Biomedical subjects

Richard M Crooks

Publications and source records attributed to Richard M Crooks.

At least 19 recordsLinked to original sources

PubMed2006

Transfer of surface polymerase reaction products to a secondary platform with conservation of spatial registration.

Here, we describe a method for directly transferring very small amounts of reaction products from one surface to another. The approach is illustrated using a T4 DNA polymerase reaction to extend primers hybridized to a surface-confined DNA template. Following the extension reaction, the resulting oligonucleotide is transferred to a product surface. The important results are that (1) the spatial registration of the product is preserved after transfer; (2) the same reactant surface can be used to generate and transfer multiple iterations of products; and (3) the reaction products are biologically active after transfer.

Biotin↗

PubMed2006

Effect of Pd nanoparticle size on the catalytic hydrogenation of allyl alcohol.

We report a particle size dependence for the rate of hydrogenation of allyl alcohol using 1.3-1.9 nm Pd dendrimer-encapsulated nanoparticle (DEN) catalysts. For particles with diameters of <1.5 nm and containing <147 Pd atoms, the modulation in catalytic activity is due to the electronic properties of the particle. For the larger particles, 1.5-1.9 nm in diameter and containing an average of 147-250 Pd atoms, the size effect is a result of geometrical constraints. Specifically, the hydrogenation reaction is shown to occur preferentially on the face atoms of the larger nanoparticles.

Catalysis↗

PubMed2006

Replication of DNA microarrays from zip code masters.

This report describes a mechanical method for efficient and accurate replication of DNA microarrays from a zip code master. The zip code master is a DNA array that defines the location of oligonucleotides consisting of two parts: a code sequence, which is complementary to one or more of the zip codes, and the functional sequence, which is terminated with biotin. Following hybridization of the zip code to the code sequence, a replica surface functionalized with streptavidin is brought into conformal contact with the surface of the master. When the two surfaces are separated, the functional and code sequences are transferred to the replica, and the zip code remains on the surface of the master. Using this approach it is possible to prepare replica arrays having any configuration from a single, universal master array. Here we demonstrate that this approach can be used to replicate master arrays having up to three different sequences, that feature sizes as small as 100 microm can be replicated, and that master arrays can be used to prepare multiple replicas.

Biotin↗

PubMed2005

Hydrophobic dendrimers as templates for au nanoparticles.

We report the synthesis, characterization, and extraction of Au dendrimer-encapsulated nanoparticles (DENs) prepared in organic solvents. DENs composed of 31 and 55 Au atoms were prepared using organic solvents and poly(amidoamine) (PAMAM) dendrimer templates modified on their periphery with dodecyl groups. The spectral and microscopic properties of the resulting materials were identical to those prepared using water-soluble PAMAM dendrimers. It was possible to extract the organic-soluble DENs into water using the water-soluble thiols tiopronin and glutathione. The properties of the resulting monolayer-protected clusters were nearly identical to those of the precursor DENs. A mechanistic model for the extraction process is discussed. The synthetic methodology reported here provides a convenient method for preparing DENs of non noble metals such as Ni and Fe.

Dendrimers↗

PubMed2005

Synthesis and characterization of covalently linked multilayer films prepared in the absence of solvent.

We report the preparation of multilayer organic thin films prepared by sequential vapor-phase coupling of monomers. The reactions were carried out at room temperature and atmospheric pressure. Films prepared using up to six sequential coupling reactions are reported. The following specific vapor-phase reactions were found to be viable: reactions between acid chlorides and both aliphatic and aromatic amine, hydrolysis reactions, anhydride activation, and reactions between anhydrides and primary amines. Homobifunctionalized monomers, such as hexamethylenediamine, react primarily via a single endgroup rather than cross coupling to the reactive surface via both reactive groups. The estimated coverage of the multilayer films is between 36 and 46%. The films were characterized using ellipsometric, contact angle, and spectroscopic measurements.

Journal Article↗

PubMed2005

Microfluidic biosensor based on an array of hydrogel-entrapped enzymes.

Here we show that a microfluidic sensor based on an array of hydrogel-entrapped enzymes can be used to simultaneously detect different concentrations of the same analyte (glucose) or multiple analytes (glucose and galactose) in real time. The concentration of paraoxon, an acetylcholine esterase inhibitor, can be quantified using the same approach. The hydrogel micropatch arrays and the microfluidic systems are easy to fabricate, and the hydrogels provide a convenient, biocompatible matrix for the enzymes. Isolation of the micropatches within different microfluidic channels eliminates the possibility of cross talk between enzymes.

Acetylcholinesterase↗

PubMed2005

Size-selective catalytic activity of Pd nanoparticles encapsulated within end-group functionalized dendrimers.

