This study looks at how proteinoid microspheres and their magnetic polystyrene (PS) hybrids behave electrochemically. It also explores their computational abilities. These systems show complex membrane potential dynamics. Pure proteinoids spike without external influence, ranging from 5.39 to 9.81 mV. In contrast, PS-modified variants exhibit sinusoidal oscillations. Their behavior can be described by the equation V(t) = A sin(2πft) + Voffset, where A is about 1.5 mV and f is around 0.05 Hz. Electrochemical impedance spectroscopy shows key differences in charge transport. The PS-modified systems have better conductivity: |Z|PS = 7.22 × 104 Ω compared to |Z|prot = 2.03 × 105 Ω. The systems can perform Boolean logic operations with a 5 mV threshold. They show time-dependent gate behavior, making them suitable for unconventional computing applications. Doping with Fe(NO3)3 changes the electrical response. This happens through redox processes where Fe3+ gains an electron to become Fe2+. As a result, there are greater potential differences and more complex timing behaviors. These findings help us understand proteinoid-based bioelectricity better. They also show how these building blocks can be used in biomolecular computing systems.

Prostate cancer remains the most common male cancer; however, treatment regimens remain unclear in some cases due to a lack of agreement in current testing methods. Therefore, there is an increasing need to identify novel biomarkers to better counsel patients about their treatment options. Microcalcifications offer one such avenue of exploration. Microfocus spectroscopy at the i18 beamline at Diamond Light Source was utilised to measure X-ray diffraction and fluorescence maps of calcifications in 10 µm thick formalin fixed paraffin embedded prostate sections. Calcifications predominantly consisted of hydroxyapatite (HAP) and whitlockite (WH). Kendall's Tau statistics showed weak correlations of 'a' and 'c' lattice parameters in HAP with GG (rτ = - 0.323, p = 3.43 × 10-4 and rτ = 0.227, p = 0.011 respectively), and a negative correlation of relative zinc levels in soft tissue (rτ = - 0.240, p = 0.022) with GG. Negative correlations of the HAP 'a' axis (rτ = - 0.284, p = 2.17 × 10-3) and WH 'c' axis (rτ = - 0.543, p = 2.83 × 10-4) with pathological stage were also demonstrated. Prostate calcification chemistry has been revealed for the first time to correlate with clinical markers, highlighting the potential of calcifications as biomarkers of prostate cancer.

Amorphous calcium phosphate (ACP), one of the most important calcium-phosphorus compounds, is widely used in dentistry, orthopedics, and medicine, but is rarely reported for fluoride removal from water. In view of this, sodium citrate-stabilized amorphous calcium phosphate (Cit-ACP) and Cit-ACP calcinated at different temperatures were successfully prepared for fluoride removal. The results showed that the adsorption data of the Cit-ACP sample could be well described by the Langmuir model, and the adsorption kinetic followed the pseudo-second-order model. The maximum adsorption capacity was 27.48 mg/g at pH 7.0 when the fluoride concentration is 100 mg/L. The thermodynamic parameters suggested that the adsorption of fluoride was a spontaneous endothermic process. The XRD, XPS, and Zeta potential analysis of the Cit-ACP sample before and after fluoride removal revealed that, owing to the core-shell structure of the Cit-ACP nanoparticles, the fluoride ions in solution and the calcium ions in shell layer of the Cit-ACP nanoparticles co-promoted the transformation of the core of the Cit-ACP nanoparticles into fluorapatite. Given the simplicity of its preparation and effectiveness of its fluoride removal properties, Cit-ACP would be a potentially economical, efficient, and biocompatible adsorbent for fluoride removal.

Glasses exposed to soil environments are of interest across various scientific fields, from nuclear waste containment to archaeological preservation and nutrient-delivery systems for plants. While immersion experiments provide valuable insights into the ion release kinetics in root- and microbe-exuded solutions, they fail to replicate the complexities of nutrient leaching in real soil conditions. To address this, the degradation behavior of nutrient-bearing glasses (41SiO2·6(10)P2O5·20K2O·33(29)MgO/CaO/MgO + CaO) with increasing sulfate contents was investigated through a soil incubation experiment simulating Central European weather variability. A comprehensive approach, combining SEM observations and EDS semi-quantitative analysis, revealed that acidic peat strongly promoted ion exchange, where protons from the medium replaced network cations. The glass composition played a crucial role in the fracture behavior: sulfate incorporation increased the network rigidity, making the glasses more prone to mechanical degradation and accelerating the reaction front advancement. The P2O5 content was also a key factor in modulating the reactivity, with higher concentrations intensifying interactions with the soil medium. Limited water availability accelerated the solution saturation, leading to secondary phase precipitation and temporary nutrient immobilization. These findings demonstrate that glass reactivity can be fine-tuned through composition adjustments and highlight the dynamic nature of glass-soil interactions, including seasonal variations in nutrient release under acidic conditions.

Due to the close spatial proximity and strong reactivity, soil humic components inevitably participate in iron (Fe) (oxyhydr)oxide formation, holding significant importance in contaminant immobilization, carbon cycling, and nutrient availability. Yet, the regulatory role of different humic components involved in the initial formation of Fe (oxyhydr)oxides is still lacking. In this study, we identified the characteristic formation periods of ferrihydrite (Fh), the initial phase of Fe (oxyhydr)oxides, through real-time monitoring of solution pH and in situ observations of precipitated Fh nanoparticles in the absence and presence of different humic components. The kinetics of Fh formation were quantified at micrometer and nanometer scales using Raman spectroscopy (RS) and atomic force microscopy (AFM), respectively. Results indicated that the extension of induction time, retardation of phase occurrence, and inhibition of nucleation rates for Fh formation were all dependent on the specific humic component with an order of fulvic acid (FA) > humic acid (HA) > humin (HM). Nanoscale data analysis revealed that the thermodynamic barrier to Fh nucleation increased by maximizing the interfacial free energy (γ) of the reaction system. Through molecular bonding quantification, AFM-based dynamic force spectroscopy (DFS) measurements demonstrated a linear relationship between Gibbs free energies (ΔGb) of soil organic matter (SOM) binding to Fh and γ within the classical nucleation theory (CNT), linking heterogeneous nucleation barriers with organo-mineral bonding. This study is the first to provide in situ evidence of the inhibitory effects of soil humic components on the formation of Fe (oxyhydr)oxides and quantitatively establish that higher energy barriers to nucleation correlate with stronger organo-mineral bonding. This relationship suggests that good organic binders are good inhibitors for mineral formation, offering a novel perspective for predicting the formation and fate of soil minerals through the lens of organo-mineral binding free energies.

Octacalcium phosphate (OCP) has been shown to exhibit an osteogenic property and, therefore, has been utilized recently as a bone substitute, clinically. However, the stimulatory capacity for induced pluripotent stem (iPS) cells is not known. This study investigated whether OCP enhances osteoblastic differentiation of three-dimensionally cultured spheroids of iPS cells compared to hydroxyapatite (HA) and β-tricalcium phosphate (β-TCP). Mouse iPS cells were mixed with smaller (less than 53 μm) or larger (300-500 μm) sizes of calcium phosphate (CaP) granules and cultured in a laboratory-developed oxygen-permeable culture chip under minimizing hypoxia for up to 21 days. Osteoblastic differentiation was estimated by the cellular alkaline phosphatase (ALP) activities. The degree of supersaturation (DS) with respect to CaP phases was determined from the media chemical compositions. Incubated CaP materials were characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The culture promoted well the formation of hybrid spheroids of CaP materials and iPS cells regardless of the type of materials and their granule sizes. The ALP activity of OCP was about 1.5 times higher than that of β-TCP and HA in smaller granule sizes. FTIR, XRD, and DS analyses showed that larger OCP granules tended to hydrolyze to HA slightly faster than smaller granules with time while HA and β-TCP materials tended to remain unchanged. In conclusion, the results suggest that OCP enhances the osteogenic differentiation of iPS cells more than HA and β-TCP through a mechanism of hydrolyzing to HA. This inherent material property of OCP is essential for enhancing the osteoblastic differentiation of iPS cells.

