Micro-contact printing of poly(3-hexylthiophene) on silicon oxide: Effect of stamp stretching

Micro-contact printing (μCP) has been applied to deposit poly(3-hexylthiophene) (P3HT) layer onto silicon oxide substrate from a polydimethylsiloxane (PDMS) stamp. The effect of the stamp stretching onto the corresponding printed P3HT layer has been analysed both from morphological (AFM) and from structural (XRD) points of view. Results show an orienting effect of the stretching towards the P3HT ultimate morphological units (i.e. fibrils) along the stretching direction. The influence of other variables involved in the deposition (substrate polarity/apolarity, mechanical pressure onto the stamp) have been studied and reported.     

Covalent microcontact printing of proteins for cell patterning

We describe a straightforward approach to the covalent immobilization of cytophilic proteins by microcontact printing, which can be used to pattern cells on substrates. Cytophilic proteins are printed in micropatterns on reactive self-assembled monolayers by using imine chemistry. An aldehyde-terminated monolayer on glass or on gold was obtained by the reaction between an amino-terminated monolayer and terephthaldialdehyde. The aldehyde monolayer was employed as a substrate for the direct microcontact printing of bioengineered, collagen-like proteins by using an oxidized poly(dimethylsiloxane) (PDMS) stamp. After immobilization of the proteins into adhesive "islands", the remaining areas were blocked with amino-poly(ethylene glycol), which forms a layer that is resistant to cell adhesion. Human malignant carcinoma (HeLa) cells were seeded and incubated onto the patterned substrate. It was found that these cells adhere to and spread selectively on the protein islands, and avoid the poly(ethylene glycol) (PEG) zones. These findings illustrate the importance of microcontact printing as a method for positioning proteins at surfaces and demonstrate the scope of controlled surface chemistry to direct cell adhesion.     

Dendrimer-mediated transfer printing of DNA and RNA microarrays

This paper describes a new method to replicate DNA and RNA microarrays. The technique, which facilitates positioning of DNA and RNA with submicron edge resolution by microcontact printing (muCP), is based on the modification of poly(dimethylsiloxane) (PDMS) stamps with dendrimers ("dendri-stamps"). The modification of PDMS stamps with generation 5 poly(propylene imine) dendrimers (G5-PPI) gives a high density of positive charge on the stamp surface that can attract negatively charged oligonucleotides in a "layer-by-layer" arrangement. DNA as well as RNA is transfer printed from the stamp to a target surface. Imine chemistry is applied to immobilize amino-modified DNA and RNA molecules to an aldehyde-terminated substrate. The labile imine bond is reduced to a stable secondary amine bond, forming a robust connection between the polynucleotide strand and the solid support. Microcontact printed oligonucleotides are distributed homogeneously within the patterned area and available for hybridization. By using a robotic spotting system, an array of hundreds of oligonucleotide spots is deposited on the surface of a flat, dendrimer-modified stamp that is subsequently used for repeated replication of the entire microarray by microcontact printing. The printed microarrays are characterized by homogeneous probe density and regular spot morphology.     

Microcontact printed antibodies on gold surfaces: function, uniformity, and silicone contamination

The function of microcontact printed protein was investigated using surface plasmon resonance (SPR) imaging, X-ray photoelectron spectroscopy spectroscopy (XPS), and XPS imaging. We chose to analyze a model protein system, the binding of an antibody from solution to a microcontact printed protein antigen immobilized to a gold surface. SPR imaging experiments indicated that the microcontact printed protein antigen was less homogeneous, had increased nonspecific binding, and bound less antibody than substrates to which the protein antigen had been physically adsorbed. SPR images of substrates contacted with a poly(dimethylsiloxane) stamp inked with buffer alone (i.e., no protein) revealed that significant amounts of silicone oligomer were transferred to the surface. The transfer of the silicone oligomer was not homogeneous, and the oligomer nonspecifically bound protein (BSA and IgG) from solution. XPS spectroscopy and imaging were used to quantify the amount of silicon (due to the presence of silicone oligomer), as well as the amounts of other elements, transferred to the surface. The results suggest that the silicone oligomer introduced by the printing process reduces the overall binding capacity of the microcontact-printed protein compared to physically adsorbed protein.     

