Materials Science and Engineering C

This work reports the first application of the ion imprinting technology for determination of potassium ion by precipitation polymerization method. Ion imprinted polymeric (IIP) nanoparticles were prepared by using dicyclohexyl 18C6 (DC18C6) as a K(+) ion selective crown ether, in the acetonitrile-dimethylsulfoxide (3:1; v/v) mixture as porogen. The imprint potassium ion was removed from the polymeric matrix using 0.5M HNO3. The scanning electron microscopy (SEM) micrographs showed colloidal nanoparticles of 60-90nm in diameter and slightly irregular in shape. The obtained ion-imprinted particles for K(+) showed selective recognition with rapid adsorption and desorption processes. It was found that imprinting results in increased affinity of the material toward K(+) ion over other competitor metal ions with the same charge and/or close ionic radius. The synthesized IIP nanobeads were shown to be promising for solid-phase extraction coupled with flame photometry for determination of trace K(+) ion in different water samples.

Here we report the synthesis of silver nanoparticles using ethanolic flower extract of Nyctanthes arbortristis, UVvisible spectra and TEM indicated the successful formation of silver nanoparticles. Crystalline nature of the silver nanoparticles was confirmed by X-ray diffraction. Fourier Transform Infra-Red Spectroscopy analysis established the capping of the synthesized silver nanoparticles with phytochemicals naturally occurring in the ethanolic flower extract of N. arbortristis. The synthesized silver nanoparticles showed antibacterial activity against the pathogenic strain of Escherichia coli MTCC 443. Furthermore, cytotoxicity of the silver nanoparticles was tested on mouse fibroblastic cell line (L929) and found to be non-toxic, which thus proved their biocompatibility. Antibacterial activity and cytotoxicity assay carried out in this study open up an important perspective of the synthesized silver nanoparticles. Copyright © 2014 Elsevier B.V. All rights reserved.

This study aimed to evaluate the cytocompatibility and early osseointegration of Ti-24 Nb-4 Zr-7.9 Sn (Ti-2448) surfaces that were modified with a nanoscale TiO2 coating. The coating was fabricated using a hydrothermal synthesis method to generate nanoTiO2/Ti-2448. The surface characteristics of the samples were evaluated using scanning electron microscopy (SEM), energy dispersive spectrometry (EDS) and X-ray diffraction (XRD). The cytotoxicity of the fabricated nanoTiO2/Ti-2448 was determined using MTT assays. The proliferation and alkaline phosphatase (ALP) activity of MC3T3-E1 osteoblasts cultured on nanoTiO2/Ti-2448 were compared with those cultured on Ti-2448. Disk-shaped implants were placed in Wistar rats. The histological sections were stained with haematoxylin and eosin (HE), and the histocompatibility was analysed at 4 and 12weeks post-implantation. Cylindrical implants were embedded in Japanese white rabbits, and the histological sections were stained with HE and anti-TGF-β1 to evaluate the histocompatibility and early osseointegration at 4, 12 and 26weeks post-implantation. NanoTiO2/Ti-2448 exhibited a rougher surface than did Ti-2448. NanoTiO2/Ti-2448 was determined to be non-cytotoxic. More osteoblasts and higher ALP activity were observed for nanoTiO2/Ti-2448 than Ti-2448 (p<0.05). Few inflammatory cells were detected around nanoTiO2/Ti-2448, and the expression of TGF-β1 on nanoTiO2/Ti-2448 peaked at earlier time than that on Ti-2448. The results indicate that the cytocompatibility and early osseointegration were enhanced by the nanoTiO2 coating. Copyright © 2014 Elsevier B.V. All rights reserved.

Cr2O3 and Al powder were used as raw powders, and were milled by the high energy ball milling method. The nanostructured 2Cr-Al2O3 composite from the milled powder was both synthesized and densificated within a short time, by the pulsed current activated sintering (PCAS) apparatus. The relative density of the sintered 2Cr-Al2O3 composite was 99%. The hardness and the fracture toughness of the specimen were 1630kg/mm(2), and 9.3MPa·m(1/2), respectively. The weight loss of the composite was measured by a pin-on-disk type apparatus, without a lubricant. Lastly, the 2Cr-Al2O3 composite has a very good cell viability. Copyright © 2014 Elsevier B.V. All rights reserved.

