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1.  Controlling Film Morphology in Conjugated Polymer 
Journal of the American Chemical Society  2008;130(47):15916-15926.
We study the effects of patterned surface chemistry on the microscale and nanoscale morphology of solution-processed donor/acceptor polymer-blend films. Focusing on combinations of interest in polymer solar cells, we demonstrate that patterned surface chemistry can be used to tailor the film morphology of blends of semiconducting polymers such as poly-[2-(3,7-dimethyloctyloxy)-5-methoxy-p-phenylenevinylene] (MDMO-PPV), poly-3-hexylthiophene (P3HT), poly[(9,9-dioctylflorenyl-2,7-diyl)-co-benzothiadiazole)] (F8BT), and poly(9,9-dioctylfluorene-co-bis-N,N’-(4-butylphenyl)-bis-N,N’-phenyl-1,4-phenylendiamine) (PFB) with the fullerene derivative, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). We present a method for generating patterned, fullerene-terminated monolayers on gold surfaces, and use microcontact printing and Dip-Pen Nanolithography (DPN) to pattern alkanethiols with both micro- and nanoscale features. After patterning with fullerenes and other functional groups, we backfill the rest of the surface with a variety of thiols to prepare substrates with periodic variations in surface chemistry. Spin coating polymer:PCBM films onto these substrates, followed by thermal annealing under nitrogen, leads to the formation of structured polymer films. We characterize these films with Atomic Force Microscopy (AFM), Raman spectroscopy, and fluorescence microscopy. The surface patterns are effective in guiding phase separation in all of the polymer:PCBM systems investigated, and lead to a rich variety of film morphologies that are inaccessible with unpatterned substrates. We demonstrate our ability to guide pattern formation in films thick enough of be of interest for actual device applications (up to 200 nm in thickness) using feature sizes as small as 100 nm. Finally, we show that the surface chemistry can lead to variations in film morphology on length scales significantly smaller than those used in generating the original surface patterns. The variety of behaviors observed and the wide range of control over polymer morphology achieved at a variety of different length scales have important implications for the development of bulk heterojunction solar cells.
doi:10.1021/ja804088j
PMCID: PMC2702008  PMID: 18983150
2.  Near-field photochemical and radiation-induced chemical fabrication of nanopatterns of a self-assembled silane monolayer 
Summary
A general concept for parallel near-field photochemical and radiation-induced chemical processes for the fabrication of nanopatterns of a self-assembled monolayer (SAM) of (3-aminopropyl)triethoxysilane (APTES) is explored with three different processes: 1) a near-field photochemical process by photochemical bleaching of a monomolecular layer of dye molecules chemically bound to an APTES SAM, 2) a chemical process induced by oxygen plasma etching as well as 3) a combined near-field UV-photochemical and ozone-induced chemical process, which is applied directly to an APTES SAM. All approaches employ a sandwich configuration of the surface-supported SAM, and a lithographic mask in form of gold nanostructures fabricated through colloidal sphere lithography (CL), which is either exposed to visible light, oxygen plasma or an UV–ozone atmosphere. The gold mask has the function to inhibit the photochemical reactions by highly localized near-field interactions between metal mask and SAM and to inhibit the radiation-induced chemical reactions by casting a highly localized shadow. The removal of the gold mask reveals the SAM nanopattern.
doi:10.3762/bjnano.5.156
PMCID: PMC4168865  PMID: 25247126
colloid lithography; contact lithography; near-field; photochemistry; self-assembled silane monolayers
3.  Colloidal lithography and current fabrication techniques producing in-plane nanotopography for biological applications 
Substrate topography plays a vital role in cell and tissue structure and function in situ, where nanometric features, for example, the detail on single collagen fibrils, influence cell behaviour and resultant tissue formation. In vitro investigations demonstrate that nanotopography can be used to control cell reactions to a material surface, indicating its potential application in tissue engineering and implant fabrication. Developments in the catalyst, optical, medical and electronics industries have resulted in the production of nanopatterned surfaces using a variety of methods. The general protocols for nanomanufacturing require high resolution and low cost for fabricating devices. With respect to biological investigations, nanotopographies should occur across a large surface area (ensuring repeatability of experiments and patterning of implant surfaces), be reproducible (allowing for consistency in experiments), and preferably, accessible (limiting the requirement for specialist equipment). Colloidal lithography techniques fit these criteria, where nanoparticles can be utilized in combination with a functionalized substrate to produce in-plane nanotopographies. Subsequent lithographic processing of colloidal substrates utilizing, for example, reactive ion etching allows the production of modified colloidal-derived nanotopographies. In addition to two-dimensional in-plane nanofabrication, functionalized structures can be dip coated in colloidal sols, imparting nanotopographical cues to cells within a three-dimensional environment.
doi:10.1098/rsif.2006.0149
PMCID: PMC2358954  PMID: 17015295
colloid; fabrication; lithography; nanotopography; cell biology; tissue engineering
4.  A multi-compartment CNS neuron-glia co-culture microfluidic platform 
We present a novel multi-compartment neuron co-culture microsystem platform for in vitro CNS axon-glia interaction research, capable of conducting up to six independent experiments in parallel for higher-throughput. We developed a new fabrication method to create microfluidic devices having both micro and macro scale structures within the same device through a single soft-lithography process, enabling mass fabrication with good repeatability.
