Nanoporous Silicon Membrane Research Articles

Ion-Selective Permeability of an Ultrathin Nanoporous Silicon Membrane as Probed by Scanning Electrochemical Microscopy Using Micropipet-Supported ITIES Tips

We report on the application of scanning electrochemical microscopy (SECM) to the measurement of the ion-selective permeability of porous nanocrystalline silicon membrane as a new type of nanoporous material with potential applications in analytical, biomedical, and biotechnology device development. The reliable measurement of high permeability in the molecularly thin nanoporous membrane to various ions is important for greater understanding of its structure-permeability relationship and also for its successful applications. In this work, this challenging measurement is enabled by introducing two novel features into amperometric SECM tips based on the micropipet-supported interface between two immiscible electrolyte solutions (ITIES) to reveal the important ion-transport properties of the ultrathin nanopore membrane. The tip of a conventional heat-pulled micropipet is milled using the focused ion beam (FIB) technique to be smoother, better aligned, and subsequently, approach closer to the membrane surface, which allows for more precise and accurate permeability measurement. The high membrane permeability to small monovalent ions is determined using FIB-milled micropipet tips to establish a theoretical formula for the membrane permeability that is controlled by free ion diffusion across water-filled nanopores. Moreover, the ITIES tips are rendered selective for larger polyions with biomedical importance, i.e., polyanionic pentasaccharide Arixtra and polycationic peptide protamine, to yield the membrane permeability that is lower than the corresponding diffusion-limited permeability. The hindered transport of the respective polyions is unequivocally ascribed to electrostatic and steric repulsions from the wall of the nanopores, i.e., the charge and size effects.

The D&T report

The D&T report

Fabrication of Nanoporous Silicon Membrane Based Micro-Direct Methanol Fuel Cell

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Charge transport and diffusion of ionic liquids in nanoporous silica membranes

Charge transport in 1-hexyl-3-methylimidazolium hexafluorophosphate ionic liquid in oxidized nanoporous silicon membranes is investigated in a wide frequency and temperature range by a combination of Broadband Dielectric Spectroscopy (BDS) and Pulsed Field Gradient Nuclear Magnetic Resonance (PFG NMR). By applying the Einstein-Smoluchowski relations to the dielectric spectra, diffusion coefficient is obtained in quantitative agreement with independent PFG NMR measurements. More than 10-fold systematic decrease in the effective diffusion coefficient from the bulk value is observed in hydrophilic silica nanopores. A model assuming a reduced mobility at the pore-matrix interface is shown to provide a quantitative explanation for the remarkable decrease of effective transport quantities (such as diffusion coefficient, dc conductivity and consequently, the dielectric loss) of the ionic liquid in non-silanized membranes. This approach is supported by the observation that silanization of porous silica membranes results in a significant increase of the effective diffusion coefficient, which approaches the value for the bulk liquid.

A Structure−Permeability Relationship of Ultrathin Nanoporous Silicon Membrane: A Comparison with the Nuclear Envelope

We report on a simple, quantitative relationship between structure and permeability of a novel ultrathin nanoporous membrane based on nanocrystalline silicon. Large permeability of the free-standing nanomembrane to Ru(NH3)63+, O2, or 1,1'-ferrocenedimethanol, which was able to be measured for the first time by employing scanning electrochemical microscopy, is proportional to the density (67 mum-2) and average radius (5.6 nm) of nanopores. As solution electrolyte concentration decreases down to 0.01 M, the nanopores are selectively "closed" against Fe(CN)64- because of electrostatic repulsion against negative charges at the pore wall. Permeability of the silicon nanomembrane was compared to permeability of the nuclear envelope to find that the channel diameter of the nuclear pore complex that perforates the nuclear envelope is much larger than the average diameter of the silicon nanopores and concomitantly a hypothetical diameter of 10 nm.

