pSi Membranes Research Articles

Electrochemical Actuation in Porous Silicon

We show large and reversible electrochemical actuation in a material based on self-organised nanoporosity in silicon (pSi) in combination with the electrically conductive polymer polypyrrole (PPy), which is introduced inside the pore space. On a single-pore scale the electrochemical actuation can be traced to the high porosity of 50 % and to potential-dependent pressures of up to 15 MPa acting at the single-pore scale. These pressures originate in charging or discharging and the related counter-ion movements. The exceptionally small operation voltages (0.4-0.9V) and the simple synthesis enable a silicon based actor. INTRODUCTION Self-organized nano-porosity in silicon has been attracting interest from a fundamental point of view and for applications due to its special thermal, electrical and optical properties and its bio compatibility [1]. However, the absence of the piezo-electric effect in silicon makes applications in the field of electro-mechanics for this widely used semiconductor difficult. The aim of this work is to study the sensor and actuator characteristics of bare pSi and pSi filled with PPy. An electrochemical change in the oxidation state of PPy can increase or decrease the number of delocalised charges in the polymer. Immersed in an electrolyte this is also accompanied by a reversible counter-ion uptake or expulsion and thus with a marcroscopic contraction or swelling under electrical potential control, making PPy one of the most employed artificial muscle materials [2]. The material is immersed in an electrolyte solution and studied by different techniques as in-situ dilatometry and in-situ X-ray diffraction. EXPERIMENTAL RESULTS AND DISCUSSIONS Porous silicon is prepared by an electrochemical anodization process in a solution of hydrofluoric acid and ethanol by applying a constant current between a platinum cathode and a highly doped silicon wafer. The resulting pores are characteristically straight and orthogonally aligned to the silicon surface. The pore diameter amounts to 7.6 nm and is determined via nitrogen sorption isotherm as is the porosity of 50 %. In a second step PPy is incorporated inside the pores via an electro-polymerisation in galvanostatic mode.Dilatometry measurements in an in-situ electrochemical setup are performed in order to characterize the actuating properties of the resulting pSi-PPy hybrid material. The sample is therefore immersed in perchloric acid (HClO4) and positioned in the setup, so that the pores are pointing in a horizontal direction, i.e. the sample is standing upright.Measuring the sample length change while recording Cyclovoltammograms (CVs) allows a detailed characterisation of the electrochemical actuation. The potential E is reversibly changed from 0.4 V to 0.9 V versus the normal hydrogen electrode potential. An increasing potential leads to an increased insertion of chlorate-anions in the PP. Vice versa, decreasing the potential expells anions from the PPy. It is found, that the repetitive change in sample length coincides linearly with E. So, the incorporation of anions leads to an expansion of the sample and the release of the anions lets the sample contract.For obtaining a further understanding of the electrochemical actuation mechanism of the PPy filled pSi membranes, the micromechanical properties are modelled based on the microstructure as recorded by electron transmission micrographs.REFERENCES[1] M. J. Sailor, Porous Silicon in Practice - Preparation, Characterization and Applications, Wiley-VCH, 2011.[2] E. Smela, Adv. Mater., 2003, 15, 481–494.

Long duration stabilization of porous silicon membranes in physiological media: Application for implantable reactors.

The natural biodegradabilty of porous silicon (pSi) in physiological media limits its wider usage for implantable systems. We report the stabilization of porous silicon (pSi) membranes by chemical surface oxidation using RCA1 and RCA2 protocols, which was followed by a PEGylation process using a silane-PEG. These surface modifications stabilized the pSi to allow a long period of immersion in PBS, while leaving the pSi surface sufficiently hydrophilic for good filtration and diffusion of several biomolecules of different sizes without any blockage of the pSi structure. The pore sizes of the pSi membranes were between 5 and 20 nm, with the membrane thickness around 70 μm. The diffusion coefficient for fluorescein through the membrane was 2 × 10-10 cm2 s-1, and for glucose was 2.2 × 10-9 cm2 s-1. The pSi membrane maintained that level of glucose diffusion for one month of immersion in PBS. After 2 months immersion in PBS the pSi membrane continued to operate, but with a reduced glucose diffusion coefficient. The chemical stabilization of pSi membranes provided almost 1 week stable and functional biomolecule transport in blood plasma and opens the possibility for its short-term implantation as a diffusion membrane in biocompatible systems.