The synthesis and size-selective catalytic activity of Pd nanoparticles encapsulated within dendrimers functionalized with different-sized end groups is described. We designed and synthesized a series of fourth-generation poly(amidoamine) dendrimers having various extents of steric crowding on their periphery. This was accomplished by reacting the terminal amine groups of these dendrimers with epoxyalkanes substituted with different-sized alkyl groups. The modified dendrimers were characterized by 1H NMR, 13C NMR, and matrix-assisted laser desorption ionization mass spectrometry. Nearly monodisperse (1.7 +/- 0.2 nm) Pd nanoparticles were encapsulated within the interior of these dendrimers, and the resulting composite catalysts were used for the hydrogenation of three alpha-allylic alcohols having different sizes. The results showed a clear correlation between the extent of steric crowding on the dendrimer surface and the turnover frequencies (TOFs) for the substrates: more steric crowding on the dendrimer surface led to lower TOFs.

Journal Article↗

PubMed2005

Replication of a DNA microarray.

A mechanical method for efficient replication of DNA microarrays is described. The approach consists of three steps. First, a master DNA microarray consisting of single-stranded DNA elements is exposed to a solution containing the biotin-functionalized complement of each array element. Following hybridization, a replica surface modified with streptavidin is brought into contact with the master. This results in linking of the biotin-functionalized complement with the replica surface. Next, the replica is separated from the master, and the complementary strands are transferred to the replica surface. The resulting complementary DNA microarray contains position-coded sequences that mirror the information contained on the master DNA microarray. Multiple replicas can be prepared from a single master, the replicas efficiently hybridize only their complement, and DNA not labeled with biotin is not transferred to the replica surface.

DNA Replication↗

PubMed2005

Electrokinetic concentration enrichment within a microfluidic device using a hydrogel microplug.

A simple and efficient approach for concentration of charged molecules in microfluidic devices is described. The functional component of the system is a hydrogel microplug photopolymerized within the main channel of a microfluidic device. When an appropriately biased voltage is applied across the hydrogel, charged analyte molecules move from the source well toward the hydrogel. Transport of the analyte through the hydrogel is slow compared to its velocity in the microfluidic channel, however, and therefore it concentrates at the hydrogel/solution interface. For an uncharged hydrogel, a bias of 100 V leads to a approximately 500-fold enrichment of the DNA concentration within 150 s, while the same conditions result in an enrichment of only 50-fold for fluorescein. Somewhat lower enrichment factors are observed when a negatively charged hydrogel is used. A qualitative model is proposed to account for the observed behavior.

Anions↗

PubMed2005

Electrochemical properties of monolayer-protected Au and Pd nanoparticles extracted from within dendrimer templates.

The electrochemical properties of Au and Pd monolayer-protected clusters (MPCs), prepared by dendrimer-templating and subsequent extraction, are described. Differential pulse voltammetry was used to estimate the size of the MPCs, and the results were compared to microscopic data and calculated values. Purification of the extracted Au and Pd nanoparticles was not required to obtain well-defined differential pulse voltammetry peaks arising from quantized double-layer charging. The calculated sizes of the nanoparticles were essentially identical to those determined from the electrochemical data. The capacitance of the particles was independent of the composition of core metal. Transmission electron microscopy data overestimated the size of the smallest Pd nanoparticles because of inadequate point-to-point resolution.

Journal Article↗

PubMed2005

Dendrimer-encapsulated Pd nanoparticles as aqueous, room-temperature catalysts for the Stille reaction.

We report that dendrimer-encapsulated Pd nanoparticles having a diameter of approximately 1.7 nm are effective and general catalysts for coupling aryl halides to organostannanes (the Stille reaction) under mild conditions. The significant results of this study are that the Stille reaction is catalyzed by dendrimer-encapsulated Pd nanoparticles in very good yield, in aqueous solution at 23 degrees C, and using only 0.100 atom % of Pd as catalyst.

Journal Article↗

PubMed2005

Electrocatalytic O2 reduction at glassy carbon electrodes modified with dendrimer-encapsulated Pt nanoparticles.

Platinum dendrimer-encapsulated nanoparticles (DENs) were prepared within fourth-generation, hydroxyl-terminated, poly(amidoamine) dendrimers and immobilized on glassy carbon electrodes using an electrochemical coupling strategy. X-ray photoelectron spectroscopy, electron microscopy, and electrochemical experiments confirmed that the Pt DENs were about 1.4 nm in diameter and that they remained within the dendrimer following surface immobilization. The resulting Pt DEN films were electrocatalytically active for the oxygen reduction reaction. The films were also robust, surviving up to 50 consecutive cyclic voltammograms and sonication.

Journal Article↗

PubMed2005

Titania-supported PdAu bimetallic catalysts prepared from dendrimer-encapsulated nanoparticle precursors.

We report the synthesis, characterization, and catalytic activity of titania-supported bimetallic PdAu particles prepared using dendrimer-encapsulated nanoparticle (DEN) precursors. Single-particle energy-dispersive spectroscopy indicates a homogeneous distribution of bimetallic nanoparticles having compositions closely related to the metal-ion ratios used to prepare the DEN precursors. The catalytic activity of the supported PdAu catalysts was compared to that of supported Pd-only and Au-only catalysts; the enhanced CO oxidation activity of the PdAu catalysts is indicative of a synergetic bimetallic interaction.

