Electron Microscopy for the Stability Assessment of Parenteral Nutrition Admixtures: Focus on Precipitation.

(1) Background: parenteral nutrition (PN) is indispensable for patients unable to receive oral or enteral feeding. However, the complexity of PN solutions presents challenges regarding stability and compatibility. Precipitation reactions may occur. The most frequent is the formation of calcium phosphate (Ca-P). The different factors influencing these reactions must be considered to ensure patient safety. (2) Methods: eight paediatric PN solutions were prepared, following standard protocols. Samples were stored at room temperature and in a refrigerator. Electron microscopy, coupled with energy dispersive X-ray spectroscopy (EDS), was employed. Precipitates were analysed for composition and morphology. (3) Results: precipitates were observed in all samples, even at day 0. Crystalline structures, predominantly composed of calcium or magnesium, sometimes associated with chlorine or phosphorus, were detected. Additionally, amorphous precipitates, contained heterogeneous compositions, including unexpected elements, were identified. (4) Conclusions: various precipitates, primarily calcium- or magnesium-based, can form in PN solutions, although it is not expected that they can form under the real conditions of use. Calcium oxalate precipitation has been characterised, but the use of organic calcium and phosphate salts appears to mitigate calcium phosphate precipitation. Electron microscopy provides interesting results on NP precipitation, but sample preparation may present technical limitations that affect the interpretation of the results.

In vitro corrosion and cytocompatibility of Mg-Zn-Ca alloys coated with FHA.

In the field of orthopedics, it's crucial to effectively slow down the degradation rate of Mg alloys. This study aims to improve the degradation behavior of Mg-Zn-Ca alloys by electrodepositing fluorohydroxyapatite (FHA). We investigated the microstructure and bond strength of the deposition, as well as degradation and cellular reactions. After 15-30 days of degradation in Hanks solution, FHA deposited alloys showed enhanced stability and less pH change. The strong interfacial bond between FHA and the Mg-Zn-Ca substrate was verified through scratch tests (Critical loads: 10.73 ± 0.014 N in Mg-Zn-0.5Ca alloys). Cellular studies demonstrated that FHA-coated alloys exhibited good cytocompatibility and promoted the growth of MC3T3-E1 cells. Further tests showed FHA-coated alloys owed improved early bone mineralization and osteogenic properties, especially in Mg-Zn-0.5Ca. This research highlighted the potential of FHA-coated Mg-Zn-0.5Ca alloys in orthopedics applications.

Independent Mutation of Two Bridging Carboxylate Ligands Stabilizes Alternate Conformers of the Photosynthetic O2-Evolving Mn4CaO5 Cluster in Photosystem II.

The O2-evolving Mn4CaO5 cluster in photosystem II is ligated by six carboxylate residues. One of these is D170 of the D1 subunit. This carboxylate bridges between one Mn ion (Mn4) and the Ca ion. A second carboxylate ligand is D342 of the D1 subunit. This carboxylate bridges between two Mn ions (Mn1 and Mn2). D170 and D342 are located on opposite sides of the Mn4CaO5 cluster. Recently, it was shown that the D170E mutation perturbs both the intricate networks of H-bonds that surround the Mn4CaO5 cluster and the equilibrium between different conformers of the cluster in two of its lower oxidation states, S1 and S2, while still supporting O2 evolution at approximately 50% the rate of the wild type. In this study, we show that the D342E mutation produces much the same alterations to the cluster's FTIR and EPR spectra as D170E, while still supporting O2 evolution at approximately 20% the rate of the wild type. Furthermore, the double mutation, D170E + D342E, behaves similarly to the two single mutations. We conclude that D342E alters the equilibrium between different conformers of the cluster in its S1 and S2 states in the same manner as D170E and perturbs the H-bond networks in a similar fashion. This is the second identification of a Mn4CaO5 metal ligand whose mutation influences the equilibrium between the different conformers of the S1 and S2 states without eliminating O2 evolution. This finding has implications for our understanding of the mechanism of O2 formation in terms of catalytically active/inactive conformations of the Mn4CaO5 cluster in its lower oxidation states.

The utility of Hibiscus sabdariffa L. to prepare metal oxides NPs for clinical application on osteoporosis supported by theoretical study.