In this study, we utilized machine learning interatomic potentials (MLIPs) to investigate the nucleation mechanisms of calcium phosphate, a critical component of bone and teeth. Our analysis encompassed the process from pre-nucleation stage to the growth of amorphous calcium phosphate (ACP) in solution. We observed fluctuations in free calcium ion concentration and tracked the formation of uniform clusters in the early nucleation phases, confirming the existence of pre-nucleation clusters (PNCs). The PNCs are characterized by the composition Ca2[(PO4)1.6(HPO4)(H2PO4)0.4] and predominantly exhibit a triangular structure formed by phosphate groups. This structure is not only the core of the short-range ordered units in ACP but also exhibits the structural characteristics of the fundamental building blocks of HAP. Importantly, these clusters interact dynamically with water molecules through hydrogen bonding and proton exchange, which is essential for their stability and growth. The gradual growth of these clusters occurs via ion attachment and cluster adsorption. This work provides insights into calcium phosphate mineralization, with implications for materials science and biomedical engineering, particularly in biomaterial synthesis. The application of MLIPs demonstrates a high-accuracy, efficient approach for simulating complex systems may advance our understanding of crystallization and biomineralization processes. STATEMENT OF SIGNIFICANCE: Calcium phosphate nucleation is crucial in biological mineralization and the synthesis of biomaterials, serving as a key aspect in the design of hydroxyapatite (HAP)-based biomaterials. However, the mechanisms of early nucleation remain unclear due to the complex ion-water interactions, which lead to rapid nucleation rates and small cluster sizes. This study combines MLIP with MD simulations to explore the nucleation process of calcium phosphate, revealing the transition from pre-nucleation to the formation of ACP. It clarifies the relationship between PNCs and the crystalline structure of HAP. This work addresses the knowledge gap regarding early-stage calcium phosphate nucleation and highlights the potential of MLIP in simulating complex ionic solutions, laying a solid foundation for AI-guided research in biological and biomedical materials.

Differential isotope effects are an emerging tool for discovering possible nontrivial quantum mechanical effects within biological systems. However, it is often nearly impossible to elucidate the exact mechanisms by which a biological isotope effect manifests due to the complexity of these systems. As such, one proposed in vitro system of study for a quantum isotope effect is calcium phosphate aggregation, where symmetric calcium phosphate molecular species, known as Posner molecules, have been theorized to have phosphorus nuclear spin-dependent self-binding rates, which could be differently modulated by doping with stable lithium isotopes. Here, we present in vitro evidence for such a differential lithium isotope effect on the formation and aggregation of amorphous calcium phosphate from solution under certain conditions. Experiments confirm that lithium incorporates into amorphous calcium phosphate, with 7Li found to promote a greater abundance of observable calcium phosphate particles than 6Li under identical solution preparations. These in vitro results offer a potential explanation for in vivo biological studies that have shown differential lithium isotope effects. Given the importance of calcium phosphate in biological systems-ranging from mitochondrial signaling pathways to key biomineralization processes, as well as the proposed role of Posner molecules as a "neural qutrit"-these results present an important step in understanding calcium phosphate nucleation as well as the potential role of calcium phosphate for quantum biology and processing.

With an ultrahigh aspect ratio and a similar chemical composition to the biomineral in bone and tooth, ultralong hydroxyapatite nanowires (UHAPNWs) exhibit a meritorious combination of high flexibility, excellent mechanical performance, high biocompatibility, and bioactivity. Despite these exciting merits, the rapid and green synthesis of UHAPNWs remains challenging. In this work, we have developed an environment-friendly, rapid, and highly efficient synthesis of ultrathin UHAPNWs by the microwave-assisted calcium oleate precursor hydrothermal method using biogenic creatine phosphate as the bio-phosphorus source. Owing to the controllable hydrolysis of bio-phosphorus-containing creatine phosphate and the highly efficient heating of microwave irradiation, ultrathin UHAPNWs with a homogeneous morphology of several nanometers in diameter (single nanowire), several hundred micrometers in length, and ultrahigh aspect ratios (>10,000) can be rapidly synthesized within 60 min. This effectively shortens the synthesis time by about two orders of magnitude compared with the traditional hydrothermal method. Furthermore, ultrathin UHAPNWs are decorated in situ with bioactive creatine and self-assembled into nanowire bundles along their longitudinal direction at the nanoscale. In addition, ultrathin UHAPNWs exhibit a relatively high specific surface area of 84.30 m2 g-1 and high ibuprofen drug loading capacity. The flexible bio-paper constructed from interwoven ibuprofen-loaded ultrathin UHAPNWs can sustainably deliver ibuprofen in phosphate-buffered saline, which is promising for various biomedical applications such as tissue regeneration with anti-inflammatory and analgesic functions.

Although models have been proposed to explain the mechanisms of bioglass (BG) dissolution and subsequent calcium phosphate (CaP) mineralization, open questions remain. The processes in which phase transition occurs in aqueous solutions and their dynamics remain underexplored partly because traditional instruments/techniques do not allow for direct observations at the adequate time and length scales at which such phase transformations occur. For instance, given the crucial role of the silica gel in CaP formation during BG dissolution, uncertainty exists about how such a silica gel forms on the BG surface. In the case of CaP formation driven by BG dissolution, questions can also be added, i.e., how CaP develops into an apatitic-like structure, how many transient phases there are, and, in general, phenomena occurring in the solid-liquid interface during BG dissolution. Several approaches were taken to study CaP mineralization driven by BG dissolution, mainly examining the solid-liquid interface and the BG after-reaction surface. This paper focuses on gaining insight into silica gel formation on the BG's surface during dissolution. Electron microscopy techniques were used, including scanning electron microscopy and focused ion beam cross sections. Other analysis techniques, such as time-of-flight secondary ion mass spectrometry, were utilized. Cross sections of reacted BG-blocks gave essential insights into the BG dissolution, particularly its strong dependency on experimental conditions, and tentative evidence has shown that soluble silica from BG dissolution may not reprecipitate/repolymerize on BG blocks' surface; thus, we wonder where it precipitates. Additionally, complementary analysis techniques determined that CaP, during BG dissolution, transitions from amorphous calcium phosphate to a calcium-deficient nanocrystalline apatitic structure with minimal contents of Si4+ and Na+ ions that may be molecularly part of CaP. The Hench model has been the core guide for BG dissolution and subsequent CaP formation for many years. However, this study shows tentative evidence that contributes to and somewhat differs from it.