Oral Mucosal Epithelial Cells Grown on Porous Silicon Membrane for Transfer to the Rat Eye

Dysfunction of limbal stem cells or their niche can result in painful, potentially sight-threatening ocular surface disease. We examined the utility of surface-modified porous-silicon (pSi) membranes as a scaffold for the transfer of oral mucosal cells to the eye. Male-origin rat oral mucosal epithelial cells were grown on pSi coated with collagen-IV and vitronectin, and characterised by immunocytochemistry. Scaffolds bearing cells were implanted into normal female rats, close to the limbus, for 8 weeks. Histology, immunohistochemistry and a multiplex nested PCR for sry were performed to detect transplanted cells. Oral mucosal epithelial cells expanded on pSi scaffolds expressed the corneal epithelial cell marker CK3/12. A large percentage of cells were p63+, indicative of proliferative potential, and a small proportion expressed ABCG2+, a putative stem cell marker. Cell-bearing scaffolds transferred to the eyes of live rats, were well tolerated, as assessed by endpoint histology. Immunohistochemistry for pan-cytokeratins demonstrated that transplanted epithelial cells were retained on the pSi membranes at 8 weeks post-implant, but were not detectable on the central cornea using PCR for sry. The pSi scaffolds supported and retained transplanted rat oral mucosal epithelial cells in vitro and in vivo and recapitulate some aspects of an artificial stem cell niche.

Immobilization of Oligonucleotides on Metal-Dielectric Nanostructures for miRNA Detection.

The development of nanostructured metal-dielectric materials, suitable for biodetection based on surface plasmon resonance and surface enhanced Raman scattering (SERS), requires the refinement of proper biological protocols for their effective exploitation. In this work, the immobilization of DNA probes on nanostructured metal-dielectric/semiconductor substrates has been optimized, to develop a bioassay for the detection of miRNA. To ensure a broad relevance, the proposed biological protocol was applied to different silver-decorated functional supports: porous silicon (pSi), TiO2 nanotube arrays, and polydimethylsiloxane (PDMS). The efficiency and the stability of the substrates were carefully analyzed by Raman spectroscopy and electron microscopy after the incubation in buffers with the appropriate combination of pH, ionic strength, and surfactant content. The customized protocol, initially developed on multiwell plates, was transferred and refined on the nanostructured substrates. The nonspecific interaction of the biological species with the surface was evaluated and reduced thanks to a tailored surface pretreatment. SERS analysis was applied to check the immobilization of DNA probes on pretreated samples. Silvered PDMS-supported pSi membranes, the most promising substrates in terms of stability, were subjected to further optimizations. Concentrations, volume, and duration of incubations were finely adapted with respect to the surface probe density and to the corresponding hybridization of the complementary miRNA. The optimized ELISA-like assay shows sensitivities comparable to those of commercial plates for the detection of miRNA222 (LOD: 485 pM), paving the way for the application of the developed protocol on metal-dielectric/semiconductor nanostructures for ultrasensitive SERS biosensing applications.

Temperature‐Controlled Antimicrobial Release from Poly(diethylene glycol methylether methacrylate)‐Functionalized Bottleneck‐Structured Porous Silicon for the Inhibition of Bacterial Growth

Bacterial infections in wounds slow down the healing process and lead to increased morbidity in affected patients. Polymer coatings on porous membranes were investigated, which facilitate the in situ detection and treatment of, e.g., Escherichia coli and Staphylococcus aureus infections. The theranostic approach relies on the thermoresponsive polymer poly(diethylene glycol methylether methacrylate) (PDEGMA). The increase of the wound temperature due to infection is targeted in this proof of concept study for triggering the release of the fluorescent antibiotic levofloxacin from bottle‐shaped porous silicon (pSi) membranes capped with PDEGMA brushes. Below their lower critical solution temperature (LCST) the PDEGMA brushes are expanded and the levofloxacin release is significantly retarded. By contrast, above the LCST the PDEGMA brushes collapse and levofloxacin is released rapidly, which is detectable in solution owing to its fluorescence properties. The concomitant inhibition of bacterial growth agrees favorably with the drug release determined by fluorescence spectroscopy. image

Porous silicon membrane-modified electrodes for label-free voltammetric detection of MS2 bacteriophage

