Early Stages Of Mineralization Research Articles

ASPECTS OF SURFACE ENAMEL MINERALIZATION IN PERMANENT TEETH OF CHILDREN FROM DIFFERENT AGE GROUPS

The purpose of our study was the examination of external surface enamel mineralization in permanent teeth of children from different age groups. We examined sections of 50 extracted for orthodontic indications premolars in patients from different age groups. A study of 16 teeth was conducted in 11-13 years old children, 8 teeth were investigated in each group of 13-15 years old, as well as 9 teeth in 15-16-year-old patients. All patients were appointed with remineralization therapy during the first six months after tooth eruption fallowed by application of “Tooth Mousse” ones a day for 2 weeks every six months with appropriate monitoring. The comparison group, on the other hand, consisted from extracted teeth taken from children who were not subjected to any preventive remineralization measures. The distribution by age and the studied material was identical to the main group. Segmentation of the teeth was carried out after the tooth extraction with separation of the crown structure and further polishing of the crown using polishing brushes without pastes. Sections 0.3-0.5 mm thick were formed with a diamond disc. The enamel samples were cleaned and degreased and then examined in a polarizing microscope (Optika B-150POL-B 40x-640x Bino) at a magnification in 500 times. The description of the enamel microscopic surface was carried out according to the following parameters: surface heterogeneity, surface opaqueness/shininess, surface roughness/smoothness. The surface homogeneity was assessed by calculating the ratio of identified surface areas that visually differed from the overall enamel texture, which was characteristic of the predominant investigated surface enamel. There were criteria for evaluating the enamel surface heterogeneity according to the research data in a polarizing microscope : the presence of numerous well-defined cracks, the visualization and number of areas from which the enamel prisms extend, the presence and number of enamel surface irregularities confirmed by a change in the direction of the light beam, the percentage of surface homogeneity, which was calculated as the ratio of the area of ​​the visually homogeneous enamel surface to the area with ​​any microscopically detected changes. To assess the opacity of the enamel surface by the microscopic polarization study, the criteria of visual assessment of shiny and dark areas of interest were used. The study suggested that microscopic changes are characterized by a decrease of total number in enamel surface irregularities and an increase of its glossiness and smoothness at the approach of structural compositional stabilization at 15-16 years. The analysis also revealed that there were marked microscopic differences observed in enamel of 15-16 years old after remineralization with the "Tooth Mousse" gel and a comparison group (without remineralization therapy).The difference between them is reliable (p<0.01) according to the indicators of the relative average level of surface heterogeneity, and also statistically different from similar indicators that were registered in the age groups 11-13 and 13-15 years old (p<0.01). The gained results can be considered as the expediency grounds for implementation of dental caries prevention at the early stages of secondary mineralization (immediately after eruption) and throughout the entire period of its intensive phase, which will further contribute to the stabilization of the caries-resistant enamel.

The age of the early stage formation of Ag-Bi-Cu-Ni-Co the Khovu-Aksyn deposit (Republic of Tyva): U-Pb (ID-TIMS) geochronological studies of garnet

Mineralogical and U-Pb (ID-TIMS) geochronological studies of garnets from three types of scarn associations of the Khovu-Aksyn Ag–Bi–Cu–Ni–Co deposit (Republic of Tyva) were carried out. The U-Pb garnet age estimate (404±2 million years) is close to the Early Devonian stage of basitic and alkaline-basitic magmatism identified within the Tuva trough of the Altay-Sayan folded region. The age of the scarn formation and the associated with it early stage of mineralization of the Khovu-Aksynskoye Ag–Bi–Cu–Ni–Co deposit has been established for the first time.

Role of in-situ electrical stimulation on early-stage mineralization and in-vitro osteogenesis of electroactive bioactive glass composites

Bioactive glass (BAG) has emerged as an effective bone graft substitute due to its diverse qualities of biocompatibility, bioactivity, osteoblast adhesion and enhanced revascularization. However, inferior osteogenic capacity of BAG compared to autologous bone grafts continues to limiting it's wide-spread clinical applications towards repairing of bone fractures and healing. In this study, we have fabricated BAG composites with 0.5 to 2 wt% bismuth ferrite (BF, a multiferroic material) with an aim to generate in-situ electrical charges pertinent to early-stage bone regeneration thus mimicking nature bone, which is a piezoelectric material. The fabricated BAG composites were characterised in terms of microstructures, phase analysis, remanent polarization, wettability and subsequently evaluated for in vitro cell proliferation and osteogenesis with and without magnetic field exposure (200 mT, 30 min./day). Pre-osteoblast cells from mice (MC3T3-E1) seeded on these composites exhibited excellent cell growth without any cytotoxicity, which is further supported by FITC/DAPI staining and a live/dead assay. The results of Alizarin Red S assay and increased levels of Alkaline Phosphatase (ALP) activity, at 21 days of culture, suggest that the BAG-BF composites promote in vitro osteogenic differentiation of pre-osteoblast cells. The enhanced osteogenesis of BAG-BF composites was also confirmed through qRT-PCR analysis, which showed rapid upregulation of osteoblastogenic specific genes namely RunX-2, Collagen-1, Bone Sialo Protein, and ALP after 21 days. Additionally, the osteogenic differentiation was assessed by the Western Blot technique, which revealed significantly higher band intensity of osteogenic markers in BAG-1.5 BF and BAG-2 BF composites than pure BAG. These findings clearly demonstrate that in-situ electrical stimulation and osteoconductive capacity of BF reinforced BAG composites have positive impact on osteoblast cell development, bone formation, and healing.

