Short communication: A simple and accurate method of measuring the zeta-potential of microfluidic channels

We describe an improved method for determining the electroosmotic mobility and zeta potential of surfaces based on a current-monitoring method. This technique eliminates the requirement for measurements of channel dimensions and sample conductivities, leading to a simple high precision measurement. The zeta potential of PDMS is measured for native surfaces and surfaces treated with a nonionic surfactant in low-conductivity electrolytes.     

Induced hydrophobic recovery of oxygen plasma-treated surfaces

Plasma treatment is a widely used method in microfabrication laboratories and the plasticware industry to functionalize surfaces for device bonding and preparation for mammalian cell culture. However, spatial control of plasma treatment is challenging because it typically requires a tedious masking step that is prone to alignment errors. Currently, there are no available methods to actively revert a surface from a treated hydrophilic state to its original hydrophobic state. Here, we describe a method that relies on physical contact treatment (PCT) to actively induce hydrophobic recovery of plasma-treated surfaces. PCT involves applying brushing and peeling processes with common wipers and tapes to reverse the wettability of hydrophilized surfaces while simultaneously preserving hydrophilicity of non-contacted surfaces. We demonstrate that PCT is a user-friendly method that allows 2D and 3D surface patterning of hydrophobic regions, and the protection of hydrophilic surfaces from unwanted PCT-induced recovery. This method will be useful in academic and industrial settings where plasma treatment is frequently used.     

Selective placement of carbon nanotubes on metal-oxide surfaces

We describe a method to selectively position carbon nanotubes on Al2O3 and HfO2 surfaces. The method exploits the selective binding of alkylphosphonic acids to oxide surfaces with large isoelectric points (i.e. basic rather than acidic surfaces). We have patterned oxide surfaces with acids using both microcontact printing and conventional lithography. With proper choice of the functional end group (e.g., -CH3 or -NH2), nanotube adhesion to the surface can be either prevented or enhanced.     

Electrochemical technique for the determination of fractal dimension of dental surfaces

Fractal dimension of a carious tooth surface was determined using an electrochemical method. The method was based on time-dependent diffusion towards electrode surfaces, which is one of the most useful and reliable methods for the determination of fractal dimension of electrode surfaces. For this purpose, the tooth was covered with a gold layer, which acted as an electrode in electrochemical experiments. It is suggested that the fractal dimension can be used as a quantitative measure of the state of dental surfaces. The method presented demonstrates the power of electrochemical techniques for the determination of fractal dimension of surface of non-conducting objects.     

Superhydrophobic surfaces prepared by microstructuring of silicon using a femtosecond laser

We present a simple method for fabricating superhydrophobic silicon surfaces. The method consists of irradiating silicon wafers with femtosecond laser pulses and then coating the surfaces with a layer of fluoroalkylsilane molecules. The laser irradiation creates a surface morphology that exhibits structure on the micro- and nanoscale. By varying the laser fluence, we can tune the surface morphology and the wetting properties. We measured the static and dynamic contact angles for water and hexadecane on these surfaces. For water, the microstructured silicon surfaces yield contact angles higher than 160 degrees and negligible hysteresis. For hexadecane, the microstructuring leads to a transition from nonwetting to wetting.     

Metal-polymer “superglue” for dirty polymer surfaces

Current methods of bonding metals to polymeric surfaces involve chemical reactions between atomically clean surfaces (S. Paul, Surface Coatings, Wiley, New York 1985). We propose a novel method of attaching metals to polymeric surfaces which does not require chemical bonding and is designed to be effective for polymeric surfaces which are not clean.     

Fluorescent nanoparticle adhesion assay: a novel method for surface pKa determination of self-assembled monolayers on silicon surfaces

