pSi Surface Research Articles

Metal Oxide Coated Porous Silicon Electrode Fabricated by Anodized Liquid Phase Depositions

The titanium oxide/PSi nanocomposite was fablicated by liquid phase deposition (LPD) method with applying anodic potential. Results of SEM-EDX measurement showed that TiO2 deposited into the fine pore (ca. 7.4 nm) only when oxidized PSi surface was used as F- scavenger or PSi was anodized under the existence of titanium ions. TiO2/PSi nanocomposite was fabricated by anodization of PSi in H2TiF6 electrolyte under constant potential. As the amount of Ti maximized at 300 mV vs. Ag/AgCl, deposition process can be controlled by applied potential in this method. The charge/discharge capacities were measured about fabricated TiO2/PSi as lithium-ion battery anode. The improvement of the capacity was derived from the increase in PSi wettability by TiO2 deposition and activation of silicon in fine structure. In addition, TiO2/PSi fabricated by anodization kept higher capacity without rapid degradation, because of free from SiO2.

Interaction of Antibiotics with Lipid Vesicles on Thin Film Porous Silicon Using Reflectance Interferometric Fourier Transform Spectroscopy

The ability to observe interactions of drugs with cell membranes is an important area in pharmaceutical research. However, these processes are often difficult to understand due to the dynamic nature of cell membranes. Therefore, artificial systems composed of lipids have been used to study membrane properties and their interaction with drugs. Here, lipid vesicle adsorption, rupture, and formation of planar lipid bilayers induced by various antibiotics (surfactin, azithromycin, gramicidin, melittin and ciprofloxacin) and the detergent dodecyl-b-D-thiomaltoside (DOTM) was studied using reflective interferometric Fourier transform spectroscopy (RIFTS) on an oxidized porous silicon (pSi) surface as a transducer. The pSi transducer surfaces are prepared as thin films of 3 μm thickness with pore dimensions of a few nanometers in diameter by electrochemical etching of crystalline silicon followed by passivation with a thermal oxide layer. Furthermore, the sensitivity of RIFTS was investigated using three different concentrations of surfactin. Complementary techniques including atomic force microscopy, fluorescence recovery after photobleaching, and fluorescence microscopy were used to validate the RIFTS-based method and confirm adsorption and consequent rupture of vesicles to form a phospholipid bilayer upon the addition of antibiotics. The method provides a sensitive and real-time approach to monitor the antibiotic-induced transition of lipid vesicles to phospholipid bilayers.

Effect of surface chemistry of porous silicon microparticles on glucagon-like peptide-1 (GLP-1) loading, release and biological activity

Recently, mesoporous silicon (PSi) microparticles have been shown to extend the duration of action of peptides, reducing the need for frequent injections. Glucagon-like peptide 1 (GLP-1) is a potential novel treatment for type 2 diabetes. The aim of this study was to evaluate whether GLP-1 loading into PSi microparticles reduce blood glucose levels over an extended period. GLP-1 (pI 5.4) was loaded and released from the negatively charged thermally oxidized (TOPSi, pI 1.8) and thermally carbonized (TCPSi, pI 2.6) PSi microparticles and from the novel positively charged amine modified microparticles, designated as TOPSi-NH2-D (pI 8.8) and TCPSi-NH2-D (pI 8.8), respectively. The adsorption of GLP-1 onto the PSi microparticles could be increased 3-4-fold by changing the PSi surface charge from negative to positive, indicating that the positive surface charge of PSi promoted an electrostatic interaction between the negatively charged peptide. All the GLP-1 loaded PSi microparticles lowered the blood glucose levels after a single s.c. injection but surprisingly, TOPSi-NH2-D and TCPSi-NH2-D were not able to prolong the effect when compared to TOPSi, TCPSi or GLP-1 solution. However, TOPSi-NH2-D and TCPSi-NH2-D microparticles were able to carry improved payloads of active GLP-1 encouraging continuing further attempts to achieve sustained release.

An In-Depth Study Linking the Infrared Spectroscopy and Photoluminescence of Porous Silicon during Ambient Hydrogen Peroxide Oxidation

We carefully tailored a porous silicon (pSi) surface by oxidation with hydrogen peroxide (H2O2) to determine the time-dependent changes in nanocrystallite surface chemistries (e.g., Si-O-Si, SiH(x) [x = 1, 2], OySiH [y = 2, 3], and SiOH/H2O) and their influence on the pSi photoluminescence (PL). The relationship between infrared band amplitudes and PL intensity were evaluated under H2O2 and O3 (previously studied) oxidation. The pSi surface composition under O3 and H2O2 oxidation conditions tended to, save the O(y)SiH (y = 2, 3) species, approach similar values at the longest oxidation times studied, but they took very different paths in reaching these end points. Furthermore, the pSi surface compositions that exhibit maximum/minimum PL under each oxidant are very different.