Green synthesis of metal oxides as a treatment for bone diseases is still exploring. Herein, MgO and Fe2O3 NPs were prepared from the extract of Hibiscus sabdariffa L. to study their effect on vit D3, Ca+2, and alkaline phosphatase enzyme ALP associated with osteoporosis. Computational chemistry was utilized to gain insight into the possible interactions. These oxides were characterized by X-ray diffraction, SEM, FTIR, and AFM. Results revealed that green synthesis of MgO and Fe2O3 NPs was successful with abundant. MgO NPs were in vitro applied on osteoporosis patients (n = 35) and showed a significant elevation of vit D3 and Ca+2 (0.0001 > p < 0.001) levels, compared to healthy volunteers (n = 25). Thus, Hibiscus sabdariffa L. is a good candidate to prepare MgO NPs, with a promising enhancing effect on vit D3 and Ca+2 in osteoporosis. In addition, interactions of Fe2O3 and MgO NPs with ALP were determined by molecular docking study.

Cobalt-based hybrid nanoparticles loaded with curcumin for ligand-enhanced synergistic nanocatalytic therapy/chemotherapy combined with calcium overload.

The therapeutic efficacy of Fenton or Fenton-like nanocatalysts is usually restricted by the inappropriate pH value and limited concentration of hydrogen peroxide (H2O2) at the tumor site. Herein, calcium carbonate (CaCO3)-mineralized cobalt silicate hydroxide hollow nanocatalysts (CSO@CaCO3, CC) were synthesized and loaded with curcumin (CCC). This hybrid system can simultaneously realize nanocatalytic therapy, chemotherapy and calcium overload. With the stabilization of liposomes, CCC is able to reach the tumor site smoothly. The CaCO3 shell first degrades in an acidic tumor environment, releasing Cur and Ca2+, and the pH value of the tumor is increased simultaneously. Then the exposed CSO catalyzes the Fenton-like reaction to convert H2O2 into ˙OH and enhances the cytotoxicity of curcumin (Cur) by catalytically oxidizing it to a ˙Cur radical. Curcumin not only induces the chemotherapy effect but also serves as a nucleophilic ligand and an electron donor in the catalytic system, enhancing the Fenton-like activity of CCC by electron transfer. In addition, calcium overload also amplifies the efficacy of ROS-based therapy. In vitro and in vivo results show that CCC exhibited an excellent synergistic tumor inhibition effect without any clear side effect. This work proposes a novel concept of nanocatalytic therapy/chemotherapy synergistic mechanism by the ligand-induced enhancement of Fenton-like catalytic activity, and inspires the construction of combined therapeutic nanoplatforms and multifunctional nanocarriers for drug and ion delivery in the future.

Pinecone derived hierarchical carbon nanostructure as a transducer in a solid-state ion-selective electrode for in vivo analysis of calcium ion.

Monitoring extracellular calcium ion (Ca2+) chemical signals in neurons is crucial for tracking physiological and pathological changes associated with brain diseases in live animals. Potentiometry based solid-state ion-selective electrodes (ISEs) with the assist of functional carbon nanomaterials as ideal solid-contact layer could realize the potential response for in vitro and in vivo analysis. Herein, we employ a kind of biomass derived porous carbon as a transducing layer to prompt efficient ion to electron transduction while stabilizes the potential drift. The eco-friendly porous carbon after activation (APB) displays a high specific area with inherit macropores, micropores, and large specific capacitance. When employed as transducer in ISEs, a stable potential response, minimized potential drift can be obtained. Benefiting from these excellent properties, a solid-state Ca2+ selective carbon fiber electrodes (CFEs) with a sandwich structure is constructed and employed for real time sensing of Ca2+ under electrical stimulation. This study presents a new approach to develop sustainable and versatile transducers in solid-state ISEs, a crucial way for in vivo sensing.

Effect of calcium and phosphorus on ammonium and nitrate nitrogen adsorption onto iron (hydr)oxides surfaces: CD-MUSIC model and DFT computation.

