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Abstract: Calcium phosphate cements (CPCs) are frequently used as bone substitute material. Despite their superior clinical handling and excellent biocompatibility, they exhibit poor degradability, which limits bone ingrowth into the implant. Microspheres were prepared from poly(d,l-lactic-co-glycolic acid) (PLGA) and included in injectable CPCs as porogens in order to enhance its macroporosity after the polymeric microspheres had degraded. Upon degradation of the PLGA microspheres, acid is produced that enhances the dissolution rate of the CPC. However, the effect of the characteristics of PLGA microspheres on the degradation rate of CPCs has never been studied before. Therefore, the purpose of the current study was to investigate the dependence of CPC degradation on the chemical and morphological characteristics of incorporated PLGA microspheres. With respect to the chemical characteristics of the PLGA microspheres, the effects of both PLGA molecular weight (5, 17 and 44kDa) and end-group functionalization (acid-terminated or end-capped) were studied. In addition, two types of PLGA microspheres, differing in morphology (hollow vs. dense), were tested. The results revealed that, although both chemical parameters clearly affected the polymer degradation rate when embedded as hollow microspheres in CPC, the PLGA and CPC degradation rates were mainly dependent on the end-group functionalization. Moreover, it was concluded that dense microspheres were more efficient porogens than hollow ones by increasing the CPC macroporosity during in vitro incubation. By combining all test parameters, it was concluded that dense PLGA microspheres consisting of acid-terminated PLGA of 17kDa exhibited the highest and fastest acid-producing capacity and correspondingly the highest and fastest amount of porosity. In conclusion, the data presented here indicate that the combination of dense, acid-terminated PLGA microspheres with CPC emerges as a successful combination to achieve enhanced apatitic CPC degradation. [Copyright &y& Elsevier]

Abstract: Although extensive efforts have been devoted to the development of polymer–ceramic composites for bone repair, those developed thus far were not able to mimic the nanostructure of bone, partly because of the aggregated, microscale organization of the mineral component. As a consequence, homogenization and intermixing of organic and inorganic components remain a major engineering challenge for the development of functional, biomimetic bone-substituting composites. In the current study, various dispersants were evaluated for their potential to be used as biocompatible dispersants in the synthesis of biomimetic composites with a nanodispersed mineral phase. Based on sedimentation experiments, tribasic sodium citrate was selected as the most effective dispersant for the stabilization of calcium phosphate (CaP) suspensions. Specific adsorption of citrate anions onto CaP nanocrystals was shown to result in a strong increase in the negative surface charge of the CaP particles and consequently increased repulsive interparticle forces that were able to overcome attractive van der Waals forces. Using sodium citrate as dispersant at a CaP/citrate ratio of 4.0, CaP–gelatin nanocomposites were fabricated which displayed a nanostructured mineral phase without occurrence of microscale CaP particles. Consequently, aggregation and sedimentation of CaP mineral phase was reduced considerably. [Copyright &y& Elsevier]

Abstract: This study describes the effect of multilayered DNA coatings on (i) the formation of mineralized depositions from simulated body fluids (SBF); and (ii) osteoblast-like cell behavior with and without pretreatment in SBF. DNA coatings were generated using electrostatic self-assembly, with poly-d-lysine or poly(allylamine hydrochloride) as cationic polyelectrolytes, on titanium substrates. Coated substrates and non-coated controls were immersed in SBF with various compositions. The deposition of calcium phosphate was enhanced on multilayered DNA coatings as compared with non-coated controls, and was dependent on the type of cationic polyelectrolyte used in the build-up of the DNA coatings. Further analysis showed that the depositions consisted of carbonated apatite. Non-pretreated DNA coatings were found to have no effect on osteoblast-like cell behavior compared with titanium controls. On the other hand, SBF-pretreatment of DNA coatings affected the differentiation of osteoblast-like cells through an increased deposition of osteocalcin. The results of this study are indicative of the bone-bonding capacities of DNA coatings. Nevertheless, future animal experiments are required to provide conclusive evidence for the bioactivity of DNA coatings. [Copyright &y& Elsevier]

