Amir Fahmi

Chitosan(PEO)/silica hybrid nanofibers as a potential biomaterial for bone regeneration.

New hybrid nanofibers prepared with chitosan (CTS), containing a total amount of polyethylene oxide (PEO) down to 3.6wt.%, and silica precursors were produced by electrospinning. The solution of modified sol-gel particles contained tetraethoxysilane (TEOS) and the organosilane 3-glycidyloxypropyltriethoxysilane (GPTEOS). This is rending stable solution toward gelation and contributing in covalent bonding with chitosan. The fibers encompass advantages of biocompatible polymer template silicate components to form self-assembled core-shell structure of the polymer CTS/PEO encapsulated by the silica. Potential applicability of this hybrid material to bone tissue engineering was studied examining its cellular compatibility and bioactivity. The nanofiber matrices were proved cytocompatible when seeded with bone-forming 7F2-cells, promoting attachment and proliferation over 7 days. These found to enhance a fast apatite formation by incorporation of Ca(2+) ions and subsequent immersion in modified simulated body fluid (m-SBF). The tunable properties of these hybrid nanofibers can find applications as active biomaterials in bone repair and regeneration.

Functional hybrid materials

Nanofabrication via self-assembly of hybrid materials into well-defined architectures is essential for the next generation of miniaturized devices. This paper describes our groups achievements towards the development of multifunctional nanostructures via self-assembly of hybrid systems based on the block copolymer PS-b-P4VP and inorganic nanoparticles (NPs) into 0D, 1D, 2D and complex 3D periodic nanostructures. The morphologies of these architectures are adjusted to gain functions via structural control at different dimensions.

Nano- and micro-sized honeycomb patterns through hierarchical self-assembly of metal-loaded diblock copolymer vesicles

Herein we present a novel approach for fabricating metallic micro- and nano-structures in thin films viaspin-coating solutions of diblock copolymer vesicles. A simple concept was developed, which is based on the metallization and self-assembly diblock copolymers. Firstly, vesicles incorporating the inorganic components are generated in solution by adjusting the solvent ratio in water–toluene mixtures. Subsequently, thin films are deposited onto a solid substrate viaspin-coating. As a result micro- and nano-sized honeycomb structures are obtained; the pore diameter is dependent on the size and size distribution of the vesicles. Hence, control over the pattern dimensions and the degree of order can be achieved by tuning the vesicle diameter prior to film deposition. Finally, the block copolymer is extracted by means of oxygen plasma etching, leaving behind inorganic Au-nanostructures that mimic the original film morphology. The surface properties of these honeycomb patterns, in terms of hydrophobicity, can be adjusted by controlling the film thickness and the characteristic dimension of the pattern.

Ion-Selective Controlled Assembly of Dendrimer-Based Functional Nanofibers and Their Ionic-Competitive Disassembly

The construction of hierarchical materials through controlled self-assembly of molecular building blocks (e.g., dendrimers) represents a unique opportunity to generate functional nanodevices in a convenient way. Transition-metal compounds are known to be able to interact with cationic dendrimers to generate diverse supramolecular structures, such as nanofibers, with interesting collective properties. In this work, molecular dynamics simulation (MD) demonstrates that acetate ions from dissociated Cd(CH(3)COO)(2) selectively generate cationic PPI-dendrimer functional fibers through hydrophobic modification of the dendrimers surface. The hydrophobic aggregation of dendrimers is triggered by the asymmetric nature of the acetate anions (AcO(-)) rather than by the precise transition metal (Cd). The assembling directionality is also controlled by the concentration of AcO(-) ions in solution. Atomic force (AFM) and transmission electron microscopy (TEM) prove these results. This well-defined directional assembly of cationic dendrimers is absent for different cadmium derivatives (i.e., CdCl(2), CdSO(4)) with symmetric anions. Moreover, since the formation of these nanofibers is controlled exclusively by selected anions, fiber disassembly can be consequently triggered via simple ionic competition by NaCl salt. Ions are here reported as a simple and cost-effective tool to drive and control actively the assembly and the disassembly of such functional nanomaterials based on dendrimers.

Inorganic/Organic (SiO2)/PEO Hybrid Electrospun Nanofibers Produced from a Modified Sol and Their Surface Modification Possibilities

Ceramic silica (SiO(2)) hybrid nanofibers were prepared by electrospinning of solutions containing biocompatible polymer and modified silica precursors. The new hybrid nanofibers are based on polyethylene oxide (PEO) and a new solution of modified sol-gel particles of mixture containing tetraethoxysilane (TEOS) and 3-glycidyloxypropyltriethoxysilane (GPTEOS) in a weight ratio of 3:1. Adding high-molecular-weight PEO into the silica sol is found to enhance the formation of the silica nanofibers and leads to reduce the water-soluble carrying polymer down to 1.2%wt. Transmission electron microscopy (TEM) and attenuated total reflection fourier transformation infrared ATR-FTIR measurements are suggested that PEO is encapsulated by the silica component. This excellent formulation renders electrospinning of SiO(2) a robust process for an easy production of controllable silicate nanofibrous matrices. For instance, nanofibers with average diameter down to 400 nm are accessible by varying the weight ratio between the polymer and the inorganic precursor. These are reduced to 120 nm after the pyrolysis process. Moreover, the surface of the nanofibers could be easily modified, either by Al(3+) leading to aluminium silicate coatings, or by incorporation of Ca(2+) ions and subsequent bioactive hydroxyl carbonate apatite (HAP) formation. These hybrid silica nanofibers are possess a unique collective properties can have a great impact either in high-temperature reinforced materials and filtration or in biomedical applications such as in dentistry and bone tissue engineering.