Since the computer industry enables us to generate smaller and smaller structures, silicon surface chemistry is becoming increasingly important for (bio-)analytical and biological applications. For controlling the binding of charged biomacromolecules such as DNA and proteins on modified silicon surfaces, the surface pK(a) is an important factor. Here we present a fluorescent nanoparticle adhesion assay as a novel method to determine the surface pK(a) of silicon surfaces modified with weak acids or bases. This method is based upon electrostatic interactions between the modified silicon surface and fluorescent nanoparticles with an opposite charge. Silicon slides were modified with 3-aminopropyltriethoxysilane (APTES) and were further derivatized with succinic anhydride. Layer thickness of these surfaces was determined by ellipsometry. After incubating the surfaces with an amine-reactive fluorescent dye, fluorescence microscopy revealed that the silicon surfaces were successfully modified with amine- and carboxyl-groups. Two surface pK(a) values were found for APTES surfaces by the fluorescent nanoparticle adhesion assay. The first surface pK(a) (6.55 ± 0.73) was comparable with the surface pK(a) obtained by contact angle titration (7.3 ± 0.8), and the second surface pK(a) (9.94 ± 0.19) was only found by using the fluorescent nanoparticle adhesion assay. The surface pK(a) of the carboxyl-modified surface by the fluorescent nanoparticle adhesion assay (4.37 ± 0.59) did not significantly differ from that found by contact angle titration (5.7 ± 1.4). In conclusion, we have developed a novel method to determine the surface pK(a) of modified silicon surfaces: the fluorescent nanoparticle adhesion assay. This method may provide a useful tool for designing pH-dependent electrostatic protein and particle binding/release and to design surfaces with a pH-dependent surface charge for (bio-)analytical lab-on-a-chip devices or drug delivery purposes.     

An attempt to simulate structure and realistic images of scratches on rough polymeric surfaces

Numerical simulation of scratching has been shown to exhibit many advantages in material development and surface design and can provide detailed information associated with the scratch structure. However, the visual appearance of simulated scratches in real-world scenarios has seldom been studied. This study simulates the structure and visual appearance of scratches on rough polymer surfaces by combining the finite element method (FEM) with computer imaging (CI) techniques. FEM modeling of scratching incorporates a wide range of microgeometries in rough surfaces to ensure that the resulting scratch surfaces contain all features, regardless of whether they are visible to the human eye. Computer graphics produce realistic images of numeric scratch surfaces in real-world lighting conditions. This method demonstrates the advantages of easily simulating scratches on rough surfaces and assessing both abrasion strength and visual scratch resistance. Scratch tests on commercial polymer surfaces at different scratch forces demonstrate that the method can satisfactorily predict the structures and scales of scratches. The simulated images correlate closely with camera-acquired photographs in terms of the visual appearance of scratch surfaces, effect of lighting conditions, and dependence of the visual width of scratches on the scratching force, material, pigment, and additive in the material.     

Surface functionalization of silicon oxide at room temperature and atmospheric pressure

A novel method to derivatize silicon surfaces with 3-mercaptopropylsilane molecules has been developed and optimized. This method is based on an argon flow that increases the evaporation rate of the silane molecules by lowering the partial pressure of the silane molecules in gas phase above the liquid silane, at room temperature. X-ray photoelectron spectroscopy studies of the surfaces showed a dense monolayer coverage as well as hydrolysis of the silane methoxy groups. Atomic force microscopy was used to investigate the roughness of the surfaces after each step of the derivatization process. Since the final surface has a measured surface roughness of 0.19 nm, this method will be especially useful for further synthetic routes and advanced single molecule detection studies of interactions on surfaces as well as improvement of existing conventional techniques for surface derivatization and analysis.     

Optimizing transition states via kernel-based machine learning

We present a method for optimizing transition state theory dividing surfaces with support vector machines. The resulting dividing surfaces require no a priori information or intuition about reaction mechanisms. To generate optimal dividing surfaces, we apply a cycle of machine-learning and refinement of the surface by molecular dynamics sampling. We demonstrate that the machine-learned surfaces contain the relevant low-energy saddle points. The mechanisms of reactions may be extracted from the machine-learned surfaces in order to identify unexpected chemically relevant processes. Furthermore, we show that the machine-learned surfaces significantly increase the transmission coefficient for an adatom exchange involving many coupled degrees of freedom on a (100) surface when compared to a distance-based dividing surface.     

