Ca Phosphate Research Articles

Spectroscopy analyses of tribofilm and surface microcracks in carburized SCM420 steel under high-pressure rolling contact fatigue

The tribofilm and surface microcracks developed on a carburized SCM420 steel through a two-roller-type pitting test were characterized. A streaky 100- to 200-nm-thick tribofilm was generated on the specimen surface after 1.0 × 105 cycles. The tribofilm was identified to be mainly composed of calcium phosphate Ca3(PO4)2 and iron phosphate Fe3(PO4)2. Microcracks having lengths of a few tens of micrometers were detected on the contact surface without the tribofilm after the test. The number of cycles corresponded to a transition of the tangential force between two rollers decreasing to a stick-slip phenomenon as a steady state. A friction modifier additive (molybdenum dialkyldithiocarbamate) was added to a lubricant to improve rolling contact fatigue (RCF) pitting resistance. This lubricant containing the friction modifier additive exhibited a lifetime that was a factor of 10 greater than the RCF lifetime for the lubricant base oil. Therefore, the tribofilm may affect the tangential force and RCF lifetime. The contact surfaces and subsurface structure, especially in the vicinity of the microcracks, were dynamically reconstructed by severe friction and damage accumulation. Oxygen was detected on the surface of the microcracks.

Detection of phosphate solubilizing bacteria from rhizospheric soil of agricultural crops in Erode district

Phosphorus is a second key plant nutrient and the ‘kingpin’ in Indian agriculture, occupies an exclusive position both in conventional as well as in alternative agriculture. However, the phosphate solubilizing bacteria (PSB) converts the insoluble phosphate into biologically available form through the production of organic acids. Hence, the present study explored the presence of PSB from the Karavalasu agricultural field, Sivagiri, Erode District. The percentages of bacterial solubilization were 14.40 % to 60.70 % in non rhizospheric and rhizospheric crops adhering to root soils respectively.Out of 14 morphologically distinct isolates of PSB, two isolates (PSB8 and PSB11) displayed high P solubilization efficiency on solid medium amended with tricalcium phosphate Ca3(PO4)2 as the insoluble source (0.2 %). They were further characterized and continued with identification used by Picovskaya’s selective medium. The selective medium was incubated for 48 hours at a temperature of 37°C. The characterization was done for two strains by looking at the colony morphology and biochemical properties. The isolates showed the optimum pH for growth of the organism was pH 7 and the optimum temperature was 37 °C. Two strains exhibited significant release of P at the concentrations of 1.96 and 2.26 mg/l by PSB – 8 and PSB – 11 respectively on 10th day of incubation in broth medium amended with Ca3(PO4)2. The strains released acids as evident by decline in pH of the broth medium. They also secreted IAA with the maximum of 17.06 mg/l by PSB - 8 with Ca3(PO4)2 as a source of P. The potential strains for P solubilization were identified using 16S rRNA as Bacillus megaterium and Pseudomonas aeruginosa for further application as bioinoculants to agricultural fields. Finally we afford some indication that the use of Phosphate solubilising microorganisms will support sustainable agriculture and conclude that this knowledge is ready for commercial utilization in various regions worldwide. Keywords: ,

Tailorable Zinc-Substituted Mesoporous Bioactive Glass/Alginate-Methylcellulose Composite Bioinks.

Bioactive glasses have been used for bone regeneration applications thanks to their excellent osteoconductivity, an osteostimulatory effect, and high degradation rate, releasing biologically active ions. Besides these properties, mesoporous bioactive glasses (MBG) are specific for their highly ordered mesoporous channel structure and high specific surface area, making them suitable for drug and growth factor delivery. In the present study, calcium (Ca) (15 mol%) in MBG was partially and fully substituted with zinc (Zn), known for its osteogenic and antimicrobial properties. Different MBG were synthesized, containing 0, 5, 10, or 15 mol% of Zn. Up to 7 wt.% of Zn-containing MBG could be mixed into an alginate-methylcellulose blend (algMC) while maintaining rheological properties suitable for 3D printing of scaffolds with sufficient shape fidelity. The suitability of these composites for bioprinting applications has been demonstrated with immortalized human mesenchymal stem cells. Uptake of Ca and phosphorus (P) (phosphate) ions by composite scaffolds was observed, while the released concentration of Zn2+ corresponded to the initial amount of this ion in prepared glasses, suggesting that it can be controlled at the MBG synthesis step. The study introduces a tailorable bioprintable material system suitable for bone tissue engineering applications.

