Aluminium-Based Metal-Organic Framework Nano Cuboids and Nanoflakes with Embedded Gold Nanoparticles for Carbon Dioxide Fixation with Epoxides into Cyclic Esters.

The fixation of carbon dioxide with epoxides is one of the most attractive methods for the green utilisation of this greenhouse gas and leads to many valuable chemicals. This process is characterised by 100% atom efficiency; however, an efficient catalyst is required to achieve satisfactory yields. Metal-organic frameworks (MOFs) are recognised as being extremely promising for this purpose. Nevertheless, many of the proposed catalysts are based on ions of rare elements or elements not entirely safe for the environment; this is notable with commercially unavailable ligands. In an effort to develop novel catalysts for CO2 fixation on an industrial scale, we propose novel MOFs, which consist of aluminium ions coordinated with commercially available 1,4-naphthalene dicarboxylic acid (Al@NDC) and their nanocomposites with gold nanoparticles entrapped inside their structure (AlAu@NDC). Due to the application of 4-amino triazole and 5-amino tetrazole as crystallization mediators, the morphology of the synthesised materials can be modified. The introduction of gold nanoparticles (AuNPs) into the structure of the synthesised Al-based MOFs causes the change in morphology from nano cuboids to nanoflakes, simultaneously decreasing their porosity. However, the homogeneity of the nanostructures in the system is preserved. All synthesised MOF materials are highly crystalline, and the simulation of PXRD patterns suggests the same tetragonal crystallographic system for all fabricated nanomaterials. The fabricated materials are proven to be highly efficient catalysts for carbon dioxide cycloaddition with a series of model epoxides: epichlorohydrin; glycidol; styrene oxide; and propylene oxide. Applying the synthesised catalysts enables the reactions to be performed under mild conditions (90 °C; 1 MPa CO2) within a short time and with high conversion and yield (90% conversion of glycidol towards glycerol carbonate with 89% product yield within 2 h). The developed nanocatalysts can be easily separated from the reaction mixture and reused several times (both conversion and yield do not change after five cycles). The excellent performance of the fabricated catalytic materials might be explained by their high microporosity (from 421 m2 g-1 to 735 m2 g-1); many catalytic centres in the structure exhibit Lewis acids' behaviour, increased capacity for CO2 adsorption, and high stability. The presence of AuNPs in the synthesised nanocatalysts (0.8% w/w) enables the reaction to be performed with a higher yield within a shorter time; this is especially important for less-active epoxides such as propylene oxide (two times higher yield was obtained using a nanocomposite, in comparison with Al-MOF without nanoparticles).

Fluoride enhances polystyrene nanoparticles cytotoxicity in colonocytes in vitro model.

Human gastrointestinal cells can be exposed to different xenobiotics present in food or drinking water. In this work, we assessed the cytotoxicity of polystyrene nanoparticles (PS-NPs) and how it is impacted by fluoride (F-) presence. We decided to examine PS-NPs and F- which can be easily found in drinking water and food. Commercially available amine-modified 100 nm PS-NPs were used in the study. Scanning Electron Microscopy with Electron Dispersive Spectroscopy (SEM-EDS) and Dynamic Light Scattering (DLS) were used to characterize PS-NPs. The colon cell lines (HT-29, Caco-2, CCD 841 CoN) were used. Cytotoxicity of PS-NPs and F- alone or in co-exposition were assessed with MTT assay in a time- and concentration-dependent manner. Flow cytometry was used to measure reactive oxygen species (ROS) production, cell cycle distribution, and apoptosis analysis. Transmission electron microscopy (TEM) was used to determine whether PS-NPs and/or F- can cause ultrastructure changes in the cells. We have shown that PS-NPs are cytotoxic to human colon cells in a time- and concentration-dependent manner. PS-NPs did not impact neither intracellular ROS production nor the cells cell cycle distribution. However, if HT-29 cells were co-exposed to PS-NPs and F-, an increased number of cells in G0/G1 phase and decreased number of cells in G2/M were observed. PS-NPs can cause apoptosis in HT-29 cells, this effect was enhanced if cells were co-exposed to PS-NP and F-. PS-NPs were internalised by the cells and caused ultrastructure changes. Fluoride itself (1 mM) was not cytotoxic to the cells and did not cause any changes in the ultrastructure of the cells. We have proven that polystyrene nanoparticles can be cytotoxic to human gastrointestinal cells and this effect is enhanced by fluoride.