Genesis of the Kateba’asu gold deposit, Western Tianshan, China: Constraints from pyrite trace element, sulfur isotope, and quartz H-O isotopes

The Kateba’asu gold deposit, situated in the Western Tianshan of China, is one of the most significant discoveries in the world-class Tianshan gold belt. The deposit features two distinct mineralization styles. The early, subordinate skarn-type copper–gold mineralization occurs in the contact zone between monzogranite, diorite, and Silurian limestone, composed of garnet, diopside, epidote, chalcopyrite, pyrite, and gold. The later, primary lode-gold mineralization is hosted in the altered monzogranite characterized by pervasive quartz-pyrite-sericite-chlorite-K-feldspar alteration and a well-develped veining systems.Pyrite is the dominant sulfide mineral related to gold mineralization in the Kateba’asu gold deposit, with four types identified: Py0 from the early skarn copper–gold mineralization, and Py1 to Py3 from the later lode-gold mineralization. All types of pyrite are homogeneous and contain very low levels of lattice-bound gold. Py0 is euhedral and fine-grained, with relatively high Cu, Au, Co, and Ni contents, and displays a magmatic sulfur isotopic signature with δ34S ranging from 0.8 to 4.3 ‰. Py1 occurs as euhedral to subhedral, coarse-grained crystals within pyrite-quartz veins with higher concentrations of Co and Ni. Py2, which develops in the quartz-pyrite veins, is medium to coarse-grained and contains elevated levels of As, Cu, Zn, and Bi relative to Py1. Py3, found in polymetallic sulfide veins of the main lode-gold stage, is anhedral and medium to fine-grained with higher contents of As, Ag, Cu, Zn, Se, Te and lowest Co and Ni concentrations compared to Py1 and Py2. The positive correlations between Au-Te, Au-Bi, Au-Cu, and Pb-Bi across all pyrite types, along with the presence of visible gold in Py3, indicate that most gold occurs as micro-/nano-sized inclusions and as fissure gold. The δ34S values of Py1, Py2, and Py3 (7.6 to 11.8 ‰, 10.1 to 12.6 ‰, and 9.8 to 12.4 ‰, respectively) were attributed to an initial magmatic source and mixed with external sulfur subsequently from the wall rocks. The H and O isotopic compositions (δDH2O = −84.1 to −93.5 ‰; δ18OH2O = 1.8 to 6.6 ‰) of quartz from the lode-gold mineralization imply that ore-forming fluids were predominantly of magmatic origin, with a additional contribution from meteoric water. Taken together, a two-episode mineralization model was proposed for the formation of the Kateba’asu gold deposit. The early skarn mineralization stage is associated with the emplacement of diorite during the Early Carboniferous. In contrast, the subsequent lode-gold mineralization, occurring between the Late Carboniferous and Permian periods, represents a overprinted magmatic-hydrothermal gold system potentially linked to a deep-seated magmatic intrusion.

Two-stage mineralization of the Jinkeng Sn-Cu deposit in Eastern Guangdong, Southeast China: Response to magmatic activities and tectonic transformation

The Jinkeng Sn-Cu polymetallic deposit in South China consists of two different types of orebodies: 1) NE-striking skarn- and vein-type Cu-Pb-Zn-Sn orebodies in volcanic rocks suffering subsequent ductile shear deformation, and 2) NW-striking quartz-cassiterite-sulfide veins filled in the faults at the porphyritic granodiorite outward from the fine-grained granite which does not exhibit deformation. The relationships among Sn-Cu polymetallic mineralization, regional magmatism, and deformation metamorphism are still controversial. To address it, the geochronological, whole-rock and mineral geochemical research along with the detailed field investigation were conducted in this study. Our zircon U-Pb dating results show that the volcanic rocks formed at 158–162 Ma, earlier than the porphyritic granodiorite which yields the emplacement age of 146–147 Ma. In-situ LA-ICP-MS U-Pb dating of cassiterite from the deformed skarn ores indicates the early-stage mineralization occurred at 146 ∼ 148 Ma, which is similar to the emplacement age of the porphyritic granodiorite, but earlier than the formation of quartz-cassiterite-sulfide veins and the fine-grained granite (141∼144 Ma). Further, the whole-rock and biotite geochemistry, and zircon Hf isotope compositions suggest that the porphyritic granodiorite exhibits a lower degree of magma differentiation, higher oxygen fugacity, higher Cl and lower F contents than the fine-grained granite. The porphyritic granodiorite might provide the most Cu-Pb-Zn budget accompanied by minor Sn for early-stage mineralization. Overall, our study suggests that the Jinkeng Sn-Cu polymetallic deposit formed in two scenarios where the early dominated Cu-Pb-Zn and minor Sn mineralization related to the emplacement of the porphyritic granodiorite is superimposed by the late vein-type Sn-dominated mineralization related to the emplacement of the fine-grained granite. The two isolated mineralizing events (∼147 Ma and ∼141 Ma, respectively) in Jinkeng were probably responded to the regional magmatic activities triggered by the tectonic transformation where two extensional tectonic events were separated by a short contractional event (147–144 Ma).