Laser-engineered net shaping (LENS™), a commercial additive manufacturing process, was used to modify the surfaces of 316L stainless steel with bioactive hydroxyapatite (HAP). The modified surfaces were characterized in terms of their microstructure, hardness and apatite forming ability. The results showed that with increase in laser energy input from 32J/mm(2) to 59J/mm(2) the thickness of the modified surface increased from 222±12μm to 355±6μm, while the average surface hardness decreased marginally from 403±18 HV0.3 to 372±8 HV0.3. Microstructural studies showed that the modified surface consisted of austenite dendrites with HAP and some reaction products primarily occurring in the inter-dendritic regions. Finally, the surface-modified 316L samples immersed in simulated body fluids showed significantly higher apatite precipitation compared to unmodified 316L samples.

The mechanical and protective properties of parylene N and C coatings (2-20μm) on stainless steel 316L implant materials were investigated. The coatings were characterized by scanning electron and confocal microscopes, microindentation and scratch tests, whereas their protective properties were evaluated in terms of quenching metal ion release from stainless steel to simulated body fluid (Hanks solution). The obtained results revealed that for parylene C coatings, the critical load for initial cracks is 3-5 times higher and the total metal ions release is reduced 3 times more efficiently compared to parylene N. It was thus concluded that parylene C exhibits superior mechanical and protective properties for application as a micrometer coating material for stainless steel implants.

Engineering biomaterial scaffolds that promote attachment and growth of mesenchymal stem cells in three dimensions is a crucial parameter for successful bone tissue engineering. Towards this direction, a lot of research effort has focused recently into the development of three-dimensional porous scaffolds, aiming to elicit positive cellular behavior. However, the fabrication of three-dimensional tissue scaffolds with a precise geometry and complex micro- and nano-features, supporting cell in-growth remains a challenge. In this study we report on a positive cellular response of human bone marrow-derived (BM) mesenchymal stem cells (MSCs) onto hybrid material scaffolds consisting of methacryloxypropyl trimethoxysilane, zirconium propoxide, and 2-(dimethylamino)ethyl methacrylate (DMAEMA). First, we use Direct fs Laser Writing, a 3D scaffolding technology to fabricate the complex structures. Subsequently, we investigate the morphology, viability and proliferation of BM-MSCs onto the hybrid scaffolds and examine the cellular response from different donors. Finally, we explore the effect of the materials' chemical composition on cell proliferation, employing three different material surfaces: (i) a hybrid consisting of methacryloxypropyl trimethoxysilane, zirconium propoxide and 50mol% DMAEMA, (ii) a hybrid material comprising methacryloxypropyl trimethoxysilane and zirconium propoxide, and (iii) a purely organic polyDMAEMA. Our results show a strong adhesion of BM-MSCs onto the hybrid material containing 50% DMAEMA from the first 2h after seeding, and up to several days, and a proliferation increase after 14 and 21days, similar to the polystyrene control, independent of cell donor. These findings support the potential use of our proposed cell-material combination in bone tissue engineering. Copyright © 2015 Elsevier B.V. All rights reserved.

Advances in nanotechnology are providing to medicine a new dimension. Multifunctional nanomaterials with diagnostics and treatment modalities integrated in one nanoparticle or in cooperative nanosystems are promoting new insights to cancer treatment and diagnosis. The recent convergence between tissue engineering and cancer is gradually moving towards the development of 3D disease models that more closely resemble in vivo characteristics of tumors. However, the current nanomaterials based therapies are accomplished mainly in 2D cell cultures or in complex in vivo models. The development of new platforms to evaluate nano-based therapies in parallel with possible toxic effects will allow the design of nanomaterials for biomedical applications prior to in vivo studies. Therefore, this review focuses on how 3D in vitro models can be applied to study tumor biology, nanotoxicology and to evaluate nanomaterial based therapies.

