Preservation of heparin-binding EGF-like growth factor activity on heparin-modified poly(N-isopropylacrylamide)-grafted surfaces

A heparin-modified poly(N-isopropylacrylamide) (PIPAAm)-grafted surface bound with heparin-binding epidermal growth factor-like growth factor (HB-EGF) was able to culture hepatocytes maintaining high albumin secretion and high expression of hepatocyte-specific genes. However, the activity of HB-EGF on the surface and its binding effects on hepatocytes remain unclear. In this study, we investigated the temperature-dependent interactions of HB-EGF and EGF receptor (EGFR) with heparin-modified PIPAAm to evaluate the activity of HB-EGF on the surface. Quartz crystal microbalance (QCM) measurements revealed that the amounts of adsorbed HB-EGF on either the heparin-modified PIPAAm-grafted surface (heparin-IC1) or PIPAAm-grafted surfaces were almost the same regardless of swelling/deswelling of grafted PIPAAm chains. The heparin-IC1 surface bound to HB-EGF at 37 °C had the ability to bind to hepatocytes through specific affinity interaction with EGFR, whose activation was confirmed by western blotting. However, the physisorbed HB-EGF on the PIPAAm surface greatly diminished its activity. Taken together, the introduction of heparin into grafted PIPAAm chains on the surface plays a pivotal role in holding HB-EGF while preserving its activity. Hydration and swelling of surface-grafted PIPAAm chains at 20 °C greatly diminished the attachment of hepatocytes with HB-EGF bound to heparin-IC1, whereas hepatocytes were able to bind to HB-EGF bound to heparin-IC1 at 37 °C. Thus, the equilibrated affinity interaction between EGFRs and surface-bound HB-EGF was considered to be attenuated by steric hindrance due to hydration and/or swelling of grafted PIPAAm chains.

Activity of HB-EGF bound to a heparin-modified poly(N-isopropylacrylamide) (PIPAAm)-grafted surface was preserved through specific binding to heparin, whereas physisorbed HB-EGF on a PIPAAm-grafted surface greatly diminished its activity.     

Dual stimuli-responsive polyphosphazene-based molecular gates for controlled drug delivery in lung cancer cells

A switchable silane derived stimuli-responsive bottle-brush polyphosphazene (PPz) was prepared and attached to the surface of mesoporous silica nanoparticles (MSNs). The hybrid polymer with PEG-like Jeffamine® M-2005 side-arms undergo conformational changes in response to both pH and temperature due to its amphiphilic substituents and protonatable main-chain, hence were investigated as a gatekeeper. Safranin O as control fluorophore or the anticancer drug camptothecin (CPT) were encapsulated in the PPz-coated MSNs. At temperatures below the lower critical solution temperature (LCST), the swollen conformation of PPz efficiently blocked the cargo within the pores. However, above the LCST, the PPz collapsed, allowing release of the payload. Additionally, protonation of the polymer backbone at lower pH values was observed to enhance opening of the pores from the surface of the MSNs and therefore the release of the dye. In vitro studies demonstrated the ability of these nanoparticles loaded with the drug camptothecin to be endocytosed in both models of tumor (A549) and healthy epithelial (BEAS-2B) lung cells. Their accumulation and the release of the chemotherapeutic drug, co-localized within lysosomes, was faster and higher for tumor than for healthy cells, further, the biocompatibility of PPz-gated nanosystem without drug was demonstrated. Tailored dual responsive polyphosphazenes thus represent novel and promising candidates in the construction of future gated mesoporous silica nanocarriers designs for lung cancer-directed treatment.

Bottle-brush polyphosphazenes as dual, thermosensitive and pH responsive gatekeepers for mesoporous silica nanoparticles, and their use in controlled drug release.     

