A sustainable bioprocess technology for producing food-flavour (+)-γ-decalactone from castor oil-derived ricinoleic acid using enzymatic activity of Candida parapsilosis: Scale-up optimization and purification using novel composite.

Ricinoleic acid (RA) from castor oil was employed in biotransformation of peach-flavoured γ-decalactone (GDL), using a Candida parapsilosis strain (MTCC13027) which was isolated from waste of pineapple crown base. Using four variables-pH, cell density, amount of RA, and temperature-the biotransformation parameters were optimized using RSM and BBD. Under optimized conditions (pH 6, 10 % of microbial cells, 10 g/L RA at 28°C), the conversion was maximum and resulted to 80 % (+)-GDL (4.4 g/L/120 h) yield in shake flask (500 mL). Furthermore, optimization was achieved by adjusting the aeration and agitation parameters in a 3 L bioreactor, which were then replicated in a 10 L bioreactor to accurately determine the amount of (+)-GDL. In bioreactor condition, 4.7 g/L (>85 %) of (+)-GDL is produced with 20 % and 40 % dissolved oxygen (1.0 vvm) at 150 rpm in 72 h and 66 h, respectively. Further, a new Al-Mg-Ca-Si composite column-chromatography method is developed to purify enantiospecific (+)-GDL (99.9 %). This (+)-GDL is 100 % nature-identical as validated through 14C-radio-carbon dating. Thorough chemical investigation of enantiospecific (+)-GDL is authenticated for its use as flavour. This bioflavour has been developed through a cost-effective biotechnological process in response to the demand from the food industry on commercial scale.

Tooth Mg/Ca ratios and Aristotle's lantern morphometrics reflect trophic types in echinoids.

Several studies have inferred the ecological significance regarding the morphometrics of Aristotle's lantern and the mechanical properties of magnesium in echinoid teeth. This study attempts to combine these aspects, connecting them to the trophic habits of three native and an invasive echinoid in the Eastern Mediterranean Sea. Spatiotemporal data from the central and southern Aegean Sea were obtained, regarding the relative size of lanterns and demi-pyramids of Arbacia lixula, Paracentrotus lividus, Sphaerechinus granularis, and the invasive echinoid Diadema setosum and the Mg/Ca ratios of four zones on the tooth cross-section. Since environmental factors affect the examined factors, data for temperature, salinity, and concentration of chlorophyll-a were included in a principal component analysis. A. lixula and P. lividus presented intraspecific differences in the relative size of the lantern and demi-pyramid, while S. granularis and D. setosum exhibited variation in the elongation index. Differences in the Mg/Ca ratios were observed for all species although in different zones. Temperature appears to be related to all Mg/Ca zones except for the stone part, while the elongation index showed an inverse trend to all other morphometric parameters. The results of the PCA for the four species on the spatiotemporal level exhibited a distinction of individuals with season but not species, except for A. lixula, an omnivore with a carnivorous tendency, which was clearly separated from the herbivorous species. Using hierarchical clustering on the principal components it was evident that the three native species occupy different clusters, but when D. setosum was added, it shared the same cluster with S. granularis. This might infer similar feeding preferences, specifically for coralline algae, which might lead to a swift in the ecological equilibrium in regions, where D. setosum is found, either by affecting habitat type, or by restricting the distribution of S. granularis as was previously observed with Diadema africanum.

In Vitro and In Vivo Analysis of the Mg-Ca-Zn Biodegradable Alloys.