Polyamide 66 microspheres metallised with in situ synthesised gold nanoparticles for a catalytic application

A simple concept is proposed to metallise polyamide 66 (PA66) spherulite structures with in situ synthesised gold nanoparticles (Au NPs) using a wet chemical method. This cost-effective approach, applied to produce a PA66/Au NP hybrid material, offers the advantages of controlling the nanoparticle size, the size distribution and the organic-inorganic interactions. These are the key factors that have to be controlled to construct consistent Au nanostructures which are essential for producing the catalytic activities of interest. The hybrid materials obtained are characterised by means of scanning electron microscopy, transmission electron microscopy, attenuated total reflection-Fourier transform infrared spectrometry and X-ray diffraction spectrometry. The results show that PA66 microspheres obtained via the crystallisation process are coated with Au NPs of 13 nm in size. It was found that controlling the metal coordination is the key parameter to template the Au NPs on the spherulite surfaces. The preparation processes and the key factors leading to the formation of PA66 spherulites coated with Au NPs are discussed. Moreover, the efficiency of the coated spherulites as a potential catalyst is proved by demonstrating the reduction of methylene blue via UV-visible spectrometry.

Water-soluble CdSe nanoparticles stabilised by dense-shell glycodendrimers

A simple and rapid method has been developed to prepare water-soluble CdSe nanoparticles at room temperature, with average particle diameters around 2 nm, stabilised by maltose-modified 2nd–5th generation poly(propylene imine) (PPI) dendrimers.

In Situ Synthesis and Alignment of Au Nanoparticles within Hexagonally Packed Cylindrical Domains of Diblock Copolymers in Bulk

We present a simple method to prepare hexagonally packed metallic nanocylinders based on gold nanoparticles embedded in a copolymeric matrix. The gold nanoparticles are generated selectively within the P4VP-rich cylindrical domains of a polystyrene-b-poly-4-vinylpyridine (PS-b-P4VP) diblock copolymer. In order to achieve this selectivity, a gold precursor (HAuCl4) is coupled to the pyridine blocks of a spherical PS327-b-P4VP27 block copolymer. In consequence, the hybrid block copolymer is able to self-assemble in a hexagonally packed cylinders morphology. The application of mechanical oscillatory shear improved markedly the alignment of these nanocylinders, while simultaneously the gold precursor was reduced in situ into gold nanoparticles. Following rheological characterization in the linear viscoelastic regime, a set of alignment parameters were comprehensively selected and checked with a series of transmission electron microscopy (TEM) micrographs. An optimal temperature of alignment was found after systematic evaluation of samples sheared at different temperatures. The block copolymer exhibited an increase in the domain period as a consequence of chain rearrangements around the newly formed gold nanoparticles. The hexagonally packed morphology was preserved, and under the optimal conditions single grain sizes showed significant improvement to macroscale order in comparison to nonaligned samples. In contrast to current multistep lithographic techniques, the present method constitutes a simple path to produce three-dimensional organic-inorganic conductive nanowires with periodicities at the macroscopic level.

Hybrid one-dimensional nanostructures: one-pot preparation of nanoparticle chains via directed self-assembly of in situ synthesized discrete Au nanoparticles.

The fabrication of well-defined one-dimensional (1D) arrays is becoming a challenge for the development of the next generation of advanced nanodevices. Herein, a simple concept is proposed for the in situ synthesis and self-assembly of gold nanoparticles (AuNPs) into 1D arrays via a one-step process. The results demonstrated the formation of nanoparticle chains (NPC) with high aspect ratio based on discrete Au nanoparticles stabilized by short thiol ligands. A model was proposed to explain the self-assembly based on the investigation of several parameters such as pH, solvent, temperature, and nature of the ligand on the 1D assembly formation. Hydrogen bonding was identified as a key factor to direct the self-assembly of the hybrid organic–inorganic nanomaterials into the well-defined 1D nanostructures. This simple and cost-effective concept could potentially be extended to the fabrication of a variety of hybrid 1D nanostructures possessing unique physical properties leading to a wide range of applications including catalysis, bionanotechnology, nanoelectronics, and photonics.

Temperature-dependent FTIR spectroscopic studies of hydrogen bonding of the copolymer poly(styrene-b-4-vinylpyridine) with pentadecylphenol

Abstract Interactions between the diblock copolymer poly(styrene- b -4-vinylpyridine) P(S4VP) and pentadecylphenol (PDP) were analysed by IR difference spectroscopy and temperature-dependent FTIR spectroscopy. Strong hydrogen bonding was found between the pyridine units of the diblock copolymer P(S4VP) and the hydroxyl groups of the amphiphile (PDP). This interaction leads to stable polymeric complexes and mesomorphic structures at two length scales. We study the nature of supermolecular interactions in the pure components as well as in the polymeric complex PDP/P(S4VP) at different temperatures ranging from room temperature up to 190 °C. The influence of temperature on the stability of the H-bonds was studied especially in the spectral region above 3000 cm −1 (OH stretching).