Li Sun

Bio: Li Sun is an academic researcher from Texas A&M University. The author has contributed to research in topics: Monolayer & Dendrimer. The author has an hindex of 33, co-authored 49 publications receiving 6187 citations. Previous affiliations of Li Sun include Peking University & Northwestern University.

Dendrimer-Encapsulated Metal Nanoparticles: Synthesis, Characterization, and Applications to Catalysis

Abstract: This Account reports the synthesis and characterization of dendrimer-encapsulated metal nanoparticles and their applications to catalysis. These materials are prepared by sequestering metal ions within dendrimers followed by chemical reduction to yield the corresponding zerovalent metal nanoparticle. The size of such particles depends on the number of metal ions initially loaded into the dendrimer. Intradendrimer hydrogenation and carbon−carbon coupling reactions in water, organic solvents, biphasic fluorous/organic solvents, and supercritical CO2 are also described.

Preparation of Cu Nanoclusters within Dendrimer Templates

Abstract: : A new template synthesis strategy for preparing Cu nanoclusters within dendrimer 'nanoreactors' is demonstrated. Hydroxyl-terminated polyamidoamine (PAMAM) dendrimers of generation higher than 2 act as monodispersed templates as well as stabilizers for nanocluster synthesis. Cu(2+) ions are first quantitatively sorbed into the dendrimer via a strong coordinative interaction with interior amines and then chemically reduced to yield Cu nanoclusters. The nanoclusters are composed of a well-defined number of atoms. Importantly, cluster size can be controlled by varying the size of the host dendrimer nanoreactor (16-atom Cu cluster in G4 and 64-atom Cu cluster in G6 dendrimers). The clusters remain trapped within the dendrimers for extended periods of time, do not agglomerate, and do not precipitate. The clusters can also be oxidized to yield dendrimer-encapsulated Cu(2+).

Electrochemistry Using Single Carbon Nanotubes

Abstract: We report here the fabrication and characterization of electrodes constructed from single carbon nanotubes. The sigmoidal voltammetric response of these nanotubular electrodes is characteristic of steady-state radial diffusion. The limiting current of uninsulated electrodes scales linearly with the depth of immersion into electrolyte solutions. However, the walls of nanotubular electrotrodes can be selectively insulated with a thin layer of polyphenol so that electrochemical activity is limited to the tip region. In this case the limiting current is essentially independent of immersion depth. These nanotubular electrodes are robust, can be fabricated in high yield, and are of uniform diameter. Most importantly, their great strength and high length-to-diameter aspect ratio will be particularly valuable for applications such as scanning electrochemical microscopy (SECM) 1,2 and electrochemical analysis of biological materials. 3-6

The resurgence of Coulter counting for analyzing nanoscale objects

Abstract: This review discusses recent advances in the science and technology of Coulter counting. The Coulter counting principle has been used to determine the size, concentration, and in favorable cases the surface charge, of nanometer-scale colloidal particles, viruses, DNA and other polymers, and metal ions. A resurgence of interest in the field of Coulter counting is occurring because of the advent of new technologies that permit fabrication of membranes containing single, robust, and chemically well-defined channels having smaller and more uniform sizes than could be prepared in the past. These channels are prepared from biological materials, such as self-assembling membrane proteins, and from synthetic materials such as polymers, carbon nanotubes, and silicon-based inorganic materials. In addition to particle characterization, there have been a few recent examples of using Coulter counters to study chemical processes, such as the dehybridization of DNA.

Dendrimer-Encapsulated Metals and Semiconductors: Synthesis, Characterization, and Applications

Abstract: This chapter describes composite materials composed of dendrimers and metals or semiconductors. Three types of dendrimer/metal-ion composites are discussed: dendrimers containing structural metal ions, nonstructural exterior metal ions, and nonstructural interior metal ions. Nonstructural interior metal ions can be reduced to yield dendrimer-encapsulated metal and semiconductor nanoparticles. These materials are the principal focus of this chapter. Poly(amidoamine) (PAMAM) and poly(propylene imine) dendrimers, which are the two commercially available families of dendrimers, are in many cases monodisperse in size. Accordingly, they have a generation-dependent number of interior tertiary amines. These are able to complex a range of metal ions including Cu2+, Pd2+, and Pt2+. The maximum number of metal ions that can be sorbed within the dendrimer interior depends on the metal ion, the dendrimer type, and the dendrimer generation. For example, a generation six PAMAM dendrimer can contain up to 64 Cu2+ ions. Nonstructural interior ions can be chemically reduced to yield dendrimer-encapsulated metal nanoparticles. Because each dendrimer contains a specific number of ions, the resulting metal nanoparticles are in many cases of nearly monodisperse size. Nanoparticles within dendrimers are stabilized by the dendrimer framework; that is, the dendrimer first acts as a molecular template to prepare the metal nanoparticles and then as a stabilizer to prevent agglomeration. These composites are useful for a range of catalytic applications including hydrogenations and Heck chemistry. The unique properties of the interior dendrimer microenvironment can result in formation of products not observed in the absence of the dendrimer. Moreover the exterior dendrimer branches act as a selective gate that controls access to the interior nanoparticle, which results in selective catalysis. In addition to single-metal nanoparticles, it is also possible to prepare bimetallic nanoclusters and dendrimer-encapsulated semiconductor nanoparticles, such as CdS, using this same general approach.

Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology.

Abstract: Although gold is the subject of one of the most ancient themes of investigation in science, its renaissance now leads to an exponentially increasing number of publications, especially in the context of emerging nanoscience and nanotechnology with nanoparticles and self-assembled monolayers (SAMs). We will limit the present review to gold nanoparticles (AuNPs), also called gold colloids. AuNPs are the most stable metal nanoparticles, and they present fascinating aspects such as their assembly of multiple types involving materials science, the behavior of the individual particles, size-related electronic, magnetic and optical properties (quantum size effect), and their applications to catalysis and biology. Their promises are in these fields as well as in the bottom-up approach of nanotechnology, and they will be key materials and building block in the 21st century. Whereas the extraction of gold started in the 5th millennium B.C. near Varna (Bulgaria) and reached 10 tons per year in Egypt around 1200-1300 B.C. when the marvelous statue of Touthankamon was constructed, it is probable that “soluble” gold appeared around the 5th or 4th century B.C. in Egypt and China. In antiquity, materials were used in an ecological sense for both aesthetic and curative purposes. Colloidal gold was used to make ruby glass 293 Chem. Rev. 2004, 104, 293−346

Formation and Structure of Self-Assembled Monolayers.

Abstract: The field of self-assembled monolayers (SAMs) has witnessed tremendous growth in synthetic sophistication and depth of characterization over the past 15 years.1 However, it is interesting to comment on the modest beginning and on important milestones. The field really began much earlier than is now recognized. In 1946 Zisman published the preparation of a monomolecular layer by adsorption (self-assembly) of a surfactant onto a clean metal surface.2 At that time, the potential of self-assembly was not recognized, and this publication initiated only a limited level of interest. Early work initiated in Kuhn’s laboratory at Gottingen, applying many years of experience in using chlorosilane derivative to hydrophobize glass, was followed by the more recent discovery, when Nuzzo and Allara showed that SAMs of alkanethiolates on gold can be prepared by adsorption of di-n-alkyl disulfides from dilute solutions.3 Getting away from the moisture-sensitive alkyl trichlorosilanes, as well as working with crystalline gold surfaces, were two important reasons for the success of these SAMs. Many self-assembly systems have since been investigated, but monolayers of alkanethiolates on gold are probably the most studied SAMs to date. The formation of monolayers by self-assembly of surfactant molecules at surfaces is one example of the general phenomena of self-assembly. In nature, self-assembly results in supermolecular hierarchical organizations of interlocking components that provides very complex systems.4 SAMs offer unique opportunities to increase fundamental understanding of self-organization, structure-property relationships, and interfacial phenomena. The ability to tailor both head and tail groups of the constituent molecules makes SAMs excellent systems for a more fundamental understanding of phenomena affected by competing intermolecular, molecular-substrates and molecule-solvent interactions like ordering and growth, wetting, adhesion, lubrication, and corrosion. That SAMs are well-defined and accessible makes them good model systems for studies of physical chemistry and statistical physics in two dimensions, and the crossover to three dimensions. SAMs provide the needed design flexibility, both at the individual molecular and at the material levels, and offer a vehicle for investigation of specific interactions at interfaces, and of the effect of increasing molecular complexity on the structure and stability of two-dimensional assemblies. These studies may eventually produce the design capabilities needed for assemblies of three-dimensional structures.5 However, this will require studies of more complex systems and the combination of what has been learned from SAMs with macromolecular science. The exponential growth in SAM research is a demonstration of the changes chemistry as a disciAbraham Ulman was born in Haifa, Israel, in 1946. He studied chemistry in the Bar-Ilan University in Ramat-Gan, Israel, and received his B.Sc. in 1969. He received his M.Sc. in phosphorus chemistry from Bar-Ilan University in 1971. After a brief period in industry, he moved to the Weizmann Institute in Rehovot, Israel, and received his Ph.D. in 1978 for work on heterosubstituted porphyrins. He then spent two years at Northwestern University in Evanston, IL, where his main interest was onedimensional organic conductors. In 1985 he joined the Corporate Research Laboratories of Eastman Kodak Company, in Rochester, NY, where his research interests were molecular design of materials for nonlinear optics and self-assembled monolayers. In 1994 he moved to Polytechnic University where he is the Alstadt-Lord-Mark Professor of Chemistry. His interests encompass self-assembled monolayers, surface engineering, polymers at interface, and surfaces phenomena. 1533 Chem. Rev. 1996, 96, 1533−1554

Chemistry and properties of nanocrystals of different shapes.

Abstract: The interest in nanoscale materials stems from the fact that new properties are acquired at this length scale and, equally important, that these properties * To whom correspondence should be addressed. Phone, 404-8940292; fax, 404-894-0294; e-mail, mostafa.el-sayed@ chemistry.gatech.edu. † Case Western Reserve UniversitysMillis 2258. ‡ Phone, 216-368-5918; fax, 216-368-3006; e-mail, burda@case.edu. § Georgia Institute of Technology. 1025 Chem. Rev. 2005, 105, 1025−1102

Chemistry of Carbon Nanotubes

Abstract: 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