Inhibiting the non-specific adhesion of cells and proteins to biomaterials such as stents, catheters and guide wires is an important interfacial issue that needs to be addressed in order to reduce surface-related implant complications. Medical grade stainless steel 316L was used as a model system to address this issue. To alter the interfacial property of the implant, self assembled monolayers of long chain phosphonic acids with -CH(3), -COOH, -OH tail groups were formed on the native oxide surface of medical grade stainless steel 316L. The effect of varying the tail groups on 3T3 fibroblast adhesion was investigated. The methyl terminated phosphonic acid significantly prevented cell adhesion however presentation of hydrophilic tail groups at the interface did not significantly reduce cell adhesion when compared to the control stainless steel 316L.

The objective of this study was to investigate porous chitosan-supported metal tetra(4-carboxyphenyl)porphyrin [Me TCPP/p-CTS] as a practical model for the structure and function of the hydrophobic pocket cavity in cytochrome P-450 enzyme. Porous and non-porous chitosan-supported Me TCPPs [Me TCPP/p- and nonp-CTS] were prepared by a similar procedure, characterized using various techniques, and then used as catalysts for the aerobic oxidation of cyclohexane. The Me TCPP/p-CTS, which contained many cavities, showed higher catalytic activity than the Me TCPP/nonp-CTS. The catalytic activities of Mn TCPP/p-CTS and Fe TCPP/p-CTS were 12.4% and 24.4% greater than those of Mn TCPP/nonp-CTS and Fe TCPP/nonp-CTS, respectively. These differences in catalytic activity were mainly influenced by the characteristics and numbers of cavities (or pores) contained in the supported catalysts. Copyright © 2015 Elsevier B.V. All rights reserved.

The effect of electro-pulsing treatment (EPT) on the microstructure, mechanical properties and corrosion behavior of cold-rolled Ti-6Al-4V alloy strips was investigated in this paper. It was found that the elongation to failure of materials obtains a noticeable enhancement with increased EPT processing time while slightly sacrificing strength. Fine recrystallized grains and the relative highest elongation to failure (32.5%) appear in the 11second-EPT samples. Grain coarsening and decreased ductility were brought in with longer EPT duration time. Fracture surface analysis shows that transition from intergranular brittle facture to transgranular dimple fracture takes place with an increase in processing time of EPT. Meanwhile, corrosion behavior of titanium alloys is greatly improved with increased EPT processing time, which is presented by polarization test and surface observation with the beneficial effect of forming a protective anatase-TiO2 film on the surface of alloys. The rapid recrystallization behavior and oxide formation of the titanium alloy strip under EPTs are attributed to the enhancement of nucleation rate, atomic diffusion and oxygen migration resulting from the coupling of the thermal and athermal effects. Copyright © 2015 Elsevier B.V. All rights reserved.

Within a research directed to developing new polymeric materials, suitable for decorating the surface of colloidal drug carriers, PEG5000 polymers containing a free carboxyl or amine group at one end were conjugated to an α-lipoamino moiety (LAA). The conjugates were characterized by FT-IR, (1)H-NMR, and MALDI-TOF mass spectrometry. They showed the same profile of solubility as the parent PEGs in water and in some polar and apolar solvents of pharmaceutical use. Representative terms showed to be well tolerated when incubated with Caco-2 or L929 cell cultures. Dedicated differential scanning calorimetry (DSC) studies were performed to prove the interaction of increasing molar fractions of the PEG5000-LAA conjugates with dipalmitoylphosphatidylcholine (DPPC) bilayers, to gain information about their possible incorporation in drug nanocarriers. While the parent PEGs affected only the superficial structure of bilayers, the amphiphilic PEG-LAA conjugates induced a perturbing effect on the thermotropic behavior of DPPC liposomes, according to the structure of the linked LAA residue. A molar concentration of these PEG-LAA between 5 and 10% was individuated as the most suitable to produce stable vesicles. Copyright © 2014 Elsevier B.V. All rights reserved.