The multi-compartment microfluidic co-culture platform is composed of one soma compartment for neurons and six axon/glia compartments for oligodendrocytes (OLs). The soma compartment and axon/glia compartments are connected b y arrays of axon-guiding microchannels that function as physical barriers to confine neuronal soma in the soma compartment, while allowing axons to grow into axon/glia compartments. OLs loaded into axon/glia compartments can interact only with axons but not with neuronal soma or dendrites, enabling localized axon-glia interaction studies. The microchannels also enabled fluidic isolation between compartments, allowing six independent experiments to be conducted on a single device for higher throughput.
Soft-lithography using poly(dimethylsiloxane) (PDMS) is a commonly used technique in biomedical microdevices. Reservoirs on these devices are commonly defined by manual punching. Although simple, poor alignment and time consuming nature of the process makes this process not suitable when large numbers of reservoirs have to be repeatedly created. The newly developed method did not require manual punching of reservoirs, overcoming such limitations. First, seven reservoirs (depth: 3.5 mm) were made on a poly(methyl methacrylate) (PMMA) block using a micro-milling machine. Then, arrays of ridge microstructures, fabricated on a glass substrate, were hot-embossed against the PMMA block to define microchannels that connect the soma and axon/glia compartments. This process resulted in macro-scale reservoirs (3.5 mm) and micro-scale channels (2.5 µm) to coincide within a single PMMA master. A PDMS replica that served as a mold master was obtained using soft-lithography and the final PDMS device was replicated from this master.
Primary neurons from E16–18 rats were loaded to the soma compartment and cultured for two weeks. After one week of cell culture, axons crossed microchannels and formed axonal only network layer inside axon/glia compartments. Axons grew uniformly throughout six axon/glia compartments and OLs from P1–2 rats were added to axon/glia compartments at 14 days in vitro for co-culture.
doi:10.3791/1399
PMCID: PMC2774404  PMID: 19745806
Neuron culture; neuron-glia interaction; microfluidics; cell culture microsystem
5.  Positioning Multiple Proteins at the Nanoscale with Electron Beam Cross-Linked Functional Polymers 
Constructing multicomponent protein structures that match the complexity of those found in Nature is essential for the next generation of medical materials. In this report, a versatile method to precisely arrange multicomponent protein nanopatterns in two-dimensional single-layer or three-dimensional multilayer formats using electron beam lithography is described. Eight arm poly(ethylene glycol)s were modified at the chain ends with either biotin, maleimide, aminooxy, or nitrilotriacetic acid. Analysis by 1H NMR spectroscopy revealed that the reactions were efficient and that end group conversions were 91-100%. The polymers were then cross-linked onto Si surfaces using electron beams to form micron sized patterns of the functional groups. Proteins with biotin binding sites, a free cysteine, an N-terminal α-oxoamide, and a histidine tag, respectively, were then incubated with the substrate in aqueous solutions without the addition of any other reagents. By fluorescence microscopy experiments it was determined that proteins reacted site-specifically with the exposed functional groups to form protein micropatterns. Multicomponent nanoscale protein patterns were then fabricated. Different PEGs with orthogonal reactivity were sequentially patterned on the same chip. Simultaneous assembly of two different proteins from a mixture of the biomolecules formed the multicomponent two dimensional patterns. Atomic force microscopy demonstrated that nanometer sized patterns of polymer were formed and fluorescence microscopy demonstrated that side-by-side patterns of the different proteins were obtained. Moreover, multilayer PEG fabrication produced micron and nanometer sized patterns of one functional group on top of the other. Precise three-dimensional arrangements of different proteins were then realized.
PMCID: PMC3050812  PMID: 19160460
6.  Selective Filling of Nanowells in Nanowell Arrays Fabricated Using Polystyrene Nanosphere Lithography with Cytochrome P450 Enzymes 
Nanotechnology  2012;23(38):385101.
This work describes an original and simple technique for protein immobilization into nanowells, fabricated using nanopatterned-array fabrication methods, while ensuring the protein retains the normal biological activity. Nanosphere-lithography was used to fabricate a nanowell array with nanowells that were 100 nm in diameter and a periodicity of 500 nm. The base of the nanowells was gold and the surrounding material was silicon dioxide. The different surface chemistries of these materials were used to attach two different self-assembled monolayers (SAM) with different affinities for the protein used here, cytochrome P450 (P450). The nanowell SAM, a methyl terminated thiol, had high affinity for the P450. The surrounding SAM, a polyethylene glycol silane, displayed very little affinity toward the P450 isozyme CYP2C9, as demonstrated by x-ray photoelectron spectroscopy and surface plasmon resonance. The regularity of the nanopatterned array was examined by scanning electron microscopy and atomic force microscopy. P450-mediated metabolism experiments of known substrates demonstrated that the nanowell bound P450 enzyme exceeded its normal activity, as compared to P450 solutions, when bound to the methyl terminated self-assembled monolayer. The nanopatterned array chips bearing P450 display long term stability and give reproducible results making them potentially useful for high throughput screening assays or as nanoelectrode arrays.