Calcium (Ca2+) and phosphorous (PO43-) significantly influence the form and effectiveness of nitrogen (N), however, the precise mechanisms governing the adsorption of ammonium nitrogen (NH4+-N) and nitrate nitrogen (NO3--N) are still lacking. This study employed batch adsorption experiments, charge distribution and multi-site complexation (CD-MUSIC) models and density functional theory (DFT) calculations to elucidate the mechanism by which Ca2+ and PO43- affect the adsorption of NH4+-N and NO3--N on the goethite (GT) surface. The results showed that the adsorption of NH4+-N on the GT exhibited an initial increase followed by a decrease as pH increased, peaking at a pH of 8.5. Conversely, the adsorption of NO3--N decreased with rising pH. According to the CD-MUSIC model, Ca2+ minimally affected the NH4+-N adsorption on the GT but enhanced NO3--N adsorption via electrostatic interaction, promoting the adsorption of ≡FeOH-NO3- and ≡Fe3O-NO3- species. Similarly, PO43- inhibited the adsorption of ≡FeOH-NO3- and ≡Fe3O-NO3- species. However, PO43- boosted NH4+-N adsorption by facilitating the formation of ≡Fe3O-NH4+ via electrostatic interaction and site competition. DFT calculations indicates that although bidentate phosphate (BP) was beneficial to stabilize NH4+-N than monodentate phosphate (SP), SP-NH4+ was the main adsorption configuration at pH 5.5-9.5 owing the prevalence of SP on the GT surface under site competition of NH4+-N. The results of CD-MUSIC model and DFT calculation were verified mutually, and provide novel insights into the mechanisms underlying N fixation and migration in soil.

Preparation, biological activity and antibacterial properties of tantalum surface-doped Ca2+/Zn2+nanorods.

In this research, we utilize porous tantalum, known for its outstanding elastic modulus and biological properties, as a base material in biomedical applications. The human skeletal system is rich in elements like Ca and Zn. The role of Zn is crucial for achieving a spectrum of sterilizing effects, while Ca is known to effectively enhance cell differentiation and boost cellular activity. The focus of this study is the modification of porous tantalum using a hydrothermal method to synthesize Ca2+/Zn2+-doped Ta2O5nanorods. These nanorods are subjected to extensive characterization techniques to confirm their structure and composition. Additionally, their biological performance is evaluated through a range of tests, including antibacterial assessments, MTT assays, and bacteria/cell scanning electron microscopy (SEM) analyses. The objective is to determine the most effective method of surface modification for porous tantalum, thereby laying a foundational theoretical framework for its surface enhancement.

Preparation of Liposome Gel by Calcium Cross-Linking Induces the Long-Term Release of DOX to Improve the Antitumor Effect.

Doxorubicin (DOX) is one of the most commonly used anticancer drugs; however, its clinical application is greatly limited due to its toxicity and chemotherapy resistance. The delivery of DOX by liposomes (Lipos) can improve the blood circulation time in vivo and reduce toxic side effects, but the drug's accumulation in the tumor is often insufficient for effective treatment. In this study, we present a calcium cross-linked liposome gel for the encapsulation of DOX, demonstrating its superior long-term release capabilities compared to conventional Lipos. By leveraging this enhanced long-term release, we can enhance drug accumulation within tumors, ultimately leading to improved antitumor efficacy. Lipos were prepared using the thin-film dispersion method in this study. We utilized the ion-responsiveness of glutathione-gelatin (GSH-GG) to form the gel outside the Lipos and named the nanoparticles coated with GSH-GG on the outside of Lipos as Lipos@GSH-GG. The average size of Lipos@GSH-GG was around 342.9 nm, with a negative charge of -25.6 mV. The in vitro experiments revealed that Lipos@GSH-GG exhibited excellent biocompatibility and slower drug release compared to conventional Lipos. Further analysis of cellular uptake and cytotoxicity demonstrated that Lipos@GSH-GG loading DOX (DOX&Lipos@GSH-GG) exhibited superior long-term release effects and lower toxic side effects compared to Lipos loading DOX (DOX&Lipos). Additionally, the findings regarding the long-term release effect in vivo and the tumor accumulation within tumor-bearing mice of Lipos@GSH-GG suggested that, compared to Lipos, it demonstrated superior long-term release capabilities and achieved greater drug accumulation within tumors. In vivo antitumor efficacy experiments showed that DOX&Lipos@GSH-GG demonstrated superior antitumor efficacy to DOX&Lipos. Our study highlights Lipos@GSH-GG as a promising nanocarrier with the potential to enhance efficacy and safety by means of long-term release effects and may offer an alternative approach for effective antitumor therapy in the future.

The impact of hydroxyapatite crystal structures and protein interactions on bone's mechanical properties.