The objective of this work was to analyze the in vitro and in vivo tests of a novel Mg-based biodegradable alloy-Mg-0.5%Ca-with various amounts of Zn (0.5, 1, 1.5, 2.0, and 3.0 wt.%). In terms of in vitro biocompatibility, MTT and Calcein-AM cell viability assays, performed on the MG-63 cell line through the extract method, revealed that all five alloy extracts are non-cytotoxic at an extraction ratio of 0.025 g alloy per mL of cell culture medium. In the in vivo histological analysis, Mg-0.5Ca-1.5Zn demonstrated exceptional potential for stimulating bone remodeling and showed excellent biocompatibility. It was observed that Mg-0.5Ca-0.5Zn, Mg-0.5Ca-1.5Zn, and Mg-0.5Ca-3Zn displayed good biocompatibility. Furthermore, the histological examination highlighted the differentiation of periosteal cells into chondrocytes and subsequent bone tissue replacement through endochondral ossification. This process highlighted the importance of the initial implant's integrity and the role of the periosteum. In summary, Mg-0.5Ca-1.5Zn stands out as a promising candidate for bone regeneration and osseointegration, supported by both in vitro and in vivo findings.

In vitro and in vivo degradation, biocompatibility and bone repair performance of strontium-doped montmorillonite coating on Mg-Ca alloy.

Poor bone growth remains a challenge for degradable bone implants. Montmorillonite and strontium were selected as the carrier and bone growth promoting elements to prepare strontium-doped montmorillonite coating on Mg-Ca alloy. The surface morphology and composition were characterized by SEM, EDS, XPS, FT-IR and XRD. The hydrogen evolution experiment and electrochemical test results showed that the Mg-Ca alloy coated with Sr-MMT coating possessed optimal corrosion resistance performance. Furthermore, in vitro studies on cell activity, ALP activity, and cell morphology confirmed that Sr-MMT coating had satisfactory biocompatibility, which can significantly avail the proliferation, differentiation, and adhesion of osteoblasts. Moreover, the results of the 90-day implantation experiment in rats indicated that, the preparation of Sr-MMT coating effectively advanced the biocompatibility and bone repair performance of Mg-Ca alloy. In addition, The Osteogenic ability of Sr-MMT coating may be due to the combined effect of the precipitation of Si4+ and Sr2+ in Sr-MMT coating and the dissolution of Mg2+ and Ca2+ during the degradation of Mg-Ca alloy. By using coating technology, this study provides a late-model strategy for biodegradable Mg alloys with good corrosion resistance, biocompatibility. This new material will bring more possibilities in bone repair.

Metabolic markers of short and long-term exogenous DL-beta-hydroxybutyrate supplementation in episodic migraine patients: an exploratory analysis of a randomized-controlled-trial.

Background: Emerging findings propose that the pathophysiology of migraine may be associated with dysfunctional metabolic mechanisms. Recent findings suggest that migraine attacks are a response to the cerebral energy deficit, and ingestion of ketone bodies stabilizes the generation of a migraine attack. Based on these findings, ketone body supplementation is postulated as a prophylactic treatment approach to restore cerebral metabolism deficiency. Metabolic markers are unexplored after exogenous ketone body supplementation in episodic migraineurs. Therefore, the present single-arm uncontrolled explorative analysis evaluated blood ketone body and glucose concentration after short and long-term 6 g exogenous DL-Mg-Ca-beta-hydroxybutyrate (DL-ßHB) supplementation. Methods: The presented data are part of the MigraKet randomized-control cross-over clinical trial of 41 episodic migraineurs (Number NCT03132233). Patients were given a single dose of 6 g DL-ßHB. Ketone body and glucose blood concentration were assessed before intake, 20, and 40 min after DL-ßHB intake. Ketone body, glucose concentration and glycated hemoglobin values were evaluated after 12 weeks of 18 g DL-ßHB ingestion (total dose), taken three times daily (6g/dose; 3x/day). Linear models explored the association between the ketone body and glucose levels. Results: Ketone body concentration increased within-group to a mean of 0.46 (0.30) mmol/L after 40 min post- DL-ßHB supplementation [estimate = 0.24 mmol/L, CI = (0.20.0.27), p < 0.01]. This within-group increase of ketone body concentration did not change after repeated daily intake of DL-ßHB supplementation over 12 weeks [estimate = 0.00 mmol/L, CI = (-0.03.0.04), p = 0.794]. DL-ßHB intake significantly reduced blood glucose concentration within-group from a mean baseline of 4.91 (0.42) mmol/L to 4.75 (0.47) mmol/L 40 min post-DL-ßHB supplementation [estimate = -0.16 mmol/L, CI = (-0.15, 0.03), p < 0.01]. Repeated DL-ßHB supplementation for 12 weeks showed no change within-group in acute ketone bodies concentration [estimate = 0.00 mmol/L, CI = (-0.03.0.04), p = 0.794] and in the HbA1c value [estimate = 0.02, CI = (-0.07.0.11), p = 0.69]. Conclusion: A single dose of 6 g DL-ßHB significantly elevated blood ketone bodies and decreased blood glucose concentration within-group in episodic migraineurs. Long-term DL-ßHB supplementation for 12 weeks showed no effect within-group on acute ketone body concentration and had not impact on HbA1c. The elevation of the ketone body concentration was moderate, indicating that nutritional ketosis was not reached. Therefore, a dose higher than 6 g of DL-ßHB is required to reach the nutritional level of ketosis. ClinicalTrials.gov Identifier: NCT03132233.