doi:10.1088/0957-4484/23/38/385101
PMCID: PMC3465080  PMID: 22947619
Nanowell array; Self-assembled monolayer; cytochrome P450
7.  Effect of functional end groups of silane self assembled monolayer surfaces on apatite formation, fibronectin adsorption and osteoblast cell function 
Bioactive glass (BG) can directly bond to living bone without fibrous tissue encapsulation. Key mechanistic steps of BG’s activity are attributed to calcium phosphate formation, surface hydroxylation and fibronectin (FN) adsorption. In the present study, self-assembled monolayers (SAMs) of alkanesilanes with different surface chemistry (OH, NH2, and COOH) were used as a model system to mimic BG’s surface activity. Calcium phosphate (Ca-P) was formed on SAMs by immersion in a solution which simulates the electrolyte content of physiological fluids. FN adsorption kinetics and monolayer coverage was determined on SAMs with or without Ca-P coating. The surface roughness was also examined on these substrates before and after FN adsorption. The effects of FN-adsorbed, Ca-P coated SAMs on the function of MC3T3-E1 were evaluated by cell growth, expression of alkaline phosphatase activity, and actin cytoskeleton formation. We demonstrate that, although the FN monolayer coverage and the rms roughness are similar on −OH and −COOH terminated SAMs with or without Ca-P coating, higher levels of ALP activity, more actin cytoskeleton formation and more cell growth are obtained on −OH and −COOH terminated SAMs with Ca-P coating. In addition, although the FN monolayer coverage is higher on Ca-P coated −NH2 terminated SAMs and SiOx surfaces, higher levels of ALP activity and more cell growth are obtained on Ca-P coated −OH and −COOH terminated SAMs. Thus with same Ca-P coatings, different surface functional groups have different effects on the function of osteoblastic cells. These findings represent new insights into the mechanism of bioactivity of BG and, thereby, may lead to designing superior constructs for bone grafting.
doi:10.1002/term.131
PMCID: PMC2610238  PMID: 19012271
self assembled monolayers; calcium phosphate; protein adsorption; cell attachment; proliferation; alkaline phosphatase activity
8.  Automated scanning probe lithography with n-alkanethiol self assembled monolayers on Au(111): Application for teaching undergraduate laboratories 
Journal of Laboratory Automation  2011;16(2):112-125.
Controllers for scanning probe instruments can be programmed for automated lithography to generate desired surface arrangements of nanopatterns of organic thin films, such as n-alkanethiol self-assembled monolayers (SAMs). In this report, atomic force microscopy (AFM) methods of lithography known as nanoshaving and nanografting are used to write nanopatterns within organic thin films. Commercial instruments provide software to control the length, direction, speed, and applied force of the scanning motion of the tip. For nanoshaving, higher forces are applied to an AFM tip to selectively remove regions of the matrix monolayer, exposing bare areas of the gold substrate. Nanografting is accomplished by force-induced displacement of molecules of a matrix SAM, followed immediately by the surface self-assembly of n-alkanethiol molecules from solution. Advancements in AFM automation enable rapid protocols for nanolithography, which can be accomplished within the tight time restraints of undergraduate laboratories. Example experiments with scanning probe lithography (SPL) will be described in this report that were accomplished by undergraduate students during laboratory course activities and research internships in the chemistry department of Louisiana State University. Students were introduced to principles of surface analysis and gained “hands-on” experience with nanoscale chemistry.
doi:10.1016/j.jala.2010.06.003
PMCID: PMC3072817  PMID: 21483651
9.  Selective patterning of ZnO nanorods on silicon substrates using nanoimprint lithography 
Nanoscale Research Letters  2011;6(1):159.
In this research, nanoimprint lithography (NIL) was used for patterning crystalline zinc oxide (ZnO) nanorods on the silicon substrate. To fabricate nano-patterned ZnO nanorods, patterning of an n-octadecyltrichlorosilane (OTS) self-assembled monolayers (SAMs) on SiO2 substrate was prepared by the polymer mask using NI. The ZnO seed layer was selectively coated only on the hydrophilic SiO2 surface, not on the hydrophobic OTS SAMs surface. The substrate patterned with the ZnO seed layer was treated with the oxygen plasma to oxidize the silicon surface. It was found that the nucleation and initial growth of the crystalline ZnO were proceeded only on the ZnO seed layer, not on the silicon oxide surface. ZnO photoluminescence spectra showed that ZnO nanorods grown from the seed layer treated with plasma showed lower intensity than those untreated with plasma at 378 nm, but higher intensity at 605 nm. It is indicated that the seed layer treated with plasma produced ZnO nanorods that had a more oxygen vacancy than those grown from seed layer untreated with plasma. Since the oxygen vacancies on ZnO nanorods serve as strong binding sites for absorption of various organic and inorganic molecules. Consequently, a nano-patterning of the crystalline ZnO nanorods grown from the seed layer treated with plasma may give the versatile applications for the electronics devices.
doi:10.1186/1556-276X-6-159
PMCID: PMC3211210  PMID: 21711665
10.  Fabrication of Interdigitated Micropatterns of Self-Assembled Polymer Nanofilms Containing Cell-adhesive Materials 
Micropatterns of different biomaterials with micro- and nanoscale features and defined spatial arrangement on a single substrate are useful tools for studying cellular-level interactions, and recent reports have highlighted the strong influence of scaffold compliance in determining cell behavior. In this paper, a simple yet versatile and precise patterning technique for the fabrication of interdigitated micropatterns of nanocomposite multilayer coatings on a single substrate is demonstrated through a combination of lithography and layer-by-layer (LbL) assembly processes, termed as Polymer Surface Micromachining (PSM). The first nanofilm pattern is constructed using lithography, followed by LbL multilayer assembly and lift-off, and the process is repeated with optical alignment to obtain interdigitated patterns on the same substrate. Thus, the method is analogous to surface micromachining, except that the deposition materials are polymers and biological materials that are used to produce multilayer nanocomposite structures. A key feature of the multilayers is the capability to tune properties such as stiffness by appropriate selection of materials, deposition conditions, and post-deposition treatments. Two- and four-component systems on glass coverslips are presented to demonstrate the versatility of the approach to construct precisely-defined, homogeneous nanofilm patterns. In addition, an example of a complex system used as a testbed for in vitro cell adhesion and growth is provided: micropatterns of poly(sodium 4-styrenesulfonate)/poly-L-lysine hydrobromide (PSS/PLL) and secreted phospholipase A2/poly(ethyleneimine) (PEI/sPLA2) multilayers. The interdigitated square nanofilm array patterns were obtained on a single coverslip with poly(diallyldimethyl ammonium chloride) (PDDA) as a cell-repellent background. Cell culture experiments show that cortical neurons respond and bind specifically to the sPLA2 micropatterns in competition with PLL micropatterns. The fabrication and the initial biological results on the nanofilm micropatterns support the usefulness of the technique for use in studies aimed at elucidating important biological structure-function relationships, but the applicability of the fabrication method is much broader and may impact electronics, photonics, and chemical microsystems.
