Reversible switching between superhydrophobic states on a hierarchically structured surface.

Nature offers exciting examples for functional wetting properties based on superhydrophobicity, such as the self-cleaning surfaces on plant leaves and trapped air on immersed insect surfaces allowing underwater breathing. They inspire biomimetic approaches in science and technology. Superhydrophobicity relies on the Cassie wetting state where air is trapped within the surface topography. Pressure can trigger an irreversible transition from the Cassie state to the Wenzel state with no trapped air--this transition is usually detrimental for nonwetting functionality and is to be avoided. Here we present a new type of reversible, localized and instantaneous transition between two Cassie wetting states, enabled by two-level (dual-scale) topography of a superhydrophobic surface, that allows writing, erasing, rewriting and storing of optically displayed information in plastrons related to different length scales.

Integration of fully microfabricated, three-dimensionally sharp electrospray ionization tips with microfluidic glass chips.

This paper presents parallel microfabrication of three-dimensionally sharp electrospray ionization emitters made out of glass. For the first time, the fabrication of glass emitters relies only on standard microfabrication techniques (i.e., deposition, photolithography, and wet etching), and all manual machining steps are omitted. We also demonstrate a straightforward integration of the three-dimensionally sharp emitter tip with a microfluidic separation channel, which has been one of the major challenges of micro total chemical analysis systems for the past 15 years. As a result, our microfabrication approach provides glass ESI emitters that allow robust performance from run to run and tip to tip and do not suffer from sample spreading at the microchannel outlet. The repeatability of the signal intensity for parallel tips was shown to be within 8.0% RSD (n = 6), and the migration time repeatability for repeated injections was within 6.2% RSD (n = 6). At best, separation plates of up to 2.7 × 10(5)/m were obtained. Since the microfabrication process readily yields three-dimensionally sharp emitter tips, very low ESI voltages (typically 1.4-1.75 kV) suffice for stable ESI, which eventually allows for the use of a variety of different solvent compositions from purely aqueous to high organic content. Here, the advantage of using aqueous conditions is demonstrated in protein analysis.

Controlled lateral spreading and pinning of oil droplets based on topography and chemical patterning.

Geometric pinning sites can be used to control the lateral spreading and pinning of oils on surfaces. The geometric pinning effect combined with lithographic surface chemistry patterning allows controlling the shapes of oil droplets. We study the confinement effect on test structures of various protruding and intruding geometries, and employ scanning electron microscopy analysis to study the shape of the meniscus at the edges of the chemical patterns. Nanopillar and micropillar topographies are compared, revealing that it is a necessity for accurate oil patterns that the length scale of the roughness is smaller than the resolution of the surface chemistry pattern. We also find that there exists a critical, geometry-dependent threshold contact angle, below which the geometric confinement does not work, as olive oil with a static advancing contact angle of 57° accurately replicated the chemical pattern on top of nanopillar topography, but hexadecane with a static advancing contact angle of 50° penetrated the pinning sites and wetted the whole surface.

Fabrication of nanocluster silicon surface with electric discharge and the application in desorption/ionization on silicon-mass spectrometry.

This study presents a new, simple, and low-cost technique to fabricate a nanocluster silicon (NCSi) surface on planar silicon using a micro-scale direct current (DC) discharge under ambient conditions. The method requires no masks, chemicals, vacuum environment, or laser, but only a high-voltage supply. The NCSi surfaces, characterized by scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectroscopy, consist of oxidized silicon nanoclusters 50-200 nm in diameter, likely formed by melting due to high temperatures in the discharge. The minimum size of the NCSi spot is determined by the size of the discharge tip (approximately 90 microm). Arbitrary NCSi areas can be produced on a silicon wafer by moving the discharge needle on the surface with the help of a computer-controlled xyz stage. NCSi surfaces can also be formed on three-dimensional (3D) surfaces, as demonstrated with silicon micropillars. NCSi surfaces can be used, for example, in various analytical applications. In this study, we demonstrate their use as sample plates in the analysis of drugs and peptides with desorption/ionization on silicon-mass spectrometry (DIOS-MS).