Neutron and XRD Single-Crystal Diffraction Study and Vibrational Properties of Whitlockite, the Natural Counterpart of Synthetic Tricalcium Phosphate

A crystal chemical investigation of a natural specimen of whitlockite, ideally Ca9Mg(PO4)6[PO3(OH)], from Palermo Mine (USA), was achieved by means of a combination of electron microprobe analysis (EMPA) in WDS mode, single-crystal neutron diffraction probe (NDP) and single-crystal X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectroscopy. The crystal-chemical characterization resulted in the empirical formula (Ca8.682Na0.274Sr0.045)Σ9.000(Ca0.034□0.996)Σ1.000(Mg0.533Fe2+0.342Mn2+0.062Al0.046)Σ0.983(P1.006O4)6[PO3(OH0.968F0.032)Σ1.000]. Crystal-structure refinement, in the space group R3c, converged to R1 = 7.12% using 3273 unique reflections from NDP data and to R1 = 2.43% using 2687 unique reflections from XRD data. Unit cell parameters from NDP are a = 10.357(3) Å, c = 37.095(15) Å and V = 3446(2) Å3, and from XRD, the parameters are a = 10.3685(4) Å, c = 37.1444(13) Å and V = 3458.2(3) Å3. NDP results allowed a deeper definition of the hydrogen-bond system and its relation with the structural unit [PO3(OH)]. The FTIR spectrum is very similar to that of synthetic tricalcium phosphate Ca3(PO4)2 and displays minor band shifts due to slightly different P-O bond lengths and to the presence of additional elements in the structure. A comparison between whitlockite, isotypic phases from the largest merrillite group, and its synthetic counterpart Ca3(PO4)2 is provided, based on the XRD/NDP and FTIR results.

Assessing calcium availability from limestone sources through bone and blood status of chickens

Calcium (Cu) availability from limestone (procured from different cement factories) was assessed through bone and blood status of chickens using the completely randomized design. Five hundred and twenty five (525) straight run broiler chicks that were 28 days Of age (trial l), four hundred and twenty (420) broiler finishers that were 56 days of age (trial 2), and 210 layers that had been laying for six months (trial 3) were used in the study. Six limestone dietary treatments and a control accounted for the seven diets that were assessed Twelve birds per treatment and 4 per replicate that had their weights close to the mean of the pen were selected in the broiler trials (trials I and 2) and three birds per pen and nine per diet were selected in the layer trial (trial 3) for bone and blood samples analysis. Bone samples were analyzed for bone weight, bone length, ash weight, percentage ash, Ca and phosphorus contents of ash and blood samples were analyzed for plasma Ca and alkaline phosphates activity. Results showed similar influence of sources on bone weight, bone length, ash weight and percentage ash. Ca and P contents of ash were significantly (P<0.05) affected by limestone sources but generally. Limestone sources produced mean values that were equal to or than the control diet in the starter phase (trail 1). In the finisher phase (trial 2), only Ca content of ashy varied significantly where Jakura source produced the least mean value. The layer trial (trial 3) also produced mean values that were significant (P <0.05) for Ca content of ash with the Sokoto source producing the least mean value. Plasma Ca and alkaline phosphates enzyme activity attained published values for chickens. It was concluded based on the information from this study that the (h from tested limestone sources was generally available for chicken production.