doi:10.1021/la0525473
PMCID: PMC2536648  PMID: 16519477
11.  Development of a Chemiresistor Sensor Based on Polymers-Dye Blend for Detection of Ethanol Vapor 
Sensors (Basel, Switzerland)  2010;10(4):2812-2820.
The conductive blend of the poly (3,4-ethylene dioxythiophene) and polystyrene sulfonated acid (PEDOT-PSS) polymers were doped with Methyl Red (MR) dye in the acid form and were used as the basis for a chemiresistor sensor for detection of ethanol vapor. This Au | Polymers-dye blend | Au device was manufactured by chemical vapor deposition and spin-coating, the first for deposition of the metal electrodes onto a glass substrate, and the second for preparation of the organic thin film forming ∼1.0 mm2 of active area. The results obtained are the following: (i) electrical resistance dependence with atmospheres containing ethanol vapor carried by nitrogen gas and humidity; (ii) sensitivity at 1.15 for limit detection of 26.25 ppm analyte and an operating temperature of 25 °C; and (iii) the sensing process is quickly reversible and shows very a low power consumption of 20 μW. The thin film morphology of ∼200 nm thickness was analyzed by Atomic Force Microscopy (AFM), where it was observed to have a peculiarly granulometric surface favorable to adsorption. This work indicates that PEDOT-PSS doped with MR dye to compose blend film shows good performance like resistive sensor.
doi:10.3390/s100402812
PMCID: PMC3274177  PMID: 22319273
chemiresistor sensor; PEDOT-PSS; MR dye; ethanol vapor
12.  Fabrication of flexible UV nanoimprint mold with fluorinated polymer-coated PET film 
Nanoscale Research Letters  2011;6(1):458.
UV curing nanoimprint lithography is one of the most promising techniques for the fabrication of micro- to nano-sized patterns on various substrates with high throughput and a low production cost. The UV nanoimprint process requires a transparent template with micro- to nano-sized surface protrusions, having a low surface energy and good flexibility. Therefore, the development of low-cost, transparent, and flexible templates is essential. In this study, a flexible polyethylene terephthalate (PET) film coated with a fluorinated polymer material was used as an imprinting mold. Micro- and nano-sized surface protrusion patterns were formed on the fluorinated polymer layer by the hot embossing process from a Si master template. Then, the replicated pattern of the fluorinated polymer, coated on the flexible PET film, was used as a template for the UV nanoimprint process without any anti-stiction coating process. In this way, the micro- to nano-sized patterns of the original master Si template were replicated on various substrates, including a flat Si substrate and curved acryl substrate, with high fidelity using UV nanoimprint lithography.
doi:10.1186/1556-276X-6-458
PMCID: PMC3211878  PMID: 21767390
13.  Substrate-mediated effects in photothermal patterning of alkanethiol self-assembled monolayers with microfocused continuous-wave lasers 
Summary
In recent years, self-assembled monolayers (SAMs) have been demonstrated to provide promising new approaches to nonlinear laser processing. Most notably, because of their ultrathin nature, indirect excitation mechanisms can be exploited in order to fabricate subwavelength structures. In photothermal processing, for example, microfocused lasers are used to locally heat the substrate surface and initiate desorption or decomposition of the coating. Because of the strongly temperature-dependent desorption kinetics, the overall process is highly nonlinear in the applied laser power. For this reason, subwavelength patterning is feasible employing ordinary continuous-wave lasers. The lateral resolution, generally, depends on both the type of the organic monolayer and the nature of the substrate. In previous studies we reported on photothermal patterning of distinct types of SAMs on Si supports. In this contribution, a systematic study on the impact of the substrate is presented. Alkanethiol SAMs on Au-coated glass and silicon substrates were patterned by using a microfocused laser beam at a wavelength of 532 nm. Temperature calculations and thermokinetic simulations were carried out in order to clarify the processes that determine the performance of the patterning technique. Because of the strongly temperature-dependent thermal conductivity of Si, surface-temperature profiles on Au/Si substrates are very narrow ensuring a particularly high lateral resolution. At a 1/e spot diameter of 2 µm, fabrication of subwavelength structures with diameters of 300–400 nm is feasible. Rapid heat dissipation, though, requires high laser powers. In contrast, patterning of SAMs on Au/glass substrates is strongly affected by the largely distinct heat conduction within the Au film and in the glass support. This results in broad surface temperature profiles. Hence, minimum structure sizes are larger when compared with respective values on Au/Si substrates. The required laser powers, though, are more than one order of magnitude lower. Also, the laser power needed for patterning decreases with decreasing Au layer thickness. These results demonstrate the impact of the substrate on the overall patterning process and provide new perspectives in photothermal laser patterning of ultrathin organic coatings.
doi:10.3762/bjnano.3.8
PMCID: PMC3304314  PMID: 22428098
femtosecond lasers; nonlinear laser processing; self-assembled monolayers; subwavelength patterning; ultrathin resists
14.  Micro-macro hybrid soft-lithography master (MMHSM) fabrication for lab-on-a-chip applications 
Biomedical microdevices  2010;12(2):345-351.