Gating is a fundamental process in ion channels configured to open and close in response to specific stimuli such as voltage across cell membranes thereby enabling the excitability of neurons. Here we report on voltage-gated solid-state nanopores by electrically tunable chemical reactions. We demonstrate repetitive precipitation and dissolution of metal phosphates in a pore through manipulations of cation flow by transmembrane voltage. Under negative voltages, precipitates grow to reduce ionic current by occluding the nanopore, while inverting the voltage polarity dissolves the phosphate compounds reopening the pore to ionic flux. Reversible actuation of these physicochemical processes creates a nanofluidic diode of rectification ratio exceeding 40000. The dynamic nature of the in-pore reactions also facilitates a memristor of sub-nanowatt power consumption. Leveraging chemical degrees of freedom, the present method may be useful for creating iontronic circuits of tunable characteristics toward neuromorphic systems.

The bionics of natural bone structures plays an essential role in the selection of materials for bone tissue engineering. Although the content of trace metallic elements in bone is low, they have significant effects on the process of bone growth and metabolism. Up to now, the applications of "green" heavy metals in bone regeneration are limited. Herein, in this study, we present a straightforward one-pot strategy for the synthesis of in situ bismuth-doped amorphous calcium phosphate nanocomposites (RBCP), effectively integrating the beneficial properties of each component. The characterization of these products can be readily optimized by adjusting reaction parameters. Our in vitro studies show that under coordination of each component, the RBCP biomaterial demonstrates distinguished biocompatibility and significantly accelerates vascular pattern formation within just 4 h by stimulating the expression of angiogenesis-related genes in human umbilical vein endothelial cells (HUVECs). In vivo experiments indicate that the incorporation of bismuth effectively enhances bone regeneration and osseointegration in a rat femur defect model. In conclusion, the as-prepared RBCP biomaterials hold promising prospects for treating segmental bone defects, owing to the facile, cost-effective, and eco-friendly preparation process, along with their remarkable capabilities.

Livestock manure, a common fertilizer in Chinese agriculture, can lead to environmental contamination and potential health risks due to elevated antibiotic and phosphorus levels. Importantly, the high phosphorus levels initiates transformations of phosphate minerals in soils, especially calcareous soils. These variations in phosphate mineralogy can significantly impact the migration and fate of antibiotics within the soil. However, the impact of the transformation process, particularly involving the metastable phase brushite (DCPD), on the fate of antibiotics remains unclear. In this study, we synthesized DCPD and hydroxylapatite (HAP) and examined their transformation process to assess their removal capacity and investigate the migration and fate of oxytetracycline (OTC). The findings reveal that HAP exhibits a maximum immobilization capacity for OTC of 20.10 mg/g, surpassing that of DCPD by 2.56 times (7.86 mg/g). This disparity in immobilization capacity between DCPD and HAP leads to a redistribution of OTC between the solid and liquid phases during the transformation process. Notably, the introduction of OTC also inhibits the transformation process, potentially impacting the fate of other potentially harmful elements. The study highlights that the transformation process of calcium phosphorus minerals has a significant impact on the mobility and fate of antibiotics in soil, which aids in better management and mitigation of the environmental risks associated with fertilizer application.

Artificial bone, primarily composed of calcium carbonate, demonstrates a higher resorption rate than calcium phosphate-based counterparts, suggesting potential for early bone replacement. Animal experiments using porous calcium carbonate ceramics have demonstrated bone formation superior to commercially available artificial bone after short-term implantation. Long-term implantation has yielded suboptimal results owing to resorption of both newly formed bone and implantation material. We prepared calcium carbonate ceramics added with silica (Si-CaCO3) to regulate the resorption rate. After 12 weeks of implantation, Si-CaCO3 ceramics exhibited bone formation comparable to that of β-tricalcium phosphate (β-TCP) but less variability in the distribution of bone formation within the tissue. An in vitro dissolution test, serving as an indicator of in vivo resorption rate, revealed that Si-CaCO3 ceramics exhibited an intermediate dissolution rate between high-purity calcium carbonate and β-TCP ceramics. Silica doping in CaCO3 ceramics presents an effective approach for aligning material resorption with bone formation and growth.

Nitrogen fertilizer delivery inefficiencies limit crop productivity and contribute to environmental pollution. Herein, we developed Zn- and Fe-doped hydroxyapatite nanomaterials (ZnHAU, FeHAU) loaded with urea (∼26% N) through hydrogen bonding and metal-ligand interactions. The nanomaterials attach to the leaf epidermal cuticle and localize in the apoplast of leaf epidermal cells, triggering a slow N release at acidic conditions (pH 5.8) that promote wheat (Triticum aestivum) growth and increased N uptake compared to conventional urea fertilizers. ZnHAU and FeHAU exhibited prolonged N release compared to urea in model plant apoplast fluid pH in vitro (up to 2 days) and in leaf membranes in plants (up to 10 days) with a high N retention (32% to 53%) under simulated high rainfall events (50 mm). Foliar N delivery doses of up to 4% as ZnHAU and FeHAU did not induce toxicity in plant cells. The foliar-applied ZnHAU and FeHAU enhanced fresh and dry biomass by ∼214% and ∼161%, and N uptake by ∼108% compared to foliar-applied urea under low soil N conditions in greenhouse experiments. Controlled N release by leaf-attached nanomaterials improves N delivery and use efficiency in crop plants, creating nanofertilizers with reduced environmental impact.

Lactoferrin is a highly safe antibacterial protein found in the human body and in foods. Calcium phosphate (CaP) nanoparticles with immobilized lactoferrin could therefore be useful as intraoral disinfectants for the prevention and treatment of dental infections because CaP is a mineral component of human teeth. In this study, we fabricated CaP nanoparticles with co-immobilized lactoferrin and heparin using a simple one-step coprecipitation process. Heparin, a negatively charged polysaccharide, was used as both an immobilizing agent for lactoferrin and a particle-dispersing agent. The immobilization efficiency for lactoferrin in the CaP nanoparticles depended on the concentrations of both the lactoferrin and heparin in the reaction solution and was over 90% under optimal conditions. The nanoparticles had a hydrodynamic diameter of about 150-200 nm and could be well dispersed in water, owing to their relatively large negative zeta potential derived from heparin. They were found to exhibit antibacterial activity against Actinomyces naeslundii, which is involved in the initial formation of dental plaque that consequently leads to dental caries and periodontal disease. These results indicate the potential of the proposed nanoparticles as intraoral disinfectants.

Retention of toxic metals/metalloids like arsenic via mineral-water interaction plays a crucial role in the environmental behavior of pollutants. However, the influence of mineral crystallinity on the retention of toxic elements, the evolution of liquid composition, and the interaction mechanism are poorly understood. This study investigated the interaction between As(V) and calcium phosphate (CaP) under oxic conditions with varying crystallinities, particularly amorphous CaP (ACP), across varying As(V) concentrations and pH conditions. Results revealed that the amorphous phase substantially influenced As(V) fate, with the As(V) retention potential of ACP and poorly crystalline hydroxylapatite (HAP) being 13.65 and 12.61 times higher than highly crystalline HAP, respectively. As(V) retention involves the dissolution of ACP and the recrystallization of As(V)-substituted HAP, correlated with three distinct ACP transformation stages during recrystallization. The lower pH (7.5) facilitated ACP dissolution, and the elevated Ca2+ concentration enhanced the volume of CaP recrystallization. Conversely, higher pH levels (8.0, 8.5, and 9.0) promoted a higher degree of recrystallization, evidenced by reduced residual Ca2+ levels after 48 hrs (post-crystallization stage). Meanwhile, As-bearing CaP forms with greater competition between PO43- and AsO43- at higher initial As(V) concentrations than lower ones. Additionally, lattice distortion, increases in species of surface bond groups, and reduced crystallinity were observed in the As(V)-bearing CaP product. Overall, this study underscores the pivotal role of ACP and its poorly crystalline counterparts in arsenic retention through the dissolution-recrystallization mechanism.