Optical temperature measurements of silicon microbridge emitters.

Microbridges are miniature suspended structures fabricated in silicon. Passing a current through the microbridge can heat it up to the point of incandescence. A glowing microbridge can be used as a wideband light source. This study presents a method for optical measurement of the temperature of a microbridge. Spectroscopic measurements of microbridges are optically challenging, because the multilayer structures cause interference effects. To determine the temperature from the emitted spectrum, the emissivity was modeled with thin-film Fresnel equations. Temperatures of 500-1100 degrees C were obtained from the measured spectra at different levels of applied power. The range is limited by the sensitivity of the detectors at lower power levels and by the stability of the bridge at higher levels. Results of the optical measurements were compared with contact temperature measurements made with a microthermocouple in the same temperature range. The results of the two methods agree within 100 K.

Suspended nanostructured alumina membranes.

Suspended thin membranes have drawn increased attention due to their exceptional thermal properties. The membranes presented here are made of alumina (Al(2)O(3)), which offers several advantages over the traditional silicon nitride membranes. Alumina films are atomic layer deposited (ALD), which enables conformal deposition profiles at low deposition temperatures. Fabrication of nanocorrugated alumina membranes is demonstrated for the first time by coating nanostructured surfaces, such as silicon nanograss and polystyrene nanobeads, with a thin layer of alumina (20-200 nm), subsequently released by sacrificial plasma etching. The low deposition temperature (80 degrees C) of alumina makes it possible to coat sensitive materials, which opens up new possibilities in the field of polymer micro- and nanofabrication. Smooth alumina membranes were implemented both in continuous and in patterned forms. The smooth membranes, both continuous and perforated, were used as thermally insulating platforms for metallic devices, such as microheaters. The mechanical strength of alumina enables large suspended microstructures to be made of metals that would not have the mechanical strength in themselves.

A microfabricated micropillar liquid chromatographic chip monolithically integrated with an electrospray ionization tip.

We present the first monolithically integrated silicon/glass liquid chromatography-electrospray ionization microchip for mass spectrometry. The microchip is fabricated by bonding a silicon wafer, which has deep reactive ion etched micropillar-filled channels, together with a glass lid. Both the silicon channel and the glass lid have a through-wafer etched sharp tip that produces a stable electrospray. The microchip is also compatible with laser induced fluorescence (LIF) detection, due to the glass lid. Separation of drugs in less than 5 minutes using either SiO(2) (normal phase) or C(18) coated (reversed-phase) pillars with good sensitivity was demonstrated with mass spectrometric detection as well as separation of fluorescent compounds with LIF detection.

A microfabricated silicon platform with 60 microfluidic chips for rapid mass spectrometric analysis.

This work presents a way of using silicon microfabrication to take advantage of the rim of a silicon wafer in a novel manner. Our circular multichip platform, which is fabricated using only standard microfabrication techniques, has 60 identical miniaturized micropillar array electrospray ionization (µPESI) chips at the periphery of a silicon wafer. The fabricated platform is fixed on a computer controlled rotating table, in front of a mass spectrometer (MS). After each MS measurement an unused µPESI chip is aligned towards the MS by the programmable rotating table. Our wafer-scale platform enabled measurement of 60 samples in 8 minutes. The samples can also be stored on the platform for later analysis.

Integrated photocatalytic micropillar nanoreactor electrospray ionization chip for mimicking phase I metabolic reactions.