The Pharmacological Effects of Silver Nanoparticles Functionalized with Eptifibatide on Platelets and Endothelial Cells.

Purpose: In the search for new drug delivery platforms for cardiovascular diseases and coating of medical devices, we synthesized eptifibatide-functionalized silver nanoparticles (AgNPs-EPI) and examined the pharmacological activity of AgNPs-EPI on platelets and endothelial cells in vitro and ex vivo. Methods: Spherical AgNPs linked to eptifibatide were synthesized and characterized. Cytotoxicity was measured in microvascular endothelial cells (HMEC-1), platelets and red blood cells. Platelet mitochondrial respiration was measured using the Oxygraph-2k, a high-resolution modular respirometry system. The effect of AgNPs-EPI on the aggregation of washed platelets was measured by light aggregometry and the ex vivo occlusion time was determined using a reference laboratory method. The surface amount of platelet receptors such as P-selectin and GPIIb/IIIa was measured. The influence of AgNPS-EPI on blood coagulation science was assessed. Finally, the effect of AgNPs-EPI on endothelial cells was measured by the levels of 6-keto-PGF1alpha, tPa, cGMP and vWF. Results: We describe the synthesis of AgNPs using eptifibatide as the stabilizing ligand. The molecules of this drug are directly bonded to the surface of the nanoparticles. The synthesized AgNPs-EPI did not affect the viability of platelets, endothelial cells and erythrocytes. Preincubation of platelets with AgNPs-EPI protected by mitochondrial oxidative phosphorylation capacity. AgNPs-EPI inhibited aggregation-induced P-selectin expression and GPIIb/IIIa conformational changes in platelets. AgNPs-EPI caused prolongation of the occlusion time in the presence of collagen/ADP and collagen/adrenaline. AgNPs-EPI regulated levels of 6-keto-PGF1alpha, tPa, vWf and cGMP produced in thrombin stimulated HMEC-1 cells. Conclusion: AgNPs-EPI show anti-aggregatory activity at concentrations lower than those required by the free drug acting via regulation of platelet aggregation, blood coagulation, and endothelial cell activity. Our results provide proof-of-principle evidence that AgNPs may be used as an effective delivery platform for antiplatelet drugs.

Silver Nanoparticles Densely Grafted with Nitroxides as a Recyclable Green Catalyst in the Selective Oxidation of Alcohols.

The selective oxidation of alcohols, leading to appropriate aldehydes, is widely recognised as one of the most important reactions in organic synthesis. With ever-increasing environmental concerns, much attention has been directed toward developing catalytic protocols that use molecular oxygen as an oxidant. An ideal green oxidation process should employ a highly active, selective and recyclable catalyst that can work with oxygen under mild conditions. This paper presents a successful application of densely grafted silver nanostructures with stable nitroxide radicals (N-AgNPs) as an effective, easily-recovered and regenerable catalyst for the selective oxidation of alcohols. The fabricated ultra-small and narrow dispersive silver nanoparticles have been fully characterised using physicochemical methods (TEM, DLS, XPS, TGA). N-AgNPs have been successfully applied to oxidise several model alcohols: benzyl alcohol, 4-pyridinemethanol, furfuryl alcohol, 1-phenyl ethanol, n-heptanol and allyl alcohol under mild conditions using oxygen as a stoichiometric oxidant. Notably, the fabricated nitroxide grafted silver nanoparticles (N-AgNPs) were reused more than ten times in the oxidation of a series of primary alcohols to corresponding aldehydes under mild conditions with very high yields and a selectivity close to 100%.

Silver Nanoparticles as Chlorhexidine and Metronidazole Drug Delivery Platforms: Their Potential Use in Treating Periodontitis.

