2-D organization of silica nanoparticles on gold surfaces: CO2 marker detection and storage

A single layer of silica nanoparticles with an average size of ∼200 nm was deposited over the surface of pristine gold wafers, aided by (3-mercaptopropyl)trimethoxysilane. The nanoparticle immobilization was driven by covalent bonding rather than a self-assembly process, leading to a cluster-assembled material which has CO₂ sensing features. Here, we show how this device can be used for CO₂ physisorption and chemisorption. We analyse the device, both spectroscopically and morphologically, before and after exposure to an atmosphere of 7 mbar of CO₂, inside a planetary atmospheres and surfaces simulation chamber, (PASC) mimiking Martian atmospheric conditions. Our studies demonstrate that these clusters are suitable for CO₂ detection and storage, under well controlled experimental Martian conditions. Their high sensitivity at a very low concentration of CO₂, 12.4 ppm, makes them ideal candidates in the nanosensor field.

A single layer of silica nanoparticles with an average size of ∼200 nm was deposited over the surface of pristine gold wafers, aided by (3-mercaptopropyl)trimethoxysilane.     

Packed hybrid silica nanoparticles as sorbents with thermo-switchable surface chemistry and pore size for fast extraction of environmental pollutants

Thermoresponsive poly(N-isopropylacrylamide)-grafted silica nanoparticles (SiNPs) have been synthesized and fully characterized by ATR-FTIR, TGA, HRTEM, BET and DLS analysis. Hybrid solid phase extraction (SPE) beds with tuneable pore size and switchable surface chemistry were prepared by packing the polymer-grafted nanoparticles inside SPE cartridges. The cartridges were tested by checking the thermo-regulated elution of model compounds, namely methylene blue, caffeine and amoxicillin. Extraction of the analytes and regeneration of the interaction sites on the sorbent surface was carried out entirely in water solution by changing the external temperature below and above the lower critical solution temperature (LCST) of the polymer. The results demonstrate that the elution of model compounds depends on the temperature-regulated size of the inter-particle voids and on the change of surface properties of the PNIPAM-grafted nanoparticles from hydrophilic to hydrophobic.

Thermoresponsive poly(N-isopropylacrylamide)-grafted silica nanoparticles were synthesized and used to prepare solid phase extraction sorbents with switchable pore size and surface chemistry for temperature-regulated extraction of water pollutants.     

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.     

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.     

The synthesis of monodispersed M-CeO2/SiO2 nanoparticles and formation of UV absorption coatings with them

CeO₂/polymer nanoparticles have drawn considerable attention for their excellent UV absorption properties. However, many challenges still exist in the successful incorporation of ceria into the polymer matrix for the easy agglomeration and photocatalytic activity of CeO₂ nanoparticles. Herein, we address these issues by constructing three-layer structured nanoparticles (M-CeO₂@SiO₂) and incorporating them into a polymer matrix through a mini-emulsion polymerization process. During this process, small-sized nano-ceria became uniformly anchored on the surfaces of monodisperse silica particles first, and then the particles were coated with an MPS/SiO₂ shield. The morphology and dispersion of the nanoparticles were investigated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The performance of the hybrid films was characterized using UV-vis absorption spectroscopy (UV-vis) and water contact angle (WCA) measurements. Results showed that the M-CeO₂@SiO₂ nanoparticles exhibited a three-layer structure with a mean diameter of 360 nm, and they possess good compatibility with acrylic monomers. After the addition of M-CeO₂@SiO₂, hybrid films exhibited enhanced UV absorption capacity as expected, accompanied by an obvious improvement in hydrophobicity (the water contact angle increased from 84.2° to 98.2°). The results showed that the hybrid films containing M-CeO₂@SiO₂ particles possess better global performance as compared with those containing no particles.

Herein, we report the synthesis of monodispersed M-CeO₂/SiO₂ nanoparticles and their use in the construction of a UV absorption coating.     

Clouding observed for surface active,mPEG-grafted silica nanoparticles

Temperature-dependent phase-separation, clouding, has been observed in suspensions of silica nanoparticles surface-functionalized with methyl-poly(ethylene glycol) silane. Interparticle interactions and conformational changes of the grafted poly(ethylene glycol) chains influence the observed cloud points, and can be controlled by electrolyte concentration and pH. These findings open new routes to tailoring properties of Pickering emulsions.