Ionic magnetic core–shell nanoparticles for DNA extraction

Magnetic nanoparticles with specific surface features are interesting materials for biomedical applications. The combination of molecular interactions on small particles with macroscopic cohesion forces offers unique opportunities. This work reports the synthesis of magnetic core–shell nanoparticles with alkylimidazolium coated surface for effective DNA extraction. A magnetic Fe₂O₃ core was coated with a silica shell and functionalized with an organic halide. This enabled a surface coating with organic cations to mediate effective molecular interactions with polyanionic DNA. The large surface area of the ∼20 nm small particles with a magnetization of 25 emu g⁻¹ enabled high DNA particle loading of 1/30 m% with easy isolation based on an external magnetic field. Moreover, the coating of the particles stabilized DNA against ultrasound initiated fragmentation.

The fabrication ionic magnetic core-shell nanoparticles were simple synthesize with a super-ferromagnetic and small particle size properties, which enabled sufficient DNA particle loading with easy isolation based on an external magnetic field.     

Structure and characterisation of hydroxyethylcellulose–silica nanoparticles

Functionalising nanoparticles with polymers has gained much interest in recent years, as it aids colloidal stability and manipulation of surface properties. Here, polymer-coated thiolated silica nanoparticles were synthesised by self-condensation of 3-mercaptopropyltrimethoxysilane in the presence of hydroxyethylcellulose. These nanoparticles were characterised by dynamic light scattering, small angle neutron scattering, Nanoparticle Tracking Analysis, Raman spectroscopy, FT-IR spectroscopy, thermogravimetric analysis, Ellman''s assay, transmission electron microscopy and cryo-transmission electron microscopy. It was found that increasing the amount of hydroxyethylcellulose in the reaction mixture increased the nanoparticle size and reduced the number of thiol groups on their surface. Additionally, by utilising small angle neutron scattering and dynamic light scattering, it was demonstrated that higher concentrations of polymer in the reaction mixture (0.5–2% w/v) resulted in the formation of aggregates, whereby several silica nanoparticles are bridged together with macromolecules of hydroxyethylcellulose. A correlation was identified between the aggregate size and number of particles per aggregate based on size discrepancies observed between DLS and SANS measurements. This information makes it possible to control the size of aggregates during a simple one-pot synthesis; a prospect highly desirable in the design of potential drug delivery systems.

Polymer-coated thiolated silica nanoparticles were synthesised by self-condensation of 3-mercaptopropyltrimethoxysilane in the presence of hydroxyethylcellulose.     

Enhanced antitumor activity of carbendazim on HeLa cervical cancer cells by aptamer mediated controlled release

Carbendazim, is a broad-spectrum fungicide and also a promising experimental antitumor drug as reproduction and developmental toxicant, which is currently under phase II preclinical trials. In this study, an approach based on controlled and targeted release with aptamers and mesoporous silica nanoparticles was investigated to improve the antitumor activity of carbendazim. To this end, we synthesized aptamer conjugated silica nanoparticles for testing cytotoxicity properties in vitro with human cervical adenocarcinoma (HeLa) cultured cells. Nucleolin (AS1411) binding aptamers were used to entrap carbendazim molecules inside nanopores of MCM-41 type silica nanoparticles to obtain a stimuli-dependent release system. The effect of carbendazim loaded aptamer silica complex was tested and compared to free carbendazim treatment on HeLa cells, demonstrating 3.3 fold increase of toxicity on targeted cells with our delivery system. In addition, cytotoxicity of the complex was determined to be mostly due to increased apoptosis and to a less extend necrosis related pathways.

Carbendazim doped and aptamer-gate functionalized mesoporous silica nanoparticles targeted nucleolin on HeLa cell surface for specific delivery. This delivery system improved antitumor activity of carbendazim by about 3 folds increase of EC₅₀ values.     

Tunable and switchable nanoparticle separation with thermo-responsive track-etched membranes prepared by controlled surface-initiated polymerization of poly(N-isopropylacrylamide)