A method of printing uniform protein lines by using flat PDMS stamps

In this paper, we report a method of printing uniform protein lines on glass slides by using UV-treated flat PDMS stamps. Unlike traditional microcontact printing (μCP) which requires microstructured PDMS stamps, this μCP method only requires a flat PDMS stamp, an UV lamp and a number of straight needles. Our results show that lines of bovine serum albumin (BSA), immunoglobin (IgG), anti-biotin, anti-human IgG and anti-mouse IgG can be printed evenly on glass slides by using this μCP method. We also demonstrate that the printed protein lines are suitable for applications such as microfluidic immunoassays.     

Click chemistry by microcontact printing on self-assembled monolayers: a structure-reactivity study by fluorescence microscopy

Microcontact printing (μCP) has developed into a powerful tool to functionalize surfaces with patterned molecular monolayers. μCP can also be used to induce a chemical reaction between a molecular ink and a self-assembled monolayer (SAM) in the nanoscale confinement between stamp and substrate. In this paper, we investigate the Huisgen 1,3-dipolar cycloaddition, the Diels-Alder cycloaddition and the thiol-ene/yne reaction induced by μCP. A range of fluorescent alkyne inks were printed on azide SAMs and fluorescence microscopy was used to monitor the extent of the 1,3-dipolar cycloaddition on a glass substrate. The rate of cycloaddition depends on the reactivity of the alkyne and on the presence of Cu(I). The cycloaddition is accelerated by Cu(I) but it also proceeds readily in the absence of Cu(I). In addition, a range of fluorescent diene inks were printed on alkene SAMs on glass. In this case, fluorescence microscopy was used to monitor the rate of the Diels-Alder cycloaddition as well as its retro-reaction. Finally, fluorescent thiol inks were printed on alkene SAMs on glass, and fluorescent alkenes and alkynes were printed on thiol SAMs. It is shown that reactions by μCP follow structure-reactivity relationships similar to solution reactions. Under optimized conditions all reactions lead to dense microarrays of addition products within minutes of printing time.     

Microfabrication using elastomeric stamp deformation

Elastomeric stamp deformation has been utilized for the contact printing (CP) of self-assembled monolayers (SAMs) and, more recently, polymers and proteins. Here, we take advantage of this well-studied phenomenon to fabricate a series of new metal thin-film patterns not present on the original stamp. The rounded patterns are of nanoscale thickness, long-range order, and are created from elastomeric stamps with only straight-edged features. The metal was printed onto the surface of an alpha,omega-alkanedithiol self-assembled monolayer (SAM). The new shapes are controlled by a combination of stamp geometry design and the application of external pressure. Previously published rules on stamp deformation for contact printing of SAMs are invalid because the coating is instead a thin-metal film. This method represents a new pathway to micropatterning metal thin films, leading to shapes with higher complexity than the original lithographic masters.     

Transferring complementary target DNA from aqueous solutions onto solid surfaces by using affinity microcontact printing

In this paper, we report a method of transferring complementary target DNA from an aqueous solution onto a solid surface by using affinity microcontact printing. In this approach, the probe DNA is first immobilized on the surface of an aminated poly(dimethylsiloxane) (PDMS) stamp. After a complementary target DNA hybridizes with the probe DNA on the stamp surface, the PDMS stamp is printed on an aminated glass slide. By using fluorescent microscopy, we show that only complementary target DNA, but not noncomplementary DNA, can be captured onto the surface of the stamp and then transferred to the aminated glass slide. The transfer of DNA can be attributed to the stronger electrostatic attraction between DNA and amine groups compared to the hydrogen bonds between the hybridized DNA molecules. We also investigate several factors that may influence the transfer of DNA, such as the surface density of amine groups, hybridization conditions, and contamination from unreacted PDMS monomers.     

