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Cu-based catalysts have shown structural instability during the electrochemical CO2 reduction reaction (CO2RR). However, studies on monometallic Cu catalysts do not allow a nuanced differentiation between the contribution of the applied potential and the local concentration of CO as the reaction intermediate since both are inevitably linked. We first use bimetallic Ag-core/porous Cu-shell nanoparticles, which utilise nanoconfinement to generate high local CO concentrations at the Ag core at potentials at which the Cu shell is still inactive for the CO2RR. Using operando liquid cell TEM in combination with ex situ TEM, we can unequivocally confirm that the local CO concentration is the main source for the Cu instability. The local CO concentration is then modulated by replacing the Ag-core with a Pd-core which further confirms the role of high local CO concentrations. Product quantification during CO2RR reveals an inherent trade-off between stability, selectivity and activity in both systems., The stability of bimetallic AgCu and PdCu catalysts for electrochemical CO2RR is investigated using the combination of operando and ex situ TEM. The local CO concentration is identified as the main link between activity, stability and selectivity.

Nanoparticle size, surface charge and material composition are known to affect the uptake of nanoparticles by cells. However, whether nanoparticle shape affects transport across various barriers inside the cell remains unclear. Here we used pair correlation microscopy to show that polymeric nanoparticles with different shapes but identical surface chemistries moved across the various cellular barriers at different rates, ultimately defining the site of drug release. We measured how micelles, vesicles, rods and worms entered the cell and whether they escaped from the endosomal system and had access to the nucleus via the nuclear pore complex. Rods and worms, but not micelles and vesicles, entered the nucleus by passive diffusion. Improving nuclear access, for example with a nuclear localization signal, resulted in more doxorubicin release inside the nucleus and correlated with greater cytotoxicity. Our results therefore demonstrate that drug delivery across the major cellular barrier, the nuclear envelope, is important for doxorubicin efficiency and can be achieved with appropriately shaped nanoparticles.

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Studying the interactions between nanoengineered materials and biological systems plays a vital role in the development of biological applications of nanotechnology and the improvement of our fundamental understanding of the bio-nano interface. A significant barrier to progress in this multidisciplinary area is the variability of published literature with regards to characterizations performed and experimental details reported. Here, we suggest a 'minimum information standard' for experimental literature investigating bio-nano interactions. This standard consists of specific components to be reported, divided into three categories: material characterization, biological characterization and details of experimental protocols. Our intention is for these proposed standards to improve reproducibility, increase quantitative comparisons of bio-nano materials, and facilitate meta analyses and in silico modelling. Refereed/Peer-reviewed

We investigate the analytical performance of label free porous silicon Bloch surface wave (BSW) devices as protease sensors. Protease detection is based on the digestion of gelatin, which was covalently immobilized onto the surface modified PSi structure. Exposure to the protease enzyme, subtilisin initiates catalytic degradation of the gelatin gel network. The degradation of this network which is present in the top layer of the sensor, causes a blue shift in the spectral position of the Bloch surface mode. The magnitude of the resonance shift is directly proportional to the concentration of subtilisin and the digestion time. The lowest concentration of subtilisin detected was 370 pM. Secondary spectral features, such as band-edge modes, are relatively insensitive to refractive index changes in the superficial layers and thus can be utilised as an internal reference to exclude any nonspecific adsorption and bonding that may occur through the bulk of the film. The advantages of the system here include fast diffusion of digested product and self-referencing capability. Refereed/Peer-reviewed

In this paper we demonstrate the possibility of modifying porous silicon (PSi) particles with surface chemistry and recognition molecules (antibodies) such that these devices could potentially be used for single-cell identification or sensing. This is achieved by modifying PSi Rugate filters viahydrosilylation with surface chemistry that serves firstly, to protect the silicon surfaces from oxidation; secondly, renders the surfaces resistant to nonspecific adsorption of proteins and cells and thirdly, allows further functionality to be added such as the coupling of antibodies. The surface chemistry remained unchanged after sonication of the PSi to form PSi microparticles. The ability to monitor the spectroscopic properties of microparticles, and shifts in the optical signature due to changes in the refractive index of the material within the pore space, is demonstrated. The particles are shown to remain stable in physiological buffers and human blood for longer than one week. Finally, the modification of the PSi particles with functional antibodies is achieved. Refereed/Peer-reviewed

Porous silicon photonics is the ideal platform for high sensitivity, high selectivity monitoring of biological molecules in a complex fluidic environment. The potential of this technology was identified almost 15 years ago, however, it has taken considerable advances in porous silicon surface chemistry, photonics, and micro-fabrication to create truly effective devices that can provide new insights into the behaviour of biological systems. In this review we provide a critical assessment of the development of porous silicon optical biosensors from the early demonstrations of affinity based sensing to the current trends in monitoring single cell activity and perspectives in the use of photonic microparticles for biomedical applications. Refereed/Peer-reviewed

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. Refereed/Peer-reviewed

The ability to impart discrete surface chemistry to the inside and outside of mesoporous silicon is of great importance for a range of biomedical applications, from selective (bio)sensing to tissue-specific drug delivery. Here we present a generic strategy toward achieving depth-resolved functionalization of the external and internal porous surfaces by a simple change in the wavelength of the light being used to promote surface chemical reactions. UV-assisted hydrosilylation, limited by the penetration depth of UV light, is used to decorate the outside of the mesoporous structure with carboxylic acid molecules, and white light illumination triggers the attachment of dialkyne molecules to the inner porous matrix.

We report on the observation of significant optical bistability in the transmission and reflection properties of mesoporous silicon microcavities when illuminated with a 150 ns pulsed laser at 532 nm. The observed optical hysteresis is shown to be transient in nature and the properties are strongly dependent on the porosity of the cavity layer. The onset and damage threshold intensity are also shown to be porosity dependent. Our modeling suggests that the observed effects are due to changes in the nonlinear refractive index where the transient lifetime increases with increasing porosity. We investigate the role of surface states on influencing the bistable process by passivating the internal porous surface with hydrosilylation chemistry. Refereed/Peer-reviewed