This work describes how the control of grafting density and grafted chain length of a thermo-responsive polymer in membrane pores can be utilized to tune the pore size and the switchability of size-based selectivity in the ultrafiltration range. Using a previously established methodology for controlled synthesis, surface-initiated atom transfer polymerization (ATRP) of poly(N-isopropylacrylamide) (PNIPAAm) to the pore walls of poly(ethylene terephthalate) track-etched membranes with experimentally determined pore diameters of 35 nm (PET30) and 110 nm (PET80) is performed. Characterization in this study is mainly done with filtration experiments, making use of the well-defined pore structure of the base membranes. It is demonstrated that both the gravimetrically determined degree of functionalization and the effective pore size determined from water permeability are a linear function of ATRP time. For the grafted PET30 membranes, it is shown that the rejection of lysozyme (diameter ∼ 4 nm) can be switched between 99% at 23 °C and 65% at 45 °C for the membrane with the highest degree of functionalization. For the grafted PET80 membranes, it is found that two different types of membranes can be obtained. Membranes with long grafted chains at low grafting density show very large changes of water permeability as a function of temperature (effective pore size switching ratio of up to 10) and, for example, rejection for 20 nm silica particles of 95% and 23% at 23 °C and 45 °C, respectively. Membranes with PNIPAAm at high grafting density show much lower switching ratios (as low as 1.4, for long enough grafted chains). Effective pore size and thermo-responsive change of pore size can therefore be tuned by the combination of both synthesis parameters, initiator density and ATRP time. The switchable thermo-responsive separation of two colloids with a tailored membrane is demonstrated for mixtures of bovine serum albumin (BSA; ∼7 nm) and silica nanoparticles (20 nm); at 23 °C silica is completely rejected and only BSA is in the permeate; at 40 °C both colloids permeate through the membrane.

This work describes how the control of grafting density and grafted chain length of a thermo-responsive polymer in membrane pores can be utilized to tune the pore size and the switchability of size-based selectivity in the ultrafiltration range.     

New protocol for optimisation of polymer composition for imprinting of peptides and proteins

We present here a novel screening tool for optimisation of polymerisation mixtures used in imprinting of peptides and proteins. To facilitate rapid synthesis and screening of a combinatorial library of polymers the solid-phase synthesis method developed by Piletsky and co-workers was scaled down to 50 mg of template-immobilised solid phase, allowing a single well of a 96-well microplate to function as an individual reaction vessel. In this way, 32 different polymer compositions containing N-isopropylacrylamide, acrylic acid, N-(3-aminopropyl)methacrylamide hydrochloride, and N-tert-butylacrylamide, were tested in imprinting of three peptides and three proteins. Utilising filtration microplates has allowed the elution and washing steps to be performed in a similar manner to the large-scale synthesis, whilst incorporation of a fluorescent monomer (N-fluoresceinylacrylamide) made it possible to analyse the binding of synthesised polymer nanoparticles to the solid phase with immobilised templates under different washing conditions. The experiment has proven that the variations in monomer compositions had an effect on the yield and affinity of synthesised molecularly imprinted polymers for the peptides, but not for the proteins. Imprinting in this way presents an ideal method for performing small-scale syntheses for testing polymerisation mixtures, as information regarding the molecularly imprinted polymers affinity can be assessed as part of the elution process, without a need for time-consuming analysis such as quartz crystal microbalance or surface plasmon resonance.

A novel screening tool for high-throughput optimisation of monomer composition for imprinting of peptides and proteins.     

UV cross-linked smart microgel membranes as free-standing diffusion barriers and nanoparticle bearing catalytic films

In this study we use poly(N-isopropylacrylamide) (PNIPAM) based copolymer microgels to create free-standing, transferable, thermoresponsive membranes. The microgels are synthesized by copolymerization of NIPAM with 2-hydroxy-4-(methacryloyloxy)–benzophenone (HMABP) and spin-coated on Si wafers. After subsequent cross-linking by UV-irradiation, the formed layers easily detach from the supporting material. We obtain free standing microgel membranes with lateral extensions of several millimetres and an average layer thickness of a few hundred nanometres. They can be transferred to other substrates. As one example for potential applications we investigate the temperature dependent ion transport through the membranes via resistance measurements revealing a sharp reversible increase in resistance when the lower critical solution temperature of the copolymer microgels is reached. In addition, prior to cross-linking, the microgels can be decorated with silver nanoparticles and cross-linked afterwards. Such free-standing nanoparticle hybrid membranes are then used as catalytic systems for the reduction of 4-nitrophenol, which is monitored by UV/Vis spectroscopy.