We present a novel micro-macro hybrid soft-lithography master (MMHSM) fabrication technique where microdevices having both microscale and macroscale features can be replicated with a single soft-lithography step. A poly(methyl methacrylate) (PMMA) master having macroscale structures was first created by a bench-top milling machine. An imprinting master mold having micro-scale structures was then imprinted on the PMMA surface through a hot-embossing process to obtain a PMMA master mold. A poly(dimethylsiloxane) (PDMS) master was then replicated from this PMMA master through a standard soft-lithography process. This process allowed both microscale (height: 3–20 μm, width: 20–500 μm) and macroscale (height: 3.5 mm, width: 1.2–7 mm) structures to co-exist on the PDMS master mold, from which final PDMS devices could be easily stamped out in large quantities. Microfluidic structures requiring macroscale dimensions in height, such as reservoirs or fluidic tubing interconnects, could be directly built into PDMS microfluidic devices without the typically used manual punching process. This significantly reduced alignment errors and time required for such manual fabrication steps. In this paper, we successfully demonstrated the utility of this novel hybrid fabrication method by fabricating a PDMS microfluidic device with 40 built-in fluidic interfaces and a PDMS multi-compartment neuron co-culture platform, where millimeter-scale compartments are connected via arrays of 20 μm wide and 200 μm long microfluidic channels. The resulting structures were characterized for the integrity of the transferred pattern sizes and the surface roughness using scanning electron microscopy and optical profilometry.
doi:10.1007/s10544-009-9390-9
PMCID: PMC2864814  PMID: 20049640
Soft-lithography; Fluidic interface; PDMS; Cast molding
15.  Fabrication of porous silicon by metal-assisted etching using highly ordered gold nanoparticle arrays 
Nanoscale Research Letters  2012;7(1):450.
A simple method for the fabrication of porous silicon (Si) by metal-assisted etching was developed using gold nanoparticles as catalytic sites. The etching masks were prepared by spin-coating of colloidal gold nanoparticles onto Si. An appropriate functionalization of the gold nanoparticle surface prior to the deposition step enabled the formation of quasi-hexagonally ordered arrays by self-assembly which were translated into an array of pores by subsequent etching in HF solution containing H2O2. The quality of the pattern transfer depended on the chosen preparation conditions for the gold nanoparticle etching mask. The influence of the Si surface properties was investigated by using either hydrophilic or hydrophobic Si substrates resulting from piranha solution or HF treatment, respectively. The polymer-coated gold nanoparticles had to be thermally treated in order to provide a direct contact at the metal/Si interface which is required for the following metal-assisted etching. Plasma treatment as well as flame annealing was successfully applied. The best results were obtained for Si substrates which were flame annealed in order to remove the polymer matrix - independent of the substrate surface properties prior to spin-coating (hydrophilic or hydrophobic). The presented method opens up new resources for the fabrication of porous silicon by metal-assisted etching. Here, a vast variety of metal nanoparticles accessible by well-established wet-chemical synthesis can be employed for the fabrication of the etching masks.
doi:10.1186/1556-276X-7-450
PMCID: PMC3463426  PMID: 22876790
Porous silicon; Nanolithography; Gold nanoparticles; Self-assembly; Metal-assisted etching; 81.05.Rm; 81.16.Nd; 81.65.Cf
16.  Site-selective growth of surface-anchored metal-organic frameworks on self-assembled monolayer patterns prepared by AFM nanografting 
Summary
Surface anchored metal-organic frameworks, SURMOFs, are highly porous materials, which can be grown on modified substrates as highly oriented, crystalline coatings by a quasi-epitaxial layer-by-layer method (liquid-phase epitaxy, or LPE). The chemical termination of the supporting substrate is crucial, because the most convenient method for substrate modification is the formation of a suitable self-assembled monolayer. The choice of a particular SAM also allows for control over the orientation of the SURMOF. Here, we demonstrate for the first time the site-selective growth of the SURMOF HKUST-1 on thiol-based self-assembled monolayers patterned by the nanografting technique, with an atomic force microscope as a structuring tool. Two different approaches were applied: The first one is based on 3-mercaptopropionic acid molecules which are grafted in a 1-decanethiolate SAM, which serves as a matrix for this nanolithography. The second approach uses 16-mercaptohexadecanoic acid, which is grafted in a matrix of an 1-octadecanethiolate SAM. In both cases a site-selective growth of the SURMOF is observed. In the latter case the roughness of the HKUST-1 is found to be significantly higher than for the 1-mercaptopropionic acid. The successful grafting process was verified by time-of-flight secondary ion mass spectrometry and atomic force microscopy. The SURMOF structures grown via LPE were investigated and characterized by atomic force microscopy and Fourier-transform infrared microscopy.
doi:10.3762/bjnano.4.71
PMCID: PMC3817682  PMID: 24205458
atomic force microscopy (AFM); metal-organic frameworks; nanografting; nanoshaving; SURMOF
17.  Exploring Cellular Contact Guidance Using Gradient Nanogratings 
Biomacromolecules  2010;11(11):3067-3072.
