Functionalizable composite nanoparticles as a dual magnetic resonance imaging/computed tomography contrast agent for medical imaging

A dual contrast agent for computed tomography (CT) and magnetic resonance imaging (MRI) was synthesized via microemulsion polymerization. This contrast agent consists of Fe₃O₄ particles (d = 7 nm) with an iodine-carrying nanopolymeric shell, with overall particle sizes ranging from 50 to 250 nm. 2-Methacryloyloxyethyl(2,3,5-triiodobenzoate) was used as the monomer. Sodium oleate was used as the surfactant and its amount was varied to control the overall particle size. The composite nanoparticles were mainly characterized via dynamic light scattering, with further analyses using transmission electron microscopy and atomic force microscopy. The particles provided a highly visible contrast in CT and MR images. A template for biomedical applications was created by adding a comonomer and the particles were further functionalized with the somatostatin analogue Tyr³-octreotate. The particles were tested for specific uptake into somatostatin receptor-positive AR42J cells. The additional uptake of the functionalized particles was investigated. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47571.     

Scanning pulsed laser ablation in liquids: An alternative route to obtaining biocompatible YbFe nanoparticles as multiplatform contrast agents for combined MRI and CT imaging

Ytterbium ferrites are being used in many promising applications, such as visible-light photocatalysis, solar cells, magnetooptic devices, electro-magnetic equipment, etc., due to their fantastic ferroelectric and ferromagnetic properties. However, despite their good magnetic and radiopaque features, the use of ytterbium ferrites as multiplatform contrast agents in magnetic resonance imaging (MRI) and X-ray computed tomography (CT) is still under-developed. This is mainly due to difficulties in obtaining stable and biocompatible aqueous colloidal dispersions of ytterbium ferrite nanoparticles. In order to overcome this limitation, this work explores an eco-friendly method to directly synthesize such dispersions by liquid-assisted pulsed laser ablation of ytterbium ferrite massive targets. First, orthorhombic bulk YbFeO₃ targets were obtained by a reaction-sintering method. Then, colloidal dispersions of nanoparticles were produced directly in both distilled water and ethanol by irradiating the bulk YbFeO₃ targets with high-power infrared nanosecond lasers pulses. A battery of techniques has been used to characterize the as synthesized YbFeO₃ targets and colloidal dispersions of YbFe nanoparticles to determine their composition, structure, magnetic properties, X-ray attenuation potentials, and colloidal properties. Moreover, the biocompatibility of the systems was also analysed by MTT cell viability assay. Results indicated that the use of distilled water as ablation medium yields colloidal dispersions consisted mainly of paramagnetic ytterbium ferrite nanoparticles. Contrarily, the use of ethanol as solvent leads to colloidal dispersions of polycrystalline nanoparticles with both ferromagnetic and paramagnetic behaviour, due to the coexistence, in each nanoparticle, of ytterbium ferrite, ytterbium oxide, and iron oxide crystalline phases. Both colloidal dispersions exhibit also high biocompatibility and suitable X-ray attenuation properties. Moreover, they show bio-safe hydrodynamic sizes (lower than 200 nm) with acceptable overall hydrodynamic polydispersity index values (under 0.4), being stable in water for several weeks. These results pave the way for the future evaluation of Yb–Fe based nanoparticles as multiplatform contrast agents in multimodal MRI and CT imaging.     

Structural and magnetic characterization of norbornene-deuterated norbornene dicarboxylic acid diblock copolymers doped with iron oxide nanoparticles

A series of iron oxide doped norbornene (NOR)/deuterated norbornene dicarboxylic acid (NORCOOH) diblock copolymers were synthesized and characterized by X-ray photoelectron spectroscopy (XPS), small angle neutron scattering (SANS) and superconducting quantum interference device (SQUID) experiments. γ-Fe₂O₃ nanoparticles were synthesized within the microdomains of diblock copolymers with volume fractions of NOR/NORCOOH 0.64/0.36, 0.50/0.50 and 0.40/0.60. A spherical nanoparticle morphology was displayed in the polymer with 0.64/0.36 volume fraction. Polymers with 0.50/0.50 and 0.40/0.60 volume fractions exhibited interconnected metal oxide nanostructures. The observed changes in the shape and peak positions of the small-angle neutron scattering profiles of polymers after metal doping were related to the scattering from the metal oxide particles and to the possible deformed morphologies due to the strong interparticle interactions between metal particles, which may influence the polymer microphase separation. The combined scattering from both polymer domains and magnetic particles was depicted in SANS profiles of metal oxide doped polymers. γ-Fe₂O₃ containing block copolymers were superparamagnetic at room temperature. An increase in the blocking temperature (T_b) of interconnected nanoparticles was observed and was related to the interparticle interactions, which depends on the average distance (d) between particles and individual particle diameter (2R). The sample with volume fraction of 0.4/0.6 have the lowest d/(2R) ratio and exhibit the highest T_b at 115 K.     

