Organosilane Monolayer Research Articles

Photopatterning Proteins and Cells in Aqueous Environment Using TiO<sub>2</sub> Photocatalysis

Organic contaminants adsorbed on the surface of titanium dioxide (TiO2) can be decomposed by photocatalysis under ultraviolet (UV) light. Here we describe a novel protocol employing the TiO2 photocatalysis to locally alter cell affinity of the substrate surface. For this experiment, a thin TiO2 film was sputter-coated on a glass coverslip, and the TiO2 surface was subsequently modified with an organosilane monolayer derived from octadecyltrichlorosilane (OTS), which inhibits cell adhesion. The sample was immersed in a cell culture medium, and focused UV light was irradiated to an octagonal region. When a neuronal cell line PC12 cells were plated on the sample, cells adhered only on the UV-irradiated area. We further show that this surface modification can also be performed in situ, i.e., even when cells are growing on the substrate. Proper modification of the surface required an extracellular matrix protein collagen to be present in the medium at the time of UV irradiation. The technique presented here can potentially be employed in patterning multiple cell types for constructing coculture systems or to arbitrarily manipulate cells under culture.

Photopatterning Proteins and Cells in Aqueous Environment Using TiO2 Photocatalysis.

Organic contaminants adsorbed on the surface of titanium dioxide (TiO2) can be decomposed by photocatalysis under ultraviolet (UV) light. Here we describe a novel protocol employing the TiO2 photocatalysis to locally alter cell affinity of the substrate surface. For this experiment, a thin TiO2 film was sputter-coated on a glass coverslip, and the TiO2 surface was subsequently modified with an organosilane monolayer derived from octadecyltrichlorosilane (OTS), which inhibits cell adhesion. The sample was immersed in a cell culture medium, and focused UV light was irradiated to an octagonal region. When a neuronal cell line PC12 cells were plated on the sample, cells adhered only on the UV-irradiated area. We further show that this surface modification can also be performed in situ, i.e., even when cells are growing on the substrate. Proper modification of the surface required an extracellular matrix protein collagen to be present in the medium at the time of UV irradiation. The technique presented here can potentially be employed in patterning multiple cell types for constructing coculture systems or to arbitrarily manipulate cells under culture.

Effects of surface water on organosilane nanostructure fabrication using particle lithography

Patterned organosilane self-assembled monolayers serve as molecular platforms for electronic, optical, and sensing applications. Among the numerous strategies to pattern organosilane monolayers, particle lithography offers a high throughput means to fabricate arrays of organosilane nanopatterns across large areas. Herein, we demonstrate that the utility of particle lithography for generating nanostructures can be further controlled by changes in sample preparation. Our systematic study of various drying conditions demonstrates a correlation between sample preparation and surface water and uses these findings to form nanopores, pillars, and rings within organosilane monolayers. Silica mesospheres deposited on Si substrates that are subjected to less rigorous drying conditions (3h at room temperature) prior to organosilane deposition yield nanopores within decyltrichlorosilane monolayers that are significantly smaller than those produced on Si substrates that are prepared under more forcing conditions (12h at room temperature and 2h at 140°C). This disparity in nanopore diameter can be rationalized by the presence or absence of water between the silica mesospheres and Si substrate. Sequential deposition of two organosilanes offers further evidence for the presence or absence of water beneath the silica mesospheres. For samples that are less rigorously dried, complete organosilane pillars are observed, and for samples that are more rigorously dried, organosilane rings are observed where the inner diameter is defined by the mesosphere-substrate contact geometry. The ability to produce varied organosilane nanostructures provides valuable insights about the water that is present on the surface and within the silica mesosphere template. These insights into the surface water and the effects of sample preparation on organosilane nanostructures enable greater hierarchical control over the fabrication process.

Influence of Solvent on Octadecyltrichlorosilane Nanostructures Fabricated Using Particle Lithography

Numerous strategies have been devised to register organosilane monolayers for applications ranging from lubricants to semiconductor surface resists. Of these patterning techniques, particle lithography offers a straightforward and high-throughput method to create periodic arrays of organosilane nanopatterns. Herein, we describe the influence of solvent on the solution-phase formation of periodic arrays of nanopores within octadecyltrichlorosilane (OTS) monolayers using particle lithography. Our systematic study of various compositions of two miscible solvents, anhydrous toluene and bicyclohexyl, demonstrates control over nanopore size and OTS surface coverage. Smaller nanopores are generated from solutions with higher anhydrous toluene composition, and larger nanopores are generated from solutions with higher bicyclohexyl composition. A study of the effect of deposition time on nanopore formation found that at shorter deposition times (<5 min), the nanopore size is limited by diffusion into the water meni...