Matrix Metalloproteinase Biosensor Based on a Porous Silicon Reflector

Matrix metalloproteinases (MMP) are proteolytic enzymes important to wound healing. In non-healing wounds, it has been suggested that MMP levels become dysfunctional, hence it is of great interest to develop sensors to detect MMP biomarkers. This study presents the development of a label-free optical MMP biosensor based on a functionalised porous silicon (pSi) thin film. The biosensor is fabricated by immobilising a peptidomimetic MMP inhibitor in the porous layer using hydrosilylation followed by amide coupling. The binding of MMP to the immobilised inhibitor translates into a change of effective optical thickness over time. We investigated the effect of surface functionalisation on the stability of the pSi surface and evaluated sensing performance. We successfully demonstrated MMP detection in buffer solution and human wound fluid at physiologically relevant concentrations. This biosensor may find application as a point-of-care device that is prognostic of the healing trajectory of chronic wounds.

Parts per Million Water in Gaseous Vapor Streams Dramatically Accelerates Porous Silicon Oxidation

Substantial research has focused on exploiting and understanding porous silicon (pSi) photoluminescence (PL) for applications in areas ranging from chemical sensing to solid-state lighting. At ambient temperature, pure H2O is well-known to slowly (over a time scale of hours to days) and irreversibly oxidize as-prepared pSi (ap-pSi) to form oxidized pSi (ox-pSi). In this paper, we report that the apparent ap-pSi to ox-pSi oxidation rates can be orders of magnitude faster in the presence of nonaqueous vapor streams that contain just ppm H2O levels. When H2O is removed from the nonaqueous vapor stream, ap-pSi oxidation ceases. The nonaqueous analyte vapors serve as a vehicle to transport H2O directly into the hydrophobic, ap-pSi matrix where the H2O then oxidizes the ap-pSi leading to ox-pSi, permanently changing the pSi PL and surface chemistry. The ap-pSi oxidation rate is much faster in the presence of nonaqueous vapors because H2O transport into the pSi matrix is no longer limited by H2O slowly percolating–oxidizing–percolating through the ap-pSi matrix.

Amine Surface Modifications and Fluorescent Labeling of Thermally Stabilized Mesoporous Silicon Nanoparticles

Mesoporous silicon (PSi) has been shown to have extensive application opportunities in biomedicine, whereas it has frequently failed to produce complex systems based on PSi due to the lack of surface functional groups or the instability of the unmodified PSi surface. In the present study, PSi nanoparticles, stabilized by thermal oxidation or thermal carbonization, were successfully modified by grafting aminosilanes on the surface. The modifications were performed by covalently bonding 3-triethoxysilylpropylamine (APTES) or 3-(2-aminoethylamino) propyldimethoxymethylsilane (AEAPMS) on thermally oxidized PSi (TOPSi) and thermally carbonized PSi (TCPSi). These materials were systematically characterized with N2 ad/desorption, TEM, contact angle, zeta potential, FT-IR, 29Si CP/MAS NMR, and elemental analysis. To evaluate their application potentials, a fluorescent dye, fluorescein 5-isothiocyanate (FITC), was coupled on the surface of amine-modified nanoparticles. The effects of PSi matrix and surface amino groups on FITC coupling efficiency, fluorescent intensity, and the stability of fluorescence in simulated body fluid (SBF) were investigated. The nanoparticles modified with AEAPMS had higher FITC coupling efficiency than those modified with APTES. FITC-coupled TOPSi nanoparticles also possessed brighter fluorescence and better fluorescent stability in SBF. Furthermore, due to the protection caused by the mesoporous structure of PSi nanoparticles, the FITC-coupled TOPSi nanoparticles showed superior photostability in photobleaching experiment.