Hydroxyapatite (HAP) constitutes the primary mineral component of bones, and its crystal structure, along with the surface interaction with proteins, significantly influences the outstanding mechanical properties of bone. This study focuses on natural hydroxyapatite, constructing a surface model with calcium vacancy defects. Employing a representative model of aspartic acid residues, we delve into the adsorption mechanism on the crystal surface and scrutinize the adsorption forms of amino acid residues on HAP and calcium-deficient hydroxyapatite (CDHA) surfaces. The research also explores the impact of different environments on adsorption energy. Furthermore, a simplified sandwich structure of crystal-polypeptide-crystal is presented, analyzing the distribution of amino acid residue adsorption sites on the crystal surface of the polypeptide fragment. This investigation aims to elucidate how the stick-slip mechanism of polypeptide molecules on the crystal surface influences the mechanical properties of the system. By uncovering the interface mechanical behavior between HAP and osteopontin peptides, this article offers valuable theoretical insights for the construction and biomimetic design of biocomposites.

Remediation of oily-produced water from high-salinity oilfield using a low-cost, high-alumina calcium bentonite hollow fiber membrane.

Discharging improperly treated oily-produced water (OPW) into the environment can have significant negative impacts on environmental sustainability. It can lead to pollution of water sources, damage to aquatic ecosystems and potential health hazards for individuals living in the affected areas. Ceramic hollow fiber membrane (CHFM) technology is one of the most effective OPW treatment methods for achieving high oil removal efficiency while maintaining membrane water permeability. In this study, low-cost calcium bentonite hollow fiber membranes (CaB-HFMs) were prepared from high-alumina calcium bentonite clay with various preparation parameters, including calcium bentonite content, sintering temperature, air gap distance and bore fluid rate. The prepared CaB-HFMs were then subjected to characterization using scanning electron microscopy (SEM), a three-point bending test, porosity, average pore size, hydraulic resistance and flux recovery ratio (FRR) analysis. Statistical analysis employing central composite design (CCD) assessed the interaction between the parameters and their effect on CaB-HFM water permeability and oil removal efficiency. Higher ceramic content and sintering temperature led to reduced porosity, smaller pore size and higher mechanical strength. In contrast, increasing the air gap distance and bore fluid rate exhibit different trends, resulting in higher porosity and pore size, along with weaker mechanical strength. Other than that, all of the CaB-HFMs displayed low hydraulic resistance (<0.01 m2 h.bar/L) and high FRR value (up to 95.2%). Based on CCD, optimal conditions for CaB-HFM were determined as follows: a calcium bentonite content of 50 wt.%, a sintering temperature of 1096 °C, an air gap distance of 5 cm and a bore fluid rate of 10 mL/min, with the desirability value of 0.937. Notably, the optimized CaB-HFMs demonstrated high oil removal efficiency of up to 99.7% with exceptional water permeability up to 535.2 L/m2.h.bar. The long-term permeation study also revealed it was capable of achieving a high average water permeation and a stable oil rejection performance of 522.15 L/m2.h.bar and 99.8%, respectively, due to their inherent hydrophilic and antifouling characteristics, making it practical for OPW treatment application.

A ROS storm generating nanocomposite for enhanced chemodynamic therapy through H2O2 self-supply, GSH depletion and calcium overload.

Catalytic generation of toxic hydroxyl radicals (˙OH) from hydrogen peroxide (H2O2) is an effective strategy for tumor treatment in chemodynamic therapy (CDT). However, the intrinsic features of the microenvironment in solid tumors, characterized by limited H2O2 and overexpressed glutathione (GSH), severely impede the accumulation of intracellular ˙OH, posing significant challenges. To circumvent these critical issues, in this work, a CaO2-based multifunctional nanocomposite with a surface coating of Cu2+ and L-buthionine sulfoximine (BSO) (named CaO2@Cu-BSO) is designed for enhanced CDT. Taking advantage of the weakly acidic environment of the tumor, the nanocomposite gradually disintegrates, and the exposed CaO2 nanoparticles subsequently decompose to produce H2O2, alleviating the insufficient supply of endogenous H2O2 in the tumor microenvironment (TME). Furthermore, Cu2+ detached from the surface of CaO2 is reduced by H2O2 and GSH to Cu+ and ROS. Then, Cu+ catalyzes H2O2 to generate highly cytotoxic ˙OH and Cu2+, forming a cyclic catalysis effect for effective CDT. Meanwhile, GSH is depleted by Cu2+ ions to eliminate possible ˙OH scavenging. In addition, the decomposition of CaO2 by TME releases a large amount of free Ca2+, resulting in the accumulation and overload of Ca2+ and mitochondrial damage in tumor cells, further improving CDT efficacy and accelerating tumor apoptosis. Besides, BSO, a molecular inhibitor, decreases GSH production by blocking γ-glutamyl cysteine synthetase. Together, this strategy allows for enhanced CDT efficiency via a ROS storm generation strategy in tumor therapy. The experimental results confirm and demonstrate the satisfactory tumor inhibition effect both in vitro and in vivo.

