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All-polymer photonic structures have attracted wide attention due to significant advances in simple strategies for their fabrication and adaptability to mass production. Their application in biosensing is particularly attractive as they possess unique optical properties and show great compatibility with biological systems. Here we report the fabrication and simple functionalisation of polystyrene photonic structures, underpinning their potential as robust and versatile optical sensing platforms. These polymer structures are created by replica moulding from porous silicon, a material known for its tunable morphological properties, versatile optical features, and promising performance as a label-free optical sensor. Ozone oxidation introduces hydrophilic functionalities onto the polystyrene surface which facilitate further immobilisation of bioreceptors via simple bioconjugate chemistry for sensing applications. Refereed/Peer-reviewed

In this study, the antibacterial efficacy of NO-releasing porous silicon nanoparticles (pSiNPs) is reported. NO-releasing pSiNPs were produced via the conjugation of S-nitrosothiol (SNO) and S-nitrosoglutathione (GSNO) donors to the nanoparticle surfaces. The release of the conjugated NO caused by the decomposition of the conjugated SNO and GSNO was boosted in the presence of ascorbic acid. The released NO was bactericidal to Gram-positive (Staphylococcus aureus) and Gram-negative bacteria (Escherichia coli), and eliminated bacterial growth within 2 h of incubation without compromising the viability of mammalian cells. These results demonstrate the advantages of NO-releasing pSiNPs for antibacterial applications, for example, in chronic wound treatment. Refereed/Peer-reviewed

A porous silicon rugate filter (pSiRF) insulin biosensor has been constructed and systematically optimised by investigating the effects of specific experimental parameters. The pSiRF biosensor is based on an optical sensing platform using interferometric reflectance spectroscopy (IRS) to monitor insulin binding to a surface-anchored insulin binding aptamer (IBA) within the pores. The aim of this study was to determine the optimal fabrication to elicit the maximum sensor response, lowest limit of detection (LOD) and fastest response time. Thermal hydrosilylation with undecylenic acid was used as a base surface modification, with IBA attached through formation of an amide bond. The following pSiRF fabrication conditions were investigated; porous film thickness and IBA concentration in the conjugation solution. The effect of solution flow speed over the pSiRF during insulin biosensing was also investigated in an effort to improve the performance. The optimised pSiRF biosensor was successfully applied for the detection of insulin secreted from human islets on stimulation with glucose.Finally, as a proof of concept, insulin sensing in the presence of human islets on the pSiRF surface was performedto demonstrate the robust performance of the biosensor and the potential for in-situ insulin biosensing. Refereed/Peer-reviewed

Continuing our research efforts in developing mesoporous silicon nanoparticle-based biomaterials for cancer therapy, we employed here porous silicon nanoparticles as a nanocarrier to deliver contrast agents to diseased cells. Nanoconfinement of small molecule Gd-chelates (L1-Gd) enhanced the T 1 contrast dramatically compared to distinct Gd-chelate (L1-Gd) by virtue of its slow tumbling rate, increased number of bound water molecules, and their occupancy time. The newly synthesized Gd-chelate (L1-Gd) was covalently grafted on silicon nanostructures and conjugated to an antibody specific for epidermal growth factor receptor (EGFR) via a hydrazone linkage. The salient feature of this nanosized contrast agent is the capability of EGFR targeted delivery to cancer cells. Mesoporous silicon nanoparticles were chosen as the nanocarrier because of their high porosity, high surface area, and excellent biodegradability. This type of nanosized contrast agent also performs well in high magnetic fields. Refereed/Peer-reviewed