Characterization of Co-bearing pyrite from the SEDEX Tuolugou Co(Au) deposit, northern Qinghai-Tibet Plateau, China

The Tuolugou sedimentary-exhalative (SEDEX) Co-Au deposit is located in the eastern Kunlun metallogenic belt of the northern Qinghai-Tibet Plateau in China. Pyrite is the prevalent Co-hosting sulfide mineral that occurs in the Tuolugou deposit. In this study, we investigated mineral characteristics of Co-bearing pyrite and effect of Co on crystal structure of the pyrite to obtain a better understanding of Co mineralization. Three pyrite generations were identified, including Co-barren pyrite (Py-1, formed during the early mineralization stage I, with Co content of 1-3844 ppm), Co-rich pyrite (Py-2, formed during the sedimentary-exhalative stage II, Co content 15–36522 ppm), and Co-rich pyrite (Py-3, formed during metamorphic stage III, with Co contents of 448–10505 ppm in Py-3A, and 1371–14904 ppm in Py-3B). As Co enters the pyrite structure, it is discovered that the octahedrons in pyrite is twisted and tilted, the lattice parameters (a0) rise, and the sulfur atom positions alter. The Co-rich Py-2 shows a similar REE and trace element distribution as those in quartz albitite, which indicates that Co mineralization is related to SEDEX genesis. Subsequent metamorphism resulted in additional Co enrichment. This detailed study of Co-bearing pyrite provides insights on the details of isomorphism Co in pyrite similar to the situation of this deposit as medium–low Co grade.

Cobalt enrichment and metallogenic mechanism of the Galinge skarn iron deposit in the Eastern Kunlun metallogenic belt, western China

Skarn iron deposits, as representative examples of Co-rich magmatic-hydrothermal deposits, are attracting increasing attention due to rising cobalt demand worldwide. However, the specific Co enrichment mechanisms and metallogenic processes in skarn deposits remain elusive. This study presents high-precision in situ U–Pb geochronological data for garnet from skarns, major and trace element analyses of sulfarsenides and sulfides, and X-ray mapping in the Galinge deposit. The Galinge skarn iron deposit formed at 237.1 ± 0.3 Ma (garnet U–Pb dating), during which time the region was in the post-collisional stage. During this period, the crust was thickened, causing delamination of the lithospheric mantle, which further led to the upwelling of asthenospheric materials and partial melting of the lower crust. As the resultant mixed magma ascended, it reacted with carbonate strata to form skarn deposits. Cobalt shows two occurrence modes in the Galinge deposit: independent cobalt minerals such as skutterudite and cobaltite, and isomorphic substitution of Co with other metals in ore minerals (arsenopyrite, pyrrhotite, sphalerite, pyrite, magnetite, and chalcopyrite). Our results revealed that arsenopyrite is the most cobalt-enriched ore mineral in the Galinge deposit, with an average Co content of 34,077 ppm. Other minerals generally contain insignificant Co contents of less than 500 ppm, including sphalerite (471 ppm) > pyrite (194 ppm) > pyrrhotite (145 ppm) > alabandite (∼100 ppm) > magnetite (7 ppm) > chalcopyrite (2 ppm). In arsenopyrite, cobalt and nickel replace iron in accordance with the inverse correlation between the concentrations of cobalt and nickel (wt%) and that of iron. In pyrite and chalcopyrite, a portion of the isomorphic cobalt substitutes for Fe or Cu. The weak correlation between Co (ppm) and Cu or Fe (wt%) indicates that only isomorphic cobalt is carried out by substituting Fe or Cu. The negative correlation between Co + Fe and Zn or Mn suggests that cobalt and iron replace Zn or Mn in sphalerite and alabandite. No evidence of element substitution was observed in pyrrhotite. Our study highlights that during the early mineralization stage, cobalt in the magmatic-hydrothermal fluids migrated in the form of CoCl42-. Subsequently, under the influence of an increase in pH, CoCl42- reacts with H3AsO30 to form CoAs3 (skutterudite). With the continuous precipitation of arsenides and sulfarsenides, the As/S (reduced) ratio decreased, leading to the CoAs3 (skutterudite) changing to CoAsS (cobaltite).