Microcontact printing of Alzheimer’s β-amyloid monomers and fibrils

Adsorption of the 40-residue Alzheimer’s β-amyloid peptide (Aβ40) on a hydrophobic surface leads to formation of potentially disease-relevant aggregates. Existing techniques are limited in characterizing the adsorbed Aβ40 and producing potentially useful Aβ40 microstructures such as microarrays and microparticles. In this paper, a novel approach based on microcontact printing (μCP) to studying and utilizing adsorption of Aβ40 monomers and fibril fragments on hydrophobic surface of polydimethylsiloxane (PDMS) stamps has been developed. By transferring the adsorbed layer from the stamp to a glass substrate, this approach allows easy measurement of thickness of the adsorbed layer. It also enables characterization of the face of the adsorbed layer in contact with the stamp surface. This face exhibits significant higher thioflavin T fluorescence than the face exposed to water, suggesting β-sheet formation induced by the PDMS surface. The intrinsic stability of the adsorbed layer is evaluated by printing the layer on a water-soluble substrate and exposing it to water vapor or water. Stable particulate microstructures in water are obtained by chemically crosslinking the adsorbed peptides. Moreover, co-micropatterning of the different states of Aβ40 (monomers and fibril fragments) is demonstrated. This μCP-based approach is simple, versatile, and holds potential for various applications.     

Ink dependence of poly(dimethylsiloxane) contamination in microcontact printing

Poly(dimethylsiloxane) (PDMS) is the most widely used stamp material in microcontact printing. It has excellent properties with respect to versatility, chemical inertness, and mechanical stability. However, it has an inclination to contaminate printed substrates with low molecular weight siloxane fragments. In this study, it is shown, by a combination of lateral force microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy, that the extent of the PDMS-induced contamination is dependent on the nature of the ink used. The highest degree of contamination was found for relatively polar inks, whereas apolar alkanethiol inks were found to shield the substrate from contamination. This is interpreted in terms of the contaminating species being polar in nature.     

Structural characterization of microcontact printed arrays of hexa(ethylene glycol)-terminated alkanethiols on gold

This paper reports on the structural characteristics of microcontact printed oligo(ethylene glycol)-terminated alkanethiol layers, HS(CH2)15CONH-(CH2CH2O)6-H (hereafter EG6), on gold. Microwetting, contact angle goniometry, imaging null ellipsometry, and infrared reflection-absorption spectroscopy (IRAS) are used to characterize the printed EG6 layers, and the quality of these layers in terms of layer thickness and the crystallinity of the alkyl and ethylene glycol portions is compared with data obtained from analogous layers prepared by solution self-assembly. The outcome of the printing process is critically dependent on the experimental parameters used to prepare the patterns. It is found that high quality layers, consisting of densely packed all-trans alkyl chains terminated with relatively helical hexa(ethylene glycol) tails, are formed by inking the poly(dimethylsiloxane) (PDMS) stamp with a 1 mM EG6 solution and contacting it with gold for 15 min. The homogeneity of printed layers is not as good as the homogeneity of those prepared from solution under similar conditions, most likely because of simultaneous transfer of low molecular weight residues from the PDMS stamp. These residues, however, can be easily removed upon ultrasonication in ethanol without affecting the quality of the printed layer. Further on, the microscopic square-shaped bare gold patterns formed after microcontact printing (muCP) are subsequently filled with 16-hexadecanoic acid (hereafter THA) or HS(CH2)15CONH-(CH2CH2O)6-COOH (hereafter EG6COOH) to provide a microarray platform for further covalent attachment of biomolecules. Well-defined structures in terms of wettability contrast, sharpness, and height differences between the printed and back-filled areas are confirmed by imaging null ellipsometry and microscopic wetting.     

High-speed microcontact printing

We have demonstrated microcontact printing (muCP) of self-assembled monolayers in the millisecond regime. The contact formation and separation of the stamp and substrate was studied with high-speed video recordings. Using high ink concentrations and contact times as short as 1 ms, we printed monolayers of hexadecanethiol on Au, which served as a selective etch resist. High-speed muCP yields defect-free monolayers that are independent of the dimensions of the printed patterns, have high contrast between printed and unprinted areas, and enable perfect reproducibility of prints.     