Biofunctional hybrid materials: bimolecular organosilane monolayers on FeCr alloys

Hybrid organic–inorganic interfaces are the key to functionalization of stainless steel (SS). We present a solution-based deposition method for fabricating uniform bimolecular organosilane monolayers on SS and show that their properties and functionalities can be further developed through site-specific biotinylation. We correlate molecular properties of the interface with its reactivity via surface sensitive synchrotron radiation mediated high-resolution photoelectron spectroscopy (HR-PES) and chemical derivatization (CD), and we demonstrate specific bonding of streptavidin proteins to the hybrid interface. The method facilitates efficient growth of uniform bimolecular organosilane monolayers on SS under ambient conditions without the need to prime the SS surface with vacuum-deposited inorganic buffer layers. The obtained insights into molecular bonding, orientation, and behaviour of surface-confined organofunctional silanes on SS enable a new generic approach to functionalization of SS surfaces with versatile nanomolecular organosilane layers.

In situ modification of cell-culture scaffolds by photocatalytic decomposition of organosilane monolayers

We demonstrate a novel application of TiO2 photocatalysis for modifying the cell affinity of a scaffold surface in a cell-culture environment. An as-deposited octadecyltrichlorosilane self-assembled monolayer (OTS SAM) on TiO2 was found to be hydrophobic and stably adsorbed serum albumins that blocked subsequent adsorption of other proteins and cells. Upon irradiation of ultraviolet (UV) light, OTS molecules were decomposed and became permissive to the adhesion of PC12 cells via adsorption of an extracellular matrix protein, collagen. Optimal UV dose was 200 J cm−2 for OTS SAM on TiO2. The amount of collagen adsorption decreased when excessive UV light was irradiated, most likely due to the surface being too hydrophilic to support its adsorption. This UV-induced modification required TiO2 to be present under the SAM and hence is a result of TiO2 photocatalysis. The UV irradiation for surface modification can be performed before cell plating or during cell culture. We also demonstrate that poly(ethylene glycol) SAM can also be patterned with this method, indicating that it is applicable to both hydrophobic and hydrophilic SAMs. This method provides a unique tool for fabricating cell microarrays and studying dynamical properties of living cells.

Barrier Integrity of Electroless Diffusion Barriers and Organosilane Monolayer against Copper Diffusion under Bias Temperature Stress

Barrier integrity of electroless NiB and CoWP/NiB thin layers against copper (Cu) diffusion was evaluated by time-dependent dielectric breakdown (TDDB) under bias temperature stress (BTS) using metal oxide semiconductor (MOS) test structures. The BTS tests were carried out also for an approximately 2.2-nm-thick organosilane monolayer (OSML), which has been used as the underlayer of the electroless barrier layers (EBLs). It was found that the barrier integrity of the EBLs was NiB 40 nm > NiB 10 nm > CoWP/NiB 40 nm = CoWP/NiB 10 nm in this order. The field acceleration parameter of the TDDB lifetime was almost the same for all EBLs. Initial failures and wide lifetime distributions were observed for CoWP/NiB when the NiB catalyst layer for CoWP was not thick enough, which is considered to be due to the large surface roughness. In addition, the OSML was found to have some barrier properties. Although the reliability of OSML was inferior to electroless NiB and CoWP/NiB barrier layers, it is considered that the barrier integrity of the EBLs was partially supported by the OSML.

Barrier Integrity of Electroless Diffusion Barriers and Organosilane Monolayer against Copper Diffusion under Bias Temperature Stress

Barrier integrity of electroless NiB and CoWP/NiB thin layers against copper (Cu) diffusion was evaluated by time-dependent dielectric breakdown (TDDB) under bias temperature stress (BTS) using metal oxide semiconductor (MOS) test structures. The BTS tests were carried out also for an approximately 2.2-nm-thick organosilane monolayer (OSML), which has been used as the underlayer of the electroless barrier layers (EBLs). It was found that the barrier integrity of the EBLs was NiB 40 nm > NiB 10 nm > CoWP/NiB 40 nm = CoWP/NiB 10 nm in this order. The field acceleration parameter of the TDDB lifetime was almost the same for all EBLs. Initial failures and wide lifetime distributions were observed for CoWP/NiB when the NiB catalyst layer for CoWP was not thick enough, which is considered to be due to the large surface roughness. In addition, the OSML was found to have some barrier properties. Although the reliability of OSML was inferior to electroless NiB and CoWP/NiB barrier layers, it is considered that the barrier integrity of the EBLs was partially supported by the OSML.

Ring patterns in liquid crystals aligned by phase-separated two-component monolayers

We investigate the alignment of 4′-pentyl-4-cynobiphenyl (5CB) liquid crystal on phase-separated two-component organosilane monolayers that consist of the protruding islands surrounded by a continuous phase. The molecular disordering at the protruding island edge locally perturbs the homeotropic alignment of the 5CB induced the phase-separated monolayers, leading to the formation of ring patterns. The edge effect on the 5CB alignment decreases with the decrease of the height difference between the protruding islands and the surrounding monolayer and increases with the decrease of the size of the protruding islands.