Comprehensive enhancement of flame retardant starch/cellulose/diatomite composite foams via metal-organic coordination.

In recent years, considerable attention has been given to the utilization of biomass for producing bio-based foams, such as starch-based foams. Despite their renewability and widespread availability, these foams still present certain drawbacks regarding their poor mechanical properties and flammability. To tackle these concerns, a metal ion cross-linking strategy was employed by incorporating calcium ions (Ca2+) solution into foamed starch/cellulose slurry. Followed by ambient drying, starch/cellulose composite foam was successfully fabricated with a remarkable enhancement in various properties. Specifically, compared to the control sample, the compressive strength and modulus increased by 26.2 % and 123.0 %, respectively. Additionally, the Ca2+ cross-linked starch/cellulose composite foam exhibited excellent heat resistance, water stability, and flame retardancy. The limiting oxygen index (LOI) reached 52 %, with a vertical combustion rating of V-0. Along with the addition of 2 phr diatomite, it demonstrated a significant enhancement on flame retardancy with a LOI of 65 %, although the apparent density of the composite foam was not low enough. This study indicated a green and simple method to obtain starch-based composite foams with enhanced comprehensive properties including thermal, water stability, mechanical, and flame retardancy, expanding their potential applications in areas such as building materials and rigid packaging.

N-terminal domain truncation yielded a unique dimer of polysaccharide hydrolase with enhanced enzymatic activity, stability and calcium ion independence.

Domain engineering, including domain truncation, fusion, or swapping, has become a common strategy to improve properties of enzymes, especially glycosyl hydrolases. However, there are few reports explaining the mechanism of increased activity from a protein structure perspective. Amy703 is an alkaline amylase with a unique N-terminal domain. Prior studies have shown that N-Amy, a mutant without an N-terminal domain, exhibits improved activity, stability, and calcium ion independence. In this study, we have used X-ray crystallography to determine the crystal structure of N-Amy and used AlphaFold2 to model the Amy703 structure, respectively. We further used size exclusion chromatography to show that Amy703 existed as a monomer, whereas N-Amy formed a unique dimer. It was found that the N-terminus of one monomer of N-Amy was inserted into the catalytic domain of its symmetrical subunit, resulting in the expansion of the catalytic pocket. This also significantly increased the pKa of the hydrogen donor Glu350, thereby enhancing substrate binding affinity and contributing to increased N-Amy activity. Meanwhile, two calcium ions were found to bind to N-Amy at different binding sites, which also contributed to the stability of protein. Therefore, this study provided new structural insights into the mechanisms of various glycosyl hydrolases.

Mechanistic study on the promotion of Ca2+ leaching in steel slag through high-temperature solid waste modification.

Indirect carbonation of steel slag is an effective method for CO2 storage, reducing emissions, and promoting cleaner production in the steel industry. However, challenges remain, such as low Ca2+ leaching rates and slag management complexities arising from variations in mineral compositions. To address this, a high-temperature modification process is proposed to alter the mineral composition and facilitate the synergistic utilization of calcium and iron. This study delves into the effects of various solid waste modifications on the leaching of Ca2+ and the total iron content within steel slag. Results show that high-basicity modified slag forms Ca2(Al, Fe)2O5, reducing calcium leaching. Low-alkalinity modified slag produces calcium-rich aluminum minerals and also reduces the leaching of Ca2+ ions. At a basicity of 2.5, coal gangue, fly ash, and blast slag achieve maximum Ca2+ leaching rates of 88.93%, 89.46%, and 90.17%, respectively, with corresponding total iron contents of 41.46%, 37.72%, and 35.29%. Upgraded coal gangue exhibits a 50.02% increase in calcium leaching and a 15.58% increase in total iron content compared to the original slag. This enhances CO2 fixation and iron resource utilization. Overall, the proposed indirect carbonation and iron enrichment modification offer a novel approach for the resource utilization and environmental stability of steel slag.