Journal Article↗

PubMed2005

Synthesis, characterization, and structure-selective extraction of 1-3-nm diameter AuAg dendrimer-encapsulated bimetallic nanoparticles.

The synthesis and characterization of 1-3-nm diameter, structurally well-defined, bimetallic AuAg dendrimer-encapsulated nanoparticles (DENs) are reported. Three different bimetallic structures were examined: AuAg alloys synthesized by cocomplexation and subsequent reduction of dendrimer-encapsulated Au3+ and Ag+ and core/shell [Au](Ag) and [AuAg alloy](Ag) structures (for structured materials, brackets indicate the core metal and parentheses indicate the shell metal) synthesized by a sequential loading method. Depending on the shell metal and its oxidation state, the AuAg nanoparticles can be extracted from the dendrimer into an organic phase using different surfactants. This provides a means for analyzing the composition of the shell. UV-vis, TEM, and single-particle X-ray energy dispersive spectroscopy (EDS) were used to characterize the bimetallic DENs before and after extraction and show that the extraction step does not alter the size or composition of the bimetallic nanoparticles.

Journal Article↗

PubMed2005

Synthesis, characterization, and applications of dendrimer-encapsulated nanoparticles.

In this article we describe the synthesis, characterization, and applications of dendrimer-encapsulated nanoparticles (DENs). These materials are synthesized by a template approach in which metal ions are extracted into the interior of dendrimers and then subsequently chemically reduced to yield nearly size-monodisperse particles having dimensions of less than 3 nm. Monometallic, bimetallic (including 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 to stabilize the nanoparticle, makes it possible to tune solubility, and provides a means for immobilization of the nanoparticle on solid supports. These materials have a number of potential applications, but the focus here is on catalysis. Homogeneous catalytic reactions, including hydrogenations, Heck coupling, and Suzuki reactions, in water, organic solvents, biphasic fluorous/organic solvents, and liquid and supercritical CO2 are discussed. In many cases it is easy to recycle catalytic DENs. DENs can also be immobilized on supports, such as silica and titania, and used for heterogeneous catalysis. Bimetallic DENs are shown to have particularly interesting catalytic properties. In addition to a discussion of current progress in this field, a number of intriguing questions related to the properties and potential applications of these materials are examined.

Catalysis↗

PubMed2004

Extraction of Au nanoparticles having narrow size distributions from within dendrimer templates.

Here, we show that Au nanoparticles having diameters of less than 2.2 nm can be extracted from within the interior of PAMAM dendrimers using n-alkanethiol extractants. Extraction proceeds quickly, regardless of the size of the nanoparticle, the dendrimer generation, or the peripheral functionalization of the dendrimer. The extraction rate is fastest for the lowest generation dendrimers, the smallest nanoparticles, and the shortest chain-length n-alkanethiols. Other important results of this study include the following. First, within the accuracy of absorbance spectroscopy, the extraction yield is quantitative. Second, NMR and FT-IR spectroscopy indicate that after extraction the dendrimer remains in the aqueous phase and can be used to template additional metal particles. Third, the size and optical characteristics of the extracted nanoparticles are the same as the precursor dendrimer-encapsulated nanoparticles (DENs). Fourth, a 100-fold excess of n-alkanethiol molecules is required to prevent aggregation of DENs during extraction.

Journal Article↗

PubMed2004

Bimetallic palladium-gold dendrimer-encapsulated catalysts.

The synthesis, characterization, and catalytic properties of 1-3 nm-diameter bimetallic PdAu dendrimer-encapsulated catalysts are reported. Both alloy and core/shell PdAu nanoparticles were prepared. The catalytic hydrogenation of allyl alcohol was significantly enhanced in the presence of the alloy and core/shell PdAu nanoparticles as compared to mixtures of single-metal nanoparticles.

Journal Article↗

PubMed2004

Comparison of nanoparticle size and electrophoretic mobility measurements using a carbon-nanotube-based coulter counter, dynamic light scattering, transmission electron microscopy, and phase analysis light scattering.

The precision and accuracy of measurements of the diameter and electrophoretic mobility (mu) of polymeric nanoparticles is compared using four different analytical approaches: carbon-nanotube-based Coulter counting, dynamic light scattering (DLS), transmission electron microscopy (TEM), and phase analysis light scattering (PALS). Carbon-nanotube-based Coulter counters (CNCCs) use a 132 nm diameter channel to simultaneously determine the diameter (28-90 nm) and mu value for individual nanoparticles. These measurements are made without calibration of the CNCC and without labeling the sample. Moreover, because CNCCs measure the properties of individual particles, they provide true averages and polydispersities that are not convoluted into the intrinsic instrumental response function of the CNCC. CNCCs can be used to measure the size of individual nanoparticles dispersed in aqueous solutions, which contrasts with the TEM-measured size of individual dehydrated particles and the ensemble size averages of dispersed particles provided by DLS. CNCCs provide more precise values of mu than PALS.

Journal Article↗