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Biomedical subjects

G M Whitesides

Publications and source records attributed to G M Whitesides.

At least 19 recordsLinked to original sources

Electron exchange between two electrodes mediated by two electroactive adsorbates.

Experimental data for electron exchange between two electrodes covered by electroactive films are presented and discussed in terms of the Gerischer model. A model Hamiltonian is proposed for such indirect electron exchange involving two intermediate species. Explicit model calculations are performed for the case in which the coupling between the two adsorbates is weak and determines the overall rate. The calculations agree well with the experimental data, and can be used to determine the energy of reorganization associated with the electron transfer.

Journal Article↗

Fabrication of a configurable, single-use microfluidic device.

This paper describes microfluidic devices that contain connections that can be opened by the user after fabrication. The devices are fabricated in poly(dimethylsiloxane) (PDMS) and comprise disconnected fluidic channels that are separated by 20 microm of PDMS. Applying voltages above the breakdown voltage of PDMS (21 V/microm) opened pathways between disconnected channels. Fluids could then be pumped through the openings. The voltage used and the ionic strength of the buffer in the channels determined the size of the opening. Opening connections in a specific order provides the means to control complex reactions on the device. A device for ELISA was fabricated to demonstrate the ability to store and deliver fluids on demand.

Dimethylpolysiloxanes↗

Microfluidic arrays of fluid-fluid diffusional contacts as detection elements and combinatorial tools.

This paper describes microfluidic systems that can be used to investigate multiple chemical or biochemical interactions in a parallel format. These three-dimensional systems are generated by crossing two sets of microfluidic channels, fabricated in two different layers, at right angles. Solutions of the reagents are placed in the channels; in different modes of operation, these solutions can be either flowing or stationary-the latter is important when one set of channels is filled with viscous gels with immobilized reagents. At every crossing, the channels are separated either by a single membrane or by a composite separator comprising a membrane, a microwell, and a second membrane. These components allow diffusive mass transport and minimize convective transport through the crossing. Polycarbonate membranes with 0.1-1-microm vertical pores were used to fabricate the devices. Each crossing of parallel channels serves as an element in which chemical or biochemical interactions can take place; interactions can be detected by monitoring changes in fluorescence and absorbance. These all-organic systems are straightforward to fabricate and to operate and may find applications as portable microanalytical systems and as tools in combinatorial research.

Journal Article↗

Pressure-driven laminar flow in tangential microchannels: an elastomeric microfluidic switch.

This paper describes laminar fluid flow through a three-dimensional elastomeric microstructure formed by two microfluidic channels, fabricated in layers that contact one another face-to-face (typically at a 90 degree angle), with the fluid flows in tangential contact. There are two ways to control fluid flow through these tangentially connected microchannels. First, the flow profiles through the crossings are sensitive to the aspect ratio of the channels; the flow can be controlled by applying external pressure and changing this aspect ratio. Second, the flow direction of an individual laminar stream in multiphase laminar flow depends on the lateral position of the stream within the channel; this position can be controlled by injecting additional streams of fluid into the channel. We describe two microfluidic switches based on these two ways for controlling fluid flow through tangential microchannels and present theoretical arguments that explain the observed dependence of the flow profiles on the aspect ratio of the channels.

Journal Article↗

An integrated fluorescence detection system in poly(dimethylsiloxane) for microfluidic applications.

This paper describes a prototype of an integrated fluorescence detection system that uses a microavalanche photodiode (microAPD) as the photodetector for microfluidic devices fabricated in poly(dimethylsiloxane) (PDMS). The prototype device consisted of a reusable detection system and a disposable microfluidic system that was fabricated using rapid prototyping. The first step of the procedure was the fabrication of microfluidic channels in PDMS and the encapsulation of a multimode optical fiber (100-microm core diameter) in the PDMS; the tip of the fiber was placed next to the side wall of one of the channels. The optical fiber was used to couple light into the microchannel for the excitation of fluorescent analytes. The photodetector, a prototype solid-state microAPD array, was embedded in a thick slab (1 cm) of PDMS. A thin (80 microm) colored polycarbonate filter was placed on the top of the embedded microAPD to absorb scattered excitation light before it reached the detector. The microAPD was placed below the microchannel and orthogonal to the axis of the optical fiber. The close proximity (approximately 200 microm) of the microAPD to the microchannel made it unnecessary to incorporate transfer optics; the pixel size of the microAPD (30 microm) matched the dimensions of the channels (50 microm). A blue light-emitting diode was used for fluorescence excitation. The microAPD was operated in Geiger mode to detect the fluorescence. The detection limit of the prototype (approximately 25 nM) was determined by finding the minimum detectable concentration of a solution of fluorescein. The device was used to detect the separation of a mixture of proteins and small molecules by capillary electrophoresis; the separation illustrated the suitability of this integrated fluorescence detection system for bioanalytical applications.

Carbonic Anhydrases↗

Basicity of the amino groups of the aminoglycoside amikacin using capillary electrophoresis and coupled CE-MS-MS techniques.

This paper describes the use of capillary electrophoresis (CE), and coupled CE and mass spectrometric techniques, to measure the values of the pKa of the amino groups of the aminoglycoside antibiotic amikacin and of its acetylated derivatives. These values of pKa (8.4, 6.7, 9.7, 8.4) were determined by measuring the electrophoretic mobilities of the molecules as a function of pH; they are within 0.7 unit of certain values reported in the literature (by 13C and 15N NMR spectroscopies) but resolved ambiguities left by these earlier studies. The range of values of pKa of amino groups also indicates the complex dependence of the acidity of a functional group (and thus the extent of ionization at a specified value of pH) on the molecular environment of that group.

Acetylation↗

Self-assembly of 10-microm-sized objects into ordered three-dimensional arrays.

This paper describes the self-assembly of small objects--polyhedral metal plates with largest dimensions of 10 to 30 microm--into highly ordered, three-dimensional arrays. The plates were fabricated using photolithography and electrodeposition techniques, and the faces of the plates were functionalized to be hydrophobic or hydrophilic using self-assembled monolayers (SAMs). Self-assembly occurs in water through capillary interactions between thin films of a hydrophobic liquid (a liquid prepolymer adhesive) coated onto the hydrophobic faces of the plates; coalescence of the adhesive films reduces the interfacial free energy of the system and drives self-assembly. By altering the size and surface-patterning of the plates, the external morphologies of the aggregates were varied. Curing the adhesive furnished mechanically stable aggregates that were characterized by scanning electron microscopy (SEM). For assemblies formed by plates partially composed of a sacrificial material, a subsequent etching step furnished fully open, three-dimensional microstructures. This work validates the use of capillary interactions for three-dimensional mesoscale self-assembly in the 10-microm-size regime and opens new avenues for the fabrication of complex, three-dimensional microscructures.

Electroplating↗

Dynamic, self-assembled aggregates of magnetized, millimeter-sized objects rotating at the liquid-air interface: macroscopic, two-dimensional classical artificial atoms and molecules.

This paper describes self-assembly of millimeter-sized, magnetized disks floating on a liquid-air interface, and rotating under the influence of a rotating external magnetic field. Spinning of the disks results in hydrodynamic repulsion between them, while the rotating magnetic field produces an average confining potential acting on all disks. The interplay between hydrodynamic and magnetic interactions leads to the formation of patterns. Theoretical analysis of hydrodynamic and magnetic forces indicates that the interactions in this system are similar to those acting in systems of finite numbers of particles behaving classically ("classical artificial atoms"). Macroscopic artificial atoms and molecules are described, and the rules governing their morphologies outlined.

Journal Article↗

Electron transport through thin organic films in metal--insulator--metal junctions based on self-assembled monolayers.

This paper describes an experimentally simple system for measuring rates of electron transport across organic thin films having a range of molecular structures. The system uses a metal--insulator--metal junction based on self-assembled monolayers (SAMs); it is particularly easy to assemble. The junction consists of a SAM supported on a silver film (Ag-SAM(1)) in contact with a second SAM supported on the surface of a drop of mercury (Hg-SAM(2))--that is, a Ag-SAM(1)SAM(2)-Hg junction. SAM(1) and SAM(2) can be derived from the same or different thiols. The current that flowed across junctions with SAMs of aliphatic thiols or aromatic thiols on Ag and a SAM of hexadecane thiol on Hg depended both on the molecular structure and on the thickness of the SAM on Ag: the current density at a bias of 0.5 V ranged from 2 x 10(-10) A/cm(2) for HS(CH(2))(15)CH(3) on Ag to 1 x 10(-6) A/cm(2) for HS(CH(2))(7)CH(3) on Ag, and from 3 x 10(-6) A/cm(2) for HS(Ph)(3)H (Ph = 1,4-C(6)H(4)) on Ag to 7 x 10(-4) A/cm(2) for HSPhH on Ag. The current density increased roughly linearly with the area of contact between SAM(1) and SAM(2), and it was not different between Ag films that were 100 or 200 nm thick. The current--voltage curves were symmetrical around V = 0. The current density decreased with increasing distance between the electrodes according to the relation I = I(0)e(-beta d(Ag,Hg)), where d(Ag,Hg) is the distance between the electrodes, and beta is the structure-dependent attenuation factor for the molecules making up SAM(1). At an applied potential of 0.5 V, beta was 0.87 +/- 0.1 A(-1) for alkanethiols, 0.61 +/- 0.1 A(-1) for oligophenylene thiols, and 0.67 +/- 0.1 A(-1) for benzylic derivatives of oligophenylene thiols. The values of beta did not depend significantly on applied potential over the range of 0.1 to 1 V. These junctions provide a test bed with which to screen the intrinsic electrical properties of SAMs made up of molecules with different structures; information obtained using these junctions will be useful in correlating molecular structure and rates of electron transport.

Electrons↗

Using three-dimensional microfluidic networks for solving computationally hard problems.

This paper describes the design of a parallel algorithm that uses moving fluids in a three-dimensional microfluidic system to solve a nondeterministically polynomial complete problem (the maximal clique problem) in polynomial time. This algorithm relies on (i) parallel fabrication of the microfluidic system, (ii) parallel searching of all potential solutions by using fluid flow, and (iii) parallel optical readout of all solutions. This algorithm was implemented to solve the maximal clique problem for a simple graph with six vertices. The successful implementation of this algorithm to compute solutions for small-size graphs with fluids in microchannels is not useful, per se, but does suggest broader application for microfluidics in computation and control.

Algorithms↗

Submicrometer patterning of charge in thin-film electrets.

Thin-film electrets have been patterned with trapped charge with submicrometer resolution using a flexible, electrically conductive electrode. A poly(dimethylsiloxane) stamp, patterned in bas-relief and supporting an 80-nanometer-thick gold film, is brought into contact with an 80-nanometer-thick film of poly(methylmethacrylate) supported on n-doped silicon. A voltage pulse between the gold film and the silicon transfers charge at the contact areas between the gold and the polymer electret. Areas as large as 1 square centimeter were patterned with trapped charges at a resolution better than 150 nanometers in less than 20 seconds. This process provides a new method for patterning; it suggests possible methods for high-density, charge-based data storage and for high-resolution charge-based printing.

Journal Article↗

A structurally biased combinatorial approach for discovering new anti-picornaviral compounds.

BACKGROUND: Picornaviruses comprise a family of small, non-enveloped RNA viruses. A common feature amongst many picornaviruses is a hydrophobic pocket in the core of VP1, one of the viral capsid proteins. The pocket is normally occupied by a mixture of unidentified, fatty acid-like moieties, which can be competed out by a family of capsid-binding, antiviral compounds. Many members of the Picornaviridae family are pathogenic to both humans and livestock, yet no adequate therapeutics exist despite over a decade's worth of research in the field. To address this challenge, we developed a strategy for rapid identification of capsid-binding anti-picornaviral ligands. The approach we took involved synthesizing structurally biased combinatorial libraries that had been targeted to the VP1 pocket of poliovirus and rhinovirus. The libraries are screened for candidate ligands with a high throughput mass spectrometry assay. RESULTS: Using the mass spectrometry assay, we were able to identify eight compounds from a targeted library of 75 compounds. The antiviral activity of these candidates was assessed by (i) measuring the effect on the kinetics of viral uncoating and (ii) the protective effect of each drug in traditional cell-based assays. All eight of the candidates exhibited antiviral activity, but three of them were particularly effective against poliovirus and rhinovirus. CONCLUSIONS: The results illustrate the utility of combining structure-based design with combinatorial chemistry. The success of our approach suggests that assessment of small, targeted libraries, which query specific chemical properties, may be the best strategy for surveying all of chemical space for ideal anti-picornaviral compounds.

Animals↗

Molecule-mimetic chemistry and mesoscale self-assembly.

Molecules are structured aggregates of atoms joined by chemical bonds; crystals are aggregates of molecules, interacting covalently or noncovalently. The work described in this Account uses molecules, crystals, and other forms of atomic/molecular matter to suggest principles that can be used in generating structured aggregates of millimeter-scale components, interacting through capillary interactions. The properties of these aggregates--that is, their "chemistry"--mimic aspects of the chemistry of molecules.

Crystallization↗

Designing a polyvalent inhibitor of anthrax toxin.

Screening peptide libraries is a proven strategy for identifying inhibitors of protein-ligand interactions. Compounds identified in these screens often bind to their targets with low affinities. When the target protein is present at a high density on the surface of cells or other biological surfaces, it is sometimes possible to increase the biological activity of a weakly binding ligand by presenting multiple copies of it on the same molecule. We isolated a peptide from a phage display library that binds weakly to the heptameric cell-binding subunit of anthrax toxin and prevents the interaction between cell-binding and enzymatic moieties. A molecule consisting of multiple copies of this nonnatural peptide, covalently linked to a flexible backbone, prevented assembly of the toxin complex in vitro and blocked toxin action in an animal model. This result demonstrates that protein-protein interactions can be inhibited by a synthetic, polymeric, polyvalent inhibitor in vivo.

Acrylic Resins↗