Construction of dopamine supported Mg(Ca)Al layered double hydroxides with enhanced adsorption properties for uranium.

A novel dopamine-supported Mg(Ca)Al layered double hydroxide composite was synthesized by co-precipitation method. The existence of Ca2+ and dopamine could promote the capture of uranium on the layered double hydroxides. In batch experiments, the composite exhibited good uranium removal performance, including high adsorption capacity (687.3 mg/g), strong anti-interference and good reusability (the removal percentage was still higher than 90 % after five cycles). At low initial uranium concentration, the uranium removal percentage on the composite exceeded 99.7 % and the residual concentration of uranium in the solution was <0.03 mg/L, reaching the limited standard of the World Health Organization. The studies of adsorption kinetics and isotherm indicated that the uranium adsorption behavior on the composite conformed to the pseudo-second-order kinetic and Langmuir isotherm models, suggesting that the process was a monolayer adsorption dominated by chemical adsorption. Furthermore, the high-efficiency uranium adsorption on the Mg(Ca)Al layered double hydroxide was mainly attributed to the strong complexation between the active sites (-OH and -NH2) and uranium, the precipitation of interlayer intercalation ions (CO32- and OH-) to uranium and the ion exchange of Ca2+ to uranium. Due to these advantages, the dopamine-supported Mg(Ca)Al layered double hydroxide composite is expected to be used as fine adsorbent to remove uranium from wastewater.

Microstructural and Electrochemical Influence of Zn in MgCaZn Biodegradable Alloys.

In recent years, biodegradable materials have included magnesium alloys with homogenous disintegration and a controllable degradation rate. Utilized in medical applications, biodegradable materials based on magnesium have been widely explored throughout the years. It is well-known that alloying Mg with biocompatible and non-toxic elements increases the biodegradability of surgical alloys. The purpose of this study was to examine the microstructure and the electrochemical response (corrosion resistance) of a new experimental Mg-based biodegradable alloy-Mg-0.5%Ca with additions of Zn as follows: 0.5, 1.5, and 3.0 wt.% in order to control the corrosion rate. Immersion tests were performed for different periods in a simulated body fluid electrolyte solution at 37 °C, and the mass loss was appreciated in order to calculate the corrosion rate (CR). The investigation led to the discovery of a dendritic Mg solid solution, a lamellar Mg2Ca compound, and a MgZn2 intermetallic phase. Scanning electron microscopy, optical microscopy, and energy dispersive spectroscopy were used for surface analysis after the immersion and electro-corrosion resistance tests. The metallic and ceramic compounds that detached themselves from the sample and passed into the solution were evaluated using the SEM-EDS system. All samples presented a generalized electro-corrosion with anodic and cathodic reactions of similar intensity. The corrosion rate was similar regardless of the percentage of zinc, with a smaller value for a higher than 3 wt.% Zn percentage based on the more protective zinc oxide that appeared on the surface.