Temperature-dependent phase-separation, clouding, has been observed in suspensions of silica nanoparticles surface-functionalized with methyl-poly(ethylene glycol) silane.     

Linear β-amino alcohol catalyst anchored on functionalized magnetite nanoparticles for enantioselective addition of dialkylzinc to aromatic aldehydes

A linear β-amino alcohol ligand, previously found to be a very efficient catalyst for enantioselective addition of dialkylzinc to aromatic aldehydes, has been anchored on differently functionalized superparamagnetic core–shell magnetite–silica nanoparticles (1a and 1b). Its catalytic activity in the addition of dialkylzinc to aldehydes has been evaluated, leading to promising results, especially in the case of 1b for which the recovery by simple magnetic decantation and reuse was successfully verified.

The catalytic activity of a linear β-amino alcohol ligand anchored on functionalized magnetite/silica core–shell nanoparticles has been evaluated in the addition of dialkylzinc to aldehydes leading to promising results.     

Enhanced catalytic activity of monodispersed porous Al2O3 colloidal spheres with NiMo for simultaneous hydrodesulfurization and hydrogenation

Novel composites made from monodispersed porous Al-glycolate spheres (NiMo/Al-SP) were synthesized through alcoholysis or hydrolysis treatments. The obtained samples were characterized by a complementary combination of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), N₂ physisorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), hydrogen temperature-programmed reduction (H₂-TPR), and pyridine Fourier transform infrared spectroscopy (Py FT-IR). In addition, the catalytic performances of the resultant catalysts were evaluated in the simultaneous HDS of dibenzothiophene (DBT) and HYD of naphthalene (DBT and naphthalene represent the sulfur-containing compounds and polycyoalkanes, respectively). The experimental results showed that, 71.22% DBT and 88.28% naphthalene were converted by NiMo/Al-SP(H) under the conditions of 270 °C temperature, 5 MPa H₂ (initial pressure at room temperature) and 10 h reaction time. The design and preparation of NiMo/Al-SP provide an effective and novel pathway for the development of high-performance catalysts and production processes.

Fabrication of monodispersed porous Al₂O₃ spheres with controlled morphologies.     

Microwave plasma-assisted silicon nanoparticles: cytotoxic,molecular, and numerical responses against cancer cells

Silicon nanoparticles (SiNPs), which have a special place in material science due to their strong luminescent property and wide applicability in various physicochemical arenas, such as solar cells and LEDs, were synthesised by a microwave plasma-assisted process using an argon–silane mixture. Several characterization tools were applied to check the crystallinity (XRD) and morphological (FESEM, TEM, ∼20 ± 2 nm size) and topographical (AFM, ∼20 nm) details of the NPs. The high-purity SiNPs were applied on myoblast cancer cells to investigate the reactivity of the NPs at different doses (200, 1000 and 2000 ng mL⁻¹) for different incubation periods (24 h, 48 h & 72 h). The MTT assay was utilized to determine the percentage of viable and non-viable cells, while the cell organization was observed via microscopy and CLSM. Additionally, the molecular responses (RT-PCR), such as apoptosis, were analyzed in presence of caspase 3 and 7, and the results showed an upregulation with SiNPs. To validate the obtained data, analytical studies were also performed for the SiNPs via statistical analysis and the most reliable data values were evaluated and acceptable as per the ICH guidelines.

Silicon nanoparticles (SiNPs), which have a special place in material science due to their strong luminescent property and wide applicability in various physicochemical arenas synthesised via a microwave plasma-assisted process using an argon–silane mixture.     

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.     

Silica modification of titania nanoparticles enhances photocatalytic production of reactive oxygen species without increasing toxicity potential in vitro

Titania (TiO₂) nanoparticles were surface modified using silica and citrate to implement a ‘safe-by-design’ approach for managing potential toxicity of titania nanoparticles by controlling surface redox reactivity. DLS and zeta-potential analyses confirmed the surface modification, and electron microscopy and surface area measurements demonstrated nanoscale dimensions of the particles. Electron paramagnetic resonance (EPR) was used to determine the exogenous generation of reactive oxygen species (ROS). All the produced spray dried nanotitania lowered levels of ROS when compared to the corresponding dispersed nanotitania, suggesting that the spray drying process is an appropriate design strategy for the control of nano TiO₂ ROS reactivity. The modification of nanotitania with silica and with citrate resulted in increased levels of ROS generation in exogenous measurements, including photoexcitation for 60 minutes. The dichlorodihydrofluorescein (DCFH) assay of dose-dependent production of oxidative stress, generated by pristine and modified nanotitania in macrophages and alveolar epithelial cells, found no significant change in toxicity originating from the generation of reactive oxygen species. Our findings show that there is no direct correlation between the photocatalytic activity of nanotitania and its oxidative stress-mediated potential toxicity, and it is possible to improve the former, for example adding silica as a modifying agent, without altering the cell redox equilibrium.