Nanopatterning of Functional Materials by Gas Phase Pattern Deposition of Self-Assembled Molecular Thin Films in Combination with Electrodeposition

We present a general methodology to pattern functional materials on the nanometer scale using self-assembled molecular templates on conducting substrates. A soft lithographic gas phase edge patterning process using poly(dimethylsiloxane) molds was employed to form electrically isolating organosilane patterns of a few nanometer thickness and a line width that could be tuned by varying the time of deposition. Electrodeposition was employed to deposit patterns of Ni and ZnO on these prepatterned substrates. Deposition occurred only on patches of the substrate where no organosilane monolayer was present. The process is simple, inexpensive, and scalable to large areas. We achieved formation of metallic and oxide material patterns with a lateral resolution of 80 nm.

In situ guidance of individual neurites by wet femtosecond-laser processing of organosilane monolayers

In situ guidance of individual neurites by wet femtosecond-laser processing of organosilane monolayers

Organosilane deposition for microfluidic applications

Treatment of surfaces to change the interaction of fluids with them is a critical step in constructing useful microfluidics devices, especially those used in biological applications. Silanization, the generic term applied to the formation of organosilane monolayers on substrates, is both widely reported in the literature and troublesome in actual application for the uninitiated. These monolayers can be subsequently modified to produce a surface of a specific functionality. Here various organosilane deposition protocols and some application notes are provided as a basis for the novice reader to construct their own silanization procedures, and as a practical resource to a broader range of techniques even for the experienced user.

Application of Organosilane Monolayer Template to Quantitative Evaluation of Cancer Cell Adhesive Ability

Application of Organosilane Monolayer Template to Quantitative Evaluation of Cancer Cell Adhesive Ability

Application of Organosilane Monolayer Template to Quantitative Evaluation of Cancer Cell Adhesive Ability

The adhesive ability of two human pancreatic cancer cell lines was evaluated using organosilane monolayer templates (OMTs). Using the OMT, the spreading area of adhered cells can be limited, and this enables us to focus on the initial attachment process of adhesion. Moreover, it becomes possible to arrange the cells in an array and to quantitatively evaluate the number of attached cells. The adhesive ability of the cancer cells cultured on the OMT was controlled by adding (-)-epigallocatechin-3-gallate (EGCG), which blocks a receptor that mediates cell adhesion and is overexpressed in cancer cells. Measurement of the relative ability of the cancer cells to attach to the OMT revealed that the ability for attachment decreased with increasing EGCG concentration. The results agreed well with the western blot analysis, indicating that the OMT can potentially be employed to evaluate the adhesive ability of various cancer cells.

Large-Scale Graphene Transistors with Enhanced Performance and Reliability Based on Interface Engineering by Phenylsilane Self-Assembled Monolayers

In this letter, we report the dielectric/graphene interface physics and engineering of large-scale, chemical vapor deposited (CVD) graphene transistors by self-assembling a molecular-scale organosilane monolayer onto the dielectric surface. We show that phenyl-alkyl-terminated self-assembled monolayers (SAM) at the dielectric/graphene interface consistently improve the graphene device performance and reliability. The extrinsic field-effect mobility of large-scale CVD graphene transistors on the phenyl-SAM engineered dielectric is currently up to 2500 cm(2)/(V s) at room temperature, considerably higher than the counterparts without the SAM. In addition, significant reduction on the bias stress instability and hysteresis is achieved by the SAM-based interface engineering. Further analysis reveals that charge injection from graphene to the dielectric/graphene interface dominates the observed hysteresis behavior. For both graphene transistors with and without SAMs, the bias stress stability, that is, Dirac point shift under bias stress, is well described by the stretched exponential model with its fitting parameters clearly indicating different interface properties.

On ice-releasing properties of rough hydrophobic coatings

Abstract In this work, ice repellency of rough hydrophobic coatings based on different materials and with different surface topographies is evaluated. The coatings were prepared either from a fluoropolymer incorporated with nanoparticles or by etching aluminum alloy substrate followed by further hydrophobization of the rough surface via an organosilane monolayer adsorbed from solution. This allowed comparing the ice-releasing performance of rough surfaces with high water contact angles (∼ 150–153°) and different dynamic hydrophobicities and mechanical properties. Artificially created glaze ice, similar to naturally occurring glaze, was accreted on the surfaces by spraying supercooled water microdroplets in a wind tunnel at subzero temperature. The ice adhesion strength was evaluated by spinning the samples in a centrifuge at constantly increasing speeds until ice detachment occurred. The results showed that, after several icing–deicing cycles, the more robust surfaces prepared by etching the aluminum substrate maintained their ice-releasing properties better, compared to their counterparts based on nanoparticle-incorporated fluoropolymer. The effect of the dynamic hydrophobicity of the coatings was also examined, clearly demonstrating that the surface with low dynamic hydrophobicity is not ice-repellent, although it demonstrates large values of water contact angle.