Response of drip water Mg/Ca and Sr/Ca variations in ventilated caves to hydroclimate.

Mg/Ca and Sr/Ca in speleothems which record valuable information regarding past variations of precipitation and cave air pCO2 are promising proxies because the degrees of water-rock interaction (WRI) and prior calcite precipitation (PCP) are directly and indirectly related to these changes. However, the controls on Mg/Ca and Sr/Ca can be complex, and most studies ignored the combined effects of rainfall and cave air pCO2. Moreover, knowledge of the influence of seasonal rainfall and cave air pCO2 on seasonal fluctuations in drip water Mg/Ca and Sr/Ca are limited for caves with different regions and ventilation types. Drip water Mg/Ca and Sr/Ca were monitored for five years at Shawan Cave. The results indicate that the irregular seasonal oscillation in drip water Mg/Ca and Sr/Ca is controlled by inverse-phase seasonal changes between rainfall and cave air pCO2. The rainfall amount may be the primary controlling factor of the interannual variation in drip water Mg/Ca, whereas the interannual variation in drip water Sr/Ca is most likely controlled by cave air pCO2. Furthermore, we compared drip water Mg/Ca and Sr/Ca of caves in different regions to fully understand how drip water Mg/Ca and Sr/Ca respond to hydroclimate changes. The drip water element/Ca, for seasonal ventilation caves with a fairly narrow range of cave air pCO2 respond well to the local hydroclimate associated with rainfall variation. If the range of cave air pCO2 is considerably large, the element/Ca in seasonal ventilation caves of subtropical humid regions may not reflect hydroclimate and that of Mediterranean and semi-arid regions may be primarily controlled by cave air pCO2. The element/Ca in the low year-round pCO2 caves could reflect the hydroclimate associated with surface temperature. Therefore, observations of drip water monitoring and comparative analysis can provide a reference for the explanation of speleothems element/Ca ratios from seasonally ventilated caves worldwide.

Effect of Radial-Shear Rolling on the Structure and Hardening of an Al-8%Zn-3.3%Mg-0.8%Ca-1.1%Fe Alloy Manufactured by Electromagnetic Casting.

Aluminum alloys are one of the most common structural materials. To improve the mechanical properties, an alloy of the Al-Zn-Mg-Ca-Fe system was proposed. In this alloy, when Fe and Ca are added, compact particles of the Al10CaFe2 compound are formed, which significantly reduces the negative effect of Fe on the mechanical properties. Because of the high solidification rate (about 600 K/s) during cylindrical ingot (~33 mm) production, the electromagnetic casting method (ECM) makes it possible to obtain a highly dispersed structure in the cast state. The size of the dendritic cell is ~7 µm, while the entire amount of Fe is bound into eutectic inclusions of the Al10CaFe2 phase with an average size of less than 3 µm. In this study, the effect of radial shear rolling (RSR) on the formation of the structure and hardening of the Al-8%Zn-3.3%Mg-0.8%Ca-1.1%Fe alloy obtained by EMC was studied. Computer simulation of the RSR process made it possible to analyze the temperature and stress-strain state of the alloy and to select the optimal rolling modes. It was shown that the flow features during RSR and the severe shear strains near the surface of the rod (10 mm) provided a refining and decrease in the size of the initial Fe-containing particles.

PCL-nHAC/Mg-Ca alloy composite and preliminary study of its osteogenesis property.