Nanoporous silicon (pSi) films on a silicon wafer were loaded with sodium perchlorate (SP) and perfluoropolyether (PFPE) oxidising agents to generate a pyrotechnic energetic material. The potentially violent reaction between the silicon and the loaded oxidising agent was studied using correlated differential scanning calorimetry (DSC) and FTIR spectroscopy for samples heated continuously between ambient and 500 degrees C. We observed that the energetic reaction between pSi and SP depended on the presence of various hydride species on the surface of freshly etched pSi, and on formation of volatile free radical species released during either oxidation of the surface in the presence of air at about 200 degrees C or during desorption of the hydride above 270 degrees C in the absence of oxygen. However, energetic reactions between pSi and PFPE were delayed until pyrolysis of the PFPE above 390 degrees C in the absence of oxygen, suggesting PFPE's suitability for pyrotechnics applications. Correlated thermal and spectroscopic methods of analysis gave new insights into the earliest stages of the reaction of these energetic materials. Refereed/Peer-reviewed

Lipopolysaccharides (LPS) are the major component of the outer membrane of all Gram-negative bacteria and some cyanobacteria and are released during growth and cell death. LPS pose a potential health risk in water, causing acute respiratory illnesses, inhalation fever, and gastrointestinal disorders. The need for rapid and accurate detection of LPS has become a major priority to facilitate more timely and efficacious intervention and, hence, avoid unsafe water distribution. In this context, a porous silicon membrane (pSiM)-based electrochemical biosensor was developed for direct and sensitive detection of LPS. pSiM, featuring arrays of nanochannels, was modified with polymyxin B (PmB), an antimicrobial peptide with strong affinity to LPS. Detection of LPS was based on measuring the changes in the diffusion through the nanochannels of an electroactive species added in solution, caused by the nanochannel blockage upon LPS binding to PmB. Results showed a limit of detection of 1.8 ng/mL, and a linear response up to 10,000 ng/mL spiked in buffer. Selectivity of the sensor toward potential interfering species in water supplies was also assessed. Sensor performance was then evaluated in water samples from a water treatment plant (WTP), and detection of LPS well below the levels encountered in episodes of water contamination and in humidifiers was demonstrated.The same platform was also tested for bacterial detection including Pseudomonas aeruginosa and Escherichia coli spiked in water samples from a WTP. Considering its performance characteristics, this platform represents a promising screening tool toidentify the presence of LPS in water supplies and provide early warning of contamination events. Refereed/Peer-reviewed

The electrochemical performance of porous silicon (pSi) stabilized via thermal decomposition of acetylene gas is investigated for the first time. In this study, pSi undergoes two thermal treatments at either 525 or 800 °C, which result in hydrogen-terminated thermally hydrocarbonized pSi (THCpSi) and hydroxyl-terminated thermally carbonized pSi (TCpSi), respectively, the latter upon dipping in hydrofluoric acid to activate the surface termination. Electrochemical characterization, using cyclic voltammetry, chronocoulometry, and electrochemical impedance spectroscopy in the presence of several redox pairs, [Fe(CN) 6 ] 3/4− , [Ru(NH 3 ) 6 ] 2/3+ , and hydroquinone/quinone, is used to demonstrate the versatility and high stability to degradation of carbon-stabilized pSi nanostructures and their excellent electrochemical performance. Added to the large surface area, adjustable pore morphology and tailorable surface chemistry of THCpSi and TCpSi, these nanostructures demonstrate fast electron-transfer kinetics, providing key advantages over conventional carbon electrodes. The versatile surface chemistry of THCpSi and TCpSi offer various possibilities to introduce multiple functional groups depending on the nature of the bioreceptor to be immobilized. For proof of principle, the use of a THCpSi-based immunosensor to detect MS2 bacteriophage is demonstrated by means of electrochemical impedance spectroscopy, showing a detection limit of 4.9 pfu mL −1 . Carbon-stabilized pSi structures represent a new class of nanostructured electrodes for biosensing applications Refereed/Peer-reviewed

Drug delivery using nanosized materials holds significant potential to resolve challenges faced by conventional enteral and parental therapeutic administration, including poor drug solubility and off-target toxic effects. Porous silicon (pSi) nanostructures possess large surface areas in relation to volume and exhibit high biocompatibility. Tunable pore size and versatile surface functionalisation allows carriers to be created to match drug characteristics, maximising loading capacity. This chapter reviews the fabrication of pSi nanoparticles and their use for targeted drug delivery. Particular emphasis is placed on surface functionalisation regimes typically employed to construct bio compatible nanoparticles. The qualification of candidate pSi nanoparticles as biocompatible and fit-for-purpose, required for progression to therapeutic use, are discussed. We particularly focus on the application of pSi nanocarriers for cancer therapies and chronic wound healing. Refereed/Peer-reviewed