β-Stabilized titanium (Ti) alloys containing non-toxic elements, particularly niobium (Nb), are promising materials for the construction of bone implants. Their biocompatibility can be further increased by oxidation of their surface. Therefore, in this study, the adhesion, growth and viability of human osteoblast-like MG 63 cells in cultures on oxidized surfaces of a β-TiNb alloy were investigated and compared with the cell behavior on thermally oxidized Ti, i.e. a metal commonly used for constructing bone implants. Four experimental groups of samples were prepared: Ti or TiNb samples annealed to 600°C for 60min in a stream of dry air, and Ti and TiNb samples treated in Piranha solution prior to annealing. We found that on all TiNb-based samples, the cell population densities on days 1, 3 and 7 after seeding were higher than on the corresponding Ti-based samples. As revealed by XPS and Raman spectroscopy, and also by isoelectric point measurements, these results can be attributed to the presence of T-Nb2O5 oxide phase in the surface of the alloy sample, which decreased its negative zeta (ζ)-potential in comparison with zeta (ζ)-potential of the Ti sample at physiological pH. This effect was tentatively explained by the presence of positively charged defects acting as Lewis sites of the surface Nb2O5 phase. Piranha treatment slightly decreases the biocompatibility of the samples, which for the alloy samples may be explained by a decrease in the number of defective sites with this treatment. Thus, the presence of Nb and thermal oxidation of β-stabilized Ti alloys play a significant role in the increased biocompatibility of TiNb alloys.

In this presented study, poly(acrylamide-glycidyl methacrylate) [poly(AAm-GMA)] cryogels were synthesized by cryopolymerization technique at sub-zero temperature. Prepared cryogels were then functionalized with iminodiacetic acid (IDA) and chelated with Fe(3+) ions in order produce the metal chelate affinity matrix. Synthesized cryogels were characterized with FTIR, ESEM and EDX analysis, and it was found that the cryogel had sponge like structure with interconnected pores and their pore diameter was about 200μm. Fe(3+) chelated poly(AAm-GMA)-IDA cryogels were used for the adsorption of catalase and optimum adsorption conditions were determined by varying the medium pH, initial catalase concentration, temperature and ionic strength. Maximum catalase adsorption onto Fe(3+) chelated poly(AAm-GMA)-IDA cryogel was found to be 12.99mg/g cryogel at 25°C, by using pH5.0 acetate buffer. Adsorbed catalase was removed from the cryogel by using 1.0M of NaCl solution and desorption yield was found to be 96%. Additionally, reusability profile of the Fe(3+) chelated poly(AAm-GMA)-IDA cryogel was also investigated and it was found that, adsorption capacity of the cryogels didn't decrease significantly at the end of the 40 reuses. Catalase activity studies were also tested and it was demonstrated that desorbed catalase retained 70% of its initial activity. Copyright © 2015 Elsevier B.V. All rights reserved.

Coronary Artery Stents have been the preferred form of treatment for vascular occlusive disease, due to the minimally invasive surgical procedure, post-operative recovery time and cost, when compared to open coronary bypass surgery. The cellular response upon applying an AC electric field to type 316LM Stainless Steel stent mimics was investigated in this paper. The highest RBC adhesion was observed at voltages higher than 88mV and lower than 74mV. Their unique alignment along the lines of fracture on the stent surface at 88mV was a phenomenon caused by an increase in electrical conductivity in these regions. Being able to control RBC adhesion may have various clinical implications such as inhibition of thrombus formation, and provide a basis to analyse whether electric fields may be applied to cancer therapy as well. Copyright © 2014 Elsevier B.V. All rights reserved.

Pure iron has been proven to be a potential biodegradable metal, but its degradation rate was too slow. To accelerate its biodegradation, micro-patterned Au disc films were deposited on the surface of pure iron by vacuum sputtering. The influence of Au disc films on the degradation of pure iron matrix in vitro was investigated in the present study. Electrochemical measurement results indicated that the corrosion current density of pure iron coated with micro-patterned Au disc films in Hank's solution was 4 times larger than that of the uncoated one, while the difference between the influences of micro-patterned Au discs with different diameters on the corrosion rate of pure iron was insignificant. Immersion test indicated that the corrosion depth for pure iron coated with Au disc films was about three times as that of bare pure iron. Both electrochemical test and immersion test revealed that the corrosion of pure iron matrix coated with Au disc array became more uniform. Copyright © 2014 Elsevier B.V. All rights reserved.