Owing to their excellent properties, magnesium alloys are widely used in bone tissue engineering. However, considerable work has been conducted to control the degradation rate and improve the cytocompatibility of magnesium alloys. In this study, low-cost production introduced a new bone repair composite (PCL-nHAC/Mg-Ca), which was composed of nano-hydroxylapatite-collagen (nHAC), polycaprolactone (PCL) and Mg-Ca alloy substrate treated by micro- arc oxidation (MAO). The experimental results showed that compared with the Mg-Ca alloy treated by MAO alone, the PCL-nHAC/Mg-Ca composite has a porous structure and a slower degradation rate. Cell experiments showed that the PCL-nHAC/Mg-Ca composite had good biocompatibility and significantly enhanced the proliferation of the MC3T3-E1 cells. The rabbit skull defect model further proved that the PCL-nHAC/Mg-Ca composite could regulate the degradation rate of the Mg-Ca alloy and promote the formation of bone tissue. Histological analyses showed that the PCL-nHAC/Mg-Ca composite had good stability in vivo and could better accelerate bone formation.

Long-term in vivo observations show biocompatibility and performance of ZX00 magnesium screws surface-modified by plasma-electrolytic oxidation in Göttingen miniature pigs.

Bioabsorbable magnesium implants for orthopedic fixation of bone have recently become available for different fields of indication. While general questions of biocompatibility have been answered, tailoring suitable degradation kinetics for specific applications as well as long-term tissue integration remain the focus of current research. The aim of this study was the evaluation of the long-term degradation behavior and osseointegration of Mg-Ca-Zn (ZX00MEO) based magnesium implants with plasma-electrolytic oxidation (PEO) surface modification (ZX00MEO-PEO) in comparison to non-surface modified implants in vivo and in vitro. Besides a general evaluation of the biological performance of the alloy over a prolonged period, the main hypothesis was that PEO surface modification significantly reduces implant degradation rate and improves tissue interaction. In vitro, the microstructure and surface of the bioabsorbable screws were characterized by SEM/EDS, cytocompatibility and degradation testing facilitating hydrogen gas evolution, carried out following ISO 10993-5/-12 and ASTM F3268-18a/ASTM G1-03 (E1:2017). In vivo, screws were implanted in the frontal bone of Minipigs for 6, 12, and 18 months, following radiological and histomorphometric analysis. A slower and more uniform degradation and improved cytocompatibility could be shown for the ZX00MEO-PEO group in vitro. A significant reduction of degradation rate and enhanced bone formation around the ZX00MEO-PEO screws in vivo was confirmed. Proficient biocompatibility and tissue integration could generally be shown in vivo regardless of surface state. The tested magnesium alloy shows generally beneficial properties as an implant material, while PEO-surface modification further improves the bioabsorption behavior both in vitro and in vivo. STATEMENT OF SIGNIFICANCE: Devices from bioabsorbable Magnesium have recently been introduced to orthopedic applications. However, the vast degradation of Magnesium within the human body still gives limitations. While reliable in-vivo data on most promising surface treatments such as Plasma-electrolytic-Oxidation is generally scarce, long-time results in large animals are to this date completely missing. To overcome this lack of evidence, we studied a Magnesium-Calzium-Zinc-alloy with surface enhancement by PEO for the first time ever over a period of 18 months in a large animal model. In-vitro, surface-modified screws showed significantly improved cytocompatibility and reduction of degradation confirmed by hydrogen gas evolution testing, while in-vivo radiological and histological evaluation generally showed good biocompatibility and bioabsorption as well as significantly enhanced reduction of degradation and faster bone regeneration in the PEO-surface-modified group.

Comparison of Mg/Ca concentration series from Patella depressa limpet shells using CF-LIBS and LA-ICP-MS.