Phosphate solubilization from adsorbents and precipitates by different AVAIL polymers

AbstractLess than 40% of phosphate fertilizer applied to soils is typically taken up by the intended crop within the year of application because of strong soil retention. AVAIL polymers are fertilizer additives that were commercially developed to enhance availability of fertilizer phosphate. Knowledge of underlying mechanisms of phosphate solubilization would help to optimize the effectiveness of these polymers for different soils. This study compared different types and levels of AVAIL polymers in solubilizing (ad)sorbed and precipitated phosphate to gain insights into the mechanisms involved. Varying inputs of four newer forms of polymers and the original AVAIL (Original) were co‐reacted with one level of phosphate (ad)sorbed on ferrihydrite or noncrystalline Al hydroxide in batch (ad)sorption experiments or with Fe and Ca phosphate precipitates in dissolution experiments. Dissolved phosphate increased with increasing levels of co‐added polymers reacted with (ad)sorbents or phosphate precipitates. Across input levels evaluated, the Original AVAIL generally solubilized more phosphate from ferrihydrite than any of the new formulations. The Original and the new Liquid 2 formulation equally solubilized the greatest phosphate from Fe phosphate, whereas Liquid 2 solubilized more phosphate from Al hydroxide and Ca phosphate. (Ad)sorption and dissolution results implied competitive (ad)sorption and complexometric dissolution as key mechanisms. Our results suggest that the effectiveness of AVAIL polymers in soils depends on the level of added polymer charge relative to phosphate adsorption capacities or the types of phosphate minerals present.

Living phosphatic stromatolites in a low-phosphorus environment: Implications for the use of phosphorus as a proxy for phosphate levels in paleo-systems.

In the geological record, fossil phosphatic stromatolites date back to the Great Oxidation Event in the Paleoproterozoic, but living phosphatic stromatolites have not been described previously. Here, we report on cyanobacterial stromatolites in a supratidal freshwater environment at Cape Recife, South African southern coast, precipitating Ca carbonate alternating with episodes of Ca phosphate deposition. In their structure and composition, the living stromatolites from Cape Recife closely resemble their fossilized analogues, showing phosphatic zonation, microbial casts, tunnel structures and phosphatic crusts of biogenic origin. The microbial communities appear to be also similar to those proposed to have formed fossil phosphatic stromatolites. Phosphatic domains in the material from Cape Recife are spatially and texturally associated with carbonate precipitates, but form distinct entities separated by sharp boundaries. Electron Probe Micro-Analysis shows that Ca/P ratios and the overall chemical compositions of phosphatic precipitates are in the range of octacalcium phosphate, amorphous tricalcium phosphate and apatite. The coincidence in time of the emergence of phosphatic stromatolites in the fossil record with a major episode of atmospheric oxidation led to the assumption that at times of increased oxygen release the underlying increased biological production may have been linked to elevated phosphorus availability. The stromatolites at Cape Recife, however, form in an environment where ambient phosphorus concentrations do not exceed 0.28μM, one to two orders of magnitude below the previously predicted minimum threshold of >5μM for biogenic phosphate precipitation in paleo-systems. Accordingly, we contest the previously proposed suitability of phosphatic stromatolites as a proxy for high ambient phosphate concentrations in supratidal to shallow ocean settings in earth history.

Alcaligenes aquatilis GTE53: Phosphate solubilising and bioremediation bacterium isolated from new biotope “phosphate sludge enriched-compost”

The isolation and identification of beneficial bacteria from the active phase of composting is considered to be a key bio-quality parameter for the assessment of the process. The aim of this work was the selection and identification of beneficial bacteria from a co-composting experiment of vegetable waste (VW), olive oil mill waste (O2MW), and phosphate sludge (PS). Phosphate-solubilizing strains were isolated from the thermophilic phase using Pikovskaya (PVK) solid medium supplemented with tricalcium phosphate Ca3(PO4) (TCP) as the sole source of phosphorus (P). Therefore, the selected isolate Alcaligenes aquatilis GTE53 was tested to tolerate abiotic stresses (different levels of temperature, variable pH, high salinity and water stress). The isolate was also assessed for indole acetic acid (IAA) and siderophores synthesis, nitrogen fixation, phenol degradation and pathogens inactivation. The quality of the co-composting process was also investigated by monitoring the physico-chemical parameters. The obtained results showed that A. aquatilis GTE53 displayed a higher solubilization index of 2.4 and was efficiently dissolved, up to 162.8 and 247.4 mg·mL−1 of inorganic phosphate from PS and phosphate rock (PR), respectively. A. aquatilis GTE53 exhibited siderophores and IAA release, along with atmospheric nitrogen fixation. In addition to that, A. aquatilis GTE53 showed a high resistance to heat and tolerance to acidic and alkaline pH, high salinity and water stress. Moreover, A. aquatilis GTE53 could degrade 99.2% of phenol from a high-concentrated medium (1100 mg·L−1 of phenol) and can inactivate the most abundant pathogens in industrial wastes: Escherichia coli, Streptococcus sp., Salmonella sp., and Fusarium oxysporum albedinis. Analysis of temperature, pH, electrical conductivity, carbon/nitrogen (C/N) ratio, indicated successful co-composting. An efficient transformation of P to the available form and a great abatement of polyphenols, were also recorded during the process. The findings of this study will help to advance the understanding of A. aquatilis GTE53 functions and will facilitate its application to promote beneficial microbial organisms during composting, thus obtaining a high-quality product.