Evolution of the hydrothermal ore-forming system of Ashele VMS-type Cu-Zn deposit in Xinjiang, NW China: Insights from mineralogy and geochemistry of sulfides

The Ashele Cu-Zn deposit is one of the largest and most typical VMS-type Cu-Zn deposits in the Chinese Altai Mountains, Central Asian Orogenic Belt. The ore-forming processes of the Ashele deposit remains elusive, with particular uncertainties surrounding the physicochemical conditions underpinning their formation. In this study, major and trace element concentrations of the two types of sphalerite and sulfide sulfur isotopic compositions have been analyzed to constrain the mineralization conditions and ore genesis. Two stages of sphalerite have been identified, i.e., euhedral sphalerite of the early Cu mineralization stage (Sp1) and anhedral sphalerite of the late Zn mineralization stage (Sp2). Results show that Sp1 has relatively higher contents of In, Cu, Sn, and Hg, but lower levels of Cd, Ga, Ge, As, and Ag compared to that of Sp2. Utilizing the sphalerite GGIMFis geothermometer, mineralization temperatures for Sp1 and Sp2 were estimated at 225-296°C (average 258°C) and 166-264°C (average 210°C), respectively. Additionally, the Ashele sphalerite geochemistry suggests a relatively high sulfur fugacity during ore formation (lgfS2 = −8.99 to −6.55 for Sp1 and −13.58 to −6.83 for Sp2). The findings suggest an evolutionary trend of ore-forming fluids, characterized by a decrease in both temperature and sulfur fugacity from the early Cu mineralization stage to the later Zn mineralization stage. In situ δ34S values of sulfides (sphalerite, chalcopyrite, and pyrite) range from 0.84 ‰ to 6.07 ‰, indicating a sulfur origin from the thermochemical reduction of seawater sulfate and leaching of the underlying volcanic rocks, with a minor contribution from direct gas release from shallow magma chambers. Overall, this work unravels the physicochemical transformation between the two identified mineralization stages, thereby enhancing the understanding of the ore-forming process of the Ashele deposit.

Citrate Improves Biomimetic Mineralization Induced by Polyelectrolyte-Cation Complexes Using PAsp-Ca&Mg Complexes.

Magnesium ions are highly enriched in early stage of biological mineralization of hard tissues. Paradoxically, hydroxyapatite (HAp) crystallization is inhibited significantly by high concentration of magnesium ions. The mechanism to regulate magnesium-doped biomimetic mineralization of collagen fibrils has never been fully elucidated. Herein, it is revealed that citrate can bioinspire the magnesium-stabilized mineral precursors to generate magnesium-doped biomimetic mineralization as follows: Citrate can enhance the electronegativity of collagen fibrils by its absorption to fibrils via hydrogen bonds. Afterward, electronegative collagen fibrils can attract highly concentrated electropositive polyaspartic acid-Ca&Mg (PAsp-Ca&Mg) complexes followed by phosphate solution via strong electrostatic attraction. Meanwhile, citrate adsorbed in/on fibrils can eliminate mineralization inhibitory effects of magnesium ions by breaking hydration layer surrounding magnesium ions and thus reduce dehydration energy barrier for rapid fulfillment of biomimetic mineralization. The remineralized demineralized dentin with magnesium-doped HAp possesses antibacterial ability, and the mineralization mediums possess excellent biocompatibility via cytotoxicity and oral mucosa irritation tests. This strategy shall shed light on cationic ions-doped biomimetic mineralization with antibacterial ability via modifying collagen fibrils and eliminating mineralization inhibitory effects of some cationic ions, as well as can excite attention to the neglected multiple regulations of small biomolecules, such as citrate, during biomineralization process.

Genesis of the Hacipushanbei Pb-polymetallic deposit in the East Kunlun Orogen, NW China: Constraints from geochronology and in situ trace-elements and sulfur isotopes of sulfides

A recent mineral exploration programme in the East Kunlun Orogen (EKO) identified the new Hacipushanbei Pb-polymetallic deposit. The ores are hosted in faults in granitic rocks and are marked by high Pb grades up to 22.5 %. U–Pb dating of calcites associated with mineralization yields an intersection age of 208 ± 9 Ma, indicating a late Triassic mineralization event. Fluid-inclusion analysis reveals that the ore-forming fluids are characterized by medium-to-high temperature, medium-to-low salinity, and low density. Fluid boiling or immiscibility during ore-formation is also noted. Three sub-generations of pyrite (Py1-1, Py1-2, and Py2) are recognized in the early mineralization stages. In situ trace element analysis shows low Co and Ni contents in Py1-1 and Py1-2 but high contents in Py2. Conversely, Au and As concentrations are the highest in Py1-2. Variations in As contents are systematically coupled with Au. Additionally, sphalerite in the second stage contains higher amounts of Co, Cu, Cd, and In, via a wide range of isomorphic elemental substitutions of X4+(Sn4+ and Ge4+) + X3+(In3+, Sb3+, and Ga3+) + X+(Ag+ and Cu+) ↔ 4Zn2+ and the associated In enrichment. The average δ34S values of in situ and single minerals of Py1-1, Py1-2, Py2, Sp2, Ccp2, and Gn3 are 2.3 ‰, 3.3 ‰, 2.6 ‰, 2.4 ‰, 2.2 ‰, and 0.9 ‰, respectively. These values display a trend of initial increase and then decrease, consistent with thermodynamic fractionation. These data collectively indicate that the ore-forming fluid originated from a deep-seated magma chamber, and subsequent fluid immiscibility led to the formation of high-grade ores. Given the conspicuous association of Pb-polymetallic deposits with magmatic rocks in the EKO, we envisage that our genetic model can be applied, to some extent, to evaluate the potential of some mineral exploration targets.