High-Throughput Screening System for Creating and Assessing Surface-Modified Porous Silicon

A high-throughput screening system has been developed to rapidly produce, screen, and assess the usefulness of organically modified silane (ORMOSIL)-based xerogel films formed on the surface of porous silicon (pSi) surfaces. The ORMOSILs tested include methyltriethoxysilane, n-octyltriethoxysilane, n-hexyltriethoxysilane, n-propyltriethoxysilane, 2-cyanoethyltriethoxysilane, phenyltriethoxysilane, benzyltriethoxysilane, vinyltriethoxysilane, tetraethoxysilane, and hexafluoroethyltriethoxysilane. Xerogel microarrays were pin-printed on the surface of O(3) oxidized pSi using a computer-controlled robotic pin-printer. The fragile pSi required careful pin-printing parameter optimization to simultaneously ensure sufficient sol application and limit pin-induced damage. These multi-functional xerogel-pSi microarrays were exposed to harsh conditions (0.1 mM NaOH, 15 min) to determine the extent to which the xerogel protected the pSi. Microarray assessment included multispectral photoluminescence and infrared imaging. Results demonstrate that the more hydrophobic/nonpolar xerogel films (n-octyltriethoxysilane, n-hexyltriethoxysilane) protect the pSi surface the most and maintained the pSi photoluminescence. Also, unlike xerogel material doped with a reporter molecule, the uniformity of the printed feature plays a role in the protection of the pSi material underneath. Areas with thinner xerogel distributions allowed the permeation of NaOH whereas the thicker areas prohibit pSi exposure to NaOH.

Properties of magnetic nickel/porous-silicon composite powders

The magnetic and photoluminescence (PL) properties of nickel/porous-silicon (Ni/PSi) composite powders are investigated. Ni/PSi composite powders are prepared by stain etching of Si powder in a HF/HNO3 solution followed by electroless plating of Ni nanoparticles on the stain-etched PSi powder in a NiCl2 solution. The Ni/PSi powders exhibit hydrophillicity, superparamagnetism caused by the deposited Ni nanoparticles, and orange-red PL owing to the nanostructured PSi surface. The degree of magnetization decreases with increasing Ni plating time, indicating its dependence on the size of the Ni nanoparticles. The Ni/PSi composite powders also show a stronger magnetization as compared to that of the Ni-particle-plated Si powder. The stronger magnetization results from the larger surface area of PSi. The PL intensity, peak wavelength, and lifetime of Ni/PSi are strongly dependent on the NiCl2 concentration. This dependence is due to the different thickness of the oxide overlayer on the PSi surface formed during the Ni plating process. The existence of the oxide overlayer also results in a small change in the PL intensity against excitation time.

Link between O2SiH Infrared Band Amplitude and Porous Silicon Photoluminescence During Ambient O3 Oxidation

We carefully evaluate how porous silicon (pSi) surface oxidation by ozone (O(3)) and the resulting changes in nanocrystallite surface chemistries (e.g., SiOSi, SiH(x) (x = 1-3), O(y)SiH (y = 1-2), and SiOH) influence the pSi photoluminescence (PL). We discover a relationship between the pSi PL and the O(2)SiH band amplitude.

Porous silicon-based nanostructured microparticles as degradable supports for solid-phase synthesis and release of oligonucleotides

We describe the preparation of several types of porous silicon (pSi) microparticles as supports for the solid-phase synthesis of oligonucleotides. The first of these supports facilitates oligonucleotide release from the nanostructured support during the oligonucleotide deprotection step, while the second type of support is able to withstand the cleavage and deprotection of the oligonucleotides post synthesis and subsequently dissolve at physiological conditions (pH = 7.4, 37°C), slowly releasing the oligonucleotides. Our approach involves the fabrication of pSi microparticles and their functionalisation via hydrosilylation reactions to generate a dimethoxytrityl-protected alcohol on the pSi surface as an initiation point for the synthesis of short oligonucleotides.

Photoluminescence decay dynamics of silver/porous-silicon nanocomposites formed by metal-assisted etching

We investigate the photoluminescence (PL) properties of silver/porous-silicon (Ag/PSi) nanocomposites prepared by metal-assisted etching in Ag2O/HF solution, on the basis of steady-state and time-resolved PL spectroscopy measurements. The PL intensity and peak position are strongly dependent on the Ag2O concentration. Time-resolved PL measurements reveal that the nonradiative rate decreases with an increase in the Ag2O concentration for the Ag/PSi nanocomposites. It is found from x-ray photoelectron spectroscopy measurements that the decrease in the nonradiative rate is caused by the formation of SiO2 layers on the PSi surfaces. Further, the number of light-emitting Si nanocrystals in the nanocomposites, which is estimated from the PL decay rate and PL intensity, increases with the Ag2O concentration. From the wavelength dependence of the PL decay rate, it is found that the nonradiative rate is considerably dispersive, i.e., the shorter the wavelength, the higher the nonradiative rate.