Olive leaves extract mediated zero-valent iron nanoparticles: synthesis,characterization, and assessment as adsorbent for nickel (II) ions in aqueous medium

Abstract

Zero-valent iron nanoparticles (NZVI-NPs) possess significantly high surface area and volume ratio, and this unique surface characteristic has enhanced reactivity to their adsorption potential. In this work, a bio-matter (Olive leaves extract) is deployed as a nature-inspired reducing agent for the synthesis of NZVI-NPs. The particle size of NZVI-NPs has been determined using particle sizer. The NZVI-NPs are characterized using analytical and morphological techniques such as ultraviolet???visible spectroscopy (UV???vis), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction spectroscopy (XRD), scanning electron microscope (SEM), Brunauer–Emmett–Teller (BET), and Fourier transform infrared (FTIR) spectroscopy. The average crystalline size of NZVI-NPs are around 30–60?nm while maximum adsorption is at 225?nm. XRD spectrum shows two distinctive diffraction peaks at 25.40° and 42.50° corresponding to lattice plane value indexed at (200) and (222) planes of faced centered cubic (FCC). At optimized experimental conditions, NZVI-NPs show 97% removal efficiency of Ni⁺² ions from aqueous solution. The equilibrium time has been found to be 55?min and the monolayer maximum adsorption capacity is 139.5?mg/g. Kinetically, Ni⁺² ions adsorption has been modelled using various physical isotherms and the data best fitted Freundlich isotherm model and pseudo-first-order kinetic; revealing a maximum adsorption capacity of 139.5?mg/g at 25?±?3?°C and pH of 6.5. Desorption tests affirm the possibility of recovering reasonable amount of NZVI-NPs after used. The specific surface area of the NZVI-NPs sample measured by BET analysis is 21.9967 m²/g indicating a high adsorption capacity.     

Preparation and characterization of polysulfone mixed matrix membrane incorporated with palladium nanoparticles in the inversed microemulsion for hydrogen separation

Polysulfone (PSf) membrane shows acceptable gas separation performance, but its application is limited by the “trade-off” between selectivity and permeability. In this study, PSf mixed matrix membranes (MMMs) incorporated with palladium (Pd) nanoparticles in the inversed microemulsion were proposed for hydrogen (H₂) separation. Pd nanoparticles can be kinetically stabilized and dispersed using electrostatic and/or steric forces of a stabilizer which is typically introduced during the formation of Pd nanoparticles in the inversed microemulsion. Pd nanoparticles were synthesized by loading (PdCl₂) into the polymeric matrix, polyethylene glycol (PEG) which acts as reducing agent and stabilizer. The dry–wet phase inversion method was applied for the preparation of asymmetric PSf MMMs. The effects of Pd (0–4 wt%) on the membrane characteristics and separation performance were studied. Experimental findings verified that the MMMs are able to achieved a high H₂/N₂ selectivity of 21.69 and a satisfactory H₂ permeance of 46.24 GPU due to the changes in membrane structure from fully developed finger-like structure to closed cell structure besides the growth of dense layer. However, the selectivity of H₂/CO₂ decreased due to the addition of PEG.     

Beyond platinum: synthesis,characterization, and in vitro toxicity of Cu(II)-releasing polymer nanoparticles for potential use as a drug delivery vector

The field of drug delivery focuses primarily on delivering small organic molecules or DNA/RNA as therapeutics and has largely ignored the potential for delivering catalytically active transition metal ions and complexes. The delivery of a variety of transition metals has potential for inducing apoptosis in targeted cells. The chief aims of this work were the development of a suitable delivery vector for a prototypical transition metal, Cu²⁺, and demonstration of the ability to impact cancer cell viability via exposure to such a Cu-loaded vector. Carboxylate-functionalized nanoparticles were synthesized by free radical polymerization and were subsequently loaded with Cu²⁺ via binding to particle-bound carboxylate functional groups. Cu loading and release were characterized via ICP MS, EDX, XPS, and elemental analysis. Results demonstrated that Cu could be loaded in high weight percent (up to 16 wt.%) and that Cu was released from the particles in a pH-dependent manner. Metal release was a function of both pH and the presence of competing ligands. The toxicity of the particles was measured in HeLa cells where reductions in cell viability greater than 95% were observed at high Cu loading. The combined pH sensitivity and significant toxicity make this copper delivery vector an excellent candidate for the targeted killing of disease cells when combined with an effective cellular targeting strategy.     