Textures and trace element geochemistry of pyrite in Gaoloushan ore section of the Yangshan gold belt, West Qinling: Implications for ore genesis

The Devonian Sanhekou Group phyllite in the Yangshan gold belt includes multiple stages of pyrite development, and Au is mainly distributed within the pyrite. Bodies within the Gaoloushan ore section of the gold belt are located in the broken and altered carbonaceous phyllite and granitic rock dykes, where quartz vein-type gold ores are more common as compared to other ore sections (Anba, Getiaowan). Studying the trace element distribution characteristics of gold-bearing and non-gold-bearing pyrite can constrain the evolution of ore-forming fluids and the types of ore deposit genesis. Based on detailed fieldwork and microscopic identification, 48 pyrite samples from the 69th exploration line of the Gaoloushan ore section were analyzed in situ by LA-ICP-MS. The following conclusions were drawn: (1) The gold-bearing pyrite formed during the ore-forming stage while the non-gold-bearing pyrite formed during the sedimentary and metamorphic period. The morphology of the pyrites differs, with gold-bearing pyrite mainly characterized by medium-fine grains, impregnation, fine veins, and reticulate structure, with crystal morphology mainly pentagonal dodecahedra or pentagonal octahedra, whereas non-gold-bearing pyrite is mainly characterized by a medium or medium-coarse grains, with stellate, strawberry, or cluster structures, and crystal morphology mainly in the form of cubes or pentagonal octahedra; (2) The As and Te content of the sedimentary pyrite is low, locally below the detection limit, and the Co and Ni contents and ratios vary greatly, with a distribution of 117–945 ppm and ratio distribution of 0.11–1.92. Pyrite from the ore-forming stage is primarily characterized by high As, Pb, Co, Ni, Cu, Sb, Zn, and Se concentrations, with Bi, Au, and trace amounts of Tl, Te, and Sn observed in later formations; (3) Au and As are positively correlated. The average Au content of 60.53 ppm in pyrite from granite dykes is higher than the average Au 15.97 ppm in carbonaceous phyllite. Pyrite particles with Au contents below the detection limit are sourced in carbonaceous phyllite. In addition, the higher As enrichment is observed in pyrite from granite dykes, averaging 35 770.60 ppm with a maximum value of 72 930.19 ppm. In comparison, the average As content in carbonaceous phyllite is 8974.66 ppm, with a maximum of 69 800.50 ppm, and the Au-As diagram indicates that gold in the Gaoloushan ore section is mainly in the form of solid solution gold within the pyrite lattice; (4) Statistical analysis of the Co/Ni ratio variation in the different lithologies and pyrite stages reveals an initial increase followed by a decrease. The median Co/Ni ratio variations during the mineralization stages of Py1s (0.51–0.7), Py1m (1.35–2.25), Py2 (1.43–1.87), Py1-2 m (1.53), Py2a (1.59), Py2b (1.4), Py2s (1.2), Py2m (1.63), and Py3 (0.19–1.40) suggest that magmatic-hydrothermal fluids dominated during the early stage of mineralization in the gold belt and metamorphic fluids during the main mineralization stage, with deep-seated metamorphic fluids playing a significant role in the late mineralization stage. The varying proportions of ore-forming fluids are likely to have been crucial in controlling gold mineralization in the Yangshan gold belt.

Bioinspired controllable CaCO3 synthesis from solid waste by an “all in one” amino acid-in strategy: Implication for CO2 mineralization

CO2 mineralization suffers from extensive consumption of acidic/alkaline reagents due to the limited kinetics, which necessitates the development of an atom/energy-efficient process. An “all in one” reagent amino acid-based Ca2+ leaching-CO2 mineralization process inspired by biomineralization was proposed. This study explored the interactions between amino acids and Ca leaching, CaCO3 pre-nucleation, nucleation, and growth by investigating the evolution of Ca concentration, solution turbidity and CaCO3 morphology in complex CFA. Promising Ca2+ leaching efficiencies were observed, being 51.1 %, 34.2 %, and 21.0 % for glycine (Gly), L-alanine (Ala), and L-arginine (Arg), respectively, negatively correlated with their pI but positively correlated with their bonding energy with Ca2+. These amino acids ultimately led to a CaCO3 production of Gly (114.8 g/kg) > Ala (78.2 g/kg) > Arg (54.5 g/kg) from CFA. Gly leachate remained transparent (1.23 NTU) in the first 3 min of CO2 bubbling even though the solution was supersaturated and then got turbid suddenly (6508.75 NTU in 10 min) as continued CO2 bubbling, indicating the inhibition of Gly on CaCO3 nucleation. Observations using Cryo-SEM confirm the presence of abundant CaCO3 nanoparticles in the early stages of mineralization, which later assemble into vaterite crystal particles with a sub-structure and coalesce into larger particles in Gly and Ala. Meanwhile, Arg inhibited calcite growth along the C-axis, leading to the formation of thin, blocky-like particles. Furthermore, 0.010 ∼ 0.027 mmol/g amino acids are occluded into the CaCO3, stabilizing the metastable vaterites and imparting thermal stability, which was believed to be associated with this multistep pathway involving a transient prenucleation cluster, nanoparticle precursor formation, and particle–particle coalescence.