Cross-linkable microgels are synthesized by copolymerization of NIPAM with 2-hydroxy-4-(methacryloyloxy)–benzophenone (HMABP) and are subsequently UV-cross-linked to obtain smart membranes exhibiting switchable resistance.     

Preparation and application of methimazole molecularly imprinted polymer based on silver-loaded dendritic fiber-type silica

Dendritic fiber-type silica (KCC-1) has attracted the attention of researchers because of its unique three-dimensional radial structure and high specific surface area. Its highly modified surface allows it to be used in catalysis, adsorption, biomedicine, and other fields. Nano-precious metals (NPs) have several excellent chemical properties, but their stability limits their applications. Dendritic fibrous silica (Ag NPs/KCC-1) loaded with silver nanoparticles was prepared via the microemulsion method using Ag NPs/KCC-1 as the carrier, methimazole as the template molecule, and a surface imprinting method to prepare sulfhydryl imidazole molecularly imprinted polymer. By characterizing the polymer, it is determined that the polymer has a regular morphology and large specific surface area. The obtained experimental results show that the polymer has a high adsorption capacity (10.35 mg g⁻¹) and good selectivity. It is used as a solid-phase extraction filler and, when combined with high-performance liquid chromatography, to detect methimazole in chicken tissue. The recovery rate reaches 87.5–94.4%.

Dendritic fiber-type silica (KCC-1) has attracted the attention of researchers because of its unique three-dimensional radial structure and high specific surface area.     

Spherical covalent organic frameworks as advanced adsorbents for preconcentration and separation of phenolic endocrine disruptors,followed by high performance liquid chromatography

As a promising generation of porous micro-materials, covalent organic frameworks (COFs) have great potentials for applications in separation and adsorption. In the present study, an advanced food-safety inspection method involving COFs as the adsorbents of solid phase extraction (SPE) is proposed for sensitive and accurate determination of target hazardous substances. Typical spherical TpBD COFs with large surface area and superior chemical stability were utilized as adsorbents for the preconcentration of phenolic endocrine disruptors (PEDs), followed by high performance liquid chromatography (HPLC) analysis. The well-prepared TpBD COFs were encapsulated in SPE cartridges and applied in food research, namely, for the separation and enrichment of four target endocrine disruptors in food samples. The possible factors influencing the SPE performance including the composition of the sample solvent, sample solution pH, sample flow rate, composition of the eluent, and the volume of the eluent were investigated and optimized. Due to the porous architecture and superior surface area of spherical TpBD, the enrichment of analytes via a COF-filled SPE column gave extremely low detection limits of 0.056–0.123 μg L⁻¹ along with a wide linear range of 0.5–100 μg L⁻¹ for all the analytes. Nine parallel determinations of the mixed standard with a concentration of 10 μg L⁻¹ produced the relative standard deviations of 2.23–3.08%, indicating the excellent repeatability of the COF-SPE assay. This study can open up a new route for the employment of COFs as efficient SPE adsorbents for the enrichment and quantification of trace/ultra-trace hazardous materials in complex food samples.

Spherical COFs as efficient adsorbents for preconcentration and separation of phenolic endocrine disruptors, followed by high performance liquid chromatography.     

In situ interfacial surface modification of hydrophilic silica nanoparticles by two organosilanes leading to stable Pickering emulsions

Oil-in-water Pickering emulsions are stabilized by in situ functionalization of hydrophilic silica nanoparticles with two organosilane precursors of opposite polarity, dodecyltriethoxysilane (DTES) and 3-(aminopropyl)triethoxysilane (APTES), in a two-step emulsification procedure. The modification of the silica nanoparticles is verified by Fourier transform infrared (FTIR) spectroscopy analysis. The stabilization of the oil droplets by silica is confirmed by tracing the localization of the colloidal silica nanoparticles at the oil–water interface, as observed by confocal fluorescence microscopy. In comparison to modification of the silica nanoparticles prior to the emulsification, in situ functionalization of silica with both organosilanes achieves enhanced emulsion stability and homogeneity, by forming a polysiloxane network between the silica nanoparticles, through polymerization of the organosilanes in the presence of water. The polysiloxane network fixes the silica in place as solid shells around the emulsion droplets, in structures called colloidosomes. These colloidosome shell structures are visualized using confocal microscopy and cryogenic scanning electron microscopy, the latter method successfully enables the direct observation of the silica nanoparticles embedded in the polysiloxane matrix around the oil droplets. Stabilizing the Pickering emulsion droplets and forming silica-based colloidosome shells is dependent on the extent of the hydrolysis and polycondensation reaction of the two organosilanes.

Oil-in-water Pickering emulsions are stabilized by in situ functionalization of hydrophilic silica nanoparticles with two organosilane precursors of opposite polarity in a two-step emulsification procedure.     

Dimpled SiO2@γ-Fe2O3 nanocomposites – fabrication and use for arsenic adsorption in aqueous medium

We report the synthesis of nanocomposites made of silica nanoparticles whose six surface dimples are decorated with magnetic maghemite nanoparticles and their use for detection and recovery of arsenic in aqueous media. Precursor silica nanoparticles have aminated polystyrene chains at the bottom of their dimples and the maghemite nanoparticles are surface functionalized with carboxylic acid groups in two steps: amination with 3-aminopropyltrimethoxysilane, then derivatization with succinic anhydride in the presence of triethylamine. In the end, the colloidal assembly consists of the regioselective grafting of the carboxylic acid-modified iron oxide nanoparticles onto the 6-dimple silica nanoparticles. Several characterization techniques such as transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR), dynamic light scattering (DLS) are employed to assess the grafting process and study the influence of the maghemite functional groups on the quality of the composites formed. The resulting magnetic nanocomposites are used for the environmentally benign detection and removal of arsenic from aqueous medium, being readily extracted through means of magnetic separation.

The process of grafting maghemite NFs onto silica dimples.     

A highly efficient nano-sized Cu2O/SiO2 egg-shell catalyst for C–C coupling reactions

Mesoporous SiO₂-supported Cu₂O nanoparticles as an egg-shell type catalyst were prepared by impregnation method. The obtained Cu₂O/SiO₂ egg-shell nanocatalyst had a large surface area and narrow pore size distribution. In addition, most of the Cu₂O nanoparticles, with sizes around 2.0 nm, were highly dispersed in the mesoporous silica. Accordingly, fast reactant diffusion to the active sites would occur, especially when the active metal sites are selectively located on the outer part of the support, i.e., the outer region of the egg shell. In solvent-free Sonogashira reactions for the synthesis of ynones from acyl chlorides and terminal alkynes, this catalyst exhibited a very high catalytic activity. The excellent catalytic performance can be attributed to the synergistic advantages of mesoporous structure and monodispersed Cu₂O nanoparticles.

Mesoporous SiO₂-supported Cu₂O nanoparticles as an egg-shell type catalyst were prepared by impregnation method.     

One-pot one-step synthesis of Au@SiO2 core–shell nanoparticles and their shell-thickness-dependent fluorescent properties

Herein, we report a one-pot one-step method for the preparation of Au@SiO₂ core–shell nanoparticles (NPs) via a facile heating treatment of an alcoholic-aqueous solution of chloroauric acid (HAuCl₄), 2-methylaminoethanol (2-MAE), cetyltrimethylammonimum bromide (CTAB), and tetraethylorthosilicate (TEOS). The size of the Au core and the thickness of the silica shell can be easily controlled by simply adjusting the volume of HAuCl₄ and TEOS, respectively, which can hardly be achieved by other approaches. The as-prepared Au@SiO₂ core–shell NPs exhibited shell-thickness-dependent fluorescent properties. The optimum fluorescence enhancement of fluorescein isothiocyanate (FITC) was found to occur at a silica shell thickness of 34 nm with an enhancement factor of 5.0. This work provides a new approach for the preparation of Au@SiO₂ core–shell NPs and promotes their potential applications in ultrasensitive analyte detection, theranostics, catalysts and thin-film solar cells.

Au@SiO₂ core–shell nanoparticles with tunable Au core size and silica shell thickness were prepared by a facile one-pot one-step method.     

Hierarchical micro-/mesoporous zeolite microspheres prepared by colloidal assembly of zeolite nanoparticles

A novel template-free colloidal assembly method that combines colloidal zeolite (silicalite-1) suspensions in a water-in-oil emulsion with an evaporation-induced assembly process has been developed for preparing hierarchical micro-/mesoporous zeolite microspheres (MZMs). Such particles have an interconnected mesoporosity and large mesopore diameters (25–40 nm) combined with 5.5 Å diameter micropores of the zeolite nanoparticles. The method developed has the advantages of employing mild synthesis conditions, a short preparation time, and not requiring the use of a mesoporogen template or post-treatment methods. The method provides a new range of micro-/mesoporous zeolites with tunable mesoporosity dictated by the size of the zeolite nanoparticles. It also offers the possibility of combining several zeolite particle sizes or optionally adding amorphous silica nanoparticles to tune the mesopore size distribution further. It should be generally applicable to other types of colloidal zeolite suspensions (e.g. ZSM-5, zeolite A, beta) and represents a new route amenable for cost-effective scale-up.

Evaporation-driven colloidal assembly of silicalite-1 nanoparticles into well-defined micro-sized spheres at low temperature and preparation times.     

Synthesis of size-controlled and highly monodispersed silica nanoparticles using a short alkyl-chain fluorinated surfactant

Highly monodispersed silica nanoparticles (SiNPs) were synthesised using a fluorinated surfactant, HOCH₂CH(CF₃)CO₂H, and its efficiency was compared with efficiencies of five other surfactants. The size of the SiNPs (∼50–200 nm) was controlled by controlling the surfactant amount. The short alkyl-chain fluoro surfactant was found to be more efficient at producing monodispersed SiNPs than its long alkyl-chain fluoro or non-fluorinated surfactant counterparts.

Shape, size, and morphology controlled synthesis of monodispersed silica nanoparticles using 3-hydroxy-2-(trifluoromethyl)-propanoic acid (MAF-OH) surfactant.     

Inorganic/organic nanocomposite ion gels with well dispersed secondary silica nanoparticles

We have previously reported tough inorganic/organic nanocomposite (NC) ion gels composed of silica particles and poly(N,N-dimethylacrylamide) (PDMAAm) networks and a large amount of ionic liquid. In this study, the network structure and toughening mechanism of NC ion gels were investigated. The NC ion gels showed characteristic mechanical properties; i.e. the stress was significantly increased at a highly elongated state. In addition, the NC ion gels showed an almost elastic mechanical property, which was completely different from that of our other developed inorganic/organic tough ion gels named double-network (DN) ion gels. It was found from structural observation that secondary silica nanoparticles dispersed well in the NC ion gel. It was also found that some of the secondary silica nanoparticles had a ring-like structure which would incorporate PDMAAm chains. From the silica particle content dependency on stress–strain curves of inorganic/organic NC ion gels, it was inferred that the secondary silica particles could serve as a movable cross-linker of PDMAAm chains in the NC ion gel.

Tough inorganic/organic nanocomposite (NC) ion gels with silica nanoparticle aggregates having a characteristic structure.     

Anisotropic mesoporous silica/microgel core–shell responsive particles

Hybrid anisotropic microgels were synthesised using mesoporous silica as core particles. By finely controlling the synthesis conditions, the latter can be obtained with different shapes such as platelets, primary particles or rods. Using the core particles as seeds for precipitation polymerisation, a crosslinked poly(N-isopropylacrylamide) (PNIPAM) microgel shell could be grown at the surface, conferring additional thermo-responsive properties. The different particles were characterised using scattering and imaging techniques. Small angle X-ray scattering (SAXS) was employed to identify the shape and porous organisation of the core particles and dynamic light scattering (DLS) to determine the swelling behaviour of the hybrid microgels. In addition, cryogenic transmission electron microscopy (cryo-TEM) imaging of the hybrids confirms the different morphologies as well as the presence of the microgel network and the core–shell conformation. Finally, the response of the particles to an alternating electric field is demonstrated for hybrid rod-shaped microgels in situ using confocal laser scanning microscopy (CLSM).