Biosensors: (Adv. Funct. Mater. 1/2010)

Advanced Functional MaterialsVolume 20, Issue 1 Inside Front CoverFree Access Biosensors: (Adv. Funct. Mater. 1/2010) First published: 28 December 2009 https://doi.org/10.1002/adfm.200990116Citations: 1AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat Graphical Abstract The inside cover portrays the work of Dorvel et al., who describe the formation of monofunctional organosilane monolayers via vapor phase deposition onto microarray glass slides on page 89. The deposition method then allows for subnanometer level biointerfacing of target proteins to the surface. This subnanometer interfacing method shows promise for the creation of biosensor platforms with higher sensitivity due to higher linker densities and reduction of background noise. Citing Literature Volume20, Issue1January 8, 2010 RelatedInformation

Metal−Dielectric Interface Toughening by Catalyzed Ring Opening in a Monolayer

We demonstrate a novel strategy for toughening metal−dielectric interfaces by catalyzed fissure of low-polarizability moieties in an organosilane monolayer. Photoelectron spectroscopy and ab initio calculations show that seven-fold toughening of Cu−silica interfaces is due to Cu-catalyzed disilacyclobutane ring opening and bonding. Our findings open up possibilities for directly integrating metals with molecularly derived low permittivity dielectrics for applications without using an intermediary glue layer, for example, by incorporating strained moieties into polymer precursors.

Patterned Organosilane Monolayers as Lyophobic−Lyophilic Guiding Templates in Surface Self-Assembly: Monolayer Self-Assembly versus Wetting-Driven Self-Assembly

Monolayer self-assembly (MSA) was discovered owing to the spectacular liquid repellency (lyophobicity) characteristic of typical self-assembling monolayers of long tail amphiphiles, which facilitates a straightforward visualization of the MSA process without the need of any sophisticated analytical equipment. It is this remarkable property that allows precise control of the self-assembly of discrete, well-defined monolayers, and it was the alternation of lyophobicity and lyophilicity (liquid affinity) in a system of monolayer-forming bifunctional organosilanes that allowed the extension of the principle of MSA to the layer-by-layer self-assembly of planed multilayers. On this basis, the possibility of generating at will patterned monolayer surfaces with lyophobic and lyophilic regions paves the way to the engineering of molecular templates for site-defined deposition of materials on a surface via either precise MSA or wetting-driven self-assembly (WDSA), namely, the selective retention of a liquid repelled by the lyophobic regions of the pattern on its lyophilic sites. Highly ordered organosilane monolayer and thicker layer-by-layer assembled structures are shown to be ideally suited for this purpose. Examples are given of novel WDSA and MSA processes, such as guided deposition by WDSA on lyophobic-lyophilic monolayer and bilayer template patterns at elevated temperatures, from melts and solutions that solidify upon cooling to the ambient temperature, and the possible extension of constructive nanolithography to thicker layer-by-layer assembled films, which paves the way to three-dimensional (3D) template patterns made of readily available monofunctional n-alkyl silanes only. It is further shown how WDSA may contribute to MSA on nanoscale template features as well as how combined MSA and WDSA modes of surface assembly may lead to composite surface architectures exhibiting rather surprising new properties. Finally, a critical evaluation is offered of the scope, advantages, and limitations of MSA and WDSA in the bottom-up fabrication of surface structures on variable length scales from nano to macro.

Self-assembly of human plasma fibrinogens on binary organosilane monolayers with micro domains

The adsorption behavior and self-assembly of human plasma fibrinogen (HPF) on binary methyl- and amino-terminated self-assembled monolayers (SAMs) were investigated by atomic force microscopy (AFM). The binary SAMs were fabricated through self-assembly mechanism of organosilane molecules. The height of domains is the domain height is 0.8 ± 0.2 nm from the AFM topographic image. It corresponds to the domain height is 0.8 ± 0.2 nm from the AFM topographic image. It corresponds to the difference between the length of the alkyl chain of octadecyltrichlorosilane (OTS) and that of n-(6-aminohexyl)aminopropyltrimethoxysilane (AHAPS). The fibrinogen solution used ultrapure water as the solvent and its pH was adjusted at 3 and 10. From the AFM results at pH 3, HPF only formed network structures on the OTS domains of the binary SAM at early immersion times, and then the network structures expanded and connected between OTS domains through the AHAPS surface at long immersion times. In this case, a few HPFs are discretely adsorbed on the AHAPS surface. However, HPF is uniformly adsorbed on the binary SAM under the other conditions of pH.