PURPOSE: Periodontal disease (PD), defined as oral inflammation caused by dental plaque, is an emerging problem. PD may lead to tooth loss, and treatment options are limited. In this study, we designed, synthesized, and characterized silver nanoparticles (AgNPs) conjugated with chlorhexidine (AgNPs-CHL) or metronidazole (AgNPs-PEG-MET) to determine whether they can be used to treat PDs. MATERIALS AND METHODS: AgNPs were synthesized and characterized by transmission electron microscopy, UV-vis spectrometry, thermogravimetric analyses, and dynamic light scattering. We determined the safety and the antimicrobial and anti-inflammatory properties of synthesized AgNPs in an in vitro model of periodontitis. Antimicrobial properties were determined by measuring the minimum inhibitory concentration (MIC) and minimum biofilm eradication concentration (MBEC) on reference strains of bacteria and fungi. Human gingival fibroblast (HGF-1), murine macrophage (RAW264.7) and human foetal osteoblast (hFOB1.19) cells were used in the study. Lipopolysaccharide (LPS) was used to induce inflammation. Cytokine levels were measured using an enzyme-linked immunosorbent assay; metalloproteinase expression was measured using Western blotting. RESULTS: The synthesized AgNPs were spherical and narrow-dispersed with an average diameter of 13.4 nm ± 3.0 nm in the case of AgNPs-CHL and 3.72 nm ± 0.72 nm in the case of AgNPs-PEG-MET. Both types of AgNPs were active against bacteria and fungi. AgNPs-CHL proved to be a more potent antimicrobial agent, although they were more cytotoxic than AgNPs-PEG-MET; however, both demonstrated beneficial properties in nontoxic concentrations. AgNPs-CHL and AgNPs-PEG-MET decreased the production of proinflammatory cytokines IL-1ß, IL-6, IL-8 and TNFα. Both agents also decreased the levels of metalloproteinases MMP3 and MMP8, which may indicate that they will inhibit tissue degradation. CONCLUSION: AgNPs-CHL and AgNPs-PEG-MET may be possible therapeutic options for PD, as they have antibacterial and anti-inflammatory properties. However, to fully understand the potential of AgNPs, our in vitro findings must be evaluated in an in vivo model.

New Photoresponsive Poly(meth)acrylates Bearing Azobenzene Moieties Obtained via ATRP Polymerization Exhibiting Liquid-Crystalline Behavior.

Here, we report our studies on photoresponsive poly(meth)acrylates containing azobenzene groups connected to a polymer backbone via a short methylene linker. A series of side-chain azobenzene polymers was synthesized via the atom transfer radical polymerization (ATRP) technique using several catalytic systems. The polymers synthesized under the optimized conditions were characterized by a narrow polydispersity (D ≤ 1.35), and they underwent a reversible transformation of their structure under light illumination. The fabricated polymers can store and release energy accumulated during the UV-light illumination by the thermal cis-trans isomerization of the chromophore groups. The enthalpy of the process (determined from DSC) was relatively high and equaled 61.9 J∙g-1 (17 Wh∙kg-1), indicating a high potential of these materials in energy storage applications. The liquid-crystalline behavior of the synthesized poly(meth)acrylates was demonstrated by the birefringent optical textures as observed in thin-films and X-ray scattering studies.

Silver-Polystyrene (Ag/PS) Nanocomposites Doped with Polyvinyl Alcohol (PVA)-Fabrication and Bactericidal Activity.

In the present work, we report the studies on perfectly homogeneous nanocomposites composed of polystyrene-grafted silver nanoparticles (Ag@PS) as a bioactive fulfilment and a mixture of polystyrene (PS) and polyvinyl alcohol (PVA) as a matrix. The procedure developed by our group of the nanocomposites' preparation consists of three steps: synthesis of narrow-dispersive AgNPs (5.96 ± 1.02 nm); grafting of narrowly dispersed polystyrene onto the surface of AgNPs; thermoforming with a mixture of PS/PVA. Kirby-Bauer (K-B) and Dynamic Shake Flask (DSF) assays revealed high antibacterial activity against a series of Gram(-) and Gram(+) bacteria strains of the fabricated nanocomposites at low silver content (0.5%). We showed that the doping of Ag/PS composites with PVA increases the antibacterial activity of composites. The hydrophilic component in the nanocomposites enables easier water migration inside the polymer matrix, which makes releasing silver nanoparticles and silver ions to the environment facile.