Hybrid anisotropic microgels with different morphologies were prepared using mesoporous silica particles as core and PNIPAM as shell. The shell thickness d and aspect ratio ρ were characterised notably via cryo-TEM (left) and DLS (right).     

Ag decorated silica nanostructures for surface plasmon enhanced photocatalysis

In this article, we present a novel synthesis of mesoporous SiO₂/Ag nanostructures for dye (methylene blue) adsorption and surface plasmon mediated photocatalysis. Mesoporous SiO₂ nanoparticles with a pore size of 3.2 nm were synthesized using cetyltrimethylammonium bromide as a structure directing agent and functionalized with (3-aminopropyl)trimethoxysilane to introduce amine groups. The adsorption behavior of non-porous SiO₂ nanoparticles was compared with that of the mesoporous silica nanoparticles. The large surface area and higher porosity of mesoporous SiO₂ facilitated better adsorption of the dye as compared to the non-porous silica. Ag decorated SiO₂ nanoparticles were synthesized by attaching silver (Ag) nanoparticles of different morphologies, i.e. spherical and triangular, on amine functionalized silica. The photocatalytic activity of the mesoporous SiO₂/Ag was compared with that of non-porous SiO₂/Ag nanoparticles and pristine Ag nanoparticles. Mesoporous SiO₂ nanoparticles (k_d = 31.3 × 10⁻³ g mg⁻¹ min⁻¹) showed remarkable improvement in the rate of degradation of methylene blue as compared to non-porous SiO₂ (k_d = 25.1 × 10⁻³ g mg⁻¹ min⁻¹) and pristine Ag nanoparticles (k_d = 19.3 × 10⁻³ g mg⁻¹ min⁻¹). Blue Ag nanoparticles, owing to their better charge carrier generation and enhanced surface plasmon resonance, exhibited superior photocatalysis performance as compared to yellow Ag nanoparticles in all nanostructures.

In this article, we present a novel synthesis of mesoporous SiO₂/Ag nanostructures for dye (methylene blue) adsorption and surface plasmon mediated photocatalysis.     

Ionic liquids strongly affect the interaction of bacteria with magnesium oxide and silica nanoparticles

Quaternary ammonium theophylline-based ionic liquids and imidazolium-based ionic liquids, magnesium oxide and silica nanoparticles were used in order to investigate the interaction with Gram negative Escherichia coli and Gram positive Bacillus cereus. The changes of bacterial sensitivity to both nanoparticles (NPs) and ionic liquids (ILs) were examined. In order to assess the impact of ILs on the interaction of nanoparticles with bacteria, respirometric analysis, activity of dehydrogenases, peroxidase analyses as well as scanning and fluorescence microscopy examinations were conducted. The interactions of ILs with nanoparticles based on adsorption and sedimentation tests were also investigated in order to assess how the ILs affect the agglomeration of NPs. It was assumed, as the main hypothesis of the present studies, that the differences in sensitivity of bacteria to combined ILs and NPs can be observed, even if the concentration of both compounds are below the minimum inhibitory concentration (MIC). The results indicated that ILs strongly affected the sensitivity of bacteria to nanoparticles however, the changes of sensitivity depended on the surface characteristics of the nanoparticles. The presence of ILs at non-lethal concentrations caused an increase of bacterial sensitivity to MgO nanoparticles. Notably, the sensitivity of Gram positive bacteria increased significantly when ILs were present. This was an important observation because the toxicity of nanoparticles toward Gram positive bacteria is usually lower than their toxicity toward Gram negative bacteria. Using silica nanoparticles, the presence of ionic liquids caused the adsorption of bacteria onto the surface of nanoparticle agglomerates. In conclusion, two opposing effects have been observed. On the one hand, the toxicity of MgO NPs in the presence of ILs has increased. On the other hand, the presence of silica nanoparticles caused a decreased sensitivity of both types of bacteria toward ILs. Our studies indicate potentially useful processes in many environmantal protection technologies like water treatment where flocculation and disinfection are extremely needed.

The antibacterial properties of nanoparticles can be strongly affected by interactions with ionic liquids.