One of the key factors of the interaction 'osteoplastic material-organism' is the state of the implant surface. Taking into account the fact that the equilibrium in regeneration conditions is reached only after the reparative histogenesis process is completed, the implant surface is constantly modified. This work is devoted to the numerical description of the dynamic bilateral material-medium interaction under close to physiological conditions, as well as to the assessment of the comparability of the model with in vitro and in vivo experimental results. The semi-empirical model obtained on the basis of chemical kinetics allows us to describe numerically the processes occurring in the in vitro systems and extrapolates well to assess the behavior of dicalcium phosphate dihydrate (DCPD) material under conditions of ectopic (subcutaneous) implantation in Wistar rats. It is shown that an experiment conducted using a perfusion-diffusion bioreactor in a cell culture medium with the addition of fetal bovine serum (FBS) allows for achieving morphologically and chemically identical changes in the surface of the material in comparison with the real organism. This fact opens up wide possibilities for the creation of an analog of a 'laboratory-on-a-chip' and the transition from classical in vivo models to more controlled and mathematically based in vitro systems.

Hydroponics, despite its potential for efficient crop production, relies heavily on chemical fertilizers derived from nonrenewable resources and thus contributes to environmental burdens and unsustainable use of phosphorus. Integrating hydroponics into a circular phosphorus economy is crucial for mitigating these impacts. This study quantitatively assessed the capacity of filtrates from nitrified biogas digestate (f-NBD), a nutrient solution derived from organic waste, to replace phosphorus and nitrogen in hydroponic chemical nutrient solutions. Additionally, the influence of pH control methods on phosphorus recovery and substitution was investigated using a novel pH-rebound approach involving acidification followed by alkalinization to pH 6. The experimental results demonstrated that the pH-rebound method effectively dissolved apatite phosphorus, the predominant form of precipitated phosphorus in NBD, without inducing significant reprecipitation upon alkalinization. This pH adjustment enhanced the phosphorus solubility and optimized the nitrogen-to-phosphorus (N/P) ratio in f-NBD, enabling it to substitute up to 77% of the phosphorus and 100% of the nitrogen in standard hydroponic nutrient solutions. The study also revealed that, under certain conditions, f-NBD is as a more viable option for phosphorus recovery than struvite, a widely recognized recovered phosphorus product. The identified substitution ratios and pH optimization strategies provide valuable insights for mitigating the environmental burdens of hydroponic fertilizers. By partially replacing chemical nutrient solutions with f-NBD, hydroponics can be integrated more effectively into a circular phosphorus economy, reducing the reliance on nonrenewable resources and curtailing the environmental impacts associated with the production and use of conventional fertilizers. This research provides a basis for future initiatives aimed at developing sustainable hydroponic systems and offering new utilization methods for biogas digestate.

Highlighting the essential role of chitosan (CS), known for its biocompatibility, biodegradability, and ability to promote cell adhesion and proliferation, this study explores its utility in modulating the biomimetic mineralization of calcium phosphate (CaP). This approach holds promise for developing biomaterials suitable for bone regeneration. However, the interactions between the CS surface and in situ precipitated CaP still require further exploration. In the theoretical section, molecular dynamics (MD) simulations demonstrate that, at an appropriate pH level during the prenucleation stage, calcium ions (Ca2+) and hydrogen phosphate ions (HPO42-) form Posner-like clusters. Additionally, the interaction between these clusters and the CS molecule enhances system stability. Together, these phenomena facilitate the transition to subsequent heterogeneous nucleation on the surface of the organic matrix, which is a more controlled process than homogeneous nucleation in solution. Dynamic simulation results suggest that CS acts as a stabilizing matrix at pH 8.0 during biomimetic mineralization. In the experimental section, the effects of pH and the molecular weight of CS were investigated, with a focus on their impact on the crystal structure of the resulting material. X-ray diffraction and scanning electron microscopy analyses reveal that, under conditions of approximately pH 8.0 and a CS molecular weight of 20 000 g/mol, and controlled ion concentration, ultrasound radiation, and temperature, the dominant CaP phases in the material are carbonate-doped hydroxyapatite (CHA) and octacalcium phosphate (OCP). These findings suggest that CS, when adjusted for molecular weight and pH, facilitates the formation of CaP crystal phases that closely resemble the natural inorganic composition of bone, highlighting its protective and regulatory roles in the growth and maturation of crystals during mineralization. The theoretical predictions and experimental outcomes confirm the crucial role of CS as a templating agent, enabling the development of a biomimetic mineralization pathway. CS's ability to guide this process may prove valuable in the design of materials for bone tissue engineering, particularly in developing effective materials for bone tissue healing and regeneration.

Interbody fusion is an orthopedic surgical procedure to connect two adjacent vertebrae in patients suffering from spinal disc disease. The combination of synthetic bone grafts with protein-based drugs is an intriguing approach to stimulate interbody bone growth, specifically in patients exhibiting restricted bone progression. Recombinant human thrombomodulin (rhTM), a novel protein drug characterized by its superior stability and potency, shows promise in enhancing bone formation. A composite bone graft, termed CaP-rhTM, has been synthesized, combining calcium phosphate (CaP) microparticles as a delivery vehicle for rhTM to facilitate interbody fusion.In vitrostudies have demonstrated that rhTM significantly promotes the proliferation and maturation of preosteoblasts at nanogram dosage, while exerting minimal impact on osteosarcoma cell growth. The expression levels of mature osteoblast markers, including osteocalcin, osteopontin, alkaline phosphatase, and calcium deposition were also enhanced by rhTM. In rat caudal disc model of interbody fusion, CaP-rhTM with 800 ng of drug dosage was implanted along with a polylactic acid cage, to ensure structural stability within the intervertebral space. Microcomputed tomography analyses revealed that from 8 to 24 weeks, CaP-rhTM substantially improves both bone volume and trabecular architecture, in addition to the textural integrity of bony endplate surfaces. Histological examination confirmed the formation of a continuous bone bridge connecting adjacent vertebrae. Furthermore, biomechanical assessment via three-point bending tests indicated an improved bone quality of the fused disc. This study has demostrated that rhTM exhibits considerable potential in promoting osteogenesis. The use of CaP-rhTM has also shown significant improvements in promoting interbody fusion.

The natural remineralization of enamel is of major importance for oral health. In principle, early erosions (demineralization) induced by acidic beverages and foods as well as initial caries lesions can be covered and remineralized by the deposition of calcium phosphate, i.e., tooth mineral. This remineralization effect is characterized by the presence of calcium and phosphate ions in saliva that form hydroxyapatite on the enamel surface. Although it is apparently a simple crystallization, it turns out that remineralization under in vivo conditions is actually a very complex process. Calcium phosphate can form a number of solid phases of which hydroxyapatite is only one. Precipitation involves the formation of metastable phases like amorphous calcium phosphate that convert into biological apatite in a number of steps. Nanoscopic clusters of calcium phosphate that can attach on the enamel surface are also present in saliva. Thus, remineralization under strictly controlled in vitro conditions (e.g., pH, ion concentrations, no additives) is already complex, but it becomes even more complicated under the actual conditions in the oral cavity. Here, biomolecules are present in saliva, which interact with the forming calcium phosphate mineral. For instance, there are salivary proteins which have the function of inhibiting crystallization to avoid overshooting remineralization. Finally, the presence of bacteria and an extracellular matrix in plaque and the presence of proteins in the pellicle have strong influences on the precipitation on the enamel surface. The current knowledge on the remineralization of the enamel is reviewed from a chemical perspective with a special focus on the underlying crystallization phenomena and the effects of biological compounds that are present in saliva, pellicle, and plaque. Basically, the remineralization of enamel follows the same principles as calculus formation. Notably, both processes are far too complex to be understood on a microscopic basis under in vivo conditions, given the complicated process of mineral formation in the presence of a plethora of foreign ions and biomolecules.

