Electrodeposition of indium from the ionic liquid trihexyl(tetradecyl)phosphonium chloride.

The electrochemical behavior of indium in the ionic liquid trihexyl(tetradecyl)phosphonium chloride (Cyphos IL 101) was studied. Cyphos IL 101 first had to be purified, as the impurities present in commercial Cyphos IL 101 interfered with the electrochemical measurements. Electrochemical deposition of indium metal from this electrolyte occurs without hydrogen evolution, increasing the cathodic current efficiency compared to deposition from water and avoiding porosity within the deposited metal. Indium(iii) is the most stable oxidation state in the ionic liquid. This ion is reduced in two steps, first from indium(iii) to indium(i) and subsequently to indium(0). The high thermal stability of Cyphos IL 101 allowed the electrodeposition of indium at 120 °C and 180 °C. At 180 °C indium was deposited as liquid indium which allows for the easy separation of the indium and the possibility to design a continuous electrowinning process. On molybdenum, indium deposits as liquid droplets even below the melting point of indium. This was explained by the combination of melting point depression and undercooling. The possibility to separate indium from iron and zinc by electrodeposition was tested. It is possible to separate indium from zinc by electrodeposition, but iron deposits together with indium.

Thermal stability of trihexyl(tetradecyl)phosphonium chloride.

Dynamic TGA studies of phosphonium ionic liquids have reported thermal stabilities of 300 °C or higher for these compounds. This is often an overestimation of the real thermal stability. The chosen technique as well as the experimental parameters can influence the thermal stability. In this paper, the thermal stability of commercially available Cyphos IL 101 is studied. The effect of the nature of the atmosphere (air or inert gas), the purity of the sample, the heating rate and presence of a metal on the short-term and long-term stability of commercial Cyphos IL 101 is investigated. The thermal decomposition products are characterized using thermogravimetric analysis coupled to mass spectrometry (TGA-MS). Impurities present and higher heating rates lead to an under- and overestimation of the thermal stability, respectively. The presence of oxygen leads to a lower thermal stability. In contrast, adding metal chlorides to the ionic liquid causes an increase in the thermal stability. The chloride anions are coordinated to the metal ion, so that the Lewis basicity of the anions is reduced. Also this paper gives insights in the behavior of Cyphos IL 101 at high temperatures, which is of relevance for possible application of this ionic liquid in high-temperature industrial processes.

Speciation of indium(iii) chloro complexes in the solvent extraction process from chloride aqueous solutions to ionic liquids.

Most metal extraction studies focus on the kinetics, the maximum loading and the extraction equilibrium, while structural information on the extracted complexes has been limited. This paper concerns the nature of the indium(iii) chloride complexes, present in the organic and aqueous phase during the solvent extraction of indium(iii) from an aqueous HCl solution by undiluted ionic liquids Cyphos® IL 101 and Aliquat® 336. In an aqueous HCl solution (0-12 M), indium(iii) exists as octahedral mixed complexes, [In(H2O)6-nCln]3-n (0 ≤ n ≤ 6). EXAFS and 115In NMR were used to characterize these species. The stoichiometric composition of the extracted complexes, which is estimated from viscosity and maximum loading studies and confirmed by EXAFS, is unaffected by the HCl concentration in the aqueous phase. Indium(iii) is present in the ionic liquid phase as the tetrahedral [InCl4]- complex. Based on the speciation results an extraction mechanism is proposed.

A Modular Approach To Study Protein Adsorption on Surface Modified Hydroxyapatite.

Biocompatible inorganic nano- and microcarriers can be suitable candidates for protein delivery. This study demonstrates facile methods of functionalization by using nanoscale linker molecules to change the protein adsorption capacity of hydroxyapatite (HA) powder. The adsorption capacity of bovine serum albumin as a model protein has been studied with respect to the surface modifications. The selected linker molecules (lysine, arginine, and phosphoserine) can influence the adsorption capacity by changing the electrostatic nature of the HA surface. Qualitative and quantitative analyses of linker-molecule interactions with the HA surface have been performed by using NMR spectroscopy, zeta-potential measurements, X-ray photoelectron spectroscopy, and thermogravimetric analyses. Additionally, correlations to theoretical isotherm models have been calculated with respect to Langmuir and Freundlich isotherms. Lysine and arginine increased the protein adsorption, whereas phosphoserine reduced the protein adsorption. The results show that the adsorption capacity can be controlled with different functionalization, depending on the protein-carrier selections under consideration. The scientific knowledge acquired from this study can be applied in various biotechnological applications that involve biomolecule-inorganic material interfaces.