Microwave-assisted synthesis and characterization of bioactive chitosan scaffolds doped with Au nanoparticles for mesenchymal stem cells culture

In this work we present a novel strategy for chitosan-based scaffolds. Chitosan is a versatile biopolymer obtained from waste biomass known of its favorable biological properties. Thus it can replace other polymers in the preparation of bioactive scaffolds. To increase its durability chitosan can be crosslinked into form of the hydrogel yet application of toxic crosslinkers may lead to loss of biocompability. Mesenchymal stem cells can be used in cell therapy for advanced wound treatment. However their culture requires special biomaterials application. In this article a novel microwave-assisted synthesis method for bioactive chitosan scaffolds is presented.     

Mussel-inspired synthesis of silver nanoparticles as fillers for preparing waterborne polyurethane/Ag nanocomposites with excellent mechanical and antibacterial properties

Silver nanoparticles (AgNPs) were synthesized by a facile, mild and green method using dopamine as a reducing and stabilizing agent and were introduced to waterborne polyurethane (WPU) via an in situ emulsification method to prepare antibacterial nanocomposite films. The formation of AgNPs was characterized by UV–visible spectroscopy and XRD. The dispersion of AgNPs was confirmed by TEM and the thermal stability of WPU/Ag nanocomposites was confirmed by TGA. The results showed that AgNPs were uniformly dispersed in the WPU matrix. The introduction of AgNPs significantly improved the thermal stability of WPU films. With incorporation of 0.1 wt% AgNPs, a five-fold increase in the tensile strength was achieved without sacrificing the ultimate strain. The WPU/Ag nanocomposite films showed antibacterial activity against Escherichia coli and Staphylococcus aureus. © 2021 Society of Industrial Chemistry.     

Novel electrically conductive and ferromagnetic composites of poly(aniline‐co‐aminonaphthalenesulfonic acid) with iron oxide nanoparticles: Synthesis and characterization

Nanocomposites of iron oxide (Fe₃O₄) with a sulfonated polyaniline, poly(aniline‐co‐aminonaphthalenesulfonic acid) [SPAN(ANSA)], were synthesized through chemical oxidative copolymerization of aniline and 5‐amino‐2‐naphthalenesulfonic acid/1‐amino‐5‐naphthalenesulfonic acid in the presence of Fe₃O₄ nanoparticles. The nanocomposites [Fe₃O₄/SPAN(ANSA)‐NCs] were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X‐ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, elemental analysis, UV–visible spectroscopy, thermogravimetric analysis (TGA), superconductor quantum interference device (SQUID), and electrical conductivity measurements. The TEM images reveal that nanocrystalline Fe₃O₄ particles were homogeneously incorporated within the polymer matrix with the sizes in the range of 10–15 nm. XRD pattern reveals that pure Fe₃O₄ particles are having spinel structure, and nanocomposites are more crystalline in comparison to pristine polymers. Differential thermogravimetric (DTG) curves obtained through TGA informs that polymer chains in the composites have better thermal stability than that of the pristine copolymers. FTIR spectra provide information on the structure of the composites. The conductivity of the nanocomposites (～ 0.5 S cm^?1) is higher than that of pristine PANI (～ 10^?3 S cm^?1). The charge transport behavior of the composites is explained through temperature difference of conductivity. The temperature dependence of conductivity fits with the quasi‐1D variable range hopping (quasi‐1D VRH) model. SQUID analysis reveals that the composites show ferromagnetic behavior at room temperature. The maximum saturation magnetization of the composite is 9.7 emu g^?1. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Cornet‐Like Phosphotriazine/Diamine Polymers as Reductant and Matrix for the Synthesis of Silver Nanocomposites with Antimicrobial Activity

The synthesis of silver nanoparticles attached on the surface of a hollow cornet‐like polymer matrix which served as a reductant and host matrix is described. This hybrid organic/inorganic macromolecular matrix is exhibiting anion‐exchange properties, porous structure and hollow morphologies, and absorptions in the visible light region. Due to the anion‐exchange property and the 3D orientation of the macromolecular chains the material is defining a new functional organic/inorganic hybrid. For the synthesis of nanoparticles, no other reducing agents were used and silver nanoparticles with a mean diameter of less than 20 nm were attached on the surface of the polymer, thus inheriting the composite with high antibacterial activity tested in bacterial strains and yeasts.