We developed a nanoreactor chip based system to mimic phase I metabolic reactions of small organic compounds. The microchip, made of silicon, has an anatase-phase titanium dioxide (TiO(2)) nanolayer coating for photocatalysis and an integrated electrospray ionization (ESI) tip for direct mass spectrometric (MS) analysis. This novel method for mimicking phase I metabolic reactions uses an on-chip TiO(2)-nanolayer and an external UV-lamp to induce photocatalyzed chemical reactions of drug compounds in aqueous solutions. The reactions of selected test compounds (verapamil, metoprolol, propranolol, lidocaine, 2-acetamidofluorene, and S-methylthiopurine) produced mostly the same main products as phase I metabolic reactions induced by human liver microsomes, rat hepatocytes, or cytochrome P enzymes, showing hydroxylation, dehydrogenation, and dealkylations as the main photocatalytic reactions. With this method it is possible to detect reactive and toxic products (mimicking reactive metabolites) due to the absence of biological matrices and an immediate analysis. The method used is sensitive: only 20-40 pmol (1-10 ng) of a substrate was needed for the experiment, thus it provides an inexpensive method for screening possible metabolites of new drug candidates. Due to small dimensions of the microchip, diffusion lengths are suitable for the high reaction rates, thus providing a rapid analysis as the reaction products can be detected and identified directly after the photoinduced reactions have occurred. The method shows a similar performance to that of electrochemistry, a commonly used technique for mimicking phase I metabolism.

Surface assisted laser desorption/ionization on two-layered amorphous silicon coated hybrid nanostructures.

Matrix-free laser desorption/ionization was studied on two-layered sample plates consisting of a substrate and a thin film coating. The effect of the substrate material was studied by depositing thin films of amorphous silicon on top of silicon, silica, polymeric photoresist SU-8, and an inorganic-organic hybrid. Des-arg(9)-bradykinin signal intensity was used to evaluate the sample plates. Silica and hybrid substrates were found to give superior signals compared with silicon and SU-8 because of thermal insulation and compatibility with amorphous silicon deposition process. The effect of surface topography was studied by growing amorphous silicon on hybrid micro- and nanostructures, as well as planar hybrid. Compared with planar sample plates, micro- and nanostructures gave weaker and stronger signals, respectively. Different coating materials were tested by growing different thin film coatings on the same substrate. Good signals were obtained from titania and amorphous silicon coated sample plates, but not from alumina coated, silicon nitride coated, or uncoated sample plates. Overall, the strongest signals were obtained from oxygen plasma treated and amorphous silicon coated inorganic-organic hybrid, which was tested for peptide-, protein-, and drug molecule analysis. Peptides and drugs were analyzed with little interference at low masses, subfemtomole detection levels were achieved for des-arg(9)-bradykinin, and the sample plates were also suitable for ionization of small proteins.

Silicon micropillar array electrospray chip for drug and biomolecule analysis.

We have developed a lidless micropillar array electrospray ionization chip (microPESI) combined with mass spectrometry (MS) for analysis of drugs and biomolecules. The microPESI chip, made of silicon, contains a sample introduction spot for a liquid sample, an array of micropillars (diameter, height, and distance between pillars in the range of 15-200, 20-40, and 2-80 microm, respectively), and a sharpened tip for direct electrospray formation. The microchips were fabricated using deep reactive ion etching (DRIE) which results in accurate dimensional control. The chip, providing a reliable open-channel filling structure based on capillary forces and a electrospray emitter tip for ionization, allows an easy operation and reliable, non-clogging liquid transfer. The microPESI chip can be used for a fast analysis using single sampling or for continuous infusion measurements using a syringe pump for sample introduction. The microPESI-MS shows high sensitivity, with limit of detection 30 pmol/L (60 amol or 28 fg) for verapamil measured with tandem mass spectrometry (MS/MS) and using a sample volume of 2.5 microL. The system shows also good quantitative linearity (r2 > 0.99) with linear dynamic range of at least six orders of magnitude and good ion current stability (standard deviation <5%) in 1-h continuous flow measurement. The microPESI-MS is shown to be a very potential method for direct analysis of drugs and biomolecules.