Calcium phosphates (CaPs) and their substituted derivatives encompass a large number of compounds with a vast presence in nature that have aroused a great interest for decades. In particular, hydroxyapatite (HAp, Ca10(OH)2(PO4)6) is the most abundant CaP mineral and is significant in the biological world, at least in part due to being a major compound in bones and teeth. HAp exhibits excellent properties, such as safety, stability, hardness, biocompatibility, and osteoconductivity, among others. Even some of its drawbacks, such as its fragility, can be redirected thanks to another essential feature: its great versatility. This is based on the compound's tendency to undergo substitutions of its constituent ions and to incorporate or anchor new molecules on its surface and pores. Thus, its affinity for biomolecules makes it an optimal compound for multiple applications, mainly, but not only, in biological and biomedical fields. The present review provides a chemical and structural context to explain the affinity of HAp for biomolecules such as proteins and nucleic acids to generate hybrid materials. A size-dependent criterium of increasing complexity is applied, ranging from amino acids/nucleobases to the corresponding macromolecules. The incorporation of metal ions or metal complexes into these functionalized compounds is also discussed.

Struvite crystallization, a promising technology for nutrient recovery from wastewater, is facing considerable challenges due to the presence of emerging contaminants such as microplastics (MPs) ubiquitously found in wastewater. Here, we investigate the roles of MPs and humic acid (HA) in struvite crystallization in batch and fluidized-bed reactors (FBRs) using synthetic and real wastewater with a Mg:N:P molar ratio of 1:3:(1-1.3) at an initial pH of 11. Batch reactor (BR) experiment results show that MPs expedited the nucleation and growth rates of struvite (e.g., the rate of crystal growth in the presence of 30 mg L-1 of polyethylene terephthalate (PET) was 1.43 times higher than that in the blank system), while HA hindered the formation of struvite. X-ray diffraction and the Rietveld refinement analysis revealed that the presence of MPs and HA can result in significant changes in phase compositions of the reclaimed precipitates, with over 80 % purity of struvite found in the precipitates from suspensions in the presence of 30 mg L-1 of MPs. Further characterizations demonstrated that MPs act as seeds of struvite nucleation, spurring the formation of well-defined struvite, while HA favors the formation of newberyite rather than struvite in both reactors. These findings highlight the need for a more comprehensive understanding of the interactions between emerging contaminants and struvite crystallization processes to optimize nutrient recovery strategies for mitigating their adverse impact on the quality and yield of struvite-based fertilizers. ENVIRONMENTAL IMPLICATION: The presence of microplastics in wastewater poses a significant challenge to struvite crystallization for nutrient recovery, as it accelerates nucleation and growth rates of struvite crystals. This can lead to changes in the phase compositions of the reclaimed precipitates, with implications for the quality and yield of struvite-based fertilizers. Additionally, the presence of humic acid hinders the formation of struvite, favoring the formation of other minerals like newberyite. Understanding the interactions between emerging contaminants and struvite crystallization processes is crucial for optimizing nutrient recovery strategies and mitigating the environmental impact of these contaminants on water quality and struvite-based fertilizers.

Biomineralization is a natural process in which organisms regulate the growth of inorganic minerals to form biominerals with unique layered structures, such as bones and teeth, primarily composed of calcium and phosphorus. Tooth decay significantly impacts our daily lives, and the key to tooth regeneration lies in restoring teeth through biomimetic approaches, utilizing mineralization strategies or materials that mimic natural processes. This review delves into the types, properties, and transformations of calcium and phosphorus minerals, followed by an exploration of the mechanisms behind physiological and pathological mineralization in living organisms. It summarizes the mechanisms and commonalities of biomineralization and discusses the advancements in dental biomineralization research, guided by insights into calcium and phosphorus mineral biomineralization. This review concludes by addressing the current challenges and future directions in the field of dental biomimetic mineralization.

Nanoparticles of a particular, evolutionarily old inorganic polymer found across the biological kingdoms have attracted increasing interest in recent years not only because of their crucial role in metabolism but also their potential medical applicability: it is inorganic polyphosphate (polyP). This ubiquitous linear polymer is composed of 10-1000 phosphate residues linked by high-energy anhydride bonds. PolyP causes induction of gene activity, provides phosphate for bone mineralization, and serves as an energy supplier through enzymatic cleavage of its acid anhydride bonds and subsequent ATP formation. The biomedical breakthrough of polyP came with the development of a successful fabrication process, in depot form, as Ca- or Mg-polyP nanoparticles, or as the directly effective polymer, as soluble Na-polyP, for regenerative repair and healing processes, especially in tissue areas with insufficient blood supply. Physiologically, the platelets are the main vehicles for polyP nanoparticles in the circulating blood. To be biomedically active, these particles undergo coacervation. This review provides an overview of the properties of polyP and polyP nanoparticles for applications in the regeneration and repair of bone, cartilage, and skin. In addition to studies on animal models, the first successful proof-of-concept studies on humans for the healing of chronic wounds are outlined.

This review elucidates the mechanisms underpinning intrafibrillar mineralization, examines various amorphous calcium phosphate (ACP) stabilizers employed in dentin's intrafibrillar mineralization, and addresses the challenges encountered in clinical applications of ACP-based bioactive materials.

The literature search for this review was conducted using three electronic databases: PubMed, Web of Science, and Google Scholar, with specific keywords. Articles were selected based on inclusion and exclusion criteria, allowing for a detailed examination and summary of current research on dentin remineralization facilitated by ACP under the influence of various types of stabilizers.

This review underscores the latest advancements in the role of ACP in promoting dentin remineralization, particularly intrafibrillar mineralization, under the regulation of various stabilizers. These stabilizers predominantly comprise non-collagenous proteins, their analogs, and polymers. Despite the diversity of stabilizers, the mechanisms they employ to enhance intrafibrillar remineralization are found to be interrelated, indicating multiple driving forces behind this process. However, challenges remain in effectively designing clinically viable products using stabilized ACP and maximizing intrafibrillar mineralization with limited materials in practical applications.

The role of ACP in remineralization has gained significant attention in dental research, with substantial progress made in the study of dentin biomimetic mineralization. Given ACP's instability without additives, the presence of ACP stabilizers is crucial for achieving in vitro intrafibrillar mineralization. However, there is a lack of comprehensive and exhaustive reviews on ACP bioactive materials under the regulation of stabilizers. A detailed summary of these stabilizers is also instrumental in better understanding the complex process of intrafibrillar mineralization. Compared to traditional remineralization methods, bioactive materials capable of regulating ACP stability and controlling release demonstrate immense potential in enhancing clinical treatment standards.

