Solid‐State NMR Study of Mn2+ for Ca2+ Substitution in Thermally Processed Hydroxyapatites

In the present study calcium hydroxyapatites enriched at 0.08 wt% in Mn²⁺ ions (Mn–HA) and their unsubstituted forms (HA) were synthesized using the same standard wet chemical route. Mn‐HA and HA were both calcined at 800°C to give Mn‐HAc and HAc, respectively or sintered at 1250°C, to give Mn‐HAs and HAs, respectively. The influence of the heat treatment on physicochemical properties of Mn‐HA was investigated using powder X‐ray diffraction (PXRD), scanning, and transmission electron microscopy (SEM and TEM), and solid‐state nuclear magnetic resonance (ssNMR). Mn‐HAc and Mn‐HAs were compared to each other and to HAc and HAs, respectively. Assignment of the proton ssNMR peaks from high‐temperature‐treated apatites has been revised. It was found that Mn–HAc and HAc were nanocrystalline, while Mn‐HAs and HAs comprised micrometer sized, partially fused particles (SEM and TEM). PXRD and ssNMR demonstrated that the incorporation of Mn²⁺ into the crystal lattice of hydroxyapatite significantly facilitates its dehydroxylation and decomposition to oxyhydroxyapatite during calcination at 800°C, and induces its transformation to tetracalcium phosphate (TTCP) and alpha‐tricalcium phosphate (α‐TCP) at 1250°C. Contamination by CaO has also been detected. The ¹H→³¹P NMR cross‐polarization experiments have indicated that the Mn²⁺ ions preferentially occupied the Ca(I) position in the crystallographic unit cell of Mn‐HAc. In Mn‐HAs, the Mn²⁺ ions were evenly distributed between the Ca(I) and Ca(II) positions.     

Study on the new bone cement based on calcium sulfate and Mg,CO3 doped hydroxyapatite

In order to improve some features of bone substitutes the new self-setting composite-type implant material based on Mg²⁺/CO₃^2? co-substituted hydroxyapatite (Mg-CHA) and calcium sulfate hemihydrate (CSH) was developed. Synthetic hydroxyapatites doped with small amounts of additives found in natural bone (e.g. Mg²⁺ and CO₃^2?) are regarded as promising components of calcium phosphate bone cements (CPCs). The CPCs, now available on the market, due to low resorption rate are too stable to permit material degradation and are slowly replaced by the newly formed bone. To improve cement resorption we used calcium sulfate which is a well-known biodegradable and biocompatible bone defect filler. Combining properties of Mg-CHA and CSH allowed developing a new, promising, easy shapeable implant material with high potential for bone regeneration.     

Novel conventional and chelating anion exchange resins with amino ligands for sorption of silver

ABSTRACT

The polymeric resins containing diethylenetriamine, tetraethylenepentamine, 2-(diethylamino)ethanol, 1-methylimidazole, and 1,2-dimethylimidazole ligands have been synthesized from vinylbenzyl chloride-divinylbenzene copolymers and used in the removal of Ag(I) from chloride solution. The best Ag(I) sorption was reached in the case of 1-methylimidazole resin. Resins retain their capacity towards Ag(I) in five consecutive sorption/desorption cycles. The resins with imidazole ligands were highly selective for Ag(I) from synthetic chloride solution and they did not sorb chloride complexes of Cu(II). Additionally, the recovery of Ag(I) was tested from real chloride solution coming from leaching of the copper concentrate from Lubin Concentrator (KGHM Polska Mied? S.A.).     