Titania (TiO₂) nanoparticles were surface modified using silica and citrate to implement a ‘safe-by-design’ approach for managing potential toxicity of titania nanoparticles by controlling surface redox reactivity.     

Preparation of glycoside polymer micelles with antioxidant polyphenolic cores using alkylated poly(arbutin)s

This paper describes the synthesis of long-chain-alkylated poly(arbutin)s (poly(Arb)-R_x, where R = alkyl-chain length and x = degree of substitution (DS)) and their aqueous micelle formation. DS was controlled by tailoring the alkyl reagent/main-chain phenol substituent feed ratio. The critical micelle concentrations (CMCs) of poly(Arb)-R_x were determined as 1.3–5.2 mg mL⁻¹ by the surface tension method. Introduction of longer alkyl substituents decreased CMC and also decreased aqueous solubility. In DLS measurement, the average micelle diameters were 225–616 nm, and micelle size decreased with increasing DS because of increased stabilization by hydrophobic alkyl substituents. Transmission electron microscopy indicated that mainly wormlike cylindrical micelles were formed, even with highly hydrophilic polymers. The alkylated polymer exhibited no cytotoxicity, and their antioxidant abilities were evaluated by the β-carotene bleaching method. Only 0.049 mol equivalents of poly(Arb)-C8₃₀ to linoleic acid was sufficient to preserve the β-carotene.

This paper describes the synthesis of long-chain-alkylated poly(arbutin)s (poly(Arb)-R_x, where R = alkyl-chain length and x = degree of substitution (DS)) and their aqueous micelle formation.     

Novel mesoporous Ag@SiO2 nanospheres as a heterogeneous catalyst with superior catalytic performance for hydrogenation of aromatic nitro compounds

Mesoporous core–shell structure Ag@SiO₂ nanospheres are constructed to prevent Ag nanoparticles from aggregation during the hydrogenation reaction. The prepared catalyst shows superior catalytic performance for hydrogenation of nitro compounds with 100% conversion and selectivity without any by-products, which also indicates good recycling performance for several times use.

Mesoporous core–shell structure Ag@SiO₂ nanospheres are constructed to prevent Ag nanoparticles from aggregation during the hydrogenation reaction.     

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.     

A low temperature organic synthesis of monodispersed NiRu nanocrystals for CO2 methanation

In this study, monodispersed NiRu nanocrystals with a diameter of 3 nm were synthesized at 90 °C via a tuning hot-inject method to lower the temperature of the organic phase synthesis of monodispersed nanomaterials. The key factor for the nanocrystalline formation of NiRu alloy nanocrystals was summarized in detail. Simultaneously, the synergistic effect of Ni and Ru in CO₂ methanation was explored. Doping trace Ru can significantly improve the conversion rate of CO₂ methanation and CH₄ selectivity. The underlying mechanism was studied in detail via X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature-programmed hydrogen reduction (H₂-TPR) and desorption (H₂-TPD) tests, and temperature-programmed desorption of CO₂ (CO₂-TPD). This study gives out a new way for the general synthesis of monodisperse nickel-based nanocrystals and provides a reference for the development and application of monodispersed nanoparticles for CO₂ methanation.

Monodisperse NiRu NPs synthesized by a tuning hot-inject method was loaded on Al₂O₃ as a building bulk for CO₂ methanation.     

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.     

Highly water-dispersible calcium lignosulfonate-capped MnO nanoparticles as a T1 MRI contrast agent with exceptional colloidal stability,low toxicity and remarkable relaxivity

A simple and efficient method to synthesize highly water-dispersible calcium lignosulfonate-coated manganese oxide nanoparticles as a potential candidate for the current magnetic resonance imaging (MRI) T₁ contrast agents was reported. Hydrophobic MnO nanoparticles with dimensions of about 10 nm were prepared by thermal decomposition of manganese(ii)acetylacetonate in the presence of oleic acid as a surfactant. The characteristics of the synthesized nanoparticles, cytotoxicity assay and in vitro MRI properties were investigated in detail. Results showed that calcium lignosulfonate has a great influence on the colloidal stability and biocompatibility of MnO nanoparticles in water. Furthermore, this coating agent ensures abundant exposure of external Mn ion with protons of water, which endows the nanoparticles with a longitudinal molar relaxivity (r₁) of 4.62 mM⁻¹ s⁻¹. An efficient contrast enhancement effect was observed in the study of MRI investigations.