Influence of Ultrasound on the Characteristics of CaP Coatings Generated Via the Micro-arc Oxidation Process in Relation to Biomedical Engineering.

Over the past decade, bone tissue engineering has been at the core of attention because of an increasing number of implant surgeries. The purpose of this study was to obtain coatings on titanium (Ti) implants with improved properties in terms of biomedical applications and to investigate the effect of ultrasound (US) on these properties during the micro-arc oxidation (MAO) process. The influence of various process parameters, such as time and current density, as well as US mode, on the properties of such coatings was evaluated. Novel porous calcium-phosphate-based coatings were obtained on commercially pure Ti. Their microstructure, chemical composition, topography, wettability, nanomechanical properties, thickness, adhesion to the substrate, and corrosion resistance were analyzed. In addition, cytocompatibility evaluation was checked with the human osteoblasts. The properties of the coatings varied significantly, depending on applied process parameters. The US application during the MAO process contributes to the increase of coating thickness, porosity, roughness, and skewness, as well as augmented calcium incorporation. The most advantageous coating was obtained at a current of 136 mA, time 450 s, and unipolar rectangular US, as it exhibits high porosity, adequate wettability, and beneficial skewness, which enabled increased adhesion and proliferation of osteoblasts during in vitro studies. Finally, the conducted research demonstrated the influence of various UMAO process parameters, which allowed for the selection of appropriate Ti implant modification for specific biomedical utilization.

Improvement of the Green-Red Förster Resonance Energy Transfer-Based Ca2+ Indicator by Using the Green Fluorescent Protein, Gamillus, with a Trans Chromophore as the Donor.

To monitor the Ca2+ dynamics in cells, various genetically encoded Ca2+ indicators (GECIs) based on Förster resonance energy transfer (FRET) between fluorescent proteins are widely used for live imaging. Conventionally, cyan and yellow fluorescent proteins have been often used as FRET pairs. Meanwhile, bathochromically shifted indicators with green and red fluorescent protein pairs have various advantages, such as low toxicity and autofluorescence in cells. However, it remains difficult to develop them with a similar level of dynamic range as cyan and yellow fluorescent protein pairs. To improve this, we used Gamillus, which has a unique trans-configuration chromophore, as a green fluorescent protein. Based on one of the best high-dynamic-range GECIs, Twitch-NR, we developed a GECI with 1.5-times higher dynamic range (253%), Twitch-GmRR, using RRvT as a red fluorescent protein. Twitch-GmRR had high brightness and photostability and was successfully applied for imaging the Ca2+ dynamics in live cells. Our results suggest that Gamillus with trans-type chromophores contributes to improving the dynamic range of GECIs. Therefore, selection of the cis-trans isomer of the chromophore may be a fundamental approach to improve the dynamic range of green-red FRET indicators, unlimited by GECIs.

Unlocking high-performance HCl adsorption at elevated temperatures: the synthesis and characterization of robust Ca-Mg-Al mixed oxides.

The presence of HCl and SO2 gas imposes limitations on syngas utilization obtained from household waste in a wide range of applications. The hydrotalcite-like compounds (HTLs) have been proved that could remove HCl efficiency. However, the research on impact of synthesis conditions of HTLs and SO2 on HCl removal was limited. In this study, a range of Ca-Mg-Al mixed oxide sorbents was synthesized by calcining HTLs, with variations in crystallization temperature, solution pH, and the Ca/Mg molar ratio. These sorbents were examined for their effectiveness in removing HCl at medium-high temperatures under diverse conditions. The adsorption performance of selected sorbents for the removal of HCl, SO2, and HCl-SO2 mixed gas at temperature of 350 °C, 450 °C, and 550 °C, respectively, was evaluated using thermogravimetric analysis (TGA). It was observed that the HTL synthesis parameters significantly influenced the HCl adsorption capacity of Ca-Mg-Al mixed oxides. Notably, HTLs synthesized at 60 °C, a solution pH of 10-11, and a Ca/Mg ratio of 4 exhibited superior crystallinity and optimal adsorption characteristics. For individual HCl and SO2 removal, temperature had a minor effect on HCl adsorption but significantly impacted SO2 adsorption rates. At temperatures above 550 °C, SO2 removal efficiency substantially decreased. When exposed to a mixed gas, the Ca-Mg-Al mixed oxides could efficