Showing papers by "George M. Whitesides published in 2001"

Soft Lithography in Biology and Biochemistry

Abstract: ▪ Abstract Soft lithography, a set of techniques for microfabrication, is based on printing and molding using elastomeric stamps with the patterns of interest in bas-relief. As a technique for fabricating microstructures for biological applications, soft lithography overcomes many of the shortcomings of photolithography. In particular, soft lithography offers the ability to control the molecular structure of surfaces and to pattern the complex molecules relevant to biology, to fabricate channel structures appropriate for microfluidics, and to pattern and manipulate cells. For the relatively large feature sizes used in biology (≥50 μm), production of prototype patterns and structures is convenient, inexpensive, and rapid. Self-assembled monolayers of alkanethiolates on gold are particularly easy to pattern by soft lithography, and they provide exquisite control over surface biochemistry.

A Survey of Structure−Property Relationships of Surfaces that Resist the Adsorption of Protein

Abstract: This paper describes the use of surface plasmon resonance (SPR) spectroscopy and self-assembled monolayers (SAMs) to determine the characteristics of functional groups that give surfaces the ability to resist the nonspecific adsorption of proteins from solution. Mixed SAMs presenting different functional groups were prepared for screening using a synthetic protocol based on the reaction of organic amines with a SAM terminated by interchain carboxylic anhydride groups. Surfaces that presented derivatives of oligo(sarcosine), N-acetylpiperazine, and permethylated sorbitol groups were particularly effective in resisting the adsorption of proteins. Incorporation of these groups into single-component SAMs resulted in surfaces that are comparable to (but slightly less good than) single-component SAMs that present oligo(ethylene glycol) in their ability to resist the adsorption of proteins. In the group of surfaces examined, those that resisted the adsorption of proteins had the following properties: they were ...

Generation of Gradients Having Complex Shapes Using Microfluidic Networks

Abstract: This paper describes the generation of gradients having complex shapes in solution using microfluidic networks. Flowing multiple streams of fluid each carrying different concentrations of substances laminarly and side-by-side generated step concentration gradients perpendicular to the direction of the flow. Appropriately designed networks of microchannels for controlled diffusive mixing of substances generated a range of shapes for the gradients, including linear, parabolic, and periodic. The lateral dimensions of the gradients ranged from 900 to 2200 μm. This paper also demonstrates the generation of overlapping gradients composed of different species. Since solutions in the microfluidic network exist as steady states and are continuously renewed, the gradients established in the capillaries are spatially and temporally constant and can be maintained easily for periods of hours. Using laminar flow to generate gradients should be useful in both biological and nonbiological research.

Zwitterionic SAMs that Resist Nonspecific Adsorption of Protein from Aqueous Buffer

Abstract: This paper describes the use of surface plasmon resonance spectroscopy and self-assembled monolayers (SAMs) of alkanethiols on gold to evaluate the ability of surfaces terminating in different combinations of charged groups to resist the nonspecific adsorption of proteins from aqueous buffer. Mixed SAMs formed from a 1:1 combination of a thiol terminated in a trimethylammonium group and a thiol terminated in a sulfonate group adsorbed less than 1% of a monolayer of two proteins with different characteristics: fibrinogen and lysozyme. Single-component SAMs formed from thiols terminating in groups combining a positively charged moiety and a negatively charged moiety were also capable of resisting the adsorption of proteins. Single-component SAMs presenting single charges adsorbed nearly a full monolayer of protein. The amount of protein that adsorbed to mixed zwitterionic SAMs did not depend on the ionic strength or the pH of the buffer in which the protein was dissolved. The amount of protein that adsorbe...

Flexible Methods for Microfluidics

Abstract: Devices for handling nanoliter quantities of fluids are creating new fabrication challenges and finding new applications in biology, chemistry, and materials science.

Self-assembled monolayers that resist the adsorption of proteins and the adhesion of bacterial and mammalian cells

Abstract: This paper examines the hypothesis that surfaces resistant to protein adsorption should also be resistant to the adhesion of bacteria (Staphylococcus aureus, Staphylococcus epidermidis) and the attachment and spreading of mammalian cells (bovine capillary endothelial (BCE) cells). The surfaces tested were those of self-assembled monolayers (SAMs) terminated with derivatives of tri(sarcosine) (Sarc), N-acetylpiperazine, permethylated sorbitol, hexamethylphosphoramide, phosphoryl choline, and an intramolecular zwitterion (−CH2N+(CH3)2CH2CH2CH2SO3-) (ZW); all are known to resist the adsorption of proteins. There seems to be little or no correlation between the adsorption of protein (fibrinogen and lysozyme) and the adhesion of cells. Surfaces terminated with derivatives of Sarc and N-acetylpiperazine resisted the adhesion of S. aureus and S. epidermidis as well as did surfaces terminated with tri(ethylene glycol). A surface that presented Sarc groups was the only one that resisted the adhesion of BCE cells a...

Electron Transport through Thin Organic Films in Metal−Insulator−Metal Junctions Based on Self-Assembled Monolayers

Abstract: 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 × 10-10 A/cm2 for HS(CH2)15CH3 on Ag to 1 × 10-6 A/cm2 for HS(CH2)7CH3 on Ag, and from 3 × 10-6 A/cm2 for HS(Ph)3H (Ph = 1,4-C6H4) on Ag to 7 × 10-4 A/cm2 for HSPhH on Ag. The current density increase...

Subcellular positioning of small molecules.

Abstract: Localized perturbation of processes that take place inside the living cell depends on molecular and spatial discrimination on a micrometre scale Here we report the use of multiple laminar streams in a microfluidic channel to deliver membrane-permeable molecules to selected subcellular microdomains This technique opens up avenues for non-invasively visualizing, probing and manipulating the cellular metabolic and structural machinery

An Integrated Fluorescence Detection System in Poly(dimethylsiloxane) for Microfluidic Applications

Abstract: This paper describes a prototype of an integrated fluorescence detection system that uses a microavalanche photodiode (μAPD) 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-μm 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 μAPD array, was embedded in a thick slab (1 cm) of PDMS. A thin (80 μm) colored polycarbonate filter was placed on the top of the embedded μAPD to absorb scattered excitation light before it reached the detector. The μAPD was placed below the microchannel an...

Submicrometer patterning of charge in thin-film electrets.

Abstract: 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.

Polymeric Thin Films That Resist the Adsorption of Proteins and the Adhesion of Bacteria

Abstract: This paper describes the design and preparation of thin polymeric films that resist the adsorption of proteins and the adhesion of bacteria to an extent comparable to, or better than, self-assembled monolayers (SAMs) that present tri(ethylene glycol) groups. These polymeric films were prepared by the reaction of a polyamine, for example, poly(ethylenimine), with a SAM that presented interchain carboxylic anhydride groups, and by the subsequent conversion of the amino groups of the polymer to amido groups on reaction with acyl chlorides. Polyamines functionalized with acetyl chloride produced films that resisted the adsorption of protein and the adhesion of bacteria to a useful extent. Functionalization of the polyamine with acyl chlorides that were derivatives of oligo(ethylene glycol) resulted in films that were 1−10 times more resistant than those obtained by acetylation. The removal of hydrogen bond donor groups from the surface of the polyamines upon acylation seems to be important for the generation ...

Method of forming articles including waveguides via capillary micromolding and microtransfer molding

Abstract: Chemically or biochemically active agents or other species are patterned on a substrate surface by providing a micromold having a contoured surface and forming, on a substrate surface, a chemically or biochemically active agent or fluid precursor of a structure. A chemically or biochemically active agent or fluid precursor also can be transferred from indentations in an applicator to a substrate surface. The substrate surface can be planar or non-planar. Fluid precursors of polymeric structures, inorganic ceramics and salts, and the like can be used to form patterned polymeric articles, inorganic salts and ceramics, reactive ion etch masks, etc. at the surface. The articles can be formed in a pattern including a portion having a lateral dimension of less than about 1 millimeter or smaller. The indentation pattern of the applicator can be used to transfer separate, distinct chemically or biochemically active agents or fluid precursors to separate, isolated regions of a substrate surface. Waveguide arrays, combinatorial chemical or biochemical libraries, etc. can be made. Differences in refractive index of waveguide and cladding can be created by subjecting the waveguide and cladding, made of identical prepolymeric material, to different polymerization or cross-linking conditions. Interferometers are defined by coupling arrays of waveguides, where coupling can be controlled by altering the difference in refractive index between cladding and waveguide at any desired location of the array. Alteration and refractive index can be created photochemically, chemically, or the like. Sensors also are disclosed, including biochemical sensors.

Designing a polyvalent inhibitor of anthrax toxin

Abstract: 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. Anthrax toxin is produced by Bacillus anthracis, the causative agent of anthrax, and is responsible for the major symptoms of the disease 1 . Clinical anthrax is rare, but there is growing concern over the potential use of B. anthracis in biological warfare and terrorism. Although a vaccine against anthrax exists, various factors make mass vaccination impractical. The bacteria can be eradicated from the host by treatment with antibiotics, but because of the continuing action of the toxin, such therapy is of little value once symptoms have become evident. Thus, a specific inhibitor of the toxin’s action might prove a valuable adjunct to antibiotic therapy. The toxin consists of a single receptor-binding moiety, termed protective antigen (PA), and two enzymatic moieties, termed edema factor (EF) and lethal factor (LF) 2

Microfluidic systems including three-dimensionally arrayed channel networks

Abstract: The present invention provides, in certain embodiments, improved microfluidic systems and methods for fabricating improved microfluidic systems, which contain one or more levels of microfluidic channels. The inventive methods can provide a convenient route to topologically complex and improved microfluidic systems. The microfluidic systems provided according to the invention can include three-dimensionally arrayed networks of fluid flow paths therein including channels that cross over or under other channels of the network without physical intersection at the points of cross over. The microfluidic networks of the invention can be fabricated via replica molding processes, also provided by the invention, utilizing mold masters including surfaces having topological features formed by photolithography. The microfluidic networks of the invention are, in some cases, comprised of a single replica molded layer, and, in other cases, are comprised of two, three, or more replica molded layers that have been assembled to form the overall microfluidic network structure. The present invention also describes various novel applications for using the microfluidic network structures provided by the invention.

Selective Deposition of Proteins and Cells in Arrays of Microwells

Abstract: This paper describes a method for depositing proteins and cells selectively into microwells fabricated in poly(dimethylsiloxane)an elastomeric organic polymer. The arrays of microwells were generated using soft lithography. The surface between the wells was coated with bovine serum albumin, and the surface within the wells was coated with fibronectin (FN)an adhesive extracellular matrix protein. Fluorescence staining of FN using antibodies indicated that the protein had adsorbed to the wells selectively. Exposure of the FN-coated wells to a suspension of bovine capillary endothelial cells resulted in attachment and spreading of the cells only in the wells. This method for patterning cells was demonstrated with wells of several diameters (≤100 μm) and depths (≤50 μm). It should be useful for (i) the development of sensors based on arrays of cells, (ii) screening combinatorial libraries of ligands on cells, and (iii) testing the effect on cells of compounds and samples relevant to problems in environmental ...

Molecule-Mimetic Chemistry and Mesoscale Self-Assembly

Abstract: 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 aggregatesthat is, their “chemistry”mimic aspects of the chemistry of molecules.

Manipulation of magnetic microbeads in suspension using micromagnetic systems fabricated with soft lithography

Abstract: Current-carrying microcircuits can generate strong magnetic-field gradients; these gradients, in turn, can control the position of magnetic microbeads in aqueous suspension. Micromagnetic systems were prepared using two representative soft lithography techniques—micromolding in capillaries and microtransfer molding—combined with electrodeposition. They can capture microbeads from solution, hold them in a fixed position, and move them along complex paths. Simply changing the current flowing in the systems can dynamically reconfigure the paths. The manipulation of magnetic microbeads using microfabricated circuits should expand current sample handling capabilities for biotechnology and combinational technology with or without the presence of net fluid flow and microfluidic channels.

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

Abstract: This paper describes the self-assembly of small objectspolyhedral metal plates with largest dimensions of 10 to 30 μminto 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 ful...

Topographical Micropatterning of Poly(dimethylsiloxane) Using Laminar Flows of Liquids in Capillaries

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Patterning of surfaces utilizing microfluidic stamps including three-dimensionally arrayed channel networks

Abstract: The present invention describes improved microfluidic systems and procedures for fabricating improved microfluidic systems, which contain one or more levels of microfluidic channels. The methods for fabrication the systems disclosed can provide a convenient route to topologically complex and improved microfluidic systems. The microfluidic systems can include three-dimensionally arrayed networks of fluid flow paths therein including channels that cross over or under other channels of the network without physical intersection at the points of cross over. The microfluidic networks can be fabricated via replica molding processes utilizing mold masters including surfaces having topological features formed by photolithography. The present invention also involves microfluidic systems and methods for fabricating complex patterns of materials, such as biological materials and cells, on surfaces utilizing the microfluidic systems. Specifically, the invention provides microfluidic surface patterning systems and methods for fabricating complex, discontinuous patterns on surfaces that can incorporate or deposit multiple materials onto the surfaces. The present invention also provides improved microfluidic stamps or applicators for microcontact surface patterning, which are able to pattern onto a surface arbitrary two-dimensional patterns, and which are able to pattern multiple substances onto a surface without the need for multiple steps of registration or stamping during patterning and without the need to selectively 'ink' different regions of the stamp with different materials.

Patterning Porous Oxides within Microchannel Networks

Abstract: A continuing challenge for materials chemists and engineers is the ability to create multifunctional composite structures with well-defined superimposed structural order from nanometer to micrometer length scales. Materials with three-dimensional structures ordered over multiple length scales can be prepared by carrying out colloidal crystallization and inorganic/organic cooperative self-assembly within microchannel networks. The resulting materials show hierarchical ordering over several discrete and tunable length scales ranging from several nanometers to micrometers. These patterned porous materials hold promise for use as advanced catalysts, sensors, low-k dielectrics, optoelectronic and integrated photonic crystal devices.

Microscope Projection Photolithography for Rapid Prototyping of Masters with Micron-Scale Features for Use in Soft Lithography

Abstract: This paper demonstrates the application of projection photolithography, using a standard commercial microscope, for the generation of masters for soft lithography. The procedure is rapid and convenient and produces features smaller in size (as small as 0.6 μm) than those available from other methods of rapid prototyping, albeit over a limited area (∼4 × 104 μm2 per exposure). A transparency photomask (prepared using high-resolution printing) is inserted into the light path of the microscope and projected through the microscope objective onto a photoresist-coated substrate. Features on the order of 1 μm can be produced routinely over the area of sharp focus (a circle of radius r ≅ 100 μm with a 100× objective) by this method without modification or precise calibration of the microscope. The microscope platform also provides two other useful functions, both characteristic of commercial steppers: step-and-repeat exposures and pattern alignment. The developed photoresist is used as a master for the fabricati...

Correlating Electron Transport and Molecular Structure in Organic Thin Films

Abstract: A convenient experimental system is described, with which electron transport through structurally well-defined, 2–5 nm-thick, organic films can be examined. Two types of junction J have been studied in which self-assembled monolayers (SAMs, for example, SAM(1) formed on Ag from aliphatic and aromatic thiols, and SAM(2), formed on Hg from hexadecanethiol) are in contact through either van der Waals interactions (see picture) or through covalent, hydrogen, or ionic bonds.

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

Abstract: 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 stationarythe 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-μm 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 b...

Fabrication of arrays of two-dimensional micropatterns using microspheres as lenses for projection photolithography

Abstract: This letter demonstrates the use of an array of transparent microspheres in forming repetitive, micrometer-scale patterns in photoresist, starting from masks with centimeter-scale patterns. A transparent microsphere with diameter d>1.5 μm acts as a lens and reduces centimeter-scale images into micrometer-scale images on its image plane. A planar array of microspheres projects the image of an illuminated mask onto a corresponding array of micropatterns on their common image plane. We have prepared arrays of polystyrene microspheres (d=1.5–10 μm) embedded in a transparent membrane to generate repetitive patterns in photoresist, and have transferred the resulting patterns into metal films by liftoff. The optical system of this technique is related to that used in conventional projection photolithography, but differs in that the lens that accomplishes size reduction is positioned within 10 μm of the photoresist. The microspheres generate uniform patterns over an area of ∼2 cm2, using a mask with area ∼25×25 c...

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

Abstract: 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 degrees 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.

Self-Assembly of Microscale Objects at a Liquid/Liquid Interface through Lateral Capillary Forces

Abstract: Small (100−600 μm in width) hexagonal polymeric plates with faces patterned into hydrophobic and hydrophilic regions, and interacting through lateral capillary forces, were allowed to self-assemble at the perfluorodecalin/water interface. These plates were fabricated from photoresist and patterned by shadow evaporation of gold onto selected faces. The arrays that assembled from the 100 μm objects were similar in structure to those that assembled from millimeter-sized objects with analogous patterns of hydrophobic and hydrophilic faces, but with three important differences. (i) The contribution of buoyancy forces in establishing the level at which the 100 μm objects floated relative to the interface was small compared to the contribution of the vertical capillary forces. (ii) As a result, the designs of hydrophobic edges necessary to generate menisci useful in self-assembly were different for 100 μm objects than for millimeter-sized objects. (iii) The arrays that formed from the 100 μm objects had higher d...