A simple and efficient method to synthesize highly water-dispersible calcium lignosulfonate-coated manganese oxide nanoparticles as a potential candidate for the current magnetic resonance imaging (MRI) T₁ contrast agents was reported.     

Water and mildew proof SiO2 & ZnO/silica sol superhydrophobic composite coating on a circuit board

In order to improve the waterproof and mildew resistance of electronic equipment, a superhydrophobic coating was prepared on a circuit board. First, hexadecyl trimethoxysilane was used to modify the nano silica and nano zinc oxide particles, and then the modified nanoparticles were mixed with the silica sol. Then the superhydrophobic coating was prepared on the surface of the printed circuit board by a spraying process. The preparation technology and physical and chemical properties of the coating were studied. The contact angle of the final sample can reach 169.47°, the sliding angle can reach 1.2°, it has good acid and alkali corrosion resistance, resistance to NaCl, self-cleaning performance and antimildew performance.

A water and mildew proof SiO₂ and ZnO/silica sol superhydrophobic composite coating was prepared by a one-step method and applied to a circuit board. The preparation method is simple and inexpensive, and convenient for large-scale preparation.     

Near-infrared polyfluorene encapsulated in poly(ε-caprolactone) nanoparticles with remarkable large Stokes shift

Near-infrared (NIR) fluorescent dyes have attracted increasing attention as fluorescent probes in biomedical applications due to their low biological autofluorescence as well as high tissue penetration depth. However, their being hydrophobic in nature limits their clinical use as they are prone to aggregate in the physiological environment. Herein, we have designed and synthesized a novel polymeric NIR fluorescent dye and then encapsulated it into a poly(ε-caprolactone) (PCL) matrix by way of an emulsion–diffusion technique. The effect of the structure of the surfactant on the nanoparticle properties is investigated. Results show that polymeric surfactant, Kolliphor® P188, allows the formation of a high fluorescence intensity of the nanoparticles with the highest level homogeneity and stability. The synthesized nanoparticles show significant advantages in terms of a remarkable large stokes shift (276 nm) in the aqueous solution and excellent biocompatibility. The fabrication process is not limited to encapsulation of polymeric fluorescent dye. The synthesized NIR polymeric nanoparticles would be potentially applicable for biomedical applications.

A near-infrared dye encapsulated in poly(ε-caprolactone) nanoparticles have been synthesized. Using Kolliphor® P188 as a surfactant, the stable nanoparticles exhibit strong fluorescence intensity and remarkable large Stokes shift.     

Stabilizing decontamination foam using surface-modified silica nanoparticles containing chemical reagent: foam stability,structures, and dispersion properties

The stabilization of decontamination foams containing a chemical reagent is a crucial requirement for their use in the decontamination of nuclear power plants. We have investigated the effects on decontamination foam stability of adding silica nanoparticles (NPs) modified with various functional groups, namely propyl (–CH₃), amine (–NH₂), and thiol (–SH) groups. The surface properties of these silica NPs were characterized with ATR-FTIR, solid NMR, and TGA analyses. We also established that the agglomeration in such foams of the amine-modified silica NPs is weaker than that of the other modified silica NPs due to their thorough dispersion in the liquid film. Further, the foam containing amine-modified silica NPs was found to be stable for 60 min at a pH of 2, i.e. under decontamination conditions. The bubble structure analysis showed that this decontamination foam has a bubble count that is approximately 5–8 times higher than the foams containing NPs modified with the other functional groups, which indicates that the decontamination foam with amine-modified silica NPs has the best foam structure of the three investigated foams. The well-dispersed and smaller amine-modified silica NPs enhance the foam stability by providing a barrier between the gas bubbles and delaying their coalescence. In contrast, the thiol- and propyl-modified silica NPs form aggregates with large diameters that reduce the maximum capillary pressure of coalescence and hence decrease the foam stability.

The stabilization of decontamination foams containing a chemical reagent is a crucial requirement for their use in the decontamination of nuclear power plants.