Nanoscale surface features that mimic extracellular matrix are critical environmental cues for cell contact guidance and are vital in advanced medical devices in order to manipulate cell behaviors. Among them, nanogratings (line-and-space grating) are common platforms to study geometric effects on cell contact guidance, especially, cell alignment, but generally are one pattern height per platform. In this study, we developed a strategy to fabricate controlled substrates with a wide range of pattern shapes and surface chemistries and to separate surface chemistry and topography effects. As a demonstration of this strategy, six nanograting platforms on three materials were fabricated and applied to examine and differentiate the effects of surface topography and surface chemistry on cell contact guidance of murine preosteoblasts. All of the six platforms contained the same gradient in pattern height (0 nm to ≈ 350 nm). They were prepared using nanoimprint lithography and annealing for thermoplastic materials (low molecular weight polystyrene (PS) and polymethylmethacrylate (PMMA)) and photo-imprint for a thermoset material (a cross-linked dimethacrylate (DMA)). Each material contains two platforms that are only different in line-and-space pitches (420 nm or 800 nm). The DMA nanogratings had a reverse line-and-space profiles to those of the PS and PMMS nanogratings. Using these platforms, a full range of cell alignment, from randomly orientated to completely parallel to the grating direction was achieved. Results from focal adhesion assay and scanning electronic microscopy (SEM) indicated a change in cell-substrate contact from a non-composite state (full contact) to a composite state (partial contact between cell and substrate) as pattern height increased. These gradient platforms allowed for the separation of surface chemistry and surface topography to provide insight into the mechanisms responsible for cell contact guidance on nanopatterned surfaces.
doi:10.1021/bm100883m
PMCID: PMC3061972  PMID: 20954734
Surface topography; nanoimprint lithography; cell contact guidance; tissue engineering; extracellular matrix; focal adhesion
18.  Soft Lithographic Functionalization and Patterning Oxide-free Silicon and Germanium 
The development of hybrid electronic devices relies in large part on the integration of (bio)organic materials and inorganic semiconductors through a stable interface that permits efficient electron transport and protects underlying substrates from oxidative degradation. Group IV semiconductors can be effectively protected with highly-ordered self-assembled monolayers (SAMs) composed of simple alkyl chains that act as impervious barriers to both organic and aqueous solutions. Simple alkyl SAMs, however, are inert and not amenable to traditional patterning techniques. The motivation for immobilizing organic molecular systems on semiconductors is to impart new functionality to the surface that can provide optical, electronic, and mechanical function, as well as chemical and biological activity.
Microcontact printing (μCP) is a soft-lithographic technique for patterning SAMs on myriad surfaces.1-9 Despite its simplicity and versatility, the approach has been largely limited to noble metal surfaces and has not been well developed for pattern transfer to technologically important substrates such as oxide-free silicon and germanium. Furthermore, because this technique relies on the ink diffusion to transfer pattern from the elastomer to substrate, the resolution of such traditional printing is essentially limited to near 1 μm.10-16
In contrast to traditional printing, inkless μCP patterning relies on a specific reaction between a surface-immobilized substrate and a stamp-bound catalyst. Because the technique does not rely on diffusive SAM formation, it significantly expands the diversity of patternable surfaces. In addition, the inkless technique obviates the feature size limitations imposed by molecular diffusion, facilitating replication of very small (<200 nm) features.17-23 However, up till now, inkless μCP has been mainly used for patterning relatively disordered molecular systems, which do not protect underlying surfaces from degradation.
Here, we report a simple, reliable high-throughput method for patterning passivated silicon and germanium with reactive organic monolayers and demonstrate selective functionalization of the patterned substrates with both small molecules and proteins. The technique utilizes a preformed NHS-reactive bilayered system on oxide-free silicon and germanium. The NHS moiety is hydrolyzed in a pattern-specific manner with a sulfonic acid-modified acrylate stamp to produce chemically distinct patterns of NHS-activated and free carboxylic acids. A significant limitation to the resolution of many μCP techniques is the use of PDMS material which lacks the mechanical rigidity necessary for high fidelity transfer. To alleviate this limitation we utilized a polyurethane acrylate polymer, a relatively rigid material that can be easily functionalized with different organic moieties. Our patterning approach completely protects both silicon and germanium from chemical oxidation, provides precise control over the shape and size of the patterned features, and gives ready access to chemically discriminated patterns that can be further functionalized with both organic and biological molecules. The approach is general and applicable to other technologically-relevant surfaces.
doi:10.3791/3478
PMCID: PMC3369651  PMID: 22214997
Bioengineering;  Issue 58;  Soft lithography;  microcontact printing;  protein arrays;  catalytic printing;  oxide-free silicon
19.  Tuning the Degradation Profiles of Poly(l-lactide)-Based Materials through Miscibility 
Biomacromolecules  2013;15(1):391-402.
The effective use of biodegradable polymers relies on the ability to control the onset of and time needed for degradation. Preferably, the material properties should be retained throughout the intended time frame, and the material should degrade in a rapid and controlled manner afterward. The degradation profiles of polyester materials were controlled through their miscibility. Systems composed of PLLA blended with poly[(R,S)-3-hydroxybutyrate] (a-PHB) and polypropylene adipate (PPA) with various molar masses were prepared through extrusion. Three different systems were used: miscible (PLLA/a-PHB5 and PLLA/a-PHB20), partially miscible (PLLA/PPA5/comp and PLLA/PPA20/comp), and immiscible (PLLA/PPA5 and PLLA/PPA20) blends. These blends and their respective homopolymers were hydrolytically degraded in water at 37 °C for up to 1 year. The blends exhibited entirely different degradation profiles but showed no diversity between the total degradation times of the materials. PLLA presented a two-stage degradation profile with a rapid decrease in molar mass during the early stages of degradation, similar to the profile of PLLA/a-PHB5. PLLA/a-PHB20 presented a single, constant linear degradation profile. PLLA/PPA5 and PLLA/PPA20 showed completely opposing degradation profiles relative to PLLA, exhibiting a slow initial phase and a rapid decrease after a prolonged degradation time. PLLA/PPA5/comp and PLLA/PPA20/comp had degradation profiles between those of the miscible and the immiscible blends. The molar masses of the materials were approximately the same after 1 year of degradation despite their different profiles. The blend composition and topographical images captured at the last degradation time point demonstrate that the blending component was not leached out during the period of study. The hydrolytic stability of degradable polyester materials can be tailored to obtain different and predetermined degradation profiles for future applications.
doi:10.1021/bm401667b
PMCID: PMC3892759  PMID: 24279455
20.  Nanopatterning on non-planar and fragile substrates with ice resists 
Nano Letters  2012;12(2):1018-1021.