An Improved Miniature Direct Formic Acid Fuel Cell Based on Nanoporous Silicon for Portable Power Generation

Silicon-based fuel cells are under active development for power generation for portable electronic devices. Previous work has demonstrated that an acid loaded nanoporous silicon membrane could be a suitable proton conducting material that is compatible with silicon microfabrication technology. In this design, the acid acts as an electrolyte while the porous silicon acts as a separator that limits fuel crossover. Unfortunately, the power output of the previous nanoporous-silicon based fuel cells was far below Nafion-based fuel cells. In this paper a new design for a nanoporous-silicon based miniature direct formic acid fuel cell is proposed and tested. The effects of the thickness, pore size, and formic acid concentration on the nanoporous silicon miniature fuel cell performance are studied. At room temperature in ambient air the fuel cell peak power density reached with a current density level of , using formic acid fuel with sulfuric acid electrolyte. This power output is three times higher than in previous work. These results show that the new design is a substantial improvement and that microfabricated silicon fuel cells using nanoporous silicon are potentially excellent power sources for portable electronic devices.

Differentiated Growth of Human Renal Tubule Cells on Thin-Film and Nanostructured Materials

Over 300,000 Americans are dependent on hemodialysis as treatment for renal failure, and kidney transplantation is limited by scarcity of donor organs. This shortage has prompted research into tissue engineering of renal replacement therapy. Existing bioartificial kidneys are large and their use labor intensive, but they have shown improved survival compared to conventional therapy in preclinical studies and an US Food and Drug Administration-approved phase 2 clinical trial. This hybrid technology will require miniaturization of hemofilters, cell culture substrates, sensors, and integration of control electronics. Using the same harvesting and isolation techniques used in preparing bioartificial kidneys for clinical use, we characterized human renal tubule cell growth on a variety of silicon and related thin-film material substrates commonly used in the construction of microelectromechanical systems (MEMS), as well as novel silicon nanopore membranes (SNMs). Human cortical tubular epithelial cells (HCTC) were seeded onto samples of single-crystal silicon, polycrystalline silicon, silicon dioxide, silicon nitride, SU-8 photoresist, SNMs, and polyester tissue culture inserts, and grown to confluence. The cells formed confluent monolayers with tight junctions and central cilia. Transepithelial resistances were similar between SNMs and polyester membranes. The differentiated growth of human tubular epithelial cells on MEMS materials strongly suggests that miniaturization of the existing bioartificial kidney will be feasible, paving the way for widespread application of this novel technology.

Evaluation of silicon nanoporous membranes and ECM-based microenvironments on neurosecretory cells

Understanding the interactions between microfabricated synthetic interfaces and cultured cells expressing a neuronal phenotype are critical for advancing research in the field of neural engineering such as neural recording and stimulation and neural microdevice interactions with the human brain. Here we explore the integration of these two components for therapeutic applications of neural prostheses. Microfabricated silicon nanoporous membranes were investigated for their effects on survival, proliferation, and differentiation of the well-known PC12 clonal line. Specifically, cell morphology, examined through fluorescence staining, were comparable in many respects on both silicon membrane and widely-used polystyrene culture surfaces. The attachment and differentiation of PC12 cells cultured on collagen and laminin-modified membranes and standard tissue culture surfaces were similar. Lastly, the differentiation response and tyrosine hydroxylase activity of PC12 cells embedded in a type I collagen matrix on experimental membrane substrates while exposed to NGF were significant and indistinguishable from tissue-culture polystyrene (TC-PS) surfaces. Results from this research suggest that microfabricated silicon nanoporous membranes may be useful, biocompatible permselective structures for neuroprosthetic applications and that collagen may be a useful immobilizing matrix for PC12 cells loaded in implantable macroencapsulation devices designed for the treatment of neurodegenerative disorders.