This review examines the possible role of mitochondria in maintaining calcium and phosphate ion homeostasis and participating in the mineralization of bone, cartilage and other vertebrate hard tissues. The paper builds on the known structural features of mitochondria and the documented observations in these tissues that the organelles contain calcium phosphate granules. Such deposits in mitochondria putatively form to buffer excessively high cytosolic calcium ion concentrations and prevent metabolic deficits and even cell death. While mitochondria protect cytosolic enzyme systems through this buffering capacity, the accumulation of calcium ions by mitochondria promotes the activity of enzymes of the tricarboxylic acid (TCA/Krebs) cycle, increases oxidative phosphorylation and ATP synthesis, and leads to changes in intramitochondrial pH. These pH alterations influence ion solubility and possibly the transitions and composition in the mineral phase structure of the granules. Based on these considerations, mitochondria are proposed to support the mineralization process by providing a mobile store of calcium and phosphate ions, in smaller cluster or larger granule form, while maintaining critical cellular activities. The rise in the mitochondrial calcium level also increases the generation of citrate and other TCA cycle intermediates that contribute to cell function and the development of extracellular mineral. This paper suggests that another key role of the mitochondrion, along with the effects just noted, is to supply phosphate ions, derived from the breakdown of ATP, to endolysosomes and autophagic vesicles originating in the endoplasmic reticulum and Golgi and at the plasma membrane. These many separate but interdependent mitochondrial functions emphasize the critical importance of this organelle in the cellular control of vertebrate mineralization.

Crystallization pathways are essential to various industrial, geological, and biological processes. In nonclassical nucleation theory, prenucleation clusters (PNCs) form, aggregate, and crystallize to produce higher order assemblies. Microscopy and X-ray techniques have limited utility for PNC analysis due to the small size (0.5-3 nm) and time stability constraints. We present a new approach for analyzing PNC formation based on 31P nuclear magnetic resonance (NMR) spin counting of vitrified molecular assemblies. The use of glassing agents ensures that vitrification generates amorphous aqueous samples and offers conditions for performing dynamic nuclear polarization (DNP)-amplified NMR spectroscopy. We demonstrate that molecular adenosine triphosphate along with crystalline, amorphous, and clustered calcium phosphate materials formed via a nonclassical growth pathway can be differentiated from one another by the number of dipolar coupled 31P spins. We also present an innovative approach for examining spin counting data, demonstrating that a knowledge-based fitting of integer multiples of cosine wave functions, instead of the traditional Fourier transform, provides a more physically meaningful retrieval of the existing frequencies. This is the first report of multiquantum spin counting of assemblies formed in solution as captured under vitrified DNP conditions, which can be useful for future analysis of PNCs and other aqueous molecular clusters.

The hierarchical assembly of nanoapatite within a type I collagen matrix was achieved through biomimetic mineralization in vitro, cooperatively regulated by non-collagenous proteins and small biomolecules. Here, we demonstrated that IP6 could significantly promote intrafibrillar mineralization in two- and three-dimensional collagen models through binding to collagen fibrils via hydrogen bonds (the interaction energy ∼10.21 kJ mol-1), as confirmed by the FTIR spectra and isothermal experimental results. In addition, we find that IP6 associated with dental collagen fibrils can also enhance the remineralization of calcium-depleted dentin and restore its mechanical properties similar to the natural dentin within 4 days. The promoting effect is mainly due to the chemical modification of IP6, which alters the interfacial physicochemical properties of collagen fibrils, strengthening the interaction of calcium phosphate minerals and mineral ions with collagen fibrils. This strategy of interfacial regulation to accelerate the mineralization of collagen fibrils is essential for dental repair and the development of a clinical product for the remineralization of hard tissue.

Living organisms in nature have undergone continuous evolution over billions of years, resulting in the formation of high-performance fracture-resistant biomineralized tissues such as bones and teeth to fulfill mechanical and biological functions, despite the fact that most inorganic biominerals that constitute biomineralized tissues are weak and brittle. During the long-period evolution process, nature has evolved a number of highly effective and smart strategies to design chemical compositions and structures of biomineralized tissues to enable superior properties and to adapt to surrounding environments. Most biomineralized tissues have hierarchically ordered structures consisting of very small building blocks on the nanometer scale (nanoparticles, nanofibers or nanoflakes) to reduce the inherent weaknesses and brittleness of corresponding inorganic biominerals, to prevent crack initiation and propagation, and to allow high defect tolerance. The bioinspired principles derived from biomineralized tissues are indispensable for designing and constructing high-performance biomimetic materials. In recent years, a large number of high-performance biomimetic materials have been prepared based on these bioinspired principles with a large volume of literature covering this topic. Therefore, a timely and comprehensive review on this hot topic is highly important and contributes to the future development of this rapidly evolving research field. This review article aims to be comprehensive, authoritative, and critical with wide general interest to the science community, summarizing recent advances in revealing the formation processes, composition, and structures of biomineralized tissues, providing in-depth insights into guidelines derived from biomineralized tissues for the design and construction of high-performance biomimetic materials, and discussing recent progress, current research trends, key problems, future main research directions and challenges, and future perspectives in this exciting and rapidly evolving research field.

Though crucial for natural bone healing, local calcium ion (Ca2+) and phosphate ion (Pi) concentrations can exceed the cytotoxic limit leading to mitochondrial overload, oxidative stress, and cell death. For bone tissue engineering applications, H2S can be employed as a cytoprotective molecule to enhance mesenchymal stem cell (MSC) tolerance to cytotoxic Ca2+/Pi concentrations. Varied concentrations of sodium hydrogen sulfide (NaSH), a fast-releasing H2S donor, were applied to assess the influence of H2S on MSC proliferation. The results suggested a toxicity limit of 4 mM for NaSH and that 1 mM of NaSH could improve cell proliferation and differentiation in the presence of cytotoxic levels of Ca2+ (32 mM) and/or Pi (16 mM). To controllably deliver H2S over time, a novel donor molecule (thioglutamic acid-GluSH) was synthesized and evaluated for its H2S release profile. Excitingly, GluSH successfully maintained cytoprotective level of H2S over 7 days. Furthermore, MSCs exposed to cytotoxic Ca2+/Pi concentrations in the presence of GluSH were able to thrive and differentiate into osteoblasts. These findings suggest that the incorporation of a sustained H2S donor such as GluSH into CaP-based bone graft substitutes can facilitate considerable cytoprotection, making it an attractive option for complex bone regenerative engineering applications.

Proteinoids, or thermal proteins, are amino acid polymers formed at high temperatures by nonbiological processes. The objective of this study is to examine the memfractance characteristics of proteinoids within a supersaturated hydroxyapatite solution. The ionic solution utilized for the current-voltage (I-V) measurements possessed an ionic strength of 0.15 mol/L, a temperature of 37 °C, and a pH value of 7.4. The I-V curves exhibited distinct spikes, which are hypothesized to arise from the capacitive charging and discharging of the proteinoid-hydroxyapatite media. The experimental results demonstrated a positive correlation between the concentration of proteinoids and the observed number of spikes in the I-V curves. This observation provides evidence in favor of the hypothesis that the spikes originate from the proteinoids' capacitive characteristics. The memfractance behavior exemplifies the capacity of proteinoids to retain electrical charge within the hydrated hydroxyapatite media. Additional investigation is required in order to comprehensively identify the memcapacitive phenomena and delve into their implications for models of protocellular membranes. In a nutshell, this study provides empirical support for the existence of capacitive membrane-memfractance mechanisms in ensembles of proteinoids.