Matrix Metalloproteinase-20 immunolocalization in rat first molar tooth development after treatment with amoxicillin

Amoxicillin is one of the most commonly prescribed antibiotics in children. It is, therefore, administered as the first choice of antibiotics for respiratory, gastrointestinal, neuronal, and skin infections. This study aimed to determine whether amoxicillin use affects the formation of dentin and enamel during the secretion and early phases of mineralization. Sixteen pregnant adult Wistar rats were equally divided into two groups. The first group that did not receive the drug was prescribed a saline solution (control group), and the other group received 250 mg/kg/day amoxicillin (study group). The treatments were administered daily by oral gavage from the 13th gestation day to the end of gestation. After birth, the newborn also received the same treatment as their mothers from the first day of birth until 7 or 12 days after birth. The newborns will be sacrificed at 7 and 12 days postnatally. The jaws will be dissected, and the maxilla, where the samples are fixed in 10% formaldehyde solution, and the upper first molars will be analyzed. Immunostaining with MMP-20 on day 7 and 12 were performed. A significant difference in the positive expression of ameloblast for MMP20 antibody between groups was observed at 7 days (P = 0.014) and no significant difference at 12 days (P = 0.347). A significant difference for positive expression of odontoblast for MMP20 antibody between groups in both durations was observed at 7 days (P = 0.178) and not a significant difference at 12 days (P = 0.143) and powerful expression in enamel matrix during early mineralization stage in the control group and strong expression in the study group. The current findings indicate that amoxicillin affects the expression of MMP20 during the secretory stage by decreasing the expression of MMP20 in ameloblast, and the expression of MMP20 decrease in cells during the early mineralization stage in both groups at different rate. Keywords: Amoxicillin, Enamel, Immunostaining, MMP20, ameloblast

New insights into the nucleation of portlandite and the effects of polymeric additives

The crystallization of calcium hydroxide (Ca(OH)2, CH, portlandite) is a key process during the early stages of cement hydration. In the present work, we have revisited the formation of this mineral through nucleation and growth from supersaturated aqueous solutions, in the light of the currently emerging picture of multistage “non-classical” crystallization. To that end, we developed a titration-based assay, in which stock solutions of both relevant ions are added simultaneously into a reservoir, where supersaturation increases slowly at constant stoichiometry until nucleation occurs. This procedure allows both pre- and early post-nucleation phenomena to be analyzed quantitatively. Complementarily, the early stages of portlandite mineralization were probed by various advanced characterization techniques, including cryo-transmission electron microscopy (cryo-TEM), in-situ small-angle X-ray scattering (SAXS), pair distribution function (PDF) analysis of high-energy X-ray scattering (HEXS) data, and analytical ultracentrifugation (AUC). The experimental data show that the formation of calcium hydroxide starts with the association of ions into complexes and clusters, which subsequently coalesce to form amorphous nanoparticles – much like what has been observed in the case of calcium carbonate and other prominent minerals. Subsequently, these particles aggregate and build networks, which eventually transform into hexagonal Ca(OH)2 crystals. The presence of a soluble polycarboxylate – as a known inhibitor of portlandite crystallization – does not change the main characteristics of this multistep nucleation pathway, but it proved capable of significantly extending the lifetime of the amorphous intermediate phase and thus delaying the transition to the final crystalline phase. Our observations confirm the notion that “non-classical” crystallization is a much more common phenomenon than initially believed – and that, for minerals forming in aqueous environments, it may actually be the rule rather than the exception.

