Calcium phosphate, due to its similarity to the inorganic fraction of mineralized tissues, has played a key role in many areas of medicine, in particular, regenerative medicine and orthopedics. It has also found application in conservative dentistry and dental surgery, in particular, as components of toothpaste and mouth rinse, coatings of dental implants, cements, and bone substitute materials for the restoration of cavities in maxillofacial surgery. In dental applications, the most important role is played by hydroxyapatite and fluorapatite, i.e., calcium phosphates characterized by the highest chemical stability and very low solubility. This paper presents the role of both apatites in dentistry and a review of recent achievements in the field of the application of these materials.

A series of nanocrystalline calcium hydroxyapatites was prepared by dry milling and characterized using proton and 31P MAS NMR, TEM, and TGA methods. The samples contained stubby rod-shaped crystals, which length and width varied in the 130–30 and 95–20 nm ranges, respectively. It was confirmed that concentration of structural hydroxyl groups in nanocrystalline apatites decreases with the decreasing crystal size. In the series of the studied apatites, the decrease was from 86 to ca. 50 % in reference to stoichiometric apatite. Water was found in the surface hydrated layer and in the c-axis channels, in which compartments existed as adsorbed and structural, respectively. Molecules of the adsorbed water were capable of moving from the crystal surface into the lattice c-axis channels of apatite. This process introduced considerable structural disorder within and around those channels and reduced the content of the structural hydroxyl groups, particularly in the region underneath the apatite crystal surface.Electronic supplementary materialThe online version of this article (doi:10.1007/s11051-013-1868-y) contains supplementary material, which is available to authorized users.

Nanocrystalline hydroxyapatite containing selenite ions (SeHA; 9.6 wt.% of selenium) was synthesized using wet method and subject to careful physicochemical analysis by powder X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, solid-state nuclear magnetic resonance, wavelength dispersive X-ray fluorescence, and inductively coupled plasma optical emission spectrometry. SeHA was then used to develop the selenium-containing hydroxyapatite/alginate (SeHA/ALG) composite granules. Risedronate sodium (RIS) was introduced to the obtained spherical microgranules of a size of about 1.1–1.5 mm in 2 ways: during the granules’ preparation (RIS solution added to a suspension of ALG and SeHA), and as a result of SeHA/ALG granules soaking in aqueous RIS solution. The analysis made using 13 C and 31 P cross-polarization magic angle spinning nuclear magnetic resonance confirmed the presence of RIS and its interaction with calcium ions. Then, the release of selenium (inductively coupled plasma optical emission spectrometry) and RIS (high-performance liquid chromatography) from microgranules was examined. Moreover, cytotoxicity of fabricated granules was assessed by MTT test. Selenium release was biphasic: the first stage was short and ascribed to a “burst release” probably from a hydrated surface layer of SeHA crystals, while the next stage was significantly longer and ascribed to a sustained release of selenium from the crystals’ interior. The study showed that the method of obtaining microgranules containing RIS significantly affects its release profile. Performed cytotoxicity test revealed that fabricated granules had high antitumor activity against osteosarcoma cells. However, because of the “burst release” of selenium during the first 10 h, the granules significantly reduced viability of normal osteoblasts as well.

Hydroxyapatites (HAs), as materials with a similar structure to bone minerals, play a key role in biomaterials engineering. They have been applied as bone substitute materials and as coatings for metallic implants, which facilitates their osseointegration. One of the beneficial characteristics of HA, when used to create biocompatible materials with improved physicochemical or biological properties, is its capacity for ionic substitution. The aim of the study was to present the current state of knowledge about HAs containing selenate ions IV or VI. The enrichment of HAs with selenium aims to create a material with advantageous effects on bone tissue metabolism, as well as having anticancer and antibacterial activity. The work is devoted to both methods of obtaining Se-HA and an evaluation of its chemical structure and physicochemical properties. In addition, the biological activity of such materials in vitro and in vivo is discussed.Pure, stoichiometric HA crystallizes in a monoclinic system, space group P2 1 /b [5]. However, it is worth mentioning that HA like this is rare and very difficult to obtain by synthesis.

Hydroxyapatite (HA) powders enriched with silver or gallium ions or both were synthesized by two different routes: standard precipitation and the solid-state method. The powders were characterized by using several methods: inductively coupled plasma optical emission spectrometry (ICP-OES), powder X-ray diffractometry (PXRD), transmission electron microscopy (TEM), infrared spectroscopy (FT-IR) and solid-state nuclear magnetic resonance spectroscopy (ssNMR). The effects of enrichment of the HAs in Ag+ or Ga3+ or both on in vitro cytotoxicity and microbiological activity were discussed. PXRD experiments showed that the samples obtained by the wet method consisted of single-phase nanocrystalline HA, while the samples prepared via the solid-state method are microcrystalline with a small amount of calcium oxide. The introduction of higher amounts of silver ions was found to be more effective than enriching HA with small amounts of Ag+. Gallium and silver ions were found not to affect the lattice parameters. Ga3+ affected the crystallinity of the samples as well as the content of structural hydroxyl groups. Among samples synthesized by the wet method, only one (5Ag-HAw) was cytotoxic, whereas all Ga-containing samples obtained by the dry method showed cytotoxicity. In the preliminary antimicrobial test all the materials containing “foreign” ions showed high antibacterial activity.

New approaches to the synthesis of 4,7-dichloro-1,10-phenanthrolines and their corresponding 9H-carbazol-9-yl-, 10H-phenothiazin-10-yl- and pyrrolidin-1-yl derivatives were developed. Their properties have been characterized by a combination of several techniques: MS, HRMS, GC-MS, electronic absorption spectroscopy and multinuclear NMR in both solution and solid state including 15N CP/MAS NMR. The structures of 5-fluoro-2,9-dimethyl-4,7-di(pyrrolidin-1-yl)-1,10-phenanthroline (5d), 4,7-di(9H-carbazol-9-yl)-9-oxo-9,10-dihydro-1,10-phenanthroline-5-carbonitrile (6a) and 4,7-di(10H-phenothiazin-10-yl)-1,10-phenanthroline-5-carbonitrile (6b) were determined by single-crystal X-ray diffraction measurements. The nucleophilic substitutions of hydrogen followed by oxidation produced compounds 6a and 6b. The electrochemical properties of selected 1,10-phenanthrolines were investigated using cyclic voltammetry and compared with commercially available reference 1,10-phenanthrolin-5-amine (5l). The spatial distribution of frontier molecular orbitals of the selected compounds has been calculated by density functional theory (DFT). It was shown that potentials of reduction and oxidation were in consistence with the level of HOMO and LUMO energies.

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