Porous Silicon Chip Research Articles

Study on the Stability of Porous Silicon Energetic Materials

Porous silicon has been widely studied due to its high explosion characteristics, less harm to the environment and compatibility with all silicon based production processes. At present, it has been used in military, national defense and other fields. In this paper, porous silicon was prepared by electrochemical anodic oxidation. The electrolysis time was 35 min, the current density was 50 mA/cm2, and the electrolyte was HF: DMAC=5:1 (volume ratio). The effects of silane coupling agents (KH550 and KH560) and cathodic reduction treatment on the life of porous silicon were investigated. The results show that the life of porous silicon chips treated by cathodic reduction+KH560 is longer, and the morphology of porous silicon chips treated by cathodic reduction+KH560 is better.

Perilymph metabolomic and proteomic MALDI-ToF profiling with porous silicon chips: A proof-of-concept study

IntroductionSensorineural hearing losses (SNHLs) are a significant public health issue, and the hearing loss field is desperately in need of effective therapy. Pathophysiological mechanisms are not yet clearly understood in the absence of validated methods to assess the inner ear content. Proteomic and metabolomic analysis of perilymph is opening new research perspectives for SNHLs. We aimed to demonstrate the feasibility of an innovative mass spectrometry (MS) strategy using porous silicon chips (PSCs) to investigate the low molecular weight (LMW) protein and metabolite content of human perilymph. Our second objective was to stratify perilymph samples according to their MS profiles and compare these results with clinical data. Material and methodsPerilymph samples obtained during cochlear implant surgery from patients with SNHLs were retrieved from a validated biobank. To focus on LMW entities, we used a PSC enrichment protocol before MALDI-ToF MS analysis. PSCs were used as a LMW molecular preanalytical stabilizer and amplifier. Patients’ clinical data and SNHL characteristics were retrieved retrospectively from medical charts. ResultsWe successfully acquired and compared 59 exploitable MS profiles out of 71 perilymph samples. There was a good correlation between duplicates. Comparing both ears from the same patient, we found good reproducibility even when there was a one-year interval between samplings. We identified three distinct groups when comparing the samples’ metabolomic profiles and four homogeneous groups comparing their LMW proteome profiles. Clinical data analysis suggested that some groups shared clinical or preanalytical characteristics. ConclusionThis proof-of-concept study confirms that LMW proteome and metabolome content of perilymph can be analyzed with PSCs. Based on protein profiles, we managed to stratify perilymp samples according to their molecular composition. These results must be confirmed with a larger population, and sampling methods require improvement, but this approach seems promising. In the future, this approach may pave the way for companion test strategies to precisely diagnose and define potential molecular targets for audioprotective therapies.

Gold nanoparticles modified porous silicon chip for SALDI-MS determination of glutathione in cells

The gold nanoparticles (Au NPs) modified porous silicon chip based surface assisted laser desorption/ionization mass spectrometry (SALDI-MS) was developed to capture and analyze glutathione (GSH) in cells. With silver-assisted chemical etching, Ag nanoparticles (Ag NPs) were generated and deposited on the silicon surface and the nanopores were etched on silicon substrate. Then Au NPs were in-situ synthesized on the ridges of silicon nanopores. This Ag-Au NPs modified porous silicon surface could specially capture and enrich thiol compounds through Au-S binding, and it could also function as matrix to assist ionization for SALDI-MS. The silicon chip was array patterned for high throughput SALDI-MS detection. GSH and cysteine could be distinguished without the interference from matrix signals. This approach was successfully applied to preconcentration and detection of GSH in Caco-2 cells. The GSH alterations in cells under drug stimulation were investigated. This invented silicon chip showed great potential for more efficient analysis of small thiol biomarkers in complex biological samples.

