written for people to read, and only incidentally for machines to execute. Secondly, we believe that the essential material to be addressed by a subject at this level, is not the syntax of particular programming language constructs, nor clever algorithms for computing particular functions of efficiently, not even the mathematical analysis of algorithms and the foundations of computing, but rather the techniques used to control the intellectual complexity of large software systems.