Abstract: The electrostatic spray deposition (ESD) technique was used for biomedical purposes in order to deposit calcium phosphate (CaP) coatings onto titanium substrates. The relationship between various deposition parameters and the chemical properties of deposited coatings was investigated in order to be able to deposit CaP coatings with tailored chemical characteristics. The results showed that the chemical properties of the coatings were determined by both physical, apparatus-related factors and chemical, solution-related parameters. By varying the processing parameters of the technique, several crystal phases and phase mixtures were obtained, ranging from carbonate-free phases such as meta- and pyrophosphates, monetite and various tricalcium phosphates to carbonate-containing phases such as various carbonate apatites and calcite. On the basis of these results, a chemical mechanism of coating formation was proposed. Essentially, the deposition of the various crystal phases was the result of an acid–base reaction between basic CO3 2− groups (originating from solvent decomposition reactions) and acidic HPO4 2− groups from an intermediate monetite (CaHPO4) phase of the CaP precipitate. The amount of carbonate incorporation (ranging from 0 to 15wt%) determined the crystal and molecular structure of the deposited coatings. [Copyright &y& Elsevier]

A novel coating technique, referred to as Electrostatic Spray Deposition (ESD), was used to deposit calcium phosphate (CaP) coatings with a variety of chemical properties. The relationship between the composition of the precursor solutions and the crystal and molecular structure of the deposited coatings was investigated by means of X-ray diffraction (XRD), Fourier-Transform Infrared Spectroscopy (FTIR) and Energy Dispersive Spectroscopy (EDS). It was shown that the relative Ca/P ratio in the precursor solution, the absolute precursor concentration, the acidity of the precursor solution and the type of Ca-precursor strongly influenced the chemical nature of the deposited CaP coatings. Various crystal phases and phase mixtures were obtained, such as carbonate apatite, β-TCP, Mg-substituted whitlockite, monetite, β/γ-pyrophosphate, and calcite.It was shown that carbonate plays an essential role in the chemical mechanism of coating formation. Carbonate is formed due to a decomposition reaction of organic solvents. Depending on deposition conditions, carbonate anions (a) react with acidic phosphate groups, (b) are incorporated into apatitic calcium phosphate phases, and (c) react with excessive Ca2+ cations in case of phosphate-deficient precursor solutions. [Copyright &y& Elsevier]

Electrostatic spray deposition (ESD) is a recently developed technique to deposit a calcium phosphate (CaP) coating upon substrates. With this technique, an organic solvent containing calcium and phosphate is pumped through a nozzle. Between the nozzle and substrate a high voltage is applied. As a consequence, droplets coming out the nozzle disperse into a spray, and this spray is deposited upon the substrate. When the solvent has evaporated, a coating is formed on the substrate. ESD allows for a variation in coating composition and morphology. Titanium alloy (TiAl6V4) substrates were coated with a CaP layer using two different methods; radio frequency magnetron sputtering, and ESD. These surfaces were characterized with X-ray diffraction, Fourier transform infrared spectroscopy, an universal surface tester, scanning electron microscopy, and energy dispersive spectrometry. Subsequently, bone marrow cells were isolated from rat femora and cultured 1, 4, 8, 14 and 16 days. Cell proliferation, alkaline phosphatase activity, and osteocalcin concentration were assayed. RT-PCR was done for collagen type I and osteocalcin. SEM was also performed to observe cellular behaviour during culture. Two separate runs of the experiment were performed. In the first run, osteoblast-like cells on both CaP coatings showed similar results in all assays. In the second run, proliferation and osteogenic expression had increased on ESD coatings. On basis of these results, we conclude that the novel ESD coating behaved similar to, or even better than the known RF magnetron sputter coating. Thus, ESD could be a valid addition to already existing CaP coating processes. [Copyright &y& Elsevier]