A novel route to enhance the dissolution of apatite: Structural incorporation of hydrogen phosphate.

Potential use of hydroxyapatite nanoparticles (HANPs) [Ca10(PO4)6(OH)2] as slow P-release fertilizer (SRF) has recently attracted wider attention. However, commercially available HANP (with Ca/P ratio = 1.667) is the least soluble calcium phosphate and thus limits its full potential as an SRF in agronomic applications. In this research, we sought to enhance the dissolution rate of HANPs by enriching hydrogen phosphate (HPO42-) species in the phosphate (PO43-) structural sites. Seven different types of pure crystalline HANPs were synthesized at a range of Ca/P ratio from 1.46 (at pH 6.0) to 2.10 (at pH 12.0). Complementary results from FTIR and solid-state 31P MAS NMR spectroscopies showed that HPO42- species is most abundant in HANPs crystallized at pH 6.0 and gradually depleted at higher pH products. The rate of depletion of HPO42- species is proportional to the increase in carbonate incorporation into the HANP lattice, which preferentially forms B-type carbonated HANPs. The enhanced dissolution rate of HANPs due to hydrogen phosphate incorporation was tested using a flow-through macro-dialysis system that limits the partial transition of HANPs to other solid phases, which otherwise interfere with dissolution. The results show that the dissolution rate of HANPs increased with decreasing pH of synthesis and was highest in HANPs at pH 6.0. The dissolution rate differed by ten times between HANPs synthesized at pH 7.0 and 10.0. Overall, the atom-efficient synthetic route developed and the ability to tune the dissolution rate of HANPs are significant steps forward in improving the P-release efficiency of a potent SRF and is expected to contribute to efforts toward enhancing agricultural sustainability.

Effect of ammonia removal and biochar detoxification on anaerobic digestion of aqueous phase from municipal sludge hydrothermal liquefaction.

Hydrothermal liquefaction is a promising method to convert municipal sludge into an energy-dense fuel. The inevitable by-product aqueous phase is rich in complex organics, which has the potential for energy and nutrient recovery and can be treated by anaerobic digestion to produce methane. However, toxic compounds such as ammonia and phenolics present would inhibit the function of micro-organisms. This study investigated the influence of ammonia and phenolics removal on anaerobic digestion. The results showed that the treated aqueous phase resulted in up to 225 ml CH4/g COD. The highest methane production was obtained in the culture with both ammonia and phenolics removal at pH 7.0, which was about 90% higher than only ammonia removal and seven times higher than only phenolics removal. The microbial community analysis results showed that these two treatments could increase microbial diversity and upregulate the relative abundance of methanogens.

Towards the control of the biological identity of nanobiomaterials: Impact of the structure of 011¯0 surface terminations of nanohydroxyapatite on the conformation of adsorbed proteins.

High-resolution transmission electron microscopy, ζ-potential and in-situ IR spectroscopy of adsorbed CO were combined for elucidating the ratio between {011¯0}_ Ca-rich: {011¯0}_ P-rich terminations of {011¯0} facets, i.e. the surfaces with the highest morphological importance, in two nanohydroxyapatite samples. Bovine serum albumin was found to form at least a monolayer on the surface left accessible to protein molecules by the agglomeration of nanoparticles when suspended in the buffered incubation medium. Noticeably, the conformation of adsorbed proteins appeared sensitive to the ratio between the two types of {011¯0} terminations, also resulting in a difference in the surface exposed toward the exterior by the adsorbed protein layer(s).

One Step up the Ladder of Prebiotic Complexity: Formation of Nonrandom Linear Polypeptides from Binary Systems of Amino Acids on Silica.

Evidence for the formation of linear oligopeptides with nonrandom sequences from mixtures of amino acids coadsorbed on silica and submitted to a simple thermal activation is presented. The amino acid couples (glutamic acid+leucine) and (aspartic acid+valine) were deposited on a fumed silica and submitted to a single heating step at moderate temperature. The evolution of the systems was characterized by X-ray diffraction, infrared spectroscopy, thermosgravimetric analysis, HPLC, and electrospray ionization mass spectrometry (ESI-MS). Evidence for the formation of amide bonds was found in all systems studied. While the products of single amino acids activation on silica could be considered as evolutionary dead ends, (glutamic acid+leucine) and, at to some extent, (aspartic acid+valine) gave rise to the high yield formation of linear peptides up to the hexamers. Oligopeptides of such length have not been observed before in surface polymerization scenarios (unless the amino acids had been deposited by chemical vapor deposition, which is not realistic in a prebiotic environment). Furthermore, not all possible amino acid sequences were present in the activation products, which is indicative of polymerization selectivity. These results are promising for origins of life studies because they suggest the emergence of nonrandom biopolymers in a simple prebiotic scenario.

On the surface effects of citrates on nano-apatites: evidence of a decreased hydrophilicity.

