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Nanomaterials are a central pillar in modern medicine. They are thought to optimize drug delivery, enhance therapeutic efficacy, and reduce side-effects. To foster this technology, analytical methods are needed to validate not only the localization and distribution of these nanomaterials, but also their compatibility with cells, drugs, and drug release. In the present work, we assessed nanoparticles based on porous silicon (pSiNPs) loaded with the clinically used tyrosine kinase inhibitor sunitinib for their effectiveness of drug delivery, release, and toxicity in colon cancer cells (HCT 116 cells) and cardiac myoblast cells (H9c2) using Raman micro-spectroscopy, highresolution fluorescence microscopy, along with biological methods for toxicological effects. We produced pSiNPs with a size of about 100 nm by grinding mesoporous silicon layers. pSiNPs allowed an effective loading of sunitinib due to their high porosity. Photoluminescence properties of the nanoparticles within the visible spectrum allowed the visualization of their uptake in cardiac cells. Raman micro-spectroscopy allowed not only the detection of the uptake and distribution of pSiNPs within the cells via a characteristic silicon Raman band at about 518-520 cm-1, but also the localization of the drug based on its characteristic molecular fingerprints. Cytotoxicity studies by Western blot analyses of apoptotic marker proteins such as caspase-3, and the detection of apoptosis by subG1-positive cell fractions in HCT 116 and MTT analyses in H9c2 cells, suggest a sustained release of sunitinib from pSiNPs and delayed cytotoxicity of sunitinib in HCT 116 cells. The analyses in cardiac cells revealed that pSiNPs are well tolerated and that they may even protect from toxic effects in these cells to some extent. Analyses of the integrity of mitochondrial networks as an early indicator for apoptotic cellular effects seem to validate these observations. Our study suggests pSiNPs-based nanocontainers for efficient and safe drug delivery and Raman micro-spectroscopy as a reliable method for their detection and monitoring. Thus, the herein presented nanocontainers and analytical methods have the potential to allow an efficient advancement of nanoparticles for targeted and sustained intracellular drug release that is of need, e.g., in chronic diseases and for the prevention of cardiac toxicity. [ABSTRACT FROM AUTHOR]

Here, a phenomenon of efficient oxygen exchange between a silicon surface and a thin layer of tin dioxide during chemical vapor deposition is presented, which leads to a unique Sn:SiO 2 layer. Under thermodynamic conditions in the temperature range of 725-735 °C, the formation of nanostructures with volcano-like shapes in "active" and "dormant" states are observed. Extensive characterization techniques, such as electron microscopy, X-ray diffraction, synchrotron radiation-based X-ray photoelectron, and X-ray absorption near-edge structure spectroscopy, are applied to study the formation. The mechanism is related to the oxygen retraction between tin(IV) oxide and silicon surface, leading to the thermodynamically unstable tin(II)oxide, which is immediately disproportionate to metallic Sn and SnO 2 localized in the SiO 2 matrix. The diffusion of metallic tin in the amorphous silicon oxide matrix leads to larger agglomerates of nanoparticles, which is similar to the formation of a magma chamber during the natural volcanic processes followed by magma eruption, which here is associated with the formation of depressions on the surface filled with metallic tin particles. This new effect contributes a new approach to the formation of functional composites but also inspires the development of unique Sn:SiO 2 nanostructures for diverse application scenarios, such as thermal energy storage., (© 2024 Wiley‐VCH GmbH.)

Therapeutic drug monitoring (TDM) is an important tool in precision medicine as it allows estimating pharmacodynamic and pharmacokinetic effects of drugs in clinical settings. An accurate, fast and real-time determination of the drug concentrations in patients ensures fast decision-making processes at the bedside to optimize the clinical treatment. Surface-enhanced Raman spectroscopy (SERS), which is based on the application of metallic nanostructured substrates to amplify the inherent weak Raman signal, is a promising technique in medical research due to its molecular specificity and trace sensitivity accompanied with short detection times. Therefore, we developed a SERS-based detection scheme using silicon nanowires decorated with silver nanoparticles, fabricated by means of top-down etching combined with chemical deposition, to detect the antibiotic ceftriaxone (CRO) in spiked fresh plasma and microdialysis samples. We successfully detected CRO in both matrices with an LOD of 94 μM in protein-depleted fresh plasma and 1.4 μM in microdialysate., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

For a very long period, tin was considered one of the most important metals for humans due to its easy access in nature and abundance of sources. In the past, tin was mainly used to make various utensils and weapons. Today, nanostructured tin and especially its oxide materials have been found to possess many characteristic physical and chemical properties that allow their use as functional materials in various fields such as energy storage, photocatalytic process, gas sensors, and solar cells. This review discusses current methods for the synthesis of Sn/SnO 2 composite materials in form of powder or thin film, as well as the application of the most advanced characterization tools based on large-scale synchrotron radiation facilities to study their chemical composition and electronic features. In addition, the applications of Sn/SnO 2 composites in various fields are presented in detail.