Polymeric microspheres containing aceclofenac were prepared by single emulsion (oil-in-water) solvent evaporation method using response surface methodology (RSM). Microspheres were prepared by changing formulation variables such as the amount of Eudragit® RS100 and the amount of polyvinyl alcohol (PVA) by statistical experimental design in order to enhance the encapsulation efficiency (E.E.) of the microspheres. The resultant microspheres were evaluated for their size, morphology, E.E., and in vitro drug release. The amount of Eudragit® RS100 and the amount of PVA were found to be significant factors respectively for determining the E.E. of the microspheres. A linear mathematical model equation fitted to the data was used to predict the E.E. in the optimal region. Optimized formulation of microspheres was prepared using optimal process variables setting in order to evaluate the optimization capability of the models generated according to IV-optimal design. The microspheres showed high E.E. (74.14±0.015% to 85.34±0.011%) and suitably sustained drug release (minimum; 40% to 60%; maximum) over a period of 12h. The optimized microspheres formulation showed E.E. of 84.87±0.005 with small error value (1.39). The low magnitudes of error and the significant value of R(2) in the present investigation prove the high prognostic ability of the design. The absence of interactions between drug and polymers was confirmed by Fourier transform infrared (FTIR) spectroscopy. Differential scanning calorimetry (DSC) and X-ray powder diffractometry (XRPD) revealed the dispersion of drug within microspheres formulation. The microspheres were found to be discrete, spherical with smooth surface. The results demonstrate that these microspheres could be promising delivery system to sustain the drug release and improve the E.E. thus prolong drug action and achieve the highest healing effect with minimal gastrointestinal side effects. Copyright © 2014 Elsevier B.V. All rights reserved.

The voltammetric behavior of a carbon paste electrode modified with Co(II)-exchanged zeolite A (Co(II)-A/ZMCPE) for determination of acetaminophen was studied. The proposed electrode showed a diffusion controlled reaction with the electron transfer rate constant (Ks) of 0.44s(-1) and charge transfer coefficient of 0.73 in the absence of acetaminophen. A linear voltammetric response was obtained in the range of 0.1 to 190μmolL(-1) of acetaminophen [r(2)=0.9979, r=0.9989 (n=10)] with a detection limit of 0.04μmolL(-1). The method was successfully applied to the analysis of acetaminophen in some drugs. Copyright © 2015 Elsevier B.V. All rights reserved.

Understanding the magnetic properties of magnetotactic bacteria (MTBs) is of great interest in fields of life sciences, geosciences, biomineralization, biomagnetism, and planetary sciences. Acidithiobacillus ferrooxidans (At. ferrooxidans), obtaining energy through the oxidation of ferrous iron and various reduced inorganic sulfur compounds, can synthesize intracellular magnetite magnetosomes. However, the magnetic properties of such microorganism remain unknown. Here we used transmission electronmicroscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD) assay, vibrating sample magnetometer (VSM), magneto-thermogravimetric analysis (MTGA), and low temperature magnetometry to comprehensively investigate the magnetic characteristics of At. ferrooxidans. Results revealed that each cell contained only 1 to 3 magnetite magnetosomes, which were arranged irregularly. The magnetosomes were generally in a stable single-domain (SD) state, but superparamagnetic (SP) magnetite particles were also found. The calcined bacteria exhibited a ferromagnetic behavior with a Curie Temperature of 454°C and a coercivity of 16.36 mT. Additionally, the low delta ratio (δFC/δZFC=1.27) indicated that there were no intact magnetosome chains in At. ferrooxidans. Our results provided the new insights on the biomineralization of bacterial magnetosomes and magnetic properties of At. ferrooxidans.