Microscale plasma-initiated patterning (muPIP)

A novel technique to create biomolecular micropatterns of varying complexity on several types of polymer substrates is presented. This method uses a patterned PDMS stamp to preferentially expose or protect areas of an underlying polymer substrate from oxygen plasma. Following plasma treatment, the substrate is immersed in a biomolecular ink, whereby molecules preferentially adsorb to either the plasma-exposed or plasma-protected substrate regions, depending on the particular substrate/ink combination. Using this method, polyethylene (PE), polystyrene (PS), poly(methyl methacrylate) (PMMA), poly(dimethylsiloxane) (PDMS), and poly(hydroxybutyrate/hydroxyvalerate) (PHBV) were micropatterned with different aqueous-based biomolecular inks (i.e., goat anti-rabbit immunoglobulin G, poly-l-lysine, and bovine serum albumin (BSA)). Water contact angle measurements performed on substrates after oxygen plasma exposure showed that the hydrophilicity of substrate areas exposed to plasma was significantly greater than that of areas protected from plasma by the PDMS stamp. In addition, scanning electron microscopy results demonstrated that substrate areas exposed to plasma were physically modified (e.g., roughened) compared to adjacent, protected areas. Areas in contact with a patterned PDMS stamp during plasma exposure were found to be physically unaffected by plasma treatment, and exhibited spatial features/dimensions consistent with the corresponding features of the patterned stamp. Last, protein patterns of BSA on the polymer substrates were stable and distinct after 4 weeks of incubation at 37 degrees C.     

Growth kinetics and morphology of self-assembled monolayers formed by contact printing 7-octenyltrichlorosilane and octadecyltrichlorosilane on Si(100) wafers

The growth kinetics and morphologies of self-assembled monolayers deposited by contact printing 7-octenyltrichlorosilane (OCT) and octadecyltrichlorosilane (OTS) on Si(100) were studied by ellipsometry and atomic force microscopy. We found that, for both OCT and OTS, full monolayers could be obtained at room temperature after printing times of 120-180 s; the printing-based monolayer assembly processes follow apparent Langmuir adsorption kinetics, with the measured film growth rates increasing both with the ambient humidity and with concentration of the ink used to load the stamp. At a dew point of 10 degrees C and an ink concentration (in toluene) of 50 mM, the observed film growth rate constant is 0.05 s(-)(1). When the printing was carried out at a lower ambient humidity (dew points of 1-3 degrees C), the measured rates of assembly were approximately a factor of 2 slower. Increasing the deposition temperature from 25 to 45 degrees C under these conditions increased the film growth rate only slightly. The morphology of the films depends on the identity of the ink. Uniform, high-coverage films could be obtained readily from the eight-carbon chain length adsorbate OCT, provided that the stamp was not overloaded with the ink; for high concentrations outside of the optimal range, the surface presented significant numbers of adsorbed particles ascribed, in part, to siloxane polymers formed by hydrolysis of the ink on the stamp before printing. In marked contrast, for the 18-carbon adsorbate OTS, the printed films always consisted of a mixture of a uniform monolayer plus adsorbed polysiloxane particles. The different film morphologies seen for OCT and OTS are proposed to result from the different transfer efficiencies of the organotrichlorosilane relative to polysiloxane hydrolysis products formed during the printing process. These transfer efficiencies exhibit sensitivities related to the permeation of the poly(dimethylsiloxane) (PDMS) stamp by the silane reagents. Short-chain inks such as OCT evidently permeate the PDMS stamp more deeply than longer-chain inks such as OTS. This difference, and the different diffusion rates of ink vs oligomeric silane hydrolysis products, determines the film morphology obtained by contact printing. The mass transfer dynamics of the process thus yield surface layers derived from varying quantities of siloxane oligomers, which subsequently transfer to the substrate along with unhydrolyzed silane adsorbate during the printing step. The structural evolution of the contact-printed films so obtained is strikingly different from that of SAMs prepared by immersion.     

A novel process for inking the stamp with biomacromolecule solution used in reactive microcontact printing

This paper describes a novel process for inking the stamp with biomacromolecule solution used in reactive microcontact printing. The stamp was first coated with biomacromolecule solution such as bovine serum albumin (BSA) solution for 20 min, and then dried by soft nitrogen flow. After cooling the stamp below the dew point for 1 min and incubated at room temperature for 10 s, a thin layer of condensed water was formed on the stamp surface. Then, an aldehyde functionalized glass slide was pressed immediately onto the stamp for certain time, yielding the covalently patterning of the biomacromolecules on the aldehyde-containing surface. A notable feature of this process is that the biomacromolecule solution can be inked onto the stamp at a controlled state, neither too “dry” nor too “wet”. As a result, the covalently grafting reaction can occur at a comparable speed with those in solution, while avoiding the contamination caused by dispersal of excessive solvent.     