Tin-containing layers with different degrees of oxidation are uniformly distributed along the length of silicon nanowires formed by a top-down method by applying metalorganic chemical vapor deposition. The electronic and atomic structure of the obtained layers is investigated by applying nondestructive surface-sensitive X-ray absorption near edge spectroscopy using synchrotron radiation. The results demonstrated, for the first time, a distribution effect of the tin-containing phases in the nanostructured silicon matrix compared to the results obtained for planar structures at the same deposition temperatures. The amount and distribution of tin-containing phases can be effectively varied and controlled by adjusting the geometric parameters (pore diameter and length) of the initial matrix of nanostructured silicon. Due to the occurrence of intense interactions between precursor molecules and decomposition by-products in the nanocapillary, as a consequence of random thermal motion of molecules in the nanocapillary, which leads to additional kinetic energy and formation of reducing agents, resulting in effective reduction of tin-based compounds to a metallic tin state for molecules with the highest penetration depth in the nanostructured silicon matrix. This effect will enable clear control of the phase distributions of functional materials in 3D matrices for a wide range of applications., (© 2023 The Authors. Small published by Wiley-VCH GmbH.)

The composition and atomic and electronic structure of a silicon nanowire (SiNW) array coated with tin oxide are studied at the spectromicroscopic level. SiNWs are covered from top to down with a wide bandgap tin oxide layer using a metal-organic chemical vapor deposition technique. Results obtained via scanning electron microscopy and X-ray diffraction showed that tin-oxide nanocrystals, 20 nm in size, form a continuous and highly developed surface with a complex phase composition responsible for the observed electronic structure transformation. The "one spot" combination, containing a chemically sensitive morphology and spectroscopic data, is examined via photoemission electron microscopy in the X-ray absorption near-edge structure spectroscopy (XANES) mode. The observed spectromicroscopy results showed that the entire SiNW surface is covered with a tin(IV) oxide layer and traces of tin(II) oxide and metallic tin phases. The deviation from stoichiometric SnO 2 leads to the formation of the density of states sub-band in the atop tin oxide layer bandgap close to the bottom of the SnO 2 conduction band. These observations open up the possibility of the precise surface electronic structures estimation using photo-electron microscopy in XANES mode., (© 2023 The Authors. Small published by Wiley-VCH GmbH.)

Li-O 2 batteries attract great attention due to their promising theoretical energy density. One of the main obstacles on the way to achieving high energy density and good cyclability is positive electrode passivation by the Li 2 O 2 discharge product as well as the presence of parasitic reactions that degrade electrode and electrolyte materials. To overcome these issues new electrolytes are being extensively searched for to ensure the bulk-mediated mechanism of the oxygen reduction reaction and inhibition of parasitic reactions. Different additives to organic solvents can significantly change the properties of electrolytes. This work is devoted to the effect of ionic liquids (ILs), which are proposed as an additive to the solvent due to their excellent solvation properties, high stability, low volatility and flammability. Using molecular dynamics simulations we investigate mixtures of the Pyr 14 TFSI ionic liquid and dimethoxyethane (DME) with different volume fractions of the IL. Our calculations show that the presence of the ionic liquid in the electrolyte stabilises solvation shells around the ions, both involved in the oxygen reduction and parasitic reactions, slowing down the kinetics of Li + and O 2 - association. This makes the usage of such mixtures promising for electrolyte design for Li-O 2 batteries.

An aprotic lithium-air battery is a promising candidate for next-generation energy storage systems, but its practical performance is still low. The addition of water to an electrolyte can substantially increase the capacity and round-trip efficiency of batteries. However, fundamental mechanisms of the water impact are still far from being fully understood. To contribute to this issue, we studied by molecular dynamics simulations the effect of water additives on the behaviour of discharge intermediates Li + and O 2 - in two frequently used solvents: dimethoxyethane (DME) and dimethyl sulfoxide (DMSO). We have estimated the structures of the solvation shells around Li + and O 2 - ions, and the residence times of various electrolyte components inside the solvation shells depending on the concentration of water additives. Furthermore, we have estimated the rate and the equilibrium of the Li + and O 2 - association. Our results reveal that water additives in electrolytes shift the equilibrium of the association reaction toward soluble Li + and O 2 - ions in both DME and DMSO. These data argue for the view that water promotes the solution discharge mechanism, thus increasing the capacity. Moreover, we show that water accelerates the kinetics of the association reaction due to the decrease of the stability of Li + and O 2 - solvation shells. This may explain the reduced discharge overpotential when water is added.