This study evaluated the biocompatibility and accuracy of 3D-printed β-tricalcium phosphate (β-TCP) pure ceramic scaffolds. A specific shaping process associating a digital light processing (DLP) 3D printer and a heat treatment was developed to produce pure β-TCP scaffolds leaving no polymer binder residue. The β-TCP was characterised using X-ray diffraction, infrared spectroscopy and the detection of pollutants. The open porosity of produced matrices and their resorption were studied by hydrostatic weighing and calcium release measures. The biocompatibility of the printed matrices was evaluated by mean of osteoblast cultures. Finally, macroporous cubic matrices were produced. They were scanned using a micro-Computed Tomography scanner (micro-CT scan) and compared to their numeric models. The results demonstrated that DLP 3D printing with heat treatment produces pure β-TCP matrices with enhanced biocompatibility. They also demonstrated the printing accuracy of our technique, associating top-down DLP with the sintering of green parts. Thus, this production process is promising and will enable us to explore complex phosphocalcic matrices with a special focus on the development of a functional vascular network.

The issue of preserving carbonatic stones of cultural heritage (CH) restored in the past that have undergone new decay phenomena is strongly emerging and conservation science has not yet found a reliable solution. In this paper, we propose the application of synchrotron radiation X-ray diffraction computed tomography (XRDCT) to explore the effects of using inorganic-mineral products (ammonium oxalate; ammonium phosphate) in sequence as a novel, compatible and effective re-treatment approach to consolidate decayed carbonatic stones already treated with inorganic-mineral treatments. High-quality XRDCT datasets were used to qualitatively/quantitatively investigate and 3D localize the complex mixture of crystalline phases formed after the conservation re-treatments within a porous carbonatic stone substrate. The XRDCT reconstruction images and the structural refinements of XRD patterns with the Rietveld methods showed that the phase composition of reaction products, their volume distribution, and weight fraction vary as a function of the treatment sequence and penetration depth. The high potential of XRDCT allows (i) assessment of peculiar trends of each treatment/treatment sequence; (ii) exploration of the reaction steps of the sequential treatments and (iii) demonstration of the consolidating effect of inorganic re-treatments, non-destructively and at the micron scale. Above all, our study (i) provides new analytical tools to support the conservation choices, (ii) showcases new analytical possibilities for XRDCT in conservation science, including in investigations of CH materials and decay processes, and (iii) opens up new perspectives in analytical chemistry and material characterisation for the non-destructive and non-invasive analysis of reactions within heterogeneous polycrystalline systems.

Amorphous inorganic solids are traditionally isotropic, thus, it is believed that they only grow in a non-preferential way without the assistance of regulators, leading to the morphologies of nanospheres or irregular aggregates of nanoparticles. However, in the presence of (ortho)phosphate (Pi) and pyrophosphate ions (PPi) which have synergistic roles in biomineralization, the highly elongated amorphous nanowires (denoted ACPPNs) form in a regulator-free aqueous solution (without templates, additives, organics, etc). Based on thorough characterization and tracking of the formation process (e.g., Cryo-TEM, spherical aberration correction high resolution TEM, solid state NMR, high energy resolution monochromated STEM-EELS), the microstructure and its preferential growth behavior are elucidated. In ACPPNs, amorphous calcium orthophosphate and amorphous calcium pyrophosphate are distributed at separated but close sites. The ACPPNs grow via either the preferential attachment of ∼2 nm nanoclusters in a 1-dimension way, or the transformation of bigger nanoparticles, indicating an inherent driving force-governed process. We propose that the anisotropy of ACPPNs microstructure, which is corroborated experimentally, causes their oriented growth. This study proves that, unlike the conventional view, amorphous minerals can form via oriented growth without external regulation, demonstrating a novel insight into the structures and growth behaviors of amorphous minerals.

The aim of this work is to test experimental cements, doped with a silicate based bioactive nanoparticle (NanoBiosilicate). Methods, we synthesized a glass nanoparticle by Sol-Gel Stöber method, used to be incorporated in a dental material for endodontic uses.

We assess the mineralizing properties and biocompatibility. Besides the crystallography characterization of the resultant new crystals. Results, After analysis, and comparison with commercial materials, the material tested was similar in mechanical properties required by ISO, The ion release was effective after 2 hr. of setting and the novel material was cell compatible accepted by ISO.

We found new formed Calcium Phosphate peaks in the spectroscopic analysis (FTIR), remarkably the crystals formed were comparable to hydroxyapatite when analyzed with a Selected Area Electron Diffractometer, with rings of 2.84 Å for 002, and the 2.77 Å is also visible for 210. The 6.83 Å and 6.88 Å, for respective 222 and 004. The incorporation of Chlorhexidine was not detrimental for this property, Significance, the features mentioned represented a progress in biomineralization field that was associated to an improved mineral structure formation with increased crystallographic similarity to natural hydroxyapatite. When chlorhexidine was added a favorable biomodification of the remaining collagen in dentinal walls and antimicrobial activity potential were also observed.

The autoimmune inflammatory myopathy disease spectrum, commonly known as myositis, is a group of systemic diseases that mainly affect the muscles, skin and lungs. Biomarker assessment helps in understanding disease mechanisms, allowing for the implementation of precise strategies in the classification, diagnosis, and management of these diseases. This review examines the pathogenic mechanisms and highlights current data on blood and tissue biomarkers of autoimmune inflammatory myopathies.

With the development of agricultural intensification, phosphorus (P) accumulation in croplands and sediments has resulted in the increasingly widespread interaction between inorganic and organic P species, which has been, previously, underestimated or even ignored. We quantified the nanoscale dissolution kinetics of sparingly soluble brushite (CaHPO4·2H2O, DCPD) over a broad range of phosphate and/or phytate concentrations by using in situ atomic force microscopy (AFM). Compared to water, we found that low concentrations of phosphate (1-1000 µM) or phytate (1-100 µM) inhibited brushite dissolution by slowing single step retraction. However, with increasing phosphate or phytate concentrations to 10 mM, there was a reverse effect of dissolution promotion at brushite-water interfaces. In situ observations of the coupled dissolution-reprecipitation showed that phosphate precipitated more readily than phytate on brushite surfaces, with the formation of amorphous calcium phosphate (ACP). For a fundamental understanding, zeta potential and in situ Raman spectroscopy (RS) revealed that the concentration-dependent dissolution is attributed to the reverse of outer-sphere to inner-sphere adsorption with increasing phosphate or phytate concentrations. In addition, the mineralization of phytate with outer-sphere adsorption by phytase was higher than that with inner-spere adsorption, and the presence of phytate delayed ACP phase transformation to hydroxylapatite (HAP). These in situ observations and analyses may fill the knowledge gaps of interaction between inorganic and organic P species in P-rich terrestrial and aquatic environments, thereby implicating their biogeochemical cycling and the associated availability.

Biomaterials have been used to supplement and restore function and structure by replacing or restoring parts of damaged tissues and organs. In ancient times, the medical use of biomaterials was limited owing to infection during surgery and poor surgical techniques. However, in modern times, the medical applications of biomaterials are diversifying owing to great developments in material science and medical technology. In this paper, we introduce biomaterials, focusing on calcium phosphate ceramics, including octacalcium phosphate, which has recently attracted attention as a bone graft material.