A proof of concept for the label-free detection of bacteriophage MS2, a model indicator of microbiological contamination, is validated in this work as a porous silicon (pSi) membrane-based electrochemical biosensor. PSi membranes were used to afford nanochannel architectures. The sensing mechanism was based on the nanochannel blockage caused by MS2 binding to immobilized capture antibodies. This blockage was quantified by measuring the oxidation current of the electroactive species reaching the electrode surface, by means of differential pulse voltammetry (DPV). The immunosensor showed a limit of detection of 6pfu/mL in buffer, allowing the detection of MS2 to levels commonly found in real-world applications, and proved to be unaffected by matrix effects when analyzing MS2 in reservoir water. This platform enables the straightforward, direct and sensitive detection of a broad range of target analytes and constitutes a promising approach towards the development of portable electronic point of sample analysis devices.

Dye effluent treatment using PVDF UF membranes with different properties

Using DMAc as solvent, water as non-solvent, modified poly(vinylidene fluoride) (PVDF) ultrafiltration membranes (PSi, PA, PS) were prepared by precipitation phase inversion, blending with nano-silica (SiO2), polyvinyl alcohol (PVA), and styrene maleic anhydride. The physical-chemical properties and morphology of PVDF membranes were characterized by FT-IR, water contact angle (WCA), swelling index, scanning electron microscopy, atomic force microscopy, etc. Considering reactive black 5 and congo red as the representatives of dye effluent pollutions, the filtration behavior to dye wastewater of four different types of PVDF UF membranes was discussed. Experimental results showed that, compared with original PVDF UF membrane, for three kinds of modified membrane, the first bubble pressure and strength (S) fell off to a certain extent, and the membrane surface roughness increased. Additionally, the cross-sectional macroporous and pure water flux (J) all increased. Especially, owing to the addition of PVA and SiO2, the WCA and the adsorption amount (Q) of PA and PSi membranes were reduced extraordinarily, and flux recovery rate increased obviously. As a result, the hydrophilicity of PVDF membrane was improved significantly. Moreover, the rejection (r) to two dyes was also remained well, which showed a better anti-fouling ability.

Luminescence of mesoporous silicon powders treated by high-pressure water vapor annealing

We have studied the photoluminescence of nanocrystalline silicon microparticle powders fabricated by fragmentation of PSi membranes. Several porosities were studied. Some powders have been subjected to further chemical etching in HF in order to reduce the size of the silicon skeleton and reach quantum sizes. High-pressure water vapor annealing was then used to enhance both the luminescence efficiency and stability. Two visible emission bands were observed. A red band characteristic of the emission of Si nanocrystals and a blue band related to localized centers in oxidized powders. The blue band included a long-lived component, with a lifetime exceeding 1 sec. Both emission bands depended strongly on the PSi initial porosity. The colors of the processed powders were tunable from brown to off-white, depending on the level of oxidation. The surface area and pore volume of some powders were also measured and discussed. The targeted applications are in cosmetics and medicine.

Fabrication of self-supporting porous silicon membranes and tuning transport properties by surface functionalization

This study presents a simple approach to perform selective mass transport through freestanding porous silicon (pSi) membranes. pSi membranes were fabricated by the electrochemical etching of silicon to produce membranes with controlled structure and pore sizes close to molecular dimensions (approximately 12 nm in diameter). While these membranes are capable of size-exclusion based separations, chemically specific filtration remains a great challenge especially in the biomedical field. Herein, we investigate the transport properties of chemically functionalized pSi membranes. The membranes were functionalized using silanes (heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethylchlorosilane (PFDS) and N-(triethoxysilylpropyl)-o-polyethylene oxide urethane (PEGS) to give membranes hydrophobic (PFDS) and hydrophilic (PEGS) properties. The transport of probe dyes tris(2,2'-bipyridyl)dichlororuthenium(ii) hexahydrate (Rubpy) and Rose Bengal (RB) through these functionalized membranes was examined to determine the effect surface functionalization has on the selectivity and separation ability of pSi membranes. This study provides the basis for further investigation into more sophisticated surface functionalization and coupled with the biocompatibility of pSi will lead to new advances in membrane based bio-separations.

Multidirectional lateral gradient films with position-dependent photonic signatures made from porous silicon

We describe here the fabrication of laterally graded porous silicon films which display gradients of photonic reflectance peaks spanning the optical spectrum. We demonstrate that up to three of these gradients can be overlayed to produce multidirectional photonic gradients with position-dependent spectral bar-codes. Each gradient is generated by asymmetric anodisation of silicon using temporal variations (sinusoidal or square-wave) in current density affording rugate and Bragg reflectors, respectively. The fabricated optical structures and the quality of the photonic resonances are characterised by optical reflectivity measurements and scanning electron microscopy. We finally remove the pSi gradient layers from the silicon substrate by applying an electropolishing current and embed the free-standing pSi membranes in polydimethylsiloxane to form flexible and foldable photonic films.

Photoinhibitory Light-induced Changes in the Composition of Chlorophyll-Protein Complexes and Photochemical Activity in Photosystem-I Submembrane Fractions¶

The effects of irradiation on photosystem (PS)-I submembrane particles using intense white light (2000 μE·m−2·s−1) at chilling temperature (4°C) were studied. PSI-dependent oxygen uptake activity was stable during the first 3 h of photoinhibitory illumination in the presence of added superoxide dismutase (SOD). Without added SOD, the oxygen uptake almost doubled during this period, presumably due to the denaturation of native membrane-bound SOD or its release from the PSI membranes. The total chlorophyll (Chl) content and the magnitude of light-induced absorbance changes at 830 nm (ΔA830) were also barely affected during the first 3–3.5 h of photoinhibitory treatment. However, further exposure to strong light markedly accelerated Chl breakdown followed by a decline in oxygen uptake rate and ΔA830. This corresponded with the disappearance of the bands attributed to PsaA/B polypeptides on electrophoretic gels. Despite the invariant maximum magnitude of ΔA830 during the first 3–3.5 h of photoinhibitory treatment, the light–response curves of P700 oxidation gradually altered, demonstrating a several-fold increase in the ability of weak actinic light to oxidize P700. The major Chl a–protein 1 (CP1) band gradually disappeared during the first 4 h of light exposure with a corresponding increase in the Chl content of a band with lower electrophoretic mobility ascribed to the formation of oligomers containing CP1, light-harvesting complex I (LHCI)-680 and LHCI-730. This aggregation of Chl–protein complexes, likely caused by photoinhibitory-induced cross-linking favoring light harvesting, is proposed to explain the enhanced capacity of weak light to oxidize P700 in photoinhibited PSI submembrane fractions compared with untreated ones.

Silicalite-filled poly(siloxane imide) membranes for removal of VOCs from water by pervaporation

Silicalite-filled poly(siloxane imide) (PSI) membranes were prepared for the separation of volatile organic compounds (VOCs) from water via pervaporation. PSI copolymer was synthesized by polycondensation of 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) with a siloxane-containing diamine, e.g., poly(dimethylsiloxane), bis(3-aminopropyl) terminated (PSX), added with 3,3-diaminodiphenyl sulfone (DDS). 2,4,6-Triamine pyrimidine (TAP) was added into the casting solution in order to enhance the compatibility between the polymeric matrix and the filler, silicalite. The PSI membranes were characterized by SEM. The surface morphology for the membrane with the addition of TAP differs from that without TAP. The latter seems to be consisting of particles in the membrane surface. The sorption selectivity of the PSI membranes for chloroform/water solutions was investigated, and there was a highest value for it around 50 wt.% of PSX content. The pervaporation performance of the membranes was studied with the separation of chloroform/water mixture. The silicalite-filled membrane with 120 μm thickness exhibit a high total permeation flux of 280 g m −2 h −1 with separation factor of 52.2 for 1.2 wt.% of the chloroform/water mixture.

Photoinhibitory light-induced changes in the composition of chlorophyll-protein complexes and photochemical activity in photosystem-I submembrane fractions.

The effects of irradiation on photosystem (PS)-I submembrane particles using intense white light (2000 micoE x m(-2) x S(-1)) at chilling temperature (4 degrees C) were studied. PSI-dependent oxygen uptake activity was stable during the first 3 h of photoinhibitory illumination in the presence of added superoxide dismutase (SOD). Without added SOD, the oxygen uptake almost doubled during this period, presumably due to the denaturation of native membrane-bound SOD or its release from the PSI membranes. The total chlorophyll (Chl) content and the magnitude of light-induced absorbance changes at 830 nm (deltaA830) were also barely affected during the first 3-3.5 h of photoinhibitory treatment. However, further exposure to strong light markedly accelerated Chl breakdown followed by a decline in oxygen uptake rate and deltaA830. This corresponded with the disappearance of the bands attributed to PsaA/B polypeptides on electrophoretic gels. Despite the invariant maximum magnitude of deltaA830 during the first 3-3.5 h of photoinhibitory treatment, the light-response curves of P700 oxidation gradually altered, demonstrating a several-fold increase in the ability of weak actinic light to oxidize P700. The major Chl a-protein 1 (CP1) band gradually disappeared during the first 4 h of light exposure with a corresponding increase in the Chl content of a band with lower electrophoretic mobility ascribed to the formation of oligomers containing CP1, light-harvesting complex I (LHCI)-680 and LHCI-730. This aggregation of Chl-protein complexes, likely caused by photoinhibitory-induced cross-linking favoring light harvesting, is proposed to explain the enhanced capacity of weak light to oxidize P700 in photoinhibited PSI submembrane fractions compared with untreated ones.

Characterization and Fuel Cell Testing of Radiation-Grafted Psi Membranes

ABSTRACTWe have demonstrated earlier the useful performance of our PSI radiation-grafted membranes in terms of the current-voltage characteristics of 30 cm2 active area fuel cells containing these membranes and their long-term testing over 6,000 h at 60 °C. We report here on testing of PSI radiation-grafted membranes in these fuel cells at 80 °C and in short stacks comprised of two or four 100 cm2 active area cells. The in-situ degradation of membranes has been investigated by characterizing membranes both before testing in fuel cells and post-mortem after testing in fuel cells. Characterization was accomplished by means of ion-exchange capacity and infrared and Raman spectroscopic measurements. In addition, a rapid screening method for our ex-situ testing of the oxidative stability of proton-conducting membranes was developed in this work. Comparison of the initial screening test results concerning the oxidative stability of some perfluorinated, partially-fluorinated, and non-fluorinated membranes compare well qualitatively with the relative stability of these same membranes during their long-term testing in fuel cells.

Competition between annihilation and trapping leads to strongly reduced yields of photochemistry under ps-flash excitation

Excitation of photosynthetic systems with short intense flashes is known to lead to exciton-exciton annihilation processes. Here we quantify the effect of competition between annihilation and trapping for Photosystem II, Photosystem I (thylakoids from peas and membranes from the cyanobacterium Synechocystis sp.), as well as for the purple bacterium Rhodospirillum rubrum. In none of the cases it was possible to reach complete product saturation (i.e. closure of reaction centers) even with an excitation energy exceeding 10 hits per photosynthetic unit. The parameter α introduced by Deprez et al. ((1990) Biochim. Biophys. Acta 1015: 295-303) describing the competition between exciton-exciton annihilation and trapping was calculated to range between ≈4.5 (PS II) and ≈6 (Rs. rubrum). The rate constants for bimolecular exciton-exciton annihilation ranged between (42 ps)(-1) and (2.5 ps)(-1) for PS II and PS I-membranes of Synechocystis, respectively. The data are interpreted in terms of hopping times (i.e. mean residence time of the excited state on a chromophore) according to random walk in isoenergetic antenna.

Preparation of reverse osmosis membranes by plasma polymerization of organic compounds

The plasma polymerization of organic compounds was used to prepare a composite reverse osmosis membrane which consists of an ultrathin semipermeable membrane formed by plasma polymerization of an organic compound or compounds and a porous substrate. Many nitrogen-containing compounds (aromatic amines, heteroaromatic compounds, aliphatic amines, and nitriles) were found to yield excellent reverse osmosis membranes by plasma polymerization directly onto porous substrates such as Millipore filters, porous polysulfone filters, and porous glass tubes. Factors involved in the preparation of reverse osmosis membranes by plasma polymerization were investigated and discussed. The plasma polymerized membranes have the following unique features: (1) very stable performance independent of salt concentration and applied pressure (practically no water flux decline was observed with many membranes): (2) salt rejection and water flux both increase with time in the initial stage of reverse osmosis (consequently, the performance of the membrane improves with time of operation); (3) very high salt rejection (over 99%) with high water flux (up to 38 gfd) can be obtained with 3.5% NaCl at 1500 psi (membranes perform equally well under conditions of sea water conversion and brakish water treatment).