Spontaneous formation of fractal structures on triglyceride surfaces with reference to their super water-repellent properties

Alkylketene dimer (AKD), a kind of wax, has been known to form fractal surfaces spontaneously and show super water-repellency. Such formation of water-repellent and fractal surfaces was also found in this work for triglycerides. Since the crystal phase transitions of these waxes were well studied, we studied the formation of their fractal surfaces through contact angle measurements, differential scanning calorimetry (DSC), and X-ray diffraction (XRD). From time-dependent contact angle measurements, it was found that the formation of super water-repellent surfaces with fractal structures occurred spontaneously also on the triglyceride surfaces at different temperatures. The freshly solidified triglyceride surfaces were almost transparent, and their initial contact angles of water were close to 110 degrees. The surfaces then became rough and clouded after being incubated for a certain time at a specified temperature. The super water-repellent surfaces were quite rough and showed fractal structures with the dimension of ca. 2.2 calculated from the scanning electron microscopic (SEM) images by the box-counting method. The phase transformation from a metastable state to a stable cystalline one after the solidification from the melt of triglycerides was clearly observed by DSC and XRD measurements. The fractal crystalline structures and the super water-repellency resulted from this phase transformation and the crystal growth. Ensuring the initial sample solidified into the metastable state and curing the surface at an appropriate temperature are key factors for the successful preparation of fractal triglyceride surfaces by the solidification method.     

Reverse nonequilibrium molecular dynamics simulation of thermal conductivity in nanoconfined polyamide-6,6

A new molecular dynamics simulation method, with coupling to external baths, is used to perform equilibrium simulations on polyamide-6,6 trimers nanoconfined between graphene surfaces, in equilibrium with the bulk polymer. The method is coupled with the reverse nonequilibrium molecular dynamics simulation technique to exchange heat in the direction normal to the surfaces. To be able to study the effect of confinement on the heat conductance in nanoconfined pores, in this work a number of simulations on systems with different pore sizes are done. It is concluded that the coefficient of heat conductivity depends on the degree of polymer layering between the surfaces and on the pore width. Our results further indicate a considerable temperature drop at the interface between the surfaces and polymer. The calculated Kapitza lengths depend on the intersurface distance and on the layering of the polymer nanoconfined between the surfaces.     

Micropatterned polymer surfaces induced by nonsolvent

In this work, we present a facile method for fabricating polymer thin films with micropatterned surfaces by evaporating polymer solution containing a small amount of nonsolvent of polymer in air. Poly(methyl methacrylate) (PMMA) and polystyrene (PS) films with densely packed micropores on the surfaces were fabricated. This method was also used to prepare three-dimensional PMMA films with micropatterned surfaces. The effects of nonsolvent content; evaporation temperature; and interactions between the polymer, solvent, and nonsolvent on the specific patterns were investigated, and the formation mechanism of the pores is discussed. This simple route can potentially be used, for example, in the large-scale production of patterned surfaces, three-dimensional painting, and hydrophobicity-enhancing coatings.     

Theoretical evaluation of potential surfaces,equilibrium geometries and vibronic transition intensities of excimers: the pyrene crystal excimer

A general method for evaluation of equilibrium geometries and vibronic transition intensities of crystalline excimers is described. The method provides realistic potential surfaces which include, in addition to the α electron surfaces, also the repulsive hard core of the α electrons and the effect of the crystal potential. The method is applied to the study of the potential surfaces of the pyrene excimer, both in the crystal and in the gas phase. The method is also used for a direct evaluation of the vibronic structure of the excimer emission. The calculations reproduce the main experimentally observed properties including the structureless envelope of the emission band and the temperature dependence of its line width.     

From the plateau problem to periodic minimal surfaces in lipids,surfactants and diblock copolymers

A novel method is presented for generating periodic surfaces. Such periodic surfaces appear in all systems which are characterized by internal interfaces and which additionally exhibit ordering. One example are systems of AB diblock copolymers, where the internal interfaces are formed by the chemical bonds between the A and B blocks. In these systems at least two bicontinuous phases are formed: the ordered bicontinuous double diamond phase and the gyroid phase. In these phases the ordered domains of A monomers and B monomers are separated by a periodic interface of the same symmetry as the phases themselves. Here we present a novel method for the generation of such periodic surfaces based on the simple Landau-Ginzburg model of microemulsions. We test the method on four known minimal periodic surfaces, find two new surfaces of cubic symmetry, and show how to obtain periodic surfaces of high genus and n-tuply continuous phases (n > 2). So far only bicontinuous (n = 2) phases have been known. We point out that the Landau model used here should be generic for all systems characterized by internal interfaces, including the diblock copolymer systems.     