     

Preparation and characterization of zinc modified calcium silicate/polycaprolactone with graphene oxide composite coating for bone repair applications

The goal of biomaterial interest is the ease of the bone tissue regeneration process or the replacement of damaged bone and other tissues with recently generated bone tissue. Calcium silicate (CaSi) bioceramic is a vital material for bone tissue engineering, predominantly for bone repair. Though, the low toughness of calcium silicate imitates its load-bearing applications. The electrophoretic deposition technique was used to coat various concentrations of Zn²⁺ substituted CaSi on TNT. In this work, a novel as-obtained an appropriate orthopedic implant hybrid material by charged calcium ions of mineralized calcium silicate united with PCL-negatively charged graphene oxide [Zn-CaSi (S₁-S₃)/PCL (P₁-P₃)/GO]. Hence, the effectively as-obtained [Zn-CaSi (S₁-S₃)/PCL (P₁-P₃)/GO] bone-like apatite on the ternary composite coatings on the surface was proven via XRD, FT-IR, FESEM with EDAX spectra, HR-TEM and BET analyses etc., Moreover, the TNT/S₂/P₂@GO ternary composite coatings exhibit better mechanical properties and antibacterial activity. The metal ions released from the coatings were calculated via ICP-AES studies. Moreover, the cell viability and also the live/dead staining of MG63 human osteoblasts cells on the subsequent composite coating material for better cell growth in orthopedic applications.     

Facile synthesis of thiol-terminated poly(styrene-ran-vinyl phenol) (PSVPh) copolymers via reversible addition-fragmentation chain transfer (RAFT) polymerization and their use in the synthesis of gold nanoparticles with controllable hydrophilicity

A facile approach to prepare thiol-terminated poly(styrene-ran-vinyl phenol) (PSVPh) copolymers and PSVPh-coated gold nanoparticles is reported with the goal of creating stabilizing ligands for nanoparticles with controlled hydrophilicity. Dithioester-terminated poly(styrene-ran-acetoxystyrene) copolymers were synthesized via RAFT polymerization using cumyl dithiobenzoate as a chain transfer agent. These copolymers were converted to thiol-terminated PSVPh copolymers by a one step hydrazinolysis reaction using hydrazine hydrate to simultaneously convert dithioester-terminal and acetoxy-pendant groups to thiol-terminal and hydroxyl-pendant groups, respectively. Spectroscopic observations including NMR and IR confirm end- and pendant-group conversion. PSVPh-coated gold nanoparticles were synthesized in the presence of a mixture of thiol-terminated PSVPh and PSVPh copolymers containing disulfides as stabilizing ligands in a water/toluene, two-phase system. The size and size distribution of core gold nanoparticles were determined by TEM and image analysis. The hydrodynamic radius of PSVPh-coated gold nanoparticles was also determined by dynamic light scattering experiment, which confirms the particle analysis by TEM. This procedure provides a facile technique to control the polarity and hydrophilicity of metal nanoparticle surfaces and could prove critical in advancing the control of nanoparticle placement in biological and hierarchically ordered systems, such as diblock copolymers.     

A simple and convenient method for the surface coating of TiO2 nanoparticles with bioactive chiral diacids containing different amino acids as the coupling agent

For practical applications, especially in an organic-solution situation, the surface of TiO₂ nanoparticles (NP)s requires modification with an organic coupling agent. Therefore, in this study, the surface of TiO₂ NPs with average diameter of 30 nm was modified with bioactive dicarboxylic acids (DA)s containing different natural amino acids such as l-valine, l-methionine, l-leucine, and l-isoleucine. The prepared DAs-modified TiO₂ NPs were studied with Fourier transform infrared spectroscopy, X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy and thermogravimetric analysis techniques. The results showed that the modifiers were grafted on the surface of TiO₂ NPs. Modified TiO₂ NPs could be environmentally friendly due to the presence of bioactive DAs.