Porous Silicon Films Micropatterned with Bioelements as Supports for Mammalian Cells

AbstractPorous silicon (pSi) surfaces have been chemically patterned via a UV initiated hydrosilylation reaction of an alkene through a photomask, introducing chemical functionality in the exposed surface areas. A secondary, UV initiated hydrosilylation reaction with a second alkene of different functionality is performed to backfill the silicon hydride terminated regions on the surface, thereby affording patterned porous films with dual, surface chemistry. UV initiated hydrosilylations were performed using the alkene undecylenic acid N‐hydroxysuccinimide (NHS) ester, and the pSi surfaces were stabilized by a second hydrosilylation reaction with a polyethylene glycol (PEG) appended alkene. NHS ester and PEG functionalized surfaces were used for the selective immobilization of the cell adhesion mediator protein fibronectin (FN), in the NHS‐functional regions. Matrix‐assisted laser desorption/ionization mass spectrometry imaging on the protein functionalized pSi surface confirmed the patterned conjugation of the FN to the NHS functionalized regions. Mammalian cells cultured on these surfaces showed attachment that was confined to the patterned areas of FN on the pSi surface.

A multimodal optical and electrochemical device for monitoring surface reactions: redox active surfaces in porous silicon Rugate filters

Herein, mesoporous silicon (PSi) is configured as a single sensing device that has dual readouts; as a photonic crystal sensor in a Rugate filter configuration, and as a high surface area porous electrode. The as-prepared PSi is chemically modified to provide it with stability in aqueous media and to allow for the subsequent coupling of chemical species, such as via Cu(I)-catalyzed cycloaddition reactions between 1-alkynes and azides ("click" reactions). The utility of the bimodal capabilities of the PSi sensor for monitoring surface coupling procedures is demonstrated by the covalent coupling of a ferrocene derivative, as well as by demonstrating ligand-exchange reactions (LER) at the PSi surface. Both types of reactions were monitored through optical reflectivity measurements, as well as electrochemically via the oxidation/reduction of the surface tethered redox species.

Surface chemical modification to control molecular interactions with porous silicon

Interactions between porous silicon (pSi) particles and probe molecules were evaluated to determine the effect of pSi and probe molecule chemistry on adsorption. Methylene blue, ethyl violet and orange G dyes were chosen for investigation as they possess distinct functionalities and charges. Several distinct pSi surface species were produced via thermal oxidation at 200–800 °C and their effect on adsorption investigated. The adsorption mechanisms were elucidated from equilibrium adsorption and desorption isotherms. Methylene blue adsorption was attributed to electrostatic attraction where a gradual increase in adsorption with oxidation temperature was observed. Significant methylene blue desorption was observed at pH 3, confirming adsorption occurs via electrostatic attraction. Ethyl violet demonstrated an increase in plateau adsorption capacity and affinity with increased oxidation temperatures and adsorption was initially attributed to electrostatic attraction, however desorption of ethyl violet was not observed, thus indicating potential chemisorption. Orange G exhibited high affinity adsorption for Si y SiH x terminated surfaces but no orange G desorption was detected, indicating a chemisorption adsorption mechanism. It has been successfully demonstrated that the surface modification of pSi enabled the manipulation of molecular interactions. By interacting probe molecules with similar functionalities to drug molecule with pSi, greater understanding of drug-pSi interactions can be ascertained which are of great importance. pSi surface chemistry can be tailored to enable control over molecular interactions and ultimately dictate loading, encapsulation and release behavior.

Dual Silane Surface Functionalization for the Selective Attachment of Human Neuronal Cells to Porous Silicon

Porous silicon (pSi) surfaces were chemically micropatterned through a combination of photolithography and surface silanization reactions. This patterning technique produces discretely defined regions on a pSi surface functionalized with a specific chemical functionality, and the surrounding surface displays a completely different functionality. The generated chemical patterns were characterized by a combination of IR microscopy and the conjugation of two different fluorescent organic dyes. Finally, the chemically patterned pSi surface was used to direct the attachment of neuronal cells to the surface. This patterning strategy will be useful for the development of high-throughput platforms for investigating cell behavior.