A Novel Strategy for the Synthesis of Amphiphilic and Thermoresponsive Poly(N-isopropylacrylamide)-b-Polystyrene Block Copolymers via ATRP.

A new synthetic approach is presented for the preparation of Poly(N-isopropylacrylamide-block-styrene) PNIPAM-b-PS via an Atom Transfer Radical Polymerization (ATRP) technique. The proposed method is based on application of 2-chloro-N-(2-hydroxyethyl)propanamide (NCPAE) as a bifunctional initiator, which enables ATRP of two monomers, differing in activity and polarity, into two stages. The synthesized copolymer molecules contain two well-defined polymer chains connected by a linker, which is a derivative of the proposed initiator. Using NCPAE led to PNIPAMs with well-planned molecular weight, low polydispersities (PDI=1.1÷1.3) and hydroxyl functionality. Activation of such blocks for initiation of styrene polymerization was performed using α-bromoisobutyryl bromide. After such a modification, the synthesized homopolymers acted as macroinitiators in ARGET ATRP and a well-defined polystyrene block, as the next one in the polymer chain was successfully formed. Both of the synthesized macromolecules, PNIPAM and PNIPAM-b-PS, exhibit a thermoresponsive behavior with explicit lower critical solution temperatures (LCST) in their aqueous solutions. The synthesized homopolymers and subsequently derived block copolymers were characterized using Size-Exclusion Chromatography, Differential Scanning Calorimetry, Dynamic Light Scattering, and NMR spectroscopy.

Surface modification using TEMPO and its derivatives.

This article provides an overview of the methods for surface modification based on the use of stable radicals: 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and its derivatives. Two approaches are discussed. The first relies on the immobilization of TEMPO moieties on the surface of various materials including silicon wafers, silica particles, organic polymers as well as diverse nanomaterials. Applications of such materials with spin labeled surface/interface, in (electro)catalysis, synthesis of novel hybrid nanostructures and nanocomposites as well as in designing of organic magnets and novel energy storage devices are also included in the discussion. The second approach utilizes TEMPO and its derivatives for the grafting of polymer chains and polymer brushes formation on flat and nanostructure surfaces via Nitroxide Mediated Radical Polymerization (NMRP). The influence of such polymer modification on surface/interface physicochemical properties is also presented.

High-density polystyrene-grafted silver nanoparticles and their use in the preparation of nanocomposites with antibacterial properties.

The achievement of uniform nanoparticles distribution in polymer matrix is still a major challenge in the design and fabrication of polymer nanocomposites with desired properties. In this paper we propose a novel approach for the preparation of homogeneous polystyrene/silver nanocomposites utilizing Nitroxide Mediated Radical Polymerization (NMRP). In the first step of the developed procedure, the polystyrene grafted silver nanoparticles (Ag@PS) with well-defined core-shell structure and exceptionally high grafting density (from 2 chains/nm2 to 5.9 chains/nm2) have been synthesized through late injection of nitroxide-coated silver nanoparticles (N-AgNPs) into a TEMPOL mediated styrene polymerization system. Afterwards, the synthesized Ag@PS have been used for the preparation of nanocomposites (PS/Ag@PS) by mixing them with narrow-dispersity polystyrenes and thermoforming at 140°C. Due to the high flexibility of polymer chains attached to silver surface through nitroxide linker, free volume effect enables interpenetration of polystyrene molecules that provides excellent mutual miscibility of Ag@PS with polymer matrix. The synthesized nanohybrids (Ag@PS) and their nanocomposites (PS/Ag@PS) exhibit effective antibacterial activity with respect to pathogenic bacteria: Pseudomonas aeruginosa (Gram-negative representative) and Staphylococcus aureus (Gram-positive representative).

Hydrogen bonding between phenols and fatty acid esters: (1)H NMR study and ab initio calculations.

[structure: see text] (1)H NMR measurements and ab initio calculations were used to study the interactions between hindered/nonhindered phenols and carboxylic acid esters. The dihedral angle (phi) between the OH group and a plane of the aromatic ring is close to 0 degrees in the hydrogen-bonded nonhindered phenols, whereas for 2,6-di-tert-butyl-4-methylphenol the OH group is completely twisted out of the aromatic plane (phi approximately 90 degrees ).