The elemental composition of marine mollusk shells can offer valuable information about environmental conditions experienced by a mollusk during its lifespan. Previous studies have shown significant correlations between Mg/Ca concentration ratios measured on biogenic carbonate of mollusk shells and sea surface temperature (SST). Here we propose the use of Laser-Induced Breakdown Spectroscopy (LIBS) and the validation of the Calibration-Free LIBS (CF-LIBS) approach for the rapid measurement and estimation of Mg/Ca molar concentration profiles within Patella depressa Pennant, 1777 limpet shells. To achieve these objectives, results derived from CF-LIBS methodology are compared with those obtained from an established analytical technique for this purpose, such as Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). Concentration series obtained with both methodologies show defined temporal patterns and reflect the season-of-capture in each specimen. The results evidence a significant correlation (R2 = 0.63-0.81) between CF-LIBS and LA-ICP-MS Mg/Ca molar concentration profiles within four live-collected P. depressa shells. Averaged error for the molar concentration estimated with CF-LIBS was lower than 10% in every specimen. The comparison between the results obtained from two techniques used in this study has allowed us to demonstrate for the first time that Mg/Ca molar concentration measured in biogenic carbonates were accurately inferred using CF-LIBS technique. The CF-LIBS approach validation represents great potential for the rapid and large-scale paleoenvironmental and archaeological analysis of this mollusk species, which is frequently found in archaeological sites.

The Kinetics of Aragonite Formation from Solution via Amorphous Calcium Carbonate.

Magnesium doped Amorphous Calcium Carbonate was synthesised from precursor solutions containing varying amounts of calcium, magnesium, H2O and D2O. The Mg/Ca ratio in the resultant Amorphous Calcium Carbonate was found to vary linearly with the Mg/Ca ratio in the precursor solution. All samples crystallised as aragonite. No Mg was found in the final aragonite crystals. Changes in the Mg to Ca ratio were found to only marginally effect nucleation rates but strongly effect crystal growth rates. These results are consistent with a dissolution-reprecipitation model for aragonite formation via an Amorphous Calcium Carbonate intermediate.

Long-Term Examination of Degradation and In Vivo Biocompatibility of Some Mg-0.5Ca-xY Alloys in Sprague Dawley Rats.

The medical field has undergone constant development in recent years, and a segment of this development is occupied by biodegradable alloys. The most common alloys in this field are those based on Mg, their main advantage being the ability to degrade gradually, without affecting the patient, and also their ability to be fully absorbed by the human body. One of their most important conditions is the regeneration and replacement of human tissue. Tissue can be engineered in different ways, one being tissue regeneration in vivo, which can serve as a template. In vivo remodeling aims to restore tissue or organs. The key processes of tissue formation and maturation are: proliferation (sorting and differentiation of cells), proliferation and organization of the extracellular matrix, biodegradation of the scaffold-remodeling, and potential tissue growth. In the present paper, the design of the alloys in the Mg-Ca-Y system is formed from the beginning using high-purity components, Mg-98.5%, master-alloys: Mg-Y (70 wt.%-30 wt.%) and Mg-Ca (85 wt.%-15 wt.%). After 8 weeks of implantation, the degradation of the implanted material is observed, and only small remaining fragments are found. At the site of implantation, no inflammatory reaction is observed, but it is observed that the process of integration and reabsorption, over time, accentuates the prosaic surface of the material. The aim of the work is to test the biocompatibility of magnesium-based alloys on laboratory rats in order to use these alloys in medical applications. The innovative parts of these analyses are the chemical composition of the alloys used and the tests performed on laboratory animals.

Living on the edge: environmental variability of a shallow late Holocene cold-water coral mound.