Peptide immobilisation on porous silicon surface for metal ions detection

In this work, a Glycyl-Histidyl-Glycyl-Histidine (GlyHisGlyHis) peptide is covalently anchored to the porous silicon PSi surface using a multi-step reaction scheme compatible with the mild conditions required for preserving the probe activity. In a first step, alkene precursors are grafted onto the hydrogenated PSi surface using the hydrosilylation route, allowing for the formation of a carboxyl-terminated monolayer which is activated by reaction with N-hydroxysuccinimide in the presence of a peptide-coupling carbodiimide N-ethyl-N'-(3-dimethylaminopropyl)-carbodiimide and subsequently reacted with the amino linker of the peptide to form a covalent amide bond. Infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy are used to investigate the different steps of functionalization.The property of peptides to form stable complexes with metal ions is exploited to achieve metal-ion recognition by the peptide-modified PSi-based biosensor. An electrochemical study of the GlyHisGlyHis-modified PSi electrode is achieved in the presence of copper ions. The recorded cyclic voltammograms show a quasi-irreversible process corresponding to the Cu(II)/Cu(I) couple. The kinetic factors (the heterogeneous rate constant and the transfer coefficient) and the stability constant of the complex formed on the porous silicon surface are determined. These results demonstrate the potential role of peptides grafted on porous silicon in developing strategies for simple and fast detection of metal ions in solution.

Effect of oligoethylene glycol moieties in porous silicon surface functionalisation on protein adsorption and cell attachment

We report on the synthesis of two carboxy-functional alkene compounds as modifiers of porous silicon (pSi) surface chemistry by means of thermal hydrosilylation. Both alkene compounds have hydrophobic, aliphatic carbon segments, with terminal carboxylic acid functionality appended through a thioether linkage. In one of the alkene linkers, we incorporated a short oligoethylene glycol (OEG) moiety to explore its low-fouling properties when attached to porous silicon. We examined surface stability of the surface-modified porous silicon in aqueous milieu. Albumin and fibronectin were adsorbed and, using carbodiimide chemistry, covalently immobilised to linker-modified porous silicon, and the propensity for mammalian cells to attach to these surfaces investigated. Surface chemistry was characterised by infrared spectroscopy and the stability of porous silicon in an aqueous milieu was investigated by interferometric reflectance spectroscopy (IRS). Surfaces functionalised with the alkene linker containing OEG displayed greater resistance to the adsorption of albumin. This linker also facilitated higher levels of covalent protein immobilisation to the functionalised pSi surface. Higher levels of cell attachment were observed on pSi surfaces with fibronectin covalently immobilised onto the OEG linker, than for fibronectin covalently immobilised on the non-OEG linker.

Tailoring the degradation kinetics of mesoporous silicon structures through PEGylation

Injectable and implantable porosified silicon (pSi) carriers and devices for prolonged and controlled delivery of biotherapeutics offer great promise for treatment of various chronic ailments and acute conditions. Polyethylene glycols (PEGs) are important surface modifiers currently used in clinic mostly to avoid uptake of particulates by reticulo-endothelial system (RES). In this work we show for the first time that covalent attachment of PEGs to the pSi surface can be used as a means to tune degradation kinetics of silicon structures. Seven PEGs with varying molecular weights (245, 333, 509, 686, 1214, 3400, and 5000 Da) were employed and the degradation of PEGylated pSi hemispherical microparticles in simulated physiological conditions was monitored by means of ICP-AES, SEM, and fluorimetry. Biocompatibility of the systems with human macrophages in vitro was also evaluated. The results clearly indicate that controlled PEGylation of silicon microparticles can offer a sensitive tool to finely tune their degradation kinetics and that the systems do not induce release of proinflammatory cytokines IL-6 and IL-8 in THP1 human macrophages.

Combined Immunocapture and Laser Desorption/Ionization Mass Spectrometry on Porous Silicon

There is considerable interest in the highly parallelized mass spectrometry analysis of complex sample mixtures without any time-consuming prepurification. Porous silicon-based laser desorption/ionization mass spectrometry (pSi LDI-MS) is enabling technology for such analysis. Previous studies have focused on pSi surface functionalization to enhance sensitivity of detection and engineer surfaces for sample capture and enrichment in LDI-MS analysis. In this report, we build on this work by showing that surface functionalization of thin pSi films can be extended to the covalent immobilization of antibodies, producing a porous immunoaffinity surface. We demonstrate highly selective mass spectrometric detection of illicit drugs (benzodiazepines) on pSi films displaying antibenzodiazepine antibodies covalently immobilized via isocyanate chemistry. The effects of antibody immobilization conditions, antibody concentration, and surface blocking on LDI-MS performance and selectivity were studied. X-ray photoelectron spectroscopy (XPS) was instrumental in characterizing surface chemistry and optimizing LDI-MS performance. Overall, our approach is suitable for rapid and sensitive confirmatory analysis in forensic toxicology requiring only minimal sample volume and may be applied to other areas requiring small molecular analysis such as metabolomics and pharmacology.