Efficient light-stimulated hydrogen generation from top-down produced highly doped n-type silicon nanowires (SiNWs) with silver nanoparticles (AgNPs) in water-containing medium under white light irradiation is reported. It is observed that SiNWs with AgNPs generate at least 2.5 times more hydrogen than SiNWs without AgNPs. The authors' results, based on vibrational, UV-vis, and X-ray spectroscopy studies, strongly suggest that the sidewalls of the SiNWs are covered by silicon suboxides, by up to a thickness of 120 nm, with wide bandgap semiconductor properties that are similar to those of titanium dioxide and remain stable during hydrogen evolution in a water-containing medium for at least 3 h of irradiation. Based on synchrotron studies, it is found that the increase in the silicon bandgap is related to the energetically beneficial position of the valence band in nanostructured silicon, which renders these promising structures for efficient hydrogen generation., (© 2021 The Authors. Small published by Wiley-VCH GmbH.)

The modern development of nanotechnology requires the discovery of simple approaches that ensure the controlled formation of functional nanostructures with a predetermined morphology. One of the simplest approaches is the self-assembly of nanostructures. The widespread implementation of self-assembly is limited by the complexity of controlled processes in a large volume where, due to the temperature, ion concentration, and other thermodynamics factors, local changes in diffusion-limited processes may occur, leading to unexpected nanostructure growth. The easiest ways to control the diffusion-limited processes are spatial limitation and localized growth of nanostructures in a porous matrix. In this paper, we propose to apply the method of controlled self-assembly of gold nanostructures in a limited pore volume of a silicon oxide matrix with submicron pore sizes. A detailed study of achieved gold nanostructures' morphology, microstructure, and surface composition at different formation stages is carried out to understand the peculiarities of realized nanostructures. Based on the obtained results, a mechanism for the growth of gold nanostructures in a limited volume, which can be used for the controlled formation of nanostructures with a predetermined geometry and composition, has been proposed. The results observed in the present study can be useful for the design of plasmonic-active surfaces for surface-enhanced Raman spectroscopy-based detection of ultra-low concentration of different chemical or biological analytes, where the size of the localized gold nanostructures is comparable with the spot area of the focused laser beam.

Nanocontainers based on solid materials have great potential for drug delivery applications. However, since nanocontainer-mediated delivery can alter the drug internalization pathways and metabolism, it is important to find out what are the mechanisms of cancer cell death induced by nanocontainers and, moreover, is it possible to regulate them. Here, we report on the detailed investigation of the internalization kinetics and intracellular spatial distribution of porous silicon nanoparticles (PSi NPs) loaded with doxorubicin (DOX) and response of cancer cells to treatment with DOX-PSi NPs as well as studies of nanocontainer biodegradation by applying various microscopy methods, Raman microspectroscopy and biological experiments with cancer cells of different etiology. The obtained results revealed the absence of toxicity of unloaded PSi NPs to cancer cells up to a concentration of 700 μg/mL during the prolonged incubation time. Thus, given the fact that the nanocontainers themselves are not toxic, it is easy to adjust the dose of the drug that they deliver to the cells. It is shown, that the treatment with DOX-loaded PSi NPs more efficiently eliminates cancer cells in comparison with the free DOX. At the same time, the obtained results demonstrate the possibility of regulating the initiation of apoptosis or necrosis in tumor cells after treatment with different concentrations of DOX-PSi NPs, as revealed by the analysis of the caspase-3 processing, the accumulation of sub-G1 cell fraction, and morphological changes determined by electron and light microscopy. The obtained results are important for future applications of porous silicon nanocontainers in drug delivery for apoptotic pathway-targeted cancer therapy.

Early stage detection of Pseudomonas infections is life-saving, especially in the case of patients with cystic fibrosis. Pyocyanin (PYO) is a specific metabolite of the Pseudomonas aeruginosa bacteria, and detection of it directly in the sputum can significantly reduce the diagnosis time of the infection. In the present study, aiming to achieve this goal, a simple and cost-effective surface-enhanced Raman spectroscopy (SERS) detection platform was proposed. For this, a silicon nanowire (SiNW) matrix, produced by metal-assisted chemical etching of silicon substrates was variously modified by noble metal (silver and gold) nanoparticles (NPs) and tested for the detection of the metabolite PYO in the complex matrix of artificial sputum. We found the SERS substrate with Ag NPs on the bottom of SiNWs and deposited bimetallic Ag/Au NPs on the top of them the best suited for the sensitive detection of PYO. The investigated plasmonic substrate showed good point-to-point and batch-to-batch signal reproducibility and allowed for the detection of PYO in artificial sputum down to 6.25 μM, which is the required sensitivity for clinical applications., (Copyright © 2019. Published by Elsevier B.V.)

The radiofrequency (RF) mild hyperthermia effect sensitized by biodegradable nanoparticles is a promising approach for therapy and diagnostics of numerous human diseases including cancer. Herein, we report the significant enhancement of local destruction of cancer cells induced by RF hyperthermia in the presence of degraded low-toxic porous silicon (PSi) nanowires (NWs). Proper selection of RF irradiation time (10 min), intensity, concentration of PSi NWs, and incubation time (24 h) decreased cell viability to 10%, which can be potentially used for cancer treatment. The incubation for 24 h is critical for degradation of PSi NWs and the formation of silicic acid ions H + and H 3 SiO 4 - in abundance. The ions drastically change the solution conductivity in the vicinity of PSi NWs, which enhances the absorption of RF radiation and increases the hyperthermia effect. The high biodegradability and efficient photoluminescence of PSi NWs were governed by their mesoporous structure. The average size of pores was 10 nm, and the sizes of silicon nanocrystals (quantum dots) were 3-5 nm. Degradation of PSi NWs was observed as a significant decrease of optical absorbance, photoluminescence, and Raman signals of PSi NW suspensions after 24 h of incubation. Localization of PSi NWs at cell membranes revealed by confocal microscopy suggested that thermal poration of membranes could cause cell death. Thus, efficient photoluminescence in combination with RF-induced cell membrane breakdown indicates promising opportunities for theranostic applications of PSi NWs., Competing Interests: The authors declare no competing financial interest.

In this work we elucidate the fundamental difference between aggregate formation of donor-π-acceptor merocyanines in their electronic ground and excited states. While increasing the π-bridge size favors formation of π-stacked aggregates in the dark, irradiation with visible light causes reorientation of the dyes to form prototype H-aggregates with compensating dipole moments. This photoannealing changes the supramolecular structure and its UV-vis spectroscopic properties dramatically, thus being of importance for the function of active layers composed of these dyes. Aggregates of the ground state dyes are bound cooperatively through ππ-London dispersion interactions and hydrogen bonds between the polar α-cyano-carboxylic acid groups. However, charge transfer upon photoexcitation leads to repulsion of the polar acid groups. Electronic excitation of the dyes approximately doubles the ground state dipole moment, thus driving molecular reorientation into prototype H-aggregate structures. We show that this photoinduced supramolecular rearrangement can disrupt the large polymeric aggregates formed in the dark. The photoinduced supramolecular structural changes reported in this work will influence the performance of optoelectronic devices composed of these structures and must be controlled to avoid morphological decomposition of active layers upon operation.

In this study, we report a method for the suppression of Escherichia coli (E. coli) vitality by means of therapeutic ultrasound irradiation (USI) using biocompatible silicon nanoparticles as cavitation sensitizers. Silicon nanoparticles without (SiNPs) and with polysaccharide (dextran) coating (DSiNPs) were used. Both types of nanoparticles were nontoxic to Hep 2 cells up to a concentration of 2 mg/mL. The treatment of bacteria with nanoparticles and application of 1 W/cm 2 USI resulted in the reduction of their viabilities up to 35 and 72% for SiNPs and DSiNPs, respectively. The higher bacterial viability reduction for DSiNPs as compared with SiNPs can be explained by the fact that the biopolymer shell of the polysaccharide provides a stronger adhesion of nanoparticles to the bacterial surface. Transmission electron microscopy (TEM) studies showed that the bacterial lipid shell was partially perforated after the combined treatment of DSiNPs and USI, which can be explained by the lysis of bacterial membrane due to the cavitation sensitized by the SiNPs. Furthermore, we have shown that 100% inhibition of E. coli bacterial colony growth is possible by coupling the treatments of DSiNPs and USI with an increased intensity of up to 3 W/cm 2 . The observed results reveal the application of SiNPs as promising antimicrobial agents.

Silicon nanowires (SiNWs) were fabricated by metal-assisted chemical etching (MACE) where hydrofluoric acid (HF), which is typically used in this method, was changed into ammonium fluoride (NH4F). The structure and optical properties of the obtained SiNWs were investigated in details. The length of the SiNW arrays is about 2 μm for 5 min of etching, and the mean diameter of the SiNWs is between 50 and 200 nm. The formed SiNWs demonstrate a strong decrease of the total reflectance near 5-15 % in the spectral region λ < 1 μm in comparison to crystalline silicon (c-Si) substrate. The interband photoluminescence (PL) and Raman scattering intensities increase strongly for SiNWs in comparison with the corresponding values of the c-Si substrate. These effects can be interpreted as an increase of the excitation intensity of SiNWs due to the strong light scattering and the partial light localization in an inhomogeneous optical medium. Along with the interband PL was also detected the PL of SiNWs in the spectral region of 500-1100 nm with a maximum at 750 nm, which can be explained by the radiative recombination of excitons in small Si nanocrystals at nanowire sidewalls in terms of a quantum confinement model. So SiNWs, which are fabricated by environment-friendly chemistry, have a great potential for use in photovoltaic and photonics applications.