Coating of an apatite layer on polyamide films containing sulfonic groups by a biomimetic process.

Coating organic polymers with hydroxyapatite is an attractive method for the development of materials for medical applications, as it allows hydroxyapatite to show its unique biological properties such as its ability for bone bonding and protein adsorption. The biomimetic process focuses attention on fabricating such hydroxyapatite-polymer hybrids, where bone-like apatite is deposited on an organic polymer surface in solutions mimicking physiological conditions. In this process, a bone-like apatite layer can be coated onto organic substrates either by using a simulated body fluid (SBF), which has ion concentrations nearly equal to those of human extracellular fluid, or by using fluids that are supersaturated with respect to apatite at ambient conditions. We previously reported that apatite was deposited on polyamide films containing carboxyl groups in a solution mimicking body fluid, when they were incorporated with calcium salts. In the present study, to find an alternative functional group effective in apatite formation, we examined the apatite-forming ability of polyamide films containing sulfonic groups in the same solution. It was found that the polyamide film containing sulfonic groups could deposit apatite on its surface in the solution when the film was incorporated with calcium salts. These results show that the sulfonic group also acts as a functional group, and is as effective for apatite deposition in the body environment as the carboxyl group.

Preparation of monolithic chelating adsorbent inside a syringe filter tip for solid phase microextraction of trace elements in natural water prior to their determination by ICP-MS.

A syringe-based sample pretreatment tool, named herein "tip-in chelating monolith", has been developed for simple and facile solid phase microextraction (SPME) of trace elements in natural waters. The tip-in chelating monolith was directly prepared within the confines of a commercially available syringe filter tip by a two-step process: (1) in situ polymerization of a monomer solution consisting of 22.5% glycidyl methacrylate (GMA), 7.5% ethylene glycol dimethacrylate (EDMA), 35% 1-propanol, 28% 1,4-butanediol, and 7% water and (2) its subsequent modification with 1molL(-1) of iminodiacetate solution (adjusted to pH 10) via ring-opening reaction of epoxide. The adsorption properties of the tip-in chelating monolith thus obtained were evaluated through an adsorption/desorption experiment, where the effects of sample solution pH and eluent on the SPME of trace metals and metalloids were systematically examined. Consequently, when sample solution pH was adjusted to 5.0 and 0.9mL of 2molL(-1) nitric acid was used as an eluent, good recoveries of more than 80% were obtained for 27 elements in a single-step extraction. The proposed SPME method was validated through the analysis of two river water certified reference materials (CRMs: JSAC 0301-1 and NMIJ 7201-a). After 50-fold preconcentration (from 50mL of the original river water sample to 1.0mL of final analysis solution), 22 trace elements including Ti, Fe, Co, Ni, Cu, Ga, Cd, Sn and REEs were quantitatively determined by inductively coupled plasma mass spectrometry (ICP-MS). The analytical detection limits were in the range from 0.000003microgL(-1) for Ho to 0.18microgL(-1) for Fe. Good agreement of the observed values with the certified or reference values indicates that the proposed SPME using the tip-in chelating monolith is practically applicable.

An in-syringe La-coprecipitation method for the preconcentration of oxo-anion forming elements in seawater prior to an ICP-MS measurement.

A lanthanum (La) coprecipitation method with low sample consumption was explored for the preconcentration of oxo-anion forming elements prior to a measurement by inductively coupled plasma mass spectrometry (ICP-MS). The preconcentration procedure was composed of two main steps: (1) the formation of a coprecipitate with the lowest possible La and (2) the redissolution of target analytes with minimal use of nitric acid, and the elimination of high concentration La from the analysis sample. Each step was performed in a 25 mL-volume syringe to reduce the sample consumption and to avoid contamination from the experimental environment. Various parameters, such as the concentration and volume of La added into the sample solution, the precipitation pH, the aging time, and the volume of HNO(3) were optimized to obtain good recoveries and high detection sensitivities for V, As, Sb, and W, which could be hardly recovered by solid-phase extraction using a chelating resin. The obtained method was evaluated through the analysis of seawater reference materials (CASS-4 and NASS-5). The recoveries exceeded 80%, and the observed values were in good agreement with the certified values.

In vitro apatite formation on polyamide containing carboxyl groups modified with silanol groups.

Modification of organic polymer with silanol groups in combination with calcium salts enables the polymer to show bioactivity, that is, the polymer forms apatite on its surface after exposure to body environment. However, how modification with silanol groups influences ability of apatite formation on the polymer substrate and adhesive strength between polymer and apatite is not yet known. In the present study, polyamide containing carboxyl groups was modified with different amounts of silanol groups, and its apatite-forming ability in 1.5SBF, which contained ion concentrations 1.5 times those of simulated body fluid (SBF), was examined. The rate of apatite formation increased with increasing content of silanol groups in the polyamide films. This may be attributed to enhancement of dipole interactions. A tendency for the adhesive strength of the apatite layer on the polyamide film to be decreased with increasing content of silanol groups was observed. This may be attributed to swelling in 1.5SBF and having a high degree of shrinkage after drying. These findings clearly show that modification of organic polymers with the functional groups induces apatite deposition, and also determines the adhesive strength of the apatite layer to the organic substrates.

Removal of formaldehyde by hydroxyapatite layer biomimetically deposited on polyamide film.

Some harmful volatile organic compounds (VOCs), such as formaldehyde, are regulated atmospheric pollutants. Therefore, development of a material to remove these VOCs is required. We focused on hydroxyapatite, which had been biomimetically coated on a polyamide film, as an adsorbent and found that formaldehyde was successfully removed by this adsorbent. The amount of formaldehyde adsorbed increased with the area of the polyamide film occupied by hydroxyapatite. The amount of adsorbed formaldehyde and its rate of adsorption were larger for hydroxyapatite deposited on polyamide film than for the commercially available calcined hydroxyapatite powder. This high adsorption ability is achieved by the use of nanosized particles of hydroxyapatite with low crystallinity and containing a large number of active surface sites. Therefore, hydroxyapatite biomimetically coated on organic substrates can become a candidate material for removing harmful VOCs such as formaldehyde.

Apatite deposition on polyamide films containing carboxyl group in a biomimetic solution.

The development of organic-inorganic hybrids composed of hydroxyapatite and organic polymers is attractive because of their novelty in being materials that show a bone-bonding ability, i.e. bioactivity, and because they have mechanical properties similar to those of natural bone. The biomimetic process has received much attention for fabricating such a hybrid, where bone-like apatite is deposited under ambient conditions on polymer substrates in a simulated body fluid (SBF) having ion concentrations nearly equal to those of human extracellular fluid or related solutions. It has been shown that the carboxyl group is effective for inducing heterogeneous nucleation of apatite in the body. In the present study, apatite deposition on polyamide films containing various numbers of carboxyl groups was investigated in 1.5 SBF, which had ion concentrations 1.5 times those of a normal SBF. The effect of incorporation of calcium chloride on the formation of apatite was examined. Polyamide films containing or=40 mass % CaCl(2) formed apatite on their surfaces in 1.5 SBF. The ability of the modified film to form an apatite layer increased, and the adhesion of the apatite layer bonded to the film improved, with increasing carboxyl group content. It is concluded that novel apatite-polyamide hybrids can be prepared by a biomimetic process.