微接触印刷法控制硫化物晶体生长

十八烷基三氯硅烷;三氯硅烷;阵列;微接触印刷法控制硫化物晶体生长     

Interface interaction controlled transport of CdTe nanoparticles in the microcontact printing process

High-quality CdTe nanoparticles stabilized with thioglycolic acid (TGA) are patterned on SiO2/Si surfaces using microcontact printing (microCP). Due to the weak interaction of the nanoparticles with the stamp surface, tailoring of gas flow rate during the inking process as well as the type and scale of the patterns on the stamp are used to control the distribution of the nanoparticles on the structured stamp surface. This distribution is then transferred the printed regions. Either edge printing or homogeneous printing can be achieved under optimized conditions. In addition, new structures such as nanowires form under certain conditions.     

A Simple Method for Fabricating Patterned Curvilinear Microstructures in Poly(dimethylsiloxane) by Selective Wetting

The fabrication of patterned microstructures in poly(dimethylsiloxane) (PDMS) is a prerequisite for soft lithography. Herein, curvilinear surface relief microstructures in PDMS are fabricated through a simple three‐stage approach combining microcontact printing (μCP), selective surface wetting/dewetting and replica molding (REM). First, using an original PDMS stamp (first‐generation stamp) with linear relief features, a chemical pattern on gold substrate is generated by μCP using hexadecanethiol (HDT) as an ink. Then, by a dip‐coating process, an ordered polyethylene glycol (PEG) polymer‐dot array forms on the HDT‐patterned gold substrate. Finally, based on a REM process, the PEG‐dot array on gold substrate is used to fabricate a second‐generation PDMS stamp with microcavity array, and the second‐generation PDMS stamp is used to generate third‐generation PDMS stamp with microbump array. These fabricated new‐generation stamps are utilized in μCP and in micromolding in capillaries (MIMIC), allowing the generation of surface micropatterns which cannot be obtained using the original PDMS stamp. The method will be useful in producing new‐generation PDMS stamps, especially for those who want to use soft lithography in their studies but have no access to the microfabrication facilities.     

Competing fracture in kinetically controlled transfer printing

Transfer printing by kinetically switchable adhesion to an elastomeric stamp shows promise as a powerful micromanufacturing method to pickup microstructures and microdevices from the donor substrate and to print them to the receiving substrate. This can be viewed as the competing fracture of two interfaces. This paper examines the mechanics of competing fracture in a model transfer printing system composed of three laminates: an elastic substrate, an elastic thin film, and a viscoelastic member (stamp). As the system is peeled apart, either the interface between the substrate and thin film fails or the interface between the thin film and the stamp fails. The speed-dependent nature of the film/stamp interface leads to the prediction of a critical separation velocity above which separation occurs between the film and the substrate (i.e., pickup) and below which separation occurs between the film and the stamp (i.e., printing). Experiments verify this prediction using films of gold adhered to glass, and the theoretical treatment extends to consider the competing fracture as it applies to discrete micro-objects. Temperature plays an important role in kinetically controlled transfer printing with its influences, making it advantageous to pickup printable objects at the reduced temperatures and to print them at the elevated ones.     

Versatile bio-ink for covalent immobilization of chimeric avidin on sol-gel substrates

A bio-ink for covalent deposition of thermostable, high affinity biotin-binding chimeric avidin onto sol-gel substrates was developed. The bio-ink was prepared from heterobifunctional crosslinker 6-maleimidohexanoic acid N-hydroxysuccinimide which was first reacted either with 3-aminopropyltriethoxysilane or 3-aminopropyldimethylethoxysilane to form silane linkers 6-maleimide-N-(3-(triethoxysilyl)propyl)hexanamide or -(ethoxydimethylsilyl)propyl)-hexanamide. C-terminal cysteine genetically engineered to chimeric avidin was reacted with the maleimide group of silane linker in methanol/PBS solution to form a suspension, which was printed on sol-gel modified PMMA film. Different concentrations of chimeric avidin and ratios between silane linkers were tested to find the best properties for the bio-ink to enable gravure or inkjet printing. Bio-ink prepared from 3-aminopropyltriethoxysilane was found to provide the highest amount of active immobilized chimeric avidin. The developed bio-ink was shown to be valuable for automated fabrication of avidin-functionalized polymer films.