Richard M. Crooks

Homogeneous Hydrogenation Catalysis with Monodisperse, Dendrimer-Encapsulated Pd and Pt Nanoparticles

Extraordinarily stable, monodisperse noble metal nanoparticles can be prepared by using dendrimers as both templates and stabilizers. Dendrimer-encapsulated Pd nanoparticles (see the schematic representation) exhibit high catalytic activity for the hydrogenation of alkenes in water. The catalytic activity and selectivity of these materials can be controlled by adjusting the dendrimer generation.

Three-Dimensional Paper Microfluidic Devices Assembled Using the Principles of Origami

We report a method, based on the principles of origami (paper folding), for fabricating three-dimensional (3-D) paper microfluidic devices. The entire 3-D device is fabricated on a single sheet of flat paper in a single photolithographic step. It is assembled by simply folding the paper by hand. Following analysis, the device can be unfolded to reveal each layer. The applicability of the device to chemical analysis is demonstrated by colorimetric and fluorescence assays using multilayer microfluidic networks.

Dendrimer-encapsulated nanoparticles: New synthetic and characterization methods and catalytic applications

In this article we describe the synthesis, characterization, and applications of dendrimer-encapsulated nanoparticles (DENs). These materials are synthesized using a template approach in which metal ions are extracted into the interior of dendrimers and then subsequently reduced chemically to yield nearly size-monodisperse particles having diameters in the 1–2 nm range. Monometallic, bimetallic (alloy and core@shell), and semiconductor nanoparticles have been prepared by this route. The dendrimer component of these composites serves not only as a template for preparing the nanoparticle replica, but also as a stabilizer for the nanoparticle. In this perspective, we report on progress in the synthesis, characterization, and applications of these materials since our last review in 2005. Significant advances in the synthesis of core@shell DENs, characterization, and applications to homogeneous and heterogeneous catalysis (including electrocatalysis) are emphasized.

Bipolar Electrodes: A Useful Tool for Concentration, Separation, and Detection of Analytes in Microelectrochemical Systems

Over the past decade, bipolar electrochemistry has emerged from relative obscurity to provide a promising new means for integrating electrochemistry into lab-on-a-chip systems. This article describes the fundamental operating principles of bipolar electrodes, as well as several interesting applications.

Preparation and characterization of dendrimer-gold colloid nanocomposites.

Au colloids in the 2-3-nm size regime were prepared by in situ reduction of HAuCl(4) in the presence of poly(amidoamine) dendrimers. The dendrimers encapsulate the colloids, imparting stability to the aqueous colloidal solutions. The nanocomposite materials can be isolated by precipitation. The dendrimer generation used in the synthesis controls the size of the resultant colloids:  lower-generation dendrimers give rise to larger colloids. The materials were characterized by infrared and UV-vis spectroscopy and transmission electron microscopy.

Aptamer-based origami paper analytical device for electrochemical detection of adenosine

Paper biosensors: an origami sensor is printed on a single piece of paper, folded into a three-dimensional fluidic device, and encapsulated by thermal lamination. Aptamer is trapped in the fluidic channel, where it binds to the target and releases an enzyme to generate a signal. The device is read out using a digital multimeter.

Paper-based electrochemical sensing platform with integral battery and electrochromic read-out.

We report a battery-powered, microelectrochemical sensing platform that reports its output using an electrochromic display. The platform is fabricated based on paper fluidics and uses a Prussian blue spot electrodeposited on an indium-doped tin oxide thin film as the electrochromic indicator. The integrated metal/air battery powers both the electrochemical sensor and the electrochromic read-out, which are in electrical contact via a paper reservoir. The sample activates the battery and the presence of analyte in the sample initiates the color change of the Prussian blue spot. The entire system is assembled on the lab bench, without the need for cleanroom facilities. The applicability of the device to point-of-care sensing is demonstrated by qualitative detection of 0.1 mM glucose and H(2)O(2) in artificial urine samples.

Reactions and Reactivity in Self-Assembled Monolayers**

Self-assembled monolayers (SAMs) are excellent models for studying interfacial reactions. Here monolayer chemistry is reviewed, focusing on the features that have no analogues in solution chemistry. The growth of surface-attached polymers, intrafilm reactions, chemistry, photochemistry and reactivity issues are all discussed.

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

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.

The resurgence of Coulter counting for analyzing nanoscale objects.

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.