Similar to their tropical counterparts, cold-water corals (CWCs) are able to build large three-dimensional reef structures. These unique ecosystems are at risk due to ongoing climate change. In particular, ocean warming, ocean acidification and changes in the hydrological cycle may jeopardize the existence of CWCs. In order to predict how CWCs and their reefs or mounds will develop in the near future one important strategy is to study past fossil CWC mounds and especially shallow CWC ecosystems as they experience a greater environmental variability compared to other deep-water CWC ecosystems. We present results from a CWC mound off southern Norway. A sediment core drilled from this relatively shallow (~ 100 m) CWC mound exposes in full detail hydrographical changes during the late Holocene, which were crucial for mound build-up. We applied computed tomography, 230Th/U dating, and foraminiferal geochemical proxy reconstructions of bottom-water-temperature (Mg/Ca-based BWT), δ18O for seawater density, and the combination of both to infer salinity changes. Our results demonstrate that the CWC mound formed in the late Holocene between 4 kiloannum (ka) and 1.5 ka with an average aggradation rate of 104 cm/kiloyears (kyr), which is significantly lower than other Holocene Norwegian mounds. The reconstructed BWTMg/Ca and seawater density exhibit large variations throughout the entire period of mound formation, but are strikingly similar to modern in situ observations in the nearby Tisler Reef. We argue that BWT does not exert a primary control on CWC mound formation. Instead, strong salinity and seawater density variation throughout the entire mound sequence appears to be controlled by the interplay between the Atlantic Water (AW) inflow and the overlying, outflowing Baltic-Sea water. CWC growth and mound formation in the NE Skagerrak was supported by strong current flow, oxygen replenishment, the presence of a strong boundary layer and larval dispersal through the AW, but possibly inhibited by the influence of fresh Baltic Water during the late Holocene. Our study therefore highlights that modern shallow Norwegian CWC reefs may be particularly endangered due to changes in water-column stratification associated with increasing net precipitation caused by climate change. Supplementary Information: The online version contains supplementary material available at 10.1007/s00338-022-02249-4.

Study on the angiogenesis ability of Polymethyl methacrylate-mineralized collagen/Mg-Ca composite material in vitro and the bone formation effect in vivo.

Magnesium (Mg) and its alloys show high degrees of biocompatibility and biodegradability, used as biodegrad able materials in biomedical applications. In this study, Polymethyl methacrylate (PMMA) - mineralized collagen (nano-Hydroxyapatite/collagen; nHAC)/Mg-Ca composite materials were prepared, to study the angiogenesis ability of its composite materials on Human umbilical vein endothelial cells (HUVECs) and its osteogenesis effect in vivo. The results showed that the PMMA-nHAC reinforcement materials can promote the proliferation and adhesion in HUVECs of Mg matrix significantly, it can enhance the migration motility and VEGF expression of HUVECs. In vivo, Micro-CT examination showed that with coated samples presenting the highest bone formation. Histologically, the materials and their corrosion products caused no systematic or local cytotoxicological effects. Therefore, the Mg matrix composites prepared in the present study has good biocompatibility and PMMA-nHAC/Mg-Ca composite may be an ideal orthopedic material to improve the bone formation, and biodegradable magnesium based implants with bioactivity have potential applications in bone tissue.

pH Stimuli-Responsive, Rapidly Self-healable Coatings Enhanced the Corrosion Resistance and Osteogenic Differentiation of Mg-1Ca Osteoimplant.

Mg-Ca alloys have emerged as a promising research direction for biomedical implants in the orthopedic field. However, their clinical use is deterred by their fast corrosion rate. In this work, a pH stimuli-responsive silk-halloysite (HNT)/phytic acid (PA) self-healing coating (Silk-HNT/PA) is constructed to slow down the corrosion rate of Mg-1Ca alloy and its cell viability and osteogenic differentiation ability are enhanced. The Silk-HNT/PA coating exhibits appealing active corrosion protection, by eliciting pH-triggerable self-healing effects, while simultaneously affording superior biocompatibility and osteogenic differentiation ability. Moreover, in vivo studies by histological analysis also demonstrate better osseointegration for the Silk-HNT/PA coated Mg-1Ca alloy. In summary, the Silk-HNT/PA coating in the present study has great potential in enhancing the biomedical utility of Mg alloys.

High Mg/Ca Molar Ratios Promote Protodolomite Precipitation Induced by the Extreme Halophilic Bacterium Vibrio harveyi QPL2.