Despite significant efforts utilizing advanced technologies, the contentious debate surrounding the intricate mechanism underlying collagen fibril mineralization, particularly with regard to amorphous precursor infiltration and phase transformation, persists. This work proposes an amorphous calcium phosphate (ACP)-mediated pathway for collagen fibril mineralization and utilizing stochastic optical reconstruction microscopy technology, and has experimentally confirmed for the first time that the ACP nanoparticles can infiltrate inside collagen fibrils. Subsequently, the ACP-mediated phase transformation occurs within collagen fibrils to form HAP crystallites, and significantly enhances the mechanical properties of the mineralized collagen fibrils compared to those achieved by the calcium phosphate ion (CPI)-mediated mineralization and resembles the natural counterpart. Furthermore, demineralized dentin can be effectively remineralized through ACP-mediated mineralization, leading to complete restoration of its mechanical properties. This work provides a new paradigm of collagen mineralization via particle-mediated phase transformation, deepens the understanding of the mechanism behind the mineralization of collagen fibrils, and offers a new strategy for hard tissue repair.

Hydroxyapatite-based materials have been widely used in countless applications, such as bone regeneration, catalysis, air and water purification or protein separation. Recently, much interest has been given to controlling the aspect ratio of hydroxyapatite crystals from bulk samples. The ability to exert control over the aspect ratio may revolutionize the applications of these materials towards new functional materials. Controlling the shape, size and orientation of HA crystals allows obtaining high aspect ratio structures, improving several key properties of HA materials such as molecule adsorption, ion exchange, catalytic reactions, and even overcoming the well-known brittleness of ceramic materials. Regulating the morphogenesis of HA crystals to form elongated oriented fibres has led to flexible inorganic synthetic sponges, aerogels, membranes, papers, among others, with applications in sustainability, energy and catalysis, and especially in the biomedical field.

The method of soil improvement by calcium phosphate precipitation is a novel, environmentally friendly, and non-toxic technique. Such technology provides advantages over ureolytic induced calcite precipitation (UICP), the most popular and widely used method in the field of geotechnical engineering. In this paper, an investigation of the consolidation of fine and coarse sand samples by enzyme induced calcium phosphate precipitation (EICPP) was carried out. Tuna bones were used as an alternative source of calcium and phosphorus ions, as one of the most popular fish species in Japan and the main source of food industry waste. Unconfined compressive strength (UCS) of the samples after 21 days of daily injection of the solution showed an increase in strength up to 6,05 MPa in fine and up to 4,3 MPa in coarse sand samples. X-ray powder diffraction (XRD), scanning electron microscope (SEM), and energy dispersive X-ray spectroscopy (SEM-EDS) analysis were performed to investigate the nature and type of deposition. Analyses confirmed that deposition is composed of brushite with needle-like crystals in the case of Toyoura sand and flower-like crystals in the case of Mikawa sand. SEM-EDS showed a presence of both, calcium, and phosphorus in the precipitate, indicating the presence of calcium phosphate compounds (CPCs). This study reveals that tuna bones are a rich source of calcium and phosphorus for EICPP, which results in a strengthening of silicate soil up to 3.4-6.05 MPa and is able to reduce ammonia emissions by 85.7 % - 97.5 % compared to UICP.

Non-collagenous proteins (NCPs) in the extracellular matrix (ECM) of bone and dentin are known to play a critical regulatory role in the induction of collagen fibril mineralization and are embedded in hyaluronic acid (HA), which acts as a water-retaining glycosaminoglycan and provides necessary biochemical and biomechanical cues. Our previous study demonstrated that HA could regulate the mineralization degree and mechanical properties of collagen fibrils, yet its kinetics dynamic mechanism on mineralization is under debate. Here, we further investigated the role of HA on collagen fibril mineralization and the possible mechanism. The HA modification can significantly promote intrafibrillar collagen mineralization by reducing the electronegativity of the collagen surface to enhance calcium ions (Ca2+) binding capacity to create a local higher supersaturation. In addition, the HA also provides additional nucleation sites and shortens the induction time of amorphous calcium phosphate (ACP)-mediated hydroxyapatite (HAP) crystallization, which benefits mineralization. The acceleration effect of HA on intrafibrillar collagen mineralization is also confirmed in collagen hydrogel and in vitro dentin remineralization. These findings offer a physicochemical view of the regulation effect of carbohydrate polymers in the body on biomineralization, the fine prospect for an ideal biomaterial to repair collagen-mineralized tissues.

The purpose of the study is to develop a novel peptide for caries management. Gallic-Acid-Polyphemusin-I (GAPI) was synthesised by grafting Polyphemusin I (PI) and gallic acid (GA). Biocompatibility was evaluated using a Cell Counting Kit-8 Assay. Antimicrobial properties were assessed using minimum inhibitory concentration (MIC) and minimum bactericidal/fungicidal concentration (MBC/MFC). The bacterial and fungal morphology after GAPI treatment was investigated using transmission electron microscopy (TEM). The architecture of a consortium biofilm consisting of Streptococcus mutans, Lacticaseibacillus casei and Candida albicans was evaluated using scanning electron microscopy (SEM) and confocal laser scanning microscopy. The growth kinetics of the biofilm was examined using a propidium monoazide-quantitative polymerase chain reaction. The surface and calcium-to-phosphorus molar ratio of GAPI-treated enamel after pH cycling were examined with SEM and energy-dispersive X-ray spectroscopy. Enamel crystal characteristics were analysed using X-ray diffraction. Lesion depths representing the enamel's mineral loss were assessed using micro-computed tomography. The MIC of GAPI against S. mutans, L. casei and C. albicans were 40 μM, 40 μM and 20 μM, respectively. GAPI destroyed the biofilm's three-dimensional structure and inhibited the growth of the biofilm. SEM showed that enamel treated with GAPI had a relatively smooth surface compared to that treated with water. The calcium-to-phosphorus molar ratio of enamel treated with GAPI was higher than that of the control. The lesion depths and mineral loss of the GAPI-treated enamel were less than the control. The crystallinity of the GAPI-treated enamel was higher than the control. This study developed a biocompatible, mineralising and antimicrobial peptide GAPI, which may have potential as an anti-caries agent.

Octacalcium phosphate (OCP), a precursor to apatite, has a layered structure that allows various molecules to be intercalated within its interlayers. Previous research on the phase conversion process of OCP to apatite indicated that the layered structures typically collapse due to the shrinking of the OCP layers. In contrast, this study presents a novel phenomenon involving OCP layer expansion during phase conversion. This expansion is based on a forced oxidation process of the intercalated molecules within the hydrous layers of OCP. By introducing NaClO to an OCP interlayer containing dithiodiglycolic acid (DSG), the OCP layers are expanded. This process involves DSG decomposition through its reaction with NaClO. Specifically, the process occurs when a DSG-substituted OCP (containing disulfide bonds (-S-S-)) is immersed in a NaClO solution. This is the first study to report the expansion phenomenon during the phase conversion process from OCP to apatite, providing a new perspective to the conventional understanding that these layers only shrink.

Hydroxyapatite (HAP) is a green catalyst that has a wide range of applications in catalysis due to its high flexibility and multifunctionality. These properties allow HAP to accommodate a large number of catalyst modifications that can selectively improve the catalytic performance in target reactions. To date, many studies have been conducted to elucidate the effect of HAP modification on the catalytic activities for various reactions. However, systematic design strategies for HAP catalysts are not established yet due to an incomplete understanding of underlying structure-activity relationships. In this review, tuning methods of HAP for improving the catalytic performance are discussed: 1) ionic composition change, 2) morphology control, 3) incorporation of other metal species, and 4) catalytic support engineering. Detailed mechanisms and effects of structural modulations on the catalytic performances for attaining the design insights of HAP catalysts are investigated. In addition, computational studies to understand catalytic reactions on HAP materials are also introduced. Finally, important areas for future research are highlighted.