Static Method to Evaluate Interaction Forces by AFM

An atomic force microscope (AFM) is a very powerful tool to evaluate interaction forces between surfaces in liquids on the molecular scale, but the apparatus was not designed to measure forces in equilibrium. Hence, data obtained by AFM are not in equilibrium in principle. Here we propose a static method to obtain interaction forces between stationary surfaces in aqueous solutions using AFM. The validity of the proposed method was confirmed by comparing interaction forces measured by this method with those by the normal dynamic method for the system of a mica plate and a silica particle in electrolyte solutions where an equilibrium was nearly achieved because water molecules and ions moved much faster than surfaces. The applicability of this method to the measurement of hydrophobic attraction was then examined, and important information on the attraction was obtained. Copyright 2001 Academic Press.     

A Quick and Reproducible Silanization Method by Using Plasma Activation for Hydrophobicity-Based Kinesin Single Molecule Fluorescence–Microscopy Assays

Single-molecule assays often require functionalized surfaces. One approach for microtubule assays renders surfaces hydrophobic and uses amphiphilic blocking agents. However, the optimal hydrophobicity is unclear, protocols take long, produce toxic waste, and are susceptible to failure. Our method uses plasma activation with hydrocarbons for hexamethyldisilazane (HMDS) silanization in the gas phase. We measured the surface hydrophobicity, its effect on how well microtubule filaments were bound to the surface, and the number of nonspecific interactions with kinesin motor proteins. Additionally, we tested and discuss the use of different silanes and activation methods. We found that even weakly hydrophobic surfaces were optimal. Our environmentally friendly method significanty reduced the overall preparation effort and resulted in reproducible, high-quality surfaces with low variability. We expect the method to be applicable to a wide range of other single-molecule assays.     

Tandem "click" reactions at acetylene-terminated Si(100) monolayers

We demonstrate a simple method for coupling alkynes to alkynes. The method involves tandem azide-alkyne cycloaddition reactions ("click" chemistry) for the immobilization of 1-alkyne species onto an alkyne modified surface in a one-pot procedure. In the case presented, these reactions take place on a nonoxidized Si(100) surface although the approach is general for linking alkynes to alkynes. The applicability of the method in the preparation of electrically well-behaved functionalized surfaces is demonstrated by coupling an alkyne-tagged ferrocene species onto alkyne-terminated Si(100) surfaces. The utility of the approach in biotechnology is shown by constructing a DNA sensing interface by derivatization of the acetylenyl surface with commercially available alkyne-tagged oligonucleotides. Cyclic voltametry, electrochemical impedance spectroscopy, X-ray photoelectron spectroscopy, and X-ray reflectometry are used to characterize the coupling reactions and performance of the final modified surfaces. These data show that this synthetic protocol gives chemically well-defined, electronically well-behaved, and robust (bio)functionalized monolayers on silicon semiconducting surfaces.     

Nanoparticle-assisted surface immobilization of phospholipid liposomes

Phospholipid liposomes (100-200 nm diameter) are deposited onto solid substrates after stabilizing them against fusion with the solid by allowing charged nanoparticles to adsorb at approximately 25% surface coverage. The immobilized vesicles remain stable over a period of days. Epifluorescence imaging shows that they diffuse freely over surfaces with the same charge but adsorb tightly onto surfaces with opposite charge. Nanoparticle adsorption to surface patterns of opposite charge provides a facile method to create large-scale surface-supported arrays of intact liposomes. This surface attachment method is simple chemically and applies generally for solid surfaces that can be hydrophobic or hydrophilic. Offering routes to localize proteins and other vesicle-contained objects at surfaces in tailored spatial patterns, these immobilized liposome arrays may find diverse applications in the emerging field of nanobiotechnology.     

A novel method of aligning molecules by local surface shape similarity

A novel shape-based method has been developed for overlaying a series of molecule surfaces into a common reference frame. The surfaces are represented by a set of circular patches of approximately constant curvature. Two molecules are overlaid using a clique-detection algorithm to find a set of patches in the two surfaces that correspond, and overlaying the molecules so that the similar patches on the two surfaces are coincident. The method is thus able to detect areas of local, rather than global, similarity. A consensus overlay for a group of molecules is performed by examining the scores of all pairwise overlays and performing a set of overlays with the highest scores. The utility of the method has been examined by comparing the overlaid and experimental configurations of 4 sets of molecules for which there are X-ray crystal structures of the molecules bound to a protein active site. Results for the overlays are generally encouraging. Of particular note is the correct prediction of the `reverse orientation' for ligands binding to human rhinovirus coat protein HRV14.