Bacterial activities have been demonstrated as critical for protodolomite precipitation in specific aqueous conditions, whereas the relationship between the various hydrochemical factors and bacterial activity has not been fully explored. In this study, biomineralization experiments were conducted using a newly isolated extreme halophilic bacterium from salina mud, Vibrio harveyi QPL2, under various Mg/Ca molar ratios (0, 3, 6, 10, and 12) and a salinity of 200‰. The mineral phases, elemental composition, morphology, and crystal lattice structure of the precipitates were analyzed by XRD, SEM, and HRTEM, respectively. The organic weight and functional groups in the biominerals were identified by TG-DSC, FTIR, and XPS analysis. The amounts of amino acids and polysaccharides in the EPS of QPL2 cultured at various Mg/Ca molar ratios were quantified by an amino acid analyzer and high-performance liquid chromatography. The results confirm that disordered stoichiometric protodolomite was successfully precipitated through the activities of bacteria in a medium with relatively high Mg/Ca molar ratios (10 and 12) but it was not identified in cultures with lower Mg/Ca molar ratios (0, 3, and 6). That bacterial activity is critical for protodolomite formation as shown by the significant bacterial relicts identified in the precipitated spherulite crystals, including pinhole structures, a mineral coating around cells, and high organic matter content within the crystals. It was also confirmed that the high Mg/Ca molar ratio affects the composition of the organic components in the bacterial EPS, leading to the precipitation of the protodolomite. Specifically, not only the total EPS amount, but also other facilitators including the acidic amino acids (Glu and Asp) and polysaccharides in the EPS, increased significantly under the high Mg/Ca molar ratios. Combined with previous studies, the present findings suggest a clear link between high Mg/Ca molar ratios and the formation of protodolomite through halophilic bacterial activity.

In vitro evaluation of freeze-drying chitosan-mineralized collagen/Mg-Ca alloy composites for osteogenesis.

Magnesium (Mg) alloy with good mechanical properties and biodegradability is considered as one of the ideal bone repair materials. However, the rapid corrosion of Mg-based metals can pose harm to the function of an implant in clinical applications. In this study, micro-arc oxidation coating was prepared on the surface of the Mg-Ca matrix, then the chitosan and mineralized collagen (nano-hydroxyapatite/collagen; nHAC) were immobilized on the surface of the MAO/Mg-Ca matrix to construct the CS-nHAC/Mg-Ca composites of different component proportions (the ratio of CS to nHAC is 2:1, 1:1, and 1:2, respectively). The corrosion resistance, osteogenic activity, and angiogenic ability were extensively investigated. The results indicated that the CS-nHAC reinforcement materials can improve the corrosion resistance of the Mg matrix significantly and promote the proliferation and adhesion of mouse embryo osteoblast precursor cells (MC3T3-E1) and human umbilical vein endothelial cells (HUVECs). In addition, the CS-nHAC/Mg-Ca composites can not only promote the alkaline phosphatase (ALP) activity and extracellular matrix mineralization of MC3T3-E1 cells but also enhance the migration motility and vascular endothelial growth factor (VEGF) expression of HUVECs. Meanwhile, the 2CS-1nHAC/Mg-Ca composite exhibited the optimum function characteristics compared with other samples. Therefore, considering the improvement of corrosion resistance and biocompatibility, the CS-nHAC/Mg-Ca composites are expected to be a promising orthopedic implant.

Microgalvanic Corrosion of Mg-Ca and Mg-Al-Ca Alloys in NaCl and Na2SO4 Solutions.

As a kind of potential biomedical material, Mg-Ca alloy has attracted much attention. However, the role of Ca-containing intermetallics in microgalvanic corrosion is still controversial. In 0.6 mol/L NaCl and Na2SO4 solutions, the microgalvanic corrosion behavior of the second phase and Mg matrix of Mg-Ca and Mg-Al-Ca alloys was examined. It was confirmed that the Mg2Ca phase acts as a microanode in microgalvanic corrosion in both NaCl and Na2SO4 solutions, with the Mg matrix acting as the cathode and the Al2Ca phase acting as the microcathode to accelerate corrosion of the adjacent Mg matrix. It was also found that Cl- and SO42- have different sensibilities to microgalvanic corrosion.