Tin transport and cassiterite precipitation from hydrothermal fluids

Cassiterite (SnO2) is the main ore mineral of tin in magmatic–hydrothermal tin deposits, but tin transport and precipitation mechanisms from hydrothermal fluids remain poorly understood. We critically evaluated aqueous tin speciation in hydrothermal fluids from extensive experimental data and thermodynamic modeling. Sn(II) chloride complexes in hydrothermal fluids exist mainly as SnCl+, SnCl2(aq), and SnCl3−. The revised Helgeson–Kirkham–Flowers model parameters of these three tin species and two tin ions (Sn4+ and Sn2+) were derived from the correlation algorithms among these parameters, and the standard molar properties of cassiterite were optimized to be internally consistent with the available thermodynamic dataset. These thermodynamic parameters, together with the available equilibrium constant equation of Sn(IV) chloride complexes, could reproduce the available solubility data of cassiterite in acidic solutions at 400–700 °C under oxygen fugacity (fO2) levels buffered by hematite–magnetite (HM) or nickel–nickel oxide (NNO). These comparisons allow modeling chemical systems of SnO2–NaCl–HCl–H2O (liquid phase) to examine tin transport and cassiterite precipitation mechanisms under tin-mineralizing conditions: 300–500 °C, 50–150 MPa, 2 molal NaCl, and fO2 levels from QFM (quartz–fayalite–magnetite) to HM. Sn(II) chloride complexes are commonly interpreted to dominate in aqueous tin speciation under fO2 = NNO, but our modeling results indicate that considerable contents of Sn(IV) chloride complexes also exist in those reduced fluids with high HCl contents, consistent with recent in situ high-temperature experiments and molecular dynamic simulations. The Sn(II)/Sn(IV) ratios in fluids depends on fO2, temperature, and HCl contents. A considerable amount of Sn(IV) possibly exist in an early mineralization stage even under fO2 = NNO; if so, redox reactions are unnecessary to precipitate cassiterite from these mineralizing fluids. We find that even if the fO2 levels are constant, simple cooling can alter mineralizing fluids to be more oxidized (e.g., from QFM to HM) and cause cassiterite precipitation, indicating that oxidizing agents are not necessary as previously thought. This explains why cassiterite can precipitate in host rocks (e.g., sandstone or quartzite) that do not provide oxidizing agents. A simple rise in fO2 levels and pH neutralization (e.g., greisenization) also cause cassiterite precipitation. Cassiterite solubility in oxidized acidic hydrothermal fluids (NNO < fO2≤HM) is high enough to account for the tin contents of fluid inclusions from typical tin deposits, but the mineralization potential of oxdized fluids is inferior to reduced fluids (fO2≤ NNO) under the same conditions.

Зміни розрахункових індексів біохімічних показників сироватки крові щурів різного віку після заповнення дефекту в метафізі стегнової кістки алогенними кістковими імплантатами, насиченими мезенхімальними стовбуровими клітинами

The purpose of the study was based on the analysis of calculated biochemical parameters of mineralization in the blood serum of laboratory rats to evaluate the course of metabolic processes in bone tissue after filling a defect of critical size in the metaphysis of the femur with allogeneic bone implants saturated with mesenchymal stem cells. Materials and methods. Indicators of mineralization of bone tissue in the blood serum of white rats were studied (the content of total protein, calcium, alkaline and acid phosphatase activity), the ratio of alkaline to acid phosphatase activity, as well as the degree of mineralization, were calculated. Results and discussion. In 3-month-old rats with alloimplants without mesenchymal stem cells on the 90th day, a decrease in the degree of mineralization was observed, which reflects the final stages of bone tissue remodeling by 1.13 times compared to the level of this in animals of a similar age and conditions of filling the defect on the 14th day (р = 0.008) and 1.12 times compared to the data on the 28th day of the experiment (р = 0.008). In 3-month-old rats with alloimplants saturated with mesenchymal stem cells, a decrease in the degree of mineralization on the 90th day was determined compared to that in experimental rats of a similar age and defect filling conditions on the 14th day by 1.13 times (p = 0.008), and compared with the data of the similar group on the 28th day – 1.14 times (p = 0.008), which reflects the delay in the course of the full stage of bone tissue remodeling due to the use of mesenchymal stem cells. The ratio of serum alkaline to acid phosphatase activity in 3-month-old rats with alloimplants saturated with mesenchymal stem cells was 1.32 times lower on the 14th day compared to the data of a group of the same age with alloimplants without mesenchymal stem cells (p = 0.008), and on the 90th day – by 1.12 times (p = 0.008), which also indicates a delay in the early stages of bone tissue mineralization due to the use of mesenchymal stem cells as part of alloimplants. In 12-month-old rats without the use of mesenchymal stem cells, on the 90th day, there was a decrease in the degree of mineralization by 1.10 times, in accordance with the level of this in a group of rats of a similar age and conditions of defect filling on the 14th day (р = 0.008) and by 1.09 times compared to that on the 28th day (p = 0.008), from which we can conclude about a progressive decrease in the activity of the final stages of bone tissue remodeling. The ratio of the activity of alkaline and acid phosphatase in 12-month-old rats with alloimplants without mesenchymal stem cells on the 90th day was significantly inferior to that in the corresponding 3-month-old animals by 1.12 times (p = 0.008), which indicates a lower activity of the initial stages of bone tissue mineralization in the late stages of defect healing. This indicator progressively decreased during the experiment. Thus, on the 28th day, it was 1.12 times smaller than on the 14th day, and on the 90th day – by 1.53 times less, in accordance with the data on the 14th day (p = 0.008) and by 1.36 times compared to that on the 28th day (p = 0.008). Conclusion. Treatment of experimental rats with a critical size defect in the femoral metaphysis with alloimplants saturated with mesenchymal stem cells, especially in the early stages, leads to a slowing down of bone tissue remodeling processes