The surface structure and hydrophilicity of synthetic nanocrystalline apatite with strongly bound citrates on their surface are here investigated at the molecular level, by combining advanced IR spectroscopy, microgravimetry and adsorption microcalorimetry. Citrate are found to form unidentate-like and ionic-like complexes with surface Ca2+ ions, with a surface coverage closely resembling that present in bone apatite platelets (i.e., 1 molecule/(n nm)2, with n ranging between 1.4 and 1.6). These surface complexes are part of a hydrated non-apatitic surface layer with a sub-nanometre thickness. Noticeably, it is found that the hydrophilicity of the nanoparticles, measured in terms of adsorption of water molecules in the form of multilayers, decreases in a significant extent in relation to the presence of citrates, most likely because of the exposure toward the exterior of -CH2 groups. Our findings provide new insights on the surface properties of bio-inspired nano-apatites, which can be of great relevance for better understanding the role of citrate in determining important interfacial properties, such as hydrophobicity, of bone apatite platelets. The evaluation and comprehension of surface composition and structure is also of paramount interest to strictly control the functions of synthetic biomaterials, since their surface chemistry strongly affects the hosting tissue response.

The formation and self-assembly of long prebiotic oligomers produced by the condensation of unactivated amino acids on oxide surfaces.

In situ IR and mass spectrometry evidence for the catalytic formation on SiO2 and TiO2 surfaces of glycine oligomers (poly-Gly) up to 16 units long by successive feeding with monomers from the vapor phase is presented. Parallel experiments carried out on hydroxyapatite resulted in the unreactive adsorption of Gly, thus indicating that the oligomerization was specifically catalyzed by the surfaces of SiO2 and TiO2 . Furthermore, the poly-Gly moved on the surface when contacted with H2 O vapor and formed self-assembled aggregates containing both helical and ß-sheet-like structural motifs. These results indicate that polypeptides formed by the condensation of amino acids adsorbed on a mineral surface can evolve into structured supramolecular assemblies.

Coordination chemistry of Ca sites at the surface of nanosized hydroxyapatite: interaction with H2O and CO.

The affinity towards water of a selection of well-defined, nanostructured hydroxyapatite (HA) samples was investigated by H(2)O vapour adsorption microcalorimetry and infrared (IR) spectroscopy. A large hydrophilicity of all investigated materials was confirmed. The surface features of hydrated HA were investigated on the as-synthesized samples pre-treated in mild conditions at T=303 K, whereas dehydrated HA features were characterized on samples activated at T=573 K. The relatively large hydrophilicity of the hydrated surface (-Δ(ads)H~100-50 kJ mol(-1)) was due to the interaction of water with the highly polarized H(2)O molecules strongly coordinated to the surface Ca(2+) cations. At the dehydrated surface, exposing coordinatively unsaturated (cus) Ca(2+) cations, H(2)O was still molecularly adsorbed but more strongly (-Δ(ads)H~120-90 kJ mol(-1)). The use of CO adsorption to quantify the Lewis acidic strength of HA surface sites revealed only a moderate strength of cus Ca(2+) cations, as confirmed by both microcalorimetric and IR spectroscopic measurements and ab initio calculations. This result implies that the large HA/H(2)O interaction energy is due to the interplay between cus Ca(2+) sites and nearby hydrophilic PO(4) groups, not revealed by the CO probe. The lower density of cus Ca(2+) cations at the 573 K activated HA surface with respect to the pristine one did not affect the whole hydrophilicity of the surface, as the polarizing effect of Ca sites is so strong to extend up to the fourth hydrated layer, as confirmed by both high-coverage microcalorimetric and IR spectroscopic data. No specific effects due to the investigated specimen preparation method and/or different morphology were observed.

Affinity of hydroxyapatite (001) and (010) surfaces to formic and alendronic acids: a quantum-mechanical and infrared study.

The affinity of the (001) and of the water reacted (010)WR hydroxyapatite surfaces towards formic and alendronic acids is studied with density functional theory (PBE functional) using periodic boundary conditions based on Gaussian basis set. Structures, energetic of the adsorption and vibrational features of the adsorbates are computed in order to understand at the atomic level both the cariogenic processes (for the formic acid) and the features of anti-osteoporosis drugs (for the alendronic acid). For both molecules the interaction energy is very high on an absolute scale, and for all examined cases, it is higher on the (010)WR HA surface than on the (001) one. For the latter, a number of cases by which the acidic proton of the adsorbate is transferred to the HA surface are also characterized. For the formic acid case, experimental infrared spectra are also measured and the position and nature of the C=O stretching bands have been found to be in excellent agreement with the quantum mechanical simulations. For alendronic acid IR experiments are still not available and the present predicted infrared spectra will be useful as a guide to interpret future experimental studies.

One more type of extrathermodynamic relationship.

A new type of extrathermodynamic relationship is presented: DeltaH = Ti[DeltaS + R Delta(ln Omega)] + beta, where Omega is the phase volume and beta is a constant. This type of relationship holds for a series of systems in the case where deltaDelta(ln Omega) is changeable. The relation between this type of correlation and linear free-energy relationships is shown. An example of the specified correlation for energy parameters of excimers forming in different dipyrenylalkanes is demonstrated.