Implantable (bio)polymer coated titanium scaffolds: a review.

In the current review we aim to give an overview of the state of the art of the research on (bio)polymer functionalised titanium implants for bone tissue engineering applications. After a short introduction on bone tissue engineering and the requirements the applied materials have to meet, an extensive discussion on titanium in bone tissue engineering will be given. Starting with a short description of both the titanium bulk and surface properties, the requirement for surface modified titanium will be highlighted. The discussion will encompass inorganic and organic chemical modifications and a combination thereof with a focus on the organic modifications. Within the latter type of modification, physical adsorption, physical incorporation and covalent immobilisation will be compared. In the final part of the review an overview will be given of the fabrication and characterisation of three-dimensional titanium scaffolds.

Vancomycin release from poly(D,L-lactic acid) spray-coated hydroxyapatite fibers.

The influence of the poly(D,L-lactic acid) (PDLLA) coating thickness on the in vitro vancomycin release from a hydroxyapatite (HA) carrier was studied. Microporous HA fibers with a porosity of 51 v% and an average pore diameter of 1.0 µm were fabricated by a diffusion-induced phase separation technique. They were loaded with 38 mg vancomycin hydrochloride (VH)/gHA, and their cylindrical shape enabled the application of the spray coating technique for the deposition of uniform PDLLA coating thicknesses, varying from 6.5 µm to 28 µm. The resulting in vitro VH release varied from a complete release within 14 days for 6.5 µm coatings to a release of 23% after 28 days for 28 µm coatings. It was clear that the VH release rate from a HA fiber can be adjusted by varying the PDLLA coating thickness. Microbiological tests of these fibers against a methicillin-resistant Staphylococcus aureus (MRSA) isolate pointed to the importance of the initial burst release and confirmed that the released antibiotics had the potential to interfere with S. aureus biofilm formation.

Evaluation of bone regeneration with an injectable, in situ polymerizable Pluronic F127 hydrogel derivative combined with autologous mesenchymal stem cells in a goat tibia defect model.

In situ forming bone substitute materials are attractive candidates for filling irregularly shaped defects. In this study, a chemically modified form of the Pluronic F127 hydrogel was used. Similar to the parent form, this derivative underwent a sol-gel transition in the body and additional radical curing resulted in a stable three-dimensional network gel with a controllable degradation rate. An extra cell source of autologous bone marrow-derived mesenchymal stem cells was mixed with the hydrogel to increase the ossification process, when implanted in noncritical size unicortical tibia defects. These cells were cultured and predifferentiated on two types of cell carrier systems, that is, gelatin CultiSpher-S microcarriers and hydroxyapatite tubular carriers. Radiographic and histological evaluation revealed that bone regeneration was comparable in the defects with the bone substitute compositions and the untreated control defects at 2 and 4 weeks postimplantation and that newly formed bone originated from the cells on the CultiSpher-S carriers. This resulted, 6 and 8 weeks postimplantation, in faster bone repair in the defects filled with the hydrogel plus CultiSpher-S carriers in comparison to the control defects. Surprisingly, there was no formation of new bone originating from the hydroxyapatite carriers. The hydrogel by itself seemed to stimulate the natural repair process.

Quantitative screening of engineered implants in a long bone defect model in rabbits.

We have standardized a long bone defect model in rabbits to quantitatively compare the bone healing performance of engineered biological implants and have tested the bone healing efficiency of porous cylindrical scaffolds (ø-h, 6-20 mm [diameter 6 mm, height 20 mm] porosity, 70%) that were produced from hydroxyapatite (HA), titanium (Ti), and a novel biodegradable polymer-bioceramic composite (PH70alphaTCP). Scaffolds were perfused with or without 20 x 10(6) rabbit periosteal cells (RPCs) in a bioreactor and implanted in a standardized 2 cm defect in rabbit tibiae. X-rays revealed that new bone had formed at 3 weeks after creation of the defects. At sacrifice after 10 weeks, bone corticalization was observed in the majority of animals. Although PH70alphaTCP scaffolds did not inhibit callus formation, histomorphometric analysis revealed that there was no bone within the biomaterial, in contrast to HA and Ti scaffolds (bone volume ranging from 10% to 25%). We found that Ti and HA scaffold had good osteoconductive properties, but only HA scaffolds seeded with RPCs contributed to long bone mechanical functionality, with the maximum energy and angle being 308% and 155% greater than in control defects without scaffold.