Electron beam (e-beam) lithography using polymer resists is an important technology that provides the spatial resolution needed for nanodevice fabrication. But it is often desirable to pattern non-planar structures on which polymeric resists cannot be reliably applied. Furthermore, fragile substrates such as free-standing nanotubes or thin films cannot tolerate the vigorous mechanical scrubbing procedures required to remove all residual traces of the polymer resist. Here we demonstrate several examples where e-beam lithography using an amorphous ice resist eliminates both of these difficulties and enables the fabrication of unique nanoscale device structures in a process we call ice lithography1,2. We demonstrate the fabrication of micro and nanostructures on the tip of atomic force microscope probes, micro cantilevers, transmission electron microscopy grids, and suspended single-walled carbon nanotubes. Our results show that by using amorphous water ice as an e-beam resist, a new generation of nanodevice structures can be fabricated on non-planar or fragile substrates.
doi:10.1021/nl204198w
PMCID: PMC3275690  PMID: 22229744
non-planar; nanopatterning; e-beam lithography; ice lithography; resists
21.  Fabrication of Tissue Engineering Scaffolds through Solid-state Foaming of Immiscible Polymer Blends 
Biofabrication  2011;3(4):045003.
In scaffold-based tissue engineering, the fabrication process is important for producing suitable microstructures for seeded cells to grow and reformulate. In this paper, we present a new approach to scaffold fabrication by combining the solid-state foaming and the immiscible polymer blending method. The proposed approach has the advantage of being versatile and able to create a wide range of pore size and porosity. The proposed method is studied with polylactic acid (PLA) and polystyrene (PS) blends. The interconnected porous structure was created by first foaming the PLA/PS blend and then extracting the PS phase. The solid-state foaming experiments were conducted under various conditions to achieve the desired pore sizes. It is shown that the PS phase of the PLA/PS blend can be extracted much faster in the foamed samples and the pore size of the scaffolds can be easily controlled with proper gas foaming parameters. The average pore size achieved in the foaming process ranged from 20-70 μm. After PS extraction, both pore size and porosity can be further improved. For example, the pore size and porosity increased from 48 μm and 49% to 59 μm and 67%, respectively, after the PS extraction process. The fabricated porous scaffolds were used to culture human osteoblast cells. Cells grew well and gradually formed a fibrous structure. The combined solid-state foaming and immiscible polymer blending method provides a new technique for fabricating tissue engineering scaffolds.
doi:10.1088/1758-5082/3/4/045003
PMCID: PMC3229687  PMID: 21904025
Immiscible polymer blends; Solid-state foaming; Tissue engineering scaffolds; Osteoblast cells; Polylactic acid; Polystyrene
22.  Interior-architectured ZnO nanostructure for enhanced electrical conductivity via stepwise fabrication process 
Nanoscale Research Letters  2014;9(1):428.
Fabrication of ZnO nanostructure via direct patterning based on sol-gel process has advantages of low-cost, vacuum-free, and rapid process and producibility on flexible or non-uniform substrates. Recently, it has been applied in light-emitting devices and advanced nanopatterning. However, application as an electrically conducting layer processed at low temperature has been limited by its high resistivity due to interior structure. In this paper, we report interior-architecturing of sol-gel-based ZnO nanostructure for the enhanced electrical conductivity. Stepwise fabrication process combining the nanoimprint lithography (NIL) process with an additional growth process was newly applied. Changes in morphology, interior structure, and electrical characteristics of the fabricated ZnO nanolines were analyzed. It was shown that filling structural voids in ZnO nanolines with nanocrystalline ZnO contributed to reducing electrical resistivity. Both rigid and flexible substrates were adopted for the device implementation, and the robustness of ZnO nanostructure on flexible substrate was verified. Interior-architecturing of ZnO nanostructure lends itself well to the tunability of morphological, electrical, and optical characteristics of nanopatterned inorganic materials with the large-area, low-cost, and low-temperature producibility.
doi:10.1186/1556-276X-9-428
PMCID: PMC4165434  PMID: 25258595
Electrical conductivity; Interior-architecturing; ZnO nanostructure; Nanoimprint Lithography(NIL); Zinc oxide (ZnO); Hydrothermal growth
23.  Development of a nanoporous and multilayer drug-delivery platform for medical implants 
Biodegradable polymers can be applied to a variety of implants for controlled and local drug delivery. The aim of this study is to develop a biodegradable and nanoporous polymeric platform for a wide spectrum of drug-eluting implants with special focus on stent-coating applications. It was synthesized by poly(DL-lactide-co-glycolide) (PLGA 65:35, PLGA 75:25) and polycaprolactone (PCL) in a multilayer configuration by means of a spin-coating technique. The antiplatelet drug dipyridamole was loaded into the surface nanopores of the platform. Surface characterization was made by atomic force microscopy (AFM) and spectroscopic ellipsometry (SE). Platelet adhesion and drug-release kinetic studies were then carried out. The study revealed that the multilayer films are highly nanoporous, whereas the single layers of PLGA are atomically smooth and spherulites are formed in PCL. Their nanoporosity (pore diameter, depth, density, surface roughness) can be tailored by tuning the growth parameters (eg, spinning speed, polymer concentration), essential for drug-delivery performance. The origin of pore formation may be attributed to the phase separation of polymer blends via the spinodal decomposition mechanism. SE studies revealed the structural characteristics, film thickness, and optical properties even of the single layers in the triple-layer construct, providing substantial information for drug loading and complement AFM findings. Platelet adhesion studies showed that the dipyridamole-loaded coatings inhibit platelet aggregation that is a prerequisite for clotting. Finally, the films exhibited sustained release profiles of dipyridamole over 70 days. These results indicate that the current multilayer phase therapeutic approach constitutes an effective drug-delivery platform for drug-eluting implants and especially for cardiovascular stent applications.