Desorption/ionization on porous silicon mass spectrometry (DIOS-MS) is shown to be a powerful technique for the sensing of low-molecular-weight compounds, including drugs and their metabolites. Surface modification of DIOS surfaces is required to increase analytical performance and ensure stability. However, common wet chemical modification techniques use fluorosilanes, which are less suitable for high-throughput manufacturing and analytical repeatability. Here, we report an alternative, rapid functionalization technique for DIOS surfaces using plasma polymerization (ppDIOS). We demonstrate the detection of drugs, metabolites, pesticides, and doping agents, directly from biological matrices, with molecular confirmation performed using the fragmentation capabilities of a tandem MS instrument. Furthermore, the ppDIOS surfaces were found to be stable over a 162 day period with no loss of reproducibility and sensitivity. This alternative functionalization technique is cost-effective and amenable to upscaling, ensuring avenues for the high-throughput manufacture and detection of hundreds of analytes across various applications while still maintaining the gold-standard clinical technique using mass spectrometry.

Mortality of glioblastoma multiforme (GBM) has not improved over the last two decades despite medical breakthroughs in the treatment of other types of cancers. Nanoparticles hold tremendous promise to overcome the pharmacokinetic challenges and off-target adverse effects. However, an inhibitory effect of nanoparticles by themselves on metastasis has not been explored. In this study, we developed transferrin-conjugated porous silicon nanoparticles (Tf@pSiNP) and studied their effect on inhibiting GBM migration by means of a microfluidic-based migration chip. This platform, designed to mimic the tight extracellular migration tracts in brain parenchyma, allowed high-content time-resolved imaging of cell migration. Tf@pSiNP were colloidally stable, biocompatible, and their uptake into GBM cells was enhanced by receptor-mediated internalisation. The migration of Tf@pSiNP-exposed cells across the confined microchannels was suppressed, but unconfined migration was unaffected. The pSiNP-induced destabilisation of focal adhesions at the leading front may partially explain the migration inhibition. More corroborating evidence suggests that pSiNP uptake reduced the plasticity of GBM cells in reducing cell volume, an effect that proved crucial in facilitating migration across the tight confined tracts. We believe that the inhibitory effect of Tf@pSiNP on cell migration, together with the drug-delivery capability of pSiNP, could potentially offer a disruptive strategy to treat GBM.

Waterborne diarrheal diseases such as travelers' diarrhea and cholera remain a threat to public health in many countries. Rapid diagnosis of an infectious disease is critical in preventing the escalation of a disease outbreak into an epidemic. Many of the diagnostic tools for infectious diseases employed today are time-consuming and require specialized laboratory settings and trained personnel. There is hence a pressing need for fit-for-purpose point-of-care diagnostic tools with emphasis in sensitivity, specificity, portability, and low cost. We report work toward thermally reversible biosensors for detection of the carbohydrate-binding domain of the Escherichia coli heat-labile enterotoxin (LTB), a toxin produced by enterotoxigenic E. coli strains, which causes travelers' diarrhea. The biosensing platform is a hybrid of two materials, combining the optical properties of porous silicon (pSi) interferometric transducers and a thermoresponsive multivalent glycopolymer, to enable recognition of LTB. Analytical performance of our biosensors allows us to detect, using a label-free format, sub-micromolar concentrations of LTB in solution as low as 0.135 μM. Furthermore, our platform shows a temperature-mediated "catch-and-release" behavior, an exciting feature with potential for selective protein capture, multiple readouts, and regeneration of the sensor over consecutive cycles of use.

Porous silicon (pSi) nanomaterials are increasingly attractive for biomedical applications due to their promising properties such as simple and feasible fabrication procedures, tunable morphology, versatile surface modification routes, biocompatibility and biodegradability. This review focuses on recent advances in surface modification of pSi for controlled drug delivery applications. A range of functionalization strategies and fabrication methods for pSi-polymer hybrids are summarized. Surface engineering solutions such as stimuli-responsive polymer grafting, stealth coatings and active targeting modifications are highlighted as examples to demonstrate what can be achieved. Finally, the current status of engineered pSi nanomaterials for in vivo applications is reviewed and future prospects and challenges in drug-delivery applications are discussed.

International audience; Porous silicon nanoparticles (pSiNP), modified to target dendritic cells (DC), provide an alternate strategy for the delivery of immunosuppressive drugs. Here, we aimed to develop a DC-targeting pSiNP displaying c-type lectin, dendritic cell-specific intercellular adhesion molecule-3-grabbing non-integrin (DC-SIGN), and CD11c monoclonal antibodies. The in vivo tracking of these fluorescent DC-targeting nanoparticles was assessed in both C57BL/6 mice and common marmosets (Callithrix jacchus) by intravenous injection (20 mg/kg). Rapamycin and ovalbumin (OVA)323–339 peptide loaded pSiNP were employed to evaluate their ability to generate murine CD4+CD25+FoxP3+ regulatory T-cells in vivo within OVA sensitized mice. In vivo, pSiNP migrated to the liver, kidneys, lungs, and spleen in both mice and marmosets. Flow cytometry confirmed pSiNP uptake by splenic and peripheral blood DC when functionalized with targeting antibodies. C57BL/6 OVA sensitized mice injected with CD11c-pSiNP loaded with rapamycin + OVA323–339 produced a 5-fold higher number of splenic regulatory T-cells compared to control mice, at 40 days post-pSiNP injection. These results demonstrate the importance of the immobilized targeting antibodies to enhance cellular uptake and enable the in vivo generation of splenic regulatory T-cells.

Controlling the release kinetics from a drug carrier is crucial to maintain a drug's therapeutic window. We report the use of biodegradable porous silicon microparticles (pSi MPs) loaded with the anticancer drug camphothecin, followed by a plasma polymer overcoating using a loudspeaker plasma reactor. Homogenous "Teflon-like" coatings were achieved by tumbling the particles by playing AC/DC's song "Thunderstruck". The overcoating resulted in a markedly slower release of the cytotoxic drug, and this effect correlated positively with the plasma polymer coating times, ranging from 2-fold up to more than 100-fold. Ultimately, upon characterizing and verifying pSi MP production, loading, and coating with analytical methods such as time-of flight secondary ion mass spectrometry, scanning electron microscopy, thermal gravimetry, water contact angle measurements, and fluorescence microscopy, human neuroblastoma cells were challenged with pSi MPs in an in-vitro assay, revealing a significant time delay in cell death onset. Refereed/Peer-reviewed

Porous silicon microparticles (pSi MPs) functionalized with fluorescent dyes (lissamine and carboxy-5-fluorescein) and intrinsically luminescent pSi MPs were explored as novel fingerprint dusting powders. The versatility of luminescent pSi MPs is demonstrated through time-gated imaging of their long-lived (lifetime>28μs) near-IR emission, and mass spectrometry analysis of fingerprints dusted with luminescent pSi MPs to provide further information on exogenous small molecules present in latent fingerprints. Refereed/Peer-reviewed

International audience; Dendritic cells (DC) are the most potent antigen-presenting cells and are fundamental for the establishment of transplant tolerance. The Dendritic Cell-Specific Intracellular adhesion molecule-3-Grabbing Non-integrin (DC-SIGN; CD209) receptor provides a target for dendritic cell therapy. Biodegradable and high-surface area porous silicon (pSi) nanoparticles displaying anti-DC-SIGN antibodies and loaded with the immunosuppressant rapamycin (Sirolimus) serve as a fit-for-purpose platform to target and modify DC. Here, we describe the fabrication of rapamycin-loaded DC-SIGN displaying pSi nanoparticles, the uptake efficiency into DC and the extent of nanoparticle-induced modulation of phenotype and function. DC-SIGN antibody displaying pSi nanoparticles favourably targeted and were phagocytosed by monocyte-derived and myeloid DC in whole human blood in a time- and dose-dependent manner. DC preconditioning with rapamycin-loaded nanoparticles, resulted in a maturation resistant phenotype and significantly suppressed allogeneic T-cell proliferation.

The emergence of nanostructured materials has opened new horizons in the development of next generation biosensors. Being able to control the design of the electrode interface at the nanoscale combined with the intrinsic characteristics of the nanomaterials engenders novel biosensing platforms with improved capabilities. The purpose of this review is to provide a comprehensive and critical overview of the latest trends in emerging nanostructured electrochemical biosensors. A detailed description and discussion of recent approaches to construct label-free electrochemical nanostructured electrodes is given with special focus on pathogen detection for environmental monitoring and food safety. This includes the use of nanoscale materials such as nanotubes, nanowires, nanoparticles, and nanosheets as well as porous nanostructured materials including nanoporous anodic alumina, mesoporous silica, porous silicon, and polystyrene nanochannels. These platforms may pave the way toward the development of point-of-care portable electronic devices for applications ranging from environmental analysis to biomedical diagnostics. Refereed/Peer-reviewed

This work focuses on an evaluation of novel composites of porous silicon (pSi) with the biocompatible polymer epsilon-polycaprolactone (PCL) for drug delivery and tissue engineering applications. The degradation behavior of the composites in terms of their morphology along with the effect of pSi on polymer degradation was monitored. PSi particles loaded with the drug camptothecin (CPT) were physically embedded into PCL films formed from electrospun PCL fiber sheets. PSi/PCL composites revealed a release profile of CPT (monitored via fluorescence spectroscopy) in accordance with the Higuchi release model, with significantly lower burst release percentage compared to pSi microparticles alone. Degradation studies of the composites, using gravimetric analysis, differential scanning calorimetry (DSC), and field emission scanning electron microscopy (FESEM), carried out in phosphate-buffered saline (PBS) under simulated physiological conditions, indicated a modest mass loss (15%) over 5 weeks due to pSi dissolution and minor polymer hydrolysis. DSC results showed that, relative to PCL-only controls, pSi suppressed crystallization of the polymer film during PBS exposure. This suppression affects the evolution of surface morphology during this exposure that, in turn, influences the degradation behavior of the polymer. The implications of the above properties of these composites as a possible therapeutic device are discussed. Refereed/Peer-reviewed

Cell culture is a powerful in vitro characterization technique to optimize the properties of a biomaterial for in vivo biomedical use by conversely revealing potential sources of cytotoxicity. A comprehensive literature survey of the range of cell types cultured on porous silicon is given, together with a discussion of how surface chemistry, topography, and porosity gradients affect cell behavior.

Metal-assisted chemical etching (MACE) affords porous silicon nanostructures control over size, shape, and porosity in a single step. Simplicity and flexibility are potential advantages over more traditional silicon bulk micromachining techniques. MACE-generated porous micro- and nanostructures are suitable as biomaterials through their length scales and biocompatibility. This work provides a comprehensive overview of the MACE reaction mechanism that yields biomedically relevant silicon nanostructures – from nanowires, nanopillars, to sub-micrometer holes and pores. We discuss their biomedical applications in biosensors, cell capture and transfection arrays, and drug delivery vectors. We assess the reported benefits of the various nanostructures and discuss whether MACE provides clear and distinct advantages over other techniques. The flexibility and simplicity of MACE comes at a cost. The reaction parameters are many and inter-related, and we lack a full model of the etching mechanism. While the cathode reaction is well understood, the anode reaction involving dissolution of the silicon remains controversial. Such uncertainties impede rational design of specific structures that address biomedical requirements. We summarize current understanding to provide design guidelines for structures used in biomedicine and review the effects of key parameters on the morphological attributes of the etched features.

Gene silencing by RNA interference is a powerful technology with broad applications. However, this technology has been hampered by the instability of small interfering RNA (siRNA) molecules in physiological conditions and their inefficient delivery into the cytoplasm of target cells. Porous silicon nanoparticles have emerged as a potential delivery vehicle to overcome these limitations-being able to encapsulate RNA molecules within the porous matrix and protect them from degradation. Here, key variables were investigated that influence siRNA loading into porous silicon nanoparticles. The effect of modifying the surface of porous silicon nanoparticles with various amino-functional molecules as well as the effects of salt and chaotropic agents in facilitating siRNA loading was examined. Maximum siRNA loading of 413 μg/(mg of porous silicon nanoparticles) was found when the nanoparticles were modified by a fourth generation polyamidoamine dendrimer. Low concentrations of urea or salt increased loading capacity: an increase in RNA loading by 19% at a concentration of 0.05 M NaCl or 21% at a concentration of 0.25 M urea was observed when compared to loading in water. Lastly, it was demonstrated that dendrimer-functionalized nanocarriers are able to deliver siRNA against ELOVL5, a target for the treatment of advanced prostate cancer.

We report the first method to introduce differential functionalities in the interior pore walls and exterior surface of highly stable thermally hydrocarbonised porous silicon (THCpSi) films. The approach exploits the hydrophobicity of the hydrosilylated THCpSi to, first, selectively functionalise the external surface, and subsequently derivatise the hydrophobic internal pore walls Refereed/Peer-reviewed

Inspired by photosynthesis, solar water electrolysis uses sunlight to produce hydrogen, a clean, sustainable and storable fuel and a promising solution to the energy storage conundrum. Semiconductor silicon has been the basis for several generations of photovoltaic cells but its use in artificial photosynthetic devices is still in its infancy. Recent progress in this area encompasses nanostructured forms of silicon including anodised porous silicon, silicon nanoparticles and silicon nanowires. At the same time, efforts are underway to explore biosilica-derived silicon from marine diatoms for photocatalysis. It is anticipated that by using these nanostructured materials, the solar conversion efficiency as well as cost effectiveness of these devices will be greatly improved. Porous silicon, porous silicon nanoparticles and silicon nanowires have been fabricated based on hydrofluoric acid etching techniques, whereas diatom-derived silicon is a naturally nanostructured form of silica, which can be converted into silicon using a magnesiothermic processes. At present, the performance of synthetic silicon nanostructures is approaching that achieved by conventional solar water splitting technology, producing photocurrent densities of up to 36mA/cm2. The device performance reported for diatom-derived silicon to date has been far lower (14μA/cm lt;sup>2) but new electrode fabrication techniques offer significant scope for improvement. This review explores the fabrication, use and potential impact of diverse silicon nanoarchitectures for solar water electrolysis. Refereed/Peer-reviewed

We report a versatile particle-based route to dense arrays of parallel submicron pores with high aspect ratio in silicon and explore the application of these arrays in sensors, optics, and polymer micro-patterning.Polystyrene (PS) spheres are convectively assembled on gold-coated silicon wafers and sputter-etched, resulting in well-defined gold disc arrays with excellent long-range order. The gold discs act as catalysts in metal-assisted chemical etching, yielding uniform pores with straight walls, flat bottoms, and high aspect ratio. The resulting pore arrays can be used as robust antireflective surfaces, in biosensing applications, and as templates for polymer replica molding. Refereed/Peer-reviewed

The antireflective properties and nanometer sizes of silicon nanoparticles can be exploited for improved solar energy conversion. We report on using porous silicon nanoparticles as a photocathode for photoelectrochemical water splitting. An enhancement in the photocurrent density was observed when porous silicon nanoparticles were decorated with indium phosphide nanocrystals and a bio-inspired iron sulfur carbonyl electrocatalyst. Our system gave a photocurrent density of -2.2 mu A cm(-2) while generating hydrogen gas. Refereed/Peer-reviewed

Open Access Article. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence., The proinflammatory cytokine, tumor necrosis factor-α (TNF-α), is elevated in several diseases such as uveitis, rheumatoid arthritis and non-healing chronic wounds. Adding Infliximab, a chimeric IgG1 monoclonal antibody raised against TNF-α, to chronic wound fluid can neutralise human TNF-α, thereby providing a potential therapeutic option for chronic wound healing. However, to avoid the need for repeated application in a clinical setting, and to protect the therapeutic antibody from the hostile environment of the wound, suitable delivery vehicles are required. Porous silicon (pSi) is a biodegradable high surface area material commonly employed for drug delivery applications. In this study, the use of pSi microparticles (pSi MPs) for the controlled release of Infliximab to disease environments, such as chronic wounds, is demonstrated. Surface chemistry and pore parameters for Infliximab loading are first optimised in pSi films and loading conditions are transferred to pSi MPs. Loading regimens exceeding 60 μg of Infliximab per mg of pSi are achieved. Infliximab is released with zero-order release kinetics over the course of 8 days. Critically, the released antibody remains functional and is able to sequester TNF-α over a weeklong timeframe; suitable for a clinical application in chronic wound therapy.

There is a strong demand for techniques that allow the fabrication of biocompatible porous nanoparticles for drug delivery applications. In this work, a new method to fabricate size- and shape-controlled porous silicon (pSi) nanodiscs is described. The process relies on a combination of colloidal lithography and metal-assisted chemical etching. Height and diameter of the pSi nanodiscs can be easily adjusted. The nanodiscs are degradable in physiological milieu and are nontoxic to mammalian cells. In order to highlight the potential of the pSi nanodiscs in drug delivery, an in vitro investigation that involved loading of nanodiscs with the anticancer agent camptothecin and functionalization of the nanodisc periphery with an antibody that targets receptors on the surface of neuroblastoma cells is carried out. The thus-prepared nanocarriers are found to selectively attach to and kill cancer cells Refereed/Peer-reviewed

Metal-assisted chemical etching (MACE) affords porous silicon nanostructures control over size, shape, and porosity in a single step. Simplicity and flexibility are potential advantages over more traditional silicon bulk micromachining techniques. MACE-generated porous micro- and nanostructures are suitable as biomaterials through their length scales and biocompatibility. This work provides a comprehensive overview of the MACE reaction mechanism that yields biomedically relevant silicon nanostructures – from nanowires, nanopillars, to sub-micrometer holes and pores. We discuss their biomedical applications in biosensors, cell capture and transfection arrays, and drug delivery vectors. We assess the reported benefits of the various nanostructures and discuss whether MACE provides clear and distinct advantages over other techniques. The flexibility and simplicity of MACE comes at a cost. The reaction parameters are many and inter-related, and we lack a full model of the etching mechanism. While the cathode reaction is well understood, the anode reaction involving dissolution of the silicon remains controversial. Such uncertainties impede rational design of specific structures that address biomedical requirements. We summarize current understanding to provide design guidelines for structures used in biomedicine and review the effects of key parameters on the morphological attributes of the etched features.

© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Chronic wounds are a major socio-economic problem. Bacterial infections in such wounds are a major contributor to lack of wound healing. An early indicator of wound infection is an increase in pH of the wound fluid. Herein, we describe the development of a pH-responsive drug delivery device that can potentially be used for wound decontamination in situ and on-demand in response to an increase in the pH of the wound environment. The device is based on a porous silicon film that provides a reservoir for encapsulation of an antibiotic within the pores. Loaded porous silicon is capped with dual plasma polymer layers of poly(1,7-octadiene) and poly(acrylic acid), which provide a pH-responsive barrier for on-demand release of the antibiotic. We demonstrate that release of the antibiotic is inhibited in aqueous buffer at pH 5, whereas the drug is released in a sustainable manner at pH 8. Importantly, the released drug was bacteriostatic against the Pseudomonas aeruginosa wound pathogen. In the future, incorporation of the delivery device into wound dressings could potentially be utilized for non-invasive decontamination of wounds.

Because reactive oxygen species are involved in a range of pathologies, developing analytical tools for this group of molecules opens new vistas for biomedical diagnostics. Herein, we fabricate a porous silicon microcavity (pSiMC) functionalized with luminescent singlet oxygen ( 1 O 2 ) probe EuA ((Eu(III)-2,2′,2″-(10-(2-((4-(2-((4-(2-((anthracen-9-ylmethyl)amino)ethyl)-1H-1,2,3-triazol-1-yl)amino)-2-oxoethyl)-2-oxo-1,2-dihydroquinolin-7-yl)amino)-2-oxoethyl)-1,4,7,10-tetraazacyclododecane-1,4,7-triyl)triacetic acid) as proof of concept of an optical sensor for reactive oxygen species. We characterize each surface modification step of the pSiMC by means of FTIR and X-ray photoelectron spectroscopy as well as by determining the optical shifts of the resonance wavelength of the pSiMC. The luminescence signal upon detection of 1 O 2 on the EuA-modified pSiMC is enhanced ∼2-fold compared to that of a single layer and a detuned microcavity. The sensing performance of the EuA probe is improved significantly on the pSiMC compared to that in aqueous solution, giving a limit of 1 O 2 detection of 3.7 × 10 -8 M. Refereed/Peer-reviewed

In order to address the issue of pathogenic bacterial colonization of diabetic wounds, a more direct and robust approach is required, which relies on a physical form of bacterial destruction in addition to the conventional biochemical approach (i.e., antibiotics). Targeted bacterial destruction through the use of photothermally active nanomaterials has recently come into the spotlight as a viable approach to solving the rising problem of antibiotic resistant microorganisms. Materials with high absorption coefficients in the near-infrared (NIR) region of the electromagnetic spectrum show promise as alternative antibacterial therapeutic agents, since they preclude the development of bacterial resistance and can be activated on demand. Here were report on a novel approach for the fabrication of gold nanoparticle decorated porous silicon nanopillars with tunable geometry that demonstrate excellent photothermal conversion properties when irradiated with a 808 nm laser. These photothermal antibacterial properties are demonstrated in vitro against the Gram-positive bacteria Staphylococcus aureus (S. aureus) and Gram-negative Escherichia coli (E. coli). Results show a reduction in bacterial viability of up to 99% after 10 min of laser irradiation. We also show an increase in antibacterial performance after modifying the nanopillars with S. aureus targeting antibodies causing up to a 10-fold increase in bactericidal efficiency compared to E. coli. In contrast, the nanomaterial resulted in minimal disruption of metabolic processes in human foreskin fibroblasts (HFF) after an equivalent period of irradiation. Refereed/Peer-reviewed

A label-free porous silicon (pSi) based, optical biosensor, using both an antibody and aptamer bioreceptor motif has been developed for the detection of insulin. Two parallel biosensors were designed and optimised independently, based on each bioreceptor. Both bioreceptors were covalently attached to a thermally hydrosilylated pSi surface though amide coupling, with unreacted surface area rendered stable and low fouling by incorporation of PEG moieties. The insulin detection ability of each biosensor was determined using interferometric reflectance spectroscopy, using a range of different media both with and without serum. Sensing performance was compared in terms of response value, response time and limit of detection (LOD) for each platform. In order to demonstrate the capability of the best performing biosensor to detect insulin from real samples, an in vitro investigation with the aptamer-modified surface was performed. This biosensor was exposed to buffer conditioned by glucose-stimulated human islets, with the result showing a positive response and a high degree of selectivity towards insulin capture. The obtained results correlated well with the ELISA used in the clinic for assaying glucose-stimulated insulin release from donor islets. We anticipate that this type of sensor can be applied as a rapid point-of-use biosensor to assess the quality of donor islets in terms of their insulin production efficiency, prior to transplantation. Refereed/Peer-reviewed

Desorption ionisation on porous silicon (DIOS) was used for the detection of nicotine from exhaled breath. This result represents proof-of-principle of the ability of DIOS to detect small molecular analytes in breath including biomarkers and illicit drugs. Refereed/Peer-reviewed