Characterization of new class III lantibiotics--erythreapeptin, avermipeptin and griseopeptin from Saccharopolyspora erythraea, Streptomyces avermitilis and Streptomyces griseus demonstrates stepwise N-terminal leader processing

Lantibiotics are a large group of ribosomally synthesized peptides post-translationally modified to incorporate the amino acid lanthionine. They are classified, according to their biosynthetic pathway and bioactivity, into three major subtypes. Of Actinomycetes type III lantibiotics, only four peptides (SapB, SapT, LabA1, and LabA2) have been described and structurally characterized, although homologous gene clusters are abundant in other Actinomycetes. All these gene clusters share a similar architecture with a characteristic Ser/Ser/Cys motif in precursor peptides, which has previously been suggested to act as a precursor for lanthionine (SapB) and labionin (LabA2) rings. Mass spectrometry screening led to the discovery and characterization of three new representatives of type III lantibiotics: Avermipeptin (Avi), Erythreapeptin (Ery), and Griseopeptin (Gri) from Streptomyces avermitilis DSM 46492, Saccharopolyspora erythraea NRRL 2338, and Streptomyces griseus DSM 40236, respectively. Apart from the assignment of these peptides to their corresponding gene clusters, additional investigations on Avi, Ery and Gri peptides indicate stepwise leader processing by putative aminopeptidase-like protease(s), thus yielding mixtures of differently N-terminal-processed lantibiotic peptides. Similar peptide processing was observed for a heterologously expressed eryth biosynthetic gene cluster expressed in a Streptomyces host system. Remarkably, all isolates of the new type III lantibiotics contain both the amino acids lanthionine and labionin, thus implying dual-mode cyclase activity of the processing lyase-kinase-cyclase enzymes. These findings have implications for the structures and maturation of other type III lantibiotics from Actinomycetes.     

Al-Tolerant Barley Mutant hvatr.g Shows the ATR-Regulated DNA Damage Response to Maleic Acid Hydrazide

ATR, a DNA damage signaling kinase, is required for cell cycle checkpoint regulation and detecting DNA damage caused by genotoxic factors including Al³⁺ ions. We analyzed the function of the HvATR gene in response to chemical clastogen-maleic acid hydrazide (MH). For this purpose, the Al-tolerant barley TILLING mutant hvatr.g was used. We described the effects of MH on the nuclear genome of hvatr.g mutant and its WT parent cv. “Sebastian”, showing that the genotoxic effect measured by TUNEL test and frequency of cells with micronuclei was much stronger in hvatr.g than in WT. MH caused a significant decrease in the mitotic activity of root cells in both genotypes, however this effect was significantly stronger in “Sebastian”. The impact of MH on the roots cell cycle, analyzed using flow cytometry, showed no differences between the mutant and WT.     

On the Nature and Location of Organic Template Molecules and Their Effect on the Stability and Redox Properties of Microporous CoAlPO-34 Catalyst

Small-pore CoAlPO-34 materials were synthesized with a variety of organic template molecules and were characterized in detail, employing microcrystal diffraction, powder diffraction and in situ combined XRD/XAS techniques. We found that, when two template molecules or two nitrogen atoms of a single template molecule are present inside the chabazitic cage, the concentration of cobalt present in the system is ca. 25?at%, which introduces instability in the framework structure during the removal of the organic template. In contrast, when only one template molecule is present, it is possible to control the concentration of Co(II) ions in the framework to ca. 10?at%; these systems show good structural integrity and redox chemistry that was exploited for the regio-selective conversion of linear alkane molecules.     

Influence of the characteristics of a water-in-CO2 microemulsion on the separation of metal species

In this study, AOT [sodium bis(2-ethylhexyl) sulfosuccinate] combined with fluorinated cosurfactant or alcohol was used to form a water-in-CO₂ (W/C) microemulsion. The amount of water uptake in the microemulsion was closely related to the PFPE-PO₄/AOT (P/A) ratio. The stability of the microemulsion decreased with the amount of water. Lower temperature and higher pressure stabilize W/C microemulsions. The extraction efficiencies of metals (Cd, Co, Cu, Pb, Zn), when this W/C microemulsion method was used, exceeded 90% (AOT + octanol). The efficiencies for the extraction of Eu, La, and Sr could exceed 94% (AOT + PFPE-PO₄) in sc-CO_2.