doi:10.2147/IJN.S31185
PMCID: PMC3469098  PMID: 23071394
drug delivery; implants; stents; polymers; spin-coating; atomic force microscopy
24.  Noninvasive Characterization of the Effect of Varying PLGA Molecular Weight Blends on In Situ Forming Implant Behavior Using Ultrasound Imaging 
Theranostics  2012;2(11):1064-1077.
In situ forming implants (ISFIs) have shown promise in drug delivery applications due to their simple manufacturing and minimally invasive administration. Precise, reproducible control of drug release from ISFIs is essential to their successful clinical application. This study investigated the effect of varying the molar ratio of different molecular weight (Mw) poly(D,L-lactic-co-glycolic acid) (PLGA) polymers within a single implant on the release of a small Mw mock drug (sodium fluorescein) both in vitro and in vivo. Implants were formulated by dissolving three different PLGA Mw (15, 29, and 53kDa), as well as three 1:1 molar ratio combinations of each PLGA Mw in 1-methyl-2-pyrrolidinone (NMP) with the mock drug fluorescein. Since implant morphology and microstructure during ISFI formation and degradation is a crucial determinant of implant performance, and the rate of phase inversion has been shown to have an effect on the implant microstructure, diagnostic ultrasound was used to noninvasively quantify the extent of phase inversion and swelling behavior in both environments. Implant erosion, degradation, as well as the in vitro and in vivo release profiles were also measured using standard techniques. A non-linear mathematical model was used to correlate the drug release behavior with polymer phase inversion, with all formulations yielding an R2 value greater than 0.95. Ultrasound was also used to create a 3D image reconstruction of an implant over a 12 day span. In this study, swelling and phase inversion were shown to be inversely related to the polymer Mw with 53kDa polymer implants increasing at an average rate of 9.4%/day compared with 18.6%/day in the case of the 15 kDa PLGA. Additionally the onset of erosion, complete phase inversion, and degradation facilitated release required 9 d for 53 kDa implants, while these same processes began 3 d after injection into PBS with the 15 kDa implants. It was also observed that PLGA blends generally had intermediate properties when compared to pure polymer formulations. However, release profiles from the blend formulations were governed by a more complex set of processes and were not simply averages of release profiles from the pure polymers preparations. This study demonstrated that implant properties such as phase inversion, swelling and drug release could be tailored to by altering the molar ratio of the polymers used in the depot formulation.
doi:10.7150/thno.4181
PMCID: PMC3516837  PMID: 23227123
in situ forming implants; polymer molecular weight; phase inversion; biodegradable polymers; controlled release; ultrasound; drug delivery; PLGA.
25.  FRET detection of Octamer-4 on a protein nanoarray made by size-dependent self-assembly 
An alternative approach for fabricating a protein array at nanoscale is suggested with a capability of characterization and/or localization of multiple components on a nanoarray. Fluorescent micro- and nanobeads each conjugated with different antibodies are assembled by size-dependent self-assembly (SDSA) onto nanometer wells that were created on a polymethyl methacrylate (PMMA) substrate by electron beam lithography (EBL). Antibody-conjugated beads of different diameters are added serially and electrostatically attached to corresponding wells through electrostatic attraction between the charged beads (confirmed by zeta potential analysis) and exposed p-doped silicon substrate underneath the PMMA layer. This SDSA method is enhanced by vibrated-wire-guide manipulation of droplets on the PMMA surface containing nanometer wells. Saturation rates of antibody-conjugated beads to the nanometer patterns are up to 97% under one component and 58–70% under two components nanoarrays. High-density arrays (up to 40,000 wells) could be fabricated, which can also be multi-component. Target detection utilizes fluorescence resonance energy transfer (FRET) from fluorescent beads to fluorescent-tagged secondary antibodies to Octamer-4 (Oct4), which eliminates the need for multiple steps of rinsing. The 100 nm green beads are covalently conjugated with anti-Oct4 to capture Oct4 peptides (39 kDa); where the secondary anti-Oct4 and F(ab)2 fragment of anti-gIgG tagged with phycoerythrin are then added to function as an indicator of Oct4 detection. FRET signals are detected through confocal microscopes, and further confirmed by Fluorolog3 spectrofluorometer. The success rates of detecting Oct4 are 32% and 14% of the beads in right place under one and two component nanoarrays, respectively. Ratiometric FRET is used to quantify the amount of Oct4 peptides per each bead, which is estimated about 2 molecules per bead.
doi:10.1007/s00216-010-3990-3
PMCID: PMC2991207  PMID: 20652550
E-beam lithography; Nanometer pattern generation system; Fluorescence resonance energy transfer (FRET); Wire-guide droplet manipulation

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