Diffusion Characteristics of Microfabricated Silicon Nanopore Membranes as Immunoisolation Membranes for Use in Cellular Therapeutics

Immunoisolating membranes protect transplanted xenogeneic tissue by physically isolating them from the host. However, most are commercial filter membranes that do not possess all the features needed for immunoisolation. Silicon nanopore membranes are thin layers of silicon containing tens of thousands of nanometer-sized channels, which allow passive diffusion of small molecules. They are excellent size-selective barriers, and the objective of this study was to further characterize their immunoprotective properties and make comparisons with commercial filter membranes. Diffusion across membranes was studied using molecules of different sizes, including fluorescein isothiocyanate-dextrans (relative molecular sizes of 4.4 kDa, 20 kDa, and 70 kDa), glucose (0.18 kDa), insulin (6.1 kDa), and immunoglobulin G (IgG) (150 kDa). Protection from complement-mediated lysis was analyzed by a hemolysis assay. Comparative studies were done with filter membranes that have been reported as immunoisolation barriers. To evaluate if silicon nanopore membranes changed insulin response patterns for glucose-stimulated islets, macrocapsules were constructed with nanopore membranes and filled with pancreatic islets, and dynamic perifusion studies were performed. Relative to commercial membranes, silicon nanopore membranes showed high rates of diffusion for glucose and insulin, and acted as efficient barriers to complement proteins and IgG. No other commercial membrane showed comparable diffusion and immunoisolating properties. Islets placed within the macrocapsule exhibited glucose-responsive insulin secretion in perifusion studies. Silicon nanopore membranes possess unique and desirable diffusion properties as immunoisolation membranes and allow rapid response times for the stimulation of islets by glucose. These features are attributed to the physical properties of the membranes, namely, the straight channels, adequate porosity, and the 5 microm thickness.

Long-Term Biocompatibility of NanoGATE Drug Delivery Implant

The fouling of components and the formation of a fibrotic tissue capsule around subcutaneously implanted medical devices are two major obstacles in developing viable, long-term implantable drug delivery systems. NanoGATE is a subcutaneous implant designed for constant-output passive diffusion of a drug of interest through a silicon nanopore membrane. To this end, we have investigated the long-term in vivo biocompatibility of the NanoGATE implant in terms of the fouling of the nanopore membrane and the formation of a fibrotic tissue capsule around the implant. We have also evaluated how these effects influence diffusion of a lysozyme surrogate from the device once implanted within the vascular compartment of a Sprague-Dawley rat model. Using several model biomolecules such as glucose, lysozyme, and albumin, our studies suggest that silicon nanopore membranes do not foul when implanted subcutaneously for 6 mo. This study also reveals the tissue capsule that naturally forms around the implant does not limit diffusion of molecules with molecular weights on the order of 14.4 kDa at therapeutic delivery rates of tens of micrograms per day. This indicates that our NanoGATE implant should be completely functional in vivo, providing constant release levels of a drug over an extended time period. Thus, by adjusting the release rate to fit the pharmacokinetic clearance profile of the Sprague-Dawley rat, long-term steady-state blood plasma concentrations can be achieved.

Acid loaded porous silicon as a proton exchange membrane for micro-fuel cells

Silicon-based fuel cells are under active development to supply chip-scale electrical power supply. In this paper, we demonstrate the use of sulfuric acid loaded nanoporous silicon as a proton electrolytic membrane (PEM) material for micro-fuel cell applications. Sulfuric acid loaded nanoporous silicon membranes with thickness of 40–70 μm have proton conductivities (0.0068–0.33 S/cm) comparable to, and in some cases better than, Nafion® (0.05 S/cm), which is the most commonly used commercial PEM material. Additionally, the permeability of formic acid at room temperature through nanoporous silicon membranes was found to be similar to that of Nafion® membranes, which increases with increasing anodization current density (4.3 × 10−8 to 3.9 × 10−7 mol/(s cm2) for nanoporous silicon as compared to 1.23 × 10−7 mol/(s cm2) for Nafion® 117). These results represent the discovery of a new class of protonic conductor that can be integrated into standard silicon microfabrication processes.