Bioglass obtained via one-pot synthesis as osseointegrative drug delivery system

Osseointegration is a fundamental process during which implantable biomaterial integrates with host bone tissue. The surgical procedure of biomaterial implantation is highly associated with the risk of bacterial infection. Thus, the research continues for biodegradable bone void fillers which are able to stimulate the bone tissue regeneration and locally deliver the antibacterial agent. Herein, we obtained bifunctional bioglass (BG) using novel, preoptimized, rapid one-pot synthesis. Following the ISO Standards, the influence of the obtained BG on osteoblast-mediated phenomena, such as osteoconduction and osteoinduction was assessed and compared to two commercial materials: bioactive glass powder 45S and bioactive glass powder 85S. Direct-contact tests revealed osteoblast adhesion to BG particles; whereas, tests on extracts confirmed high viability of cells incubated with BG extract. Analyses of gene expression, alkaline phosphatase activity, and calcium phosphates deposition confirmed the stimulation of early and late stages of osteoblast differentiation and mineralization. Additionally, an extended evaluation of intracellular calcium fluctuations revealed a possible correlation between osteoblast calcium uptake and extracellular matrix mineralization. Moreover, proposed bioglass exhibited satisfactory doxycycline adsorption capacity and release profile. The obtained results confirmed the bifunctionality of the proposed BG and indicated its potential as osseointegrative bone drug delivery system.

Tin-bearing magnetite with nanoscale Mg-Si defects: Evidence for the early stages of mineralization in a skarn system

Tin-bearing magnetite is reported from several types of magmatic-hydrothermal ore deposits. The question of whether tin is incorporated within solid solution, as Sn4+, or as nanoinclusions remains open, however. We report a micron- to nanoscale investigation of Sn (Mg, Si)-bearing magnetite from serpentinite in the Dulong Zn-Sn-In skarn, South China, with the dual aims of understanding the mechanisms involved in accommodating Sn and associated elements into the Fe-oxide, and the inferences that this carries for constraining the early stages of skarn formation. Magnetite preserves a range of textures that record the evolution of metasomatism during prograde growth of grain cores and retrograde rim replacement. Observations reveal the presence of chondrodite and sellaite (MgF2) as nanoscale inclusions preserved in magnetite. This implies initiation of the Dulong mineralizing system during a humite-bearing, magnesium skarn stage. Magnesium-Si defects, forming along (110) planes prior to Sn-enrichment, are recognized for the first time. Release of high volatile, F-rich fluids is interpreted to lead to precipitation of cassiterite inclusions along &amp;lt;111*&amp;gt; directions in magnetite.

Important roles of odontoblast membrane phospholipids in early dentin mineralization.

The objective of this study was to first identify the timing and location of early mineralization of mouse first molar, and subsequently, to characterize the nucleation site for mineral formation in dentin from a materials science viewpoint and evaluate the effect of environmental cues (pH) affecting early dentin formation. Early dentin mineralization in mouse first molars began in the buccal central cusp on post-natal day 0 (P0), and was first hypothesized to involve collagen fibers. However, elemental mapping indicated the co-localization of phospholipids with collagen fibers in the early mineralization area. Co-localization of phosphatidylserine and annexin V, a functional protein that binds to plasma membrane phospholipids, indicated that phospholipids in the pre-dentin matrix were derived from the plasma membrane. A 3-dimensional in vitro biomimetic mineralization assay confirmed that phospholipids from the plasma membrane are critical factors initiating mineralization. Additionally, the direct measurement of the tooth germ pH, indicated it to be alkaline. The alkaline environment markedly enhanced the mineralization of cell membrane phospholipids. These results indicate that cell membrane phospholipids are nucleation sites for mineral formation, and could be important materials for bottom-up approaches aiming for rapid and more complex fabrication of dentin-like structures.

Genesis and Evolution of Hydrothermal Fluids in the Formation of the High-Grade Hishikari Gold Deposit: Carbon, Oxygen, and Sulfur Isotopic Evidence

The Hishikari low-sulfidation epithermal gold (Au) deposit in Kyushu, Japan, is world-famous for its premium ore. It has been hypothesized that magmatic contributions to the hydrothermal fluid during early stages of mineralization is possible, even if the hydrothermal fluids for many Au occurrences near the Hishikari deposit are of meteoric origin and are influenced by basement sedimentary rocks. The purpose of this study is to obtain constraints on the genesis and evolution of hydrothermal fluids in the formation of the high-grade Hishikari Au deposit by carbon and oxygen isotope ratios of calcite-bearing samples. Since the microanalysis of carbon and oxygen isotope ratios in every 12 μm of the calcite-bearing sample along the growth direction (corresponding to 10 years of the Hishikari mineralization) scatter in a particular range, the fluid evolution might not be a gradual change from a magmatic to a meteoric origin. Alternatively, a rapid turnover of two fluids might be happening locally. The average sulfur isotope ratio of hydrothermal pyrite is similar to that of the adjacent magma. However, according to the secondary ion mass spectrometry (SIMS) microanalysis, local pyrite with extremely low sulfur isotope ratios may interact with basement sedimentary rocks. Unlike other epithermal Au deposits in the vicinity, rapid local mixing of the magmatic-origin deep fluid and meteoric-origin fluid reacted with organic matter containing basement sedimentary rocks might cause gold precipitation at the Hishikari deposit.