Отходы чистят отходы.

Cost-effective and eco-friendly methods of novel sorbentproductionbased on a Ti, Ca and Mg phosphates have been carried out. The solid precursors were ammonium titanyl sulfate and calcined dolomite, which were used as titanium, calcium, and magnesium sources. The heterogeneous synthesis procedure in-cludes stepwise interaction between solid precursors and liquid phosphorus-containing agents. In mech-anochemical way to obtain the sorbent was usedonly solid reactants. Synthesiswas carriedout in a plan-etary ball mill. The final product wasa composite material, whichconsistsof the following components: TiO(OH)H2PO4·H2O, Ti(HPO4)2·H2O, CaHPO4·2H2O, MgНPO4·3H2O, and NH4MgPO4·6H2O. The new sorbent shows high sorption ability towards radionuclides in multicomponent liquid radioactive waste (LRW) sys-tems. Purification effect is based on both precipitation and ion exchange mechanism.

Responses of Corpuscles of Stannius to intra-peritoneal vitamin-D3 administration in teleost Labeo rohita (Hamilton, 1822) reared in water with two different levels of calcium concentration.

This study assessed the responses of vitamin-D3 intraperitoneally injected to Rohu, Labeo rohita @ of 0 IU/kg bw (only solvent), 100 IU/kg bw and 500 IU/kg bw reared in 20 and 40 ppm of calcium (Ca) enriched water. The cellular changes in Corpuscles of Stannius (CS) gland, serum Ca, and inorganic phosphate (Pi) level were analysed up to the 60th day. Rohu administered with 100 IU/kg bw D3 and exposed to 40 ppm Ca-rich water exhibited notable hyperplasia of CS compared with their control groups. Notable changes with high serum Ca level (13.87 ± 0.3 mg/dl) was detected on the 5th day in fish exposed to 40 ppm Ca-rich water, while related values attained (13.74 ± 0.1 mg/dl) only after 7 days in 20 ppm Ca-rich water of 500 IU/kg bw vitamin D3 injection. Similarly, high serum Pi level (7.66 ± 0.2 mg/dl) in 40 ppm Ca injected with D3 at 500 IU/kg bw. The results demonstrated that the Ca homeostasis of Labeo rohita is influenced by intra-peritoneal vitamin D3. Progressive studies should be conducted by increasing the dose of vitamin D3 to investigate optimum dose/supplement in feed for commercially important aquaculture teleost Labeo rohita for maximum and sustainable absorption of Ca from the variable water Calcium levels to maintain Ca2+ homeostasis.

Setting behavior, apatite-forming ability, mechanical strength of polymethylmethacrylate bone cement through bioactivity modification of phosphate functional groups combined with Ca2+ ions

Bioactivity modification helps polymethylmethacrylate (PMMA) bone cement to reinforce its interfacial adhesion to bone tissues through the chemical bonding of apatite. Since Si-OH groups combined with Ca2+ ions have succeeded in inducing apatite formation, more combinations of functional groups and active ions are being explored. In this study, Bis[2-(methacryloyloxy)ethyl] phosphate (B2meP) containing phosphate (=PO4H) groups and Ca(CH3COO)2 supplying Ca2+ ion were adopted to investigate the feasibility of equipping PMMA bone cement with apatite-forming ability in vitro, more effects under designed contents on setting behavior, injectability, contact angle, cytotoxicity and mechanical strength were also investigated. Results showed B2meP copolymerized with MMA and became one section of PMMA chains, surface = PO4H groups and released Ca2+ ions pushed spherical apatite individuals nucleating and agglomerating into layer horizontally, Increasing B2meP content lowered the contact angle and the peak temperature, enhanced the cell viability of MC3T3-E1, but prolonged apatite forming period. Injectability rate performed a similar trend to setting time. Lower adding content and deposited apatite layer contributed to reduce the strength loss in soaking. Taking biological performance and other properties into balance, cement added with B2meP of 10 wt% in MMA and Ca(CH3COO)2 of 20 wt% in PMMA performed better.

Biyo–Seramik Bileşimine Silisyum Katkısının Osteokondüktif ve Osteoindüktif Özelliklere Etkisi

Bone replacing Ca–phosphate based materials with strong bioactive and osteoconductive properties are being used in many medical and dental applications as coating materials on implant surfaces and as scaffold for the regeneration of bone and dentin. It is possible to produce materials with enhanced biological or physico–chemical properties by doping different suitable ions into hydroxyapatite (HA) structure. Silicon (Si) is the most found element in Earth crust and has many effective properties in living bodies. The main aim of the present study is to supply the current knowledge about apatite materials which contain Si ions. After defining bone, the factors affecting new bone formation, osteoconductivity and osteoinductivity properties, the effect of Si doping into HA structure on osteoconductivite and osteoinductivite features will be mentioned.

Thermodynamic properties of calcium alkali phosphates Ca(Na,K)PO4

Calcium alkali phosphates Ca(Na,K)PO4 are main constituents of bioceramics and thermochemically produced phosphorus fertilizers because of their bioavailability. Sparse thermodynamic data are available for the endmembers CaNaPO4 and CaKPO4. In this work, the missing data were determined for the low-temperature phase modifications of the endmembers CaNaPO4 and CaKPO4 and three intermediate Ca(Na,K)PO4 compositions. Standard enthalpy of formation ranges from − 2018.3 ± 2.2 kJ mol−1 to − 2030.5 ± 2.1 kJ mol−1 and standard entropy from 137.2 ± 1.0 J mol−1 K−1 to 148.6 ± 1.0 J mol−1 K−1 from sodium endmember β-CaNaPO4 to potassium endmember β′-CaKPO4. Thermodynamic functions are calculated up to 1400 K for endmembers and the sodium-rich intermediate phase β-Ca(Na0.93K0.07)PO4. Functions above 640 K are extrapolated because of the phase transition from low- to high-temperature phase. Impurities in the synthesized intermediate phases γ-Ca(Na0.4K0.6)PO4 and γ-Ca(Na0.35K0.65)PO4 and one additional phase transition around 500 K impeded the determination of high-temperature thermodynamic functions. In general, data for phase transition temperatures agree with the previously reported phase diagrams.

Stocks and fraction composition of phosphorus in the Ili Alatau foothill soils and their change under long-term use

In soils of Ili Alatau (dark kastanozems, light kastanozems, mountain chernozems) both in continuous cropping system of sugar beet and in crop rotation with prolonged use of fertilizers the soil agrochemical indices, phosphorus reserves and group composition (total, organic and mineral) vary significantly. The total phosphorus content in the soils was 1720–2330 mg/kg and decreased in the series: virgin mountain chernozems > arable dark kastanozems > arable mountain chernozems > light kashtanozems > virgin dark kastanozems. It was observed, that in arable dark kastanozems, as compared to virgin soils, the content of available forms of phosphorus (loose-bound phosphates Ca-PI and miscellaneous calcium phosphates Ca-PII) increased, and the content of plant unavailable forms of phosphorus (poorly soluble Ca phosphates Ca-PIII, phosphates of aluminum Al-P and iron Fe-P) decreased. In arable mountain chernozems, in comparison with virgin mountain chernozems, the content of all fractions of phosphorus decreased. Arable light kastanozems contain the least amount of available phosphates and the highest of phosphates of aluminum and iron. When cultivating beets on light kastanozems, the content of all fractions of phosphorus, except iron phosphates, increased with increasing dose of fertilizers. The effectiveness of the application of the organic-mineral fertilizers was comparable to the introduction of NK + P 1.5 and NK + P 2 , the yield of sugar beet in the crop rotation in these variants is the highest and amounts to 614 and 577 centner/ha; in the control value (obtained without fertilizers) – 197 centner/ha, and in the variant with application of only NK fertilizers – 277 centner/ha. In continuous cropping system these values were 576 and 561 centner/ha; 311 and 327 centner/ha respectively. Close values of crop yield were obtained in two variants: with the organo-mineral system and NK + P 1.5 , due to the additional use by the plants of sugar beet phosphorus of newly formed organic compounds .

Synthesis of Calcium Phosphate Powders in Nonaqueous Media for Stereolithography 3D Printing

Methods were presented to synthesize tricalcium phosphate Ca3(PO4)2 (TCP), calcium pyrophosphate Ca2P2O7 (CPP), and TCP/CPP composites in nonaqueous media in the temperature range 25–300°C. It was shown that solvo- and ionothermal synthesis methods can give phosphates of complex composition. The phase composition, micromorphology, and particle size distribution of the obtained powders and their evolution during synthesis were described. The synthesis at 110°C while slowly adding ammonium hydrophosphate to a solution of calcium ethylene glycolate in ethylene glycol gives a nanocrystalline β-TCP powder with an average size of aggregates of platy crystals of 150 nm and a distribution width of 50 nm. The morphological characteristics and sinterability of the powders synthesized in solutions in ethylene glycol make them suitable for producing macroporous ceramics by stereolithography 3D printing methods.

Quantifying Uncertainties in Sequential Chemical Extraction of Soil Phosphorus Using XANES Spectroscopy.

Sequential chemical extraction has been widely used to study soil phosphorus (P) dynamics and inform nutrient management, but its efficacy for assigning P into biologically meaningful pools remains unknown. Here, we evaluated the accuracy of the modified Hedley extraction scheme using P K-edge X-ray absorption near-edge structure (XANES) spectroscopy for nine carbonate-free soil samples with diverse chemical and mineralogical properties resulting from different degrees of soil development. For most samples, the extraction markedly overestimated the pool size of calcium-bound P (Ca-P, extracted by 1 M HCl) due to (1) P redistribution during the alkaline extractions (0.5 M NaHCO3 and then 0.1 M NaOH), creating new Ca-P via formation of Ca phosphates between NaOH-desorbed phosphate and exchangeable Ca2+ and/or (2) dissolution of poorly crystalline Fe and Al oxides by 1 M HCl, releasing P occluded by these oxides into solution. The first mechanism may occur in soils rich in well-crystallized minerals and exchangeable Ca2+ regardless of the presence or absence of CaCO3, whereas the second mechanism likely operates in soils rich in poorly crystalline Fe and Al minerals. The overestimation of Ca-P simultaneously caused underestimation of the pools extracted by the alkaline solutions. Our findings identify key edaphic parameters that remarkably influenced the extractions, which will strengthen our understanding of soil P dynamics using this widely accepted procedure.

Elucidation of soil phosphorus speciation in mid-Atlantic soils using synchrotron-based microspectroscopic techniques.

Phosphorus deficiency and excess are concomitant problems in agricultural soils of the mid-Atlantic region. A fundamental understanding of soil P speciation is essential to assess P fate and transport in these soils. Current methods for soil P speciation often rely on sequential chemical extractions, which can introduce artifacts during analysis. To overcome limitations of current methods, this study evaluated synchrotron-based micro-focused X-ray fluorescence (µ-XRF) and X-ray absorption near-edge spectroscopy (µ-XANES) techniques to assess soil P speciation in agricultural soils collected from the mid-Atlantic region of the United States. Three soils with varying chemical and physical properties were analyzed with µ-XRF maps collected at high (12,000eV) and tender (2240eV) energies to evaluate colocation of P with Fe, Al, Ca, and Si in soil samples, and µ-XANES spectra were collected at the P K-edge for P hotspots. Combined µ-XRF and µ-XANES analysis was useful for identifying Ca phosphate, Fe phosphate, Al-sorbed P, and Fe-sorbed P species in heterogeneous soil samples. X-ray fluorescence maps were valuable to distinguish Al-oxide sorbed P from Fe-oxide sorbed P species. A low signal-to-noise ratio often limited µ-XANES data collection in regions with diffuse, low concentrations of P. Therefore, some P species may not have been detected during analysis. Even with varying degrees of self-absorption and signal-to-noise ratios in µ-XANES spectra, important inferences regarding P speciation in mid-Atlantic soils were made. This study highlights the potential of µ-XANES analysis for use in environmental and agricultural sciences to provide insights into P fate and transport in soils.

Molecular Understanding of Humic Acid-Limited Phosphate Precipitation and Transformation.

Phosphorus (P) availability is widely assumed to be limited by the formation of metal (Ca, Fe, or Al) phosphate precipitates that are modulated by soil organic matter (SOM), but the SOM-precipitate interactions remain uncertain because of their environmental complexities. Here, we present a model system by quantifying the in situ nanoscale nucleation kinetics of calcium phosphates (Ca-Ps) on mica in environmentally relevant aqueous solutions by liquid-cell atomic force microscopy. We find that Ca-P precipitate formation is slower when humic acid (HA) concentration is higher. High-resolution transmission electron microscopy observations demonstrate that HA strongly stabilizes amorphous calcium phosphate (ACP), delaying its subsequent transformation to thermodynamically more stable phases. Consistent with the formation of molecular organo-mineral bonding, dynamic force spectroscopy measurements display larger binding energies of organic ligands with certain chemical functionalities on HA to the initially formed ACP than to mica that are responsible for stabilization of ACP through stronger HA-ACP interactions. Our results provide direct evidence for the proposed importance of SOM in inhibiting Ca-P precipitation/transformation. We suggest that similar studies of binding strength in SOM-Fe/Al-P may reveal how both organic matter and metal ions control P availability and fate, and thus the eventual P management for agronomical and environmental sustainability.

Crystal structure of a NIR‐Emitting DNA‐Stabilized Ag16 Nanocluster

AbstractDNA has been used as a scaffold to stabilize small, atomically monodisperse silver nanoclusters, which have attracted attention due to their intriguing photophysical properties. Herein, we describe the X‐ray crystal structure of a DNA‐encapsulated, near‐infrared emitting Ag16 nanocluster (DNA–Ag16NC). The asymmetric unit of the crystal contains two DNA–Ag16NCs and the crystal packing between the DNA–Ag16NCs is promoted by several interactions, such as two silver‐mediated base pairs between 3′‐terminal adenines, two phosphate–Ca2+–phosphate interactions, and π‐stacking between two neighboring thymines. Each Ag16NC is confined by two DNA decamers that take on a horse‐shoe‐like conformation and is almost fully shielded from the solvent environment. This structural insight will aid in the determination of the structure/photophysical property relationship for this class of emitters and opens up new research opportunities in fluorescence imaging and sensing using noble‐metal clusters.

Morphological studies on the development of chemical conversion coating on surface of Mg–4Zn alloy and its corrosion and bio mineralisation behaviour in simulated body fluid

Nucleation and growth of chemical conversion coating on Mg–4Zn alloy prepared by immersion in saturated NaHCO3 at ambient temperature and its corrosion behaviour in simulated body fluid (SBF) is investigated in this paper. Compact dense coating obtained up on 24 h of immersion at ambient temperature is found to provide complete coverage of the surface and a high initial corrosion resistance in SBF. With sustained exposure to SBF, the coating dissolves and slowly cracks to expose the substrate to the corrosion medium. The 24 h coated sample shows high levels of bio mineralisation, with flower shaped crystals of phosphates of Ca and Mg on the surface. The combined effects of slow first hydrogen evolution rate and precipitation of phosphates, and similarities to the carbonate coating developed in vivo makes the conversion coating discussed in this paper a suitable choice for Mg alloys for temporary bio implant applications.