Optical nose based on porous silicon photonic crystal infiltrated with ionic liquids

A photonic-nose for the detection and discrimination of volatile organic compounds (VOCs) was constructed. Each sensing element on the photonic sensor array was formed by infiltrating a specific type of ionic liquid (IL) into the pore channel of a patterned porous silicon (PSi) chip. Upon exposure to VOC, the density of IL dramatically decreased due to the nano-confinement effect. As a result, the IL located in pore channel expanded its volume and protrude out of the pore channel, leading to the formation of microdroplets on the PSi surface. These VOC-stimulated microdroplets could scatter the light reflected from the PSi rugate filter, thereby producing an optical response to VOC. The intensity of the optical response produced by IL/PSi sensor mainly depends on the size and shape of microdroplets, which is related to the concentration of VOC and the physi-chemical propertied of ILs. For ethanol vapor, the optical response has linear relationship with its relative vapor pressure within 0–60%. The LOD of the IL/PSi sensor for ethanol detection is calculated to be 1.3 ppm. It takes around 30 s to reach a full optical response, while the time for recovery is less than 1 min. In addition, the sensor displayed good stability and reproducibility. Owing to the different molecular interaction between IL and VOC, the ILs/PSi sensor array can generate a unique cross-reactive “fingerprint” in response to a specific type of VOC analyte. With the assistance of image technologies and principle components analysis (PCA), rapid discrimination of VOC analyte could be achieved based on the pattern recognition of photonic sensor array. The technology established in this work allows monitoring in-door air pollution in a visualized way.

Facile routes of manufacturing silicon quantum dots on a silicon wafer and their surface activation by esters of N-hydroxysuccinimide

Fluorescent silicon quantum dots (SiQDs) could be prepared by reduction of hydrogen silsesquioxane, etching of silicon powers with wetting chemistry techniques or electrolysis of a wafer catalyzed by polyoxometalates. Chemical modifications are indispensable for the stability of the SiQDs photoluminescence and wider applications of SiQDs. Facile routes of manufacturing SiQDs derived from a silicon wafer and its surface functionalization by N-hydroxysuccinimide (NHS) esters were described in this work in detail. Firstly, the porous silicon chip was prepared by nanosilver-assisted electroless chemical etching. Then the chip was etched successively with hydrofluoric acid/nitric acid solutions until it emitted dazzling red fluorescence which claimed the achieved SiQDs on silicon substrates (SiQDs/Si). Finally, surface NHS esters were fabricated on such an SiQDs/Si chipthrough stepwise modifications, which were tested by the amidation between the NHS esters and n-octylamine. The fluorescence emission of the SiQDs/Si chip almost remained unchanged during the successively chemical modifications, which indicated the SiQDs had capabilities of enduring the sustained high temperature and organic media. Meanwhile, the SiQDs did not leave from the silicon substrate during the surface tuning. The SiQDs obtained by ultrasonication of an SiQDs/Si chip in water were investigated by transmission electron and atomic force microscopies.

Catalysis by silver nanoparticles/porous silicon for the reduction of nitroaromatics in the presence of sodium borohydride

A facile approach of preparing well-dispersed silver nanoparticles (Ag NPs) which fabricated on surface of porous silicon (PSi) generating Ag NPs/PSi chip and the catalyses towards reduction of nitro aromatics are described in detail in this work. Aqueous silver ions are reduced readily by the surface SiHx (x=1, 2 or 3) species of PSi within dozens of seconds at room temperature. The resulted Ag NPs are demonstrated by scanning and transmission electron microscopes, ultraviolet-visible spectrum and X-ray powder diffraction. A proposed mechanism of forming Ag NPs on PSi chip is discussed in light of the observed phenomena and the analyses of infrared and energy dispersive X-ray spectra. The stably porous architecture of PSi and the well-dispersed Ag NPs on PSi surface guarantee the highly catalytic activities of the Ag NPs/PSi chip. The progresses of reducing nitro aromatics catalyzed by the Ag NPs/PSi chip in the presence of sodium borohydride are traced by ultraviolet-visible measurements to estimate the catalytic performance of the Ag NPs/PSi chip.

Sol-Gel SELEX Circumventing Chemical Conjugation of Low Molecular Weight Metabolites Discovers Aptamers Selective to Xanthine

Sensitive detection of the metabolites indicative of a particular disease contributes to improved therapy outcomes. Developing binding reagents for detection of low molecular weight metabolites is hampered by the difficulty with immobilization of targets through appropriate covalent chemical linkage while ensuring that selected reagents retain specificity to unmodified metabolites. To circumvent chemical modification of targets, we employed sol-gel droplets deposited onto a porous silicon chip to entrap a purine metabolite, xanthine, which was found at lower levels in urine samples from patients with non-Hodgkin lymphoma. By sol-gel SELEX (systematic evolution of ligands by exponential enrichment) against xanthine, specific aptamers (KD ∼ 10 μM) with sensitivity of detection at as low as 1 μM were isolated, which bound to other purine metabolites at more than 100-fold lower affinity. In contrast, we failed to isolate xanthine-specific aptamers when SELEX was performed against xanthine covalently linked to polymer resin. This study demonstrates that the sol-gel platform for entrapping low molecular weight metabolites without chemical modifications can be utilized for SELEX to discover aptamers against clinical metabolite markers for diagnosis application.

Rapid Antibiotic Susceptibility Testing in a Microfluidic pH Sensor

For appropriate selection of antibiotics in the treatment of pathogen infection, rapid antibiotic susceptibility testing (AST) is urgently needed in clinical practice. This study reports the utilization of a microfluidic pH sensor for monitoring bacterial growth rate in culture media spiked with different kinds of antibiotics. The microfluidic pH sensor was fabricated by integration of pH-sensitive chitosan hydrogel with poly(dimethylsiloxane) (PDMS) microfluidic channels. For facilitating the reflectometric interference spectroscopic measurements, the chitosan hydrogel was coated on an electrochemically etched porous silicon chip, which was used as the substrate of the microfluidic channel. Real-time observation of the pH change in the microchannel can be realized by Fourier transform reflectometric interference spectroscopy (FT-RIFS), in which the effective optical thickness (EOT) was selected as the optical signal for indicating the reversible swelling process of chitosan hydrogel stimulated by pH change. With this microfluidic pH sensor, we demonstrate that confinement of bacterial cells in a nanoliter size channel allows rapid accumulation of metabolic products and eliminates the need for long-time preincubation, thus reducing the whole detection time. On the basis of this technology, the whole bacterial growth curve can be obtained in less than 2 h, and consequently rapid AST can be realized. Compared with conventional methods, the AST data acquired from the bacterial growth curve can provide more detailed information for studying the antimicrobial behavior of antibiotics during different stages. Furthermore, the new technology also provides a convenient method for rapid minimal inhibition concentration (MIC) determination of individual antibiotics or the combinations of antibiotics against human pathogens that will find application in clinical and point-of-care medicine.

Mass Spectrometry Imaging on Porous Silicon: Investigating the Distribution of Bioactives in Marine Mollusc Tissues

Desorption/ionization on porous silicon-mass spectrometry (DIOS-MS) is an attractive alternative to conventional matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) for the analysis of low molecular weight compounds. Porous silicon (pSi) chips are also suitable as support for mass spectrometry imaging (MSI). Here, we report an implementation of DIOS-MSI using the biosynthetic organs of a marine mollusc for proof of principle. The tissue section is stamped onto a fluorocarbon-functionalized pSi chip, which extracts and traps small hydrophobic molecules from the tissue under retention of their relative spatial distribution. The section is subsequently removed and the chip is imaged without any remaining tissue. We apply this novel tissue contact printing approach to investigate the distribution of biologically active brominated precursors to Tyrian purple in the hypobranchial gland of the marine mollusc, Dicathais orbita, using DIOS-MSI. The tissue contact printing is also compatible with other types of desorption/ionization surfaces, such as nanoassisted laser desorption/ionization (NALDI) targets.

Porous silicon antibody microarrays for quantitative analysis: Measurement of free and total PSA in clinical plasma samples

The antibody microarrays have become widespread, but their use for quantitative analyses in clinical samples has not yet been established. We investigated an immunoassay based on nanoporous silicon antibody microarrays for quantification of total prostate-specific-antigen (PSA) in 80 clinical plasma samples, and provide quantitative data from a duplex microarray assay that simultaneously quantifies free and total PSA in plasma. To further develop the assay the porous silicon chips was placed into a standard 96-well microtiter plate for higher throughput analysis. The samples analyzed by this quantitative microarray were 80 plasma samples obtained from men undergoing clinical PSA testing (dynamic range: 0.14–44ng/ml, LOD: 0.14ng/ml). The second dataset, measuring free PSA (dynamic range: 0.40–74.9ng/ml, LOD: 0.47ng/ml) and total PSA (dynamic range: 0.87–295ng/ml, LOD: 0.76ng/ml), was also obtained from the clinical routine. The reference for the quantification was a commercially available assay, the ProStatus PSA Free/Total DELFIA. In an analysis of 80 plasma samples the microarray platform performs well across the range of total PSA levels. This assay might have the potential to substitute for the large-scale microtiter plate format in diagnostic applications. The duplex assay paves the way for a future quantitative multiplex assay, which analyzes several prostate cancer biomarkers simultaneously.

Fabrication of Human IgG Sensors Based on Porous Silicon Interferometer Containing Bragg Structures

A simply modified biosensor based on protein A-modified distributed Bragg reflectors (DBR) porous silicon (PSi) chip for the detection of human immunoglobin G (IgG) are developed. The fabrication, optical characterization, and surface derivatization of DBR PSi are investigated. The sensor system studied consist of multi-layer of porous silicon modified with protein-A. The sensor is operated by the measurement of the reflection peak in the white light reflection spectrum. Molecular binding is detected as a shift in wavelength of reflection peaks.

Switching of fluorescence mediated by a peroxynitrite–glutathione redox reaction in a porous silicon nanoreactor

A nanostructured porous silicon chip functionalized with dichlorofluorescein is employed as a nanoreactor to respond to Reactive Oxygen Species (ROS) and to real-time studying redox reactions.

Superparamagnetic iron oxide nanoparticle attachment on array of micro test tubes and microbeakers formed on p-type silicon substrate for biosensor applications

A uniformly distributed array of micro test tubes and microbeakers is formed on a p-type silicon substrate with tunable cross-section and distance of separation by anodic etching of the silicon wafer in N, N-dimethylformamide and hydrofluoric acid, which essentially leads to the formation of macroporous silicon templates. A reasonable control over the dimensions of the structures could be achieved by tailoring the formation parameters, primarily the wafer resistivity. For a micro test tube, the cross-section (i.e., the pore size) as well as the distance of separation between two adjacent test tubes (i.e., inter-pore distance) is typically approximately 1 μm, whereas, for a microbeaker the pore size exceeds 1.5 μm and the inter-pore distance could be less than 100 nm. We successfully synthesized superparamagnetic iron oxide nanoparticles (SPIONs), with average particle size approximately 20 nm and attached them on the porous silicon chip surface as well as on the pore walls. Such SPION-coated arrays of micro test tubes and microbeakers are potential candidates for biosensors because of the biocompatibility of both silicon and SPIONs. As acquisition of data via microarray is an essential attribute of high throughput bio-sensing, the proposed nanostructured array may be a promising step in this direction.

Multi-Spot Porous Silicon Chip Prepared from Asymmetric Electrochemical Etching for Human Immunoglobin G Sensor

Multi-spot porous silicon (MSPS)-based optical biosensor was developed to specify the biomolecules. MSPS chip was generated by an electrochemical etching of silicon wafer using an asymmetric electrode configuration in aqueous ethanolic HF solution and constituted with nine arrayed porous silicon. MSPS prepared from anisotropic etching conditions displayed the Fabry-Pérot fringe patterns which varied spatially across the porous silicon (PS). Each spot displayed different reflection resonances and different pore characteristics as a function of the lateral distance from the Pt counter electrode. The sensor system consists of the 3 x 3 spot array of porous silicon modified with Protein A. The system was probed with various fragments of an aqueous Human Immunoglobin G (Ig G) analyte. The sensor operated by measurement of the reflection patterns in the white light reflection spectrum of MSPS. Molecular binding and specificity was detected as a shift in wavelength of these Fabry-Pérot fringe patterns.

Bioelectrochemical studies of azurin and laccase confined in three-dimensional chips based on gold-modified nano-/microstructured silicon

Double-sided three-dimensional porous silicon chips, 6 mm × 6 mm, covered with a 40 nm gold (nano)layer, were fabricated from a porous silicon wafer. Scanning electron microscopy along with electrochemical characterisation showed sample conductivity, mechanical stability, and high surface area of the thus fabricated devices, viz. 10 times higher electrochemically active surface area compared to the geometric area. The three-dimensional gold coated silicon chips were further modified with thiol layers, followed by immobilisation of a simple copper-containing redox protein, azurin, or a complex multicopper redox enzyme, laccase. The bioelectrochemical studies showed very high surface concentrations of azurin and laccase, i. e. close to the theoretical monolayer coverage. However, direct electron transfer reactions between the biomolecules and gold surfaces were observed only for a small percentage of the immobilised redox protein and enzyme, respectively. Thus, highly efficient oxygen-bioelectroreduction on laccase-modified 3D thiol-gold-porous silicon chips (as compared to planar laccase-modified gold electrodes, 42 μA/cm 2 vs. 7 μA/cm 2, respectively) was obtained only in the presence of an efficient soluble redox mediator.

Gel-pad microarrays templated by patterned porous silicon for dual-mode detection of proteins

A proof-of-concept study demonstrated the feasibility of a novel gel-pad microarray on porous silicon chips, by initiation of an atom transfer radical propagation (ATRP) polymerisation of (polyethylene glycol) methacrylate (PEGMA) with surface Si-H species, stepwise chemical conversions of the gel membrane to an NTA-Ni2+/histidine-tagged protein system, and matrix-assisted laser desorption/ionisation mass spectroscopy (MALDI MS) and fluorescence detections.

Oligonucleotides direct synthesis on porous silicon chip

A solid phase oligonucleotide (ON) synthesis on porous silicon (PSi) chip is presented. The prepared Si-OH surface were analyzed by FT-IR and the OH functions were quantified by reaction with 3'-phosphoramidite nucleotide building block. Short ONs were synthesized on the chip surface and the coupling yields evaluated.

Detection of G-Type Nerve Agent Simulants Based on a Double Reflection DBR Porous Silicon Interferometer

Distributed Bragg re ector (DBR) porous silicon (PSi) chips with two re ection peaks were fabricated by electrochemical etching in an aqueous ethanolic HF solution and were used to detect of chemical nerve agent simulants. Dimethyl methylphosphonate (DMMP) is a simulant for G-type nerve agents. The manufactured DBR PSi chips exhibit two sharp photonic bands, 560 and 717 nm, with narrow full widths at half maximum (FWHM) of 15 and 20 nm, respectively. The detection method involved the shift of the DBR re ection peaks in the re ectivity spectra under exposure to vapors of the analyte. Rapid detection was achieved in few seconds in situ and the observed red shift of the DBR peaks resulted from an increase in the refractive indices in DBR PSi. When the DBR PSi chips were exposed to vapor of DMMP, the two re ection peaks from DBR PSi were red-shifted by 22 and 32 nm, respectively. Real-time detection for the stimulant indicated that the detection measurements were reversible. Detection of other analytes, such as triethyl phosphate (TEP) and diethyl ethylphosphonate (DEEP), has been also achieved.

Detection of Toxic Organophosphate Nerve Agents Using DBR Porous Silicon Chip

The efficient detection method based on nanostructured photonic DBR PSi has been developed for DMMP, which is a simulant for G-type nerve agents. The manufactured DBR PSi chip exhibits a sharp photonic band gap at 520 nm. The detection method involves the shift of DBR peak in reflectivity spectra under the exposure of vapors of analyte. Rapid detection has been achieved in few seconds, in situ, and observed by the red-shift of DBR peak resulted from the increase of refractive indices in DBR PSi. When DBR PSi chip is exposed to DMMP, TEP, and DEEP-saturated air, DBR peak in reflectivity is red shifted by 10 nm, 25 nm, and 10 nm, respectively. Real-time detection for the nerve gases indicates that the measurement is reversible. Detection limit of DMMP (1.5 ppm) using DBR PSi is 8.8 mg/m3 for 1 min.

Glutamine-Binding Protein fromEscherichiacoliSpecifically Binds a Wheat Gliadin Peptide Allowing the Design of a New Porous Silicon-Based Optical Biosensor

In this work, the binding of the recombinant glutamine-binding protein (GlnBP) from Escherichia coli to gliadin peptides, toxic for celiac patients, was investigated by mass spectrometry experiments and optical techniques. Mass spectrometry experiments demonstrated that GlnBP binds the following amino acid sequence: XXQPQPQQQQQQQQQQQQL, present only into the toxic prolamines. The binding of GlnBP to gliadin suggested us to design a new optical biosensor based on nanostructured porous silicon (PSi) for the detection of trace amounts of gliadin in food. The GlnBP, which acts as a molecular probe for the gliadin, was covalently linked to the surface of the PSi wafer by a proper passivation process. The GlnBP-gliadin interaction was revealed as a shift in wavelength of the fringes in the reflectivity spectrum of the PSi layer. The GlnBP, covalently bonded to the PSi chip, selectively recognized the toxic peptide. Finally, the sensor response to the protein concentration was measured in the range 2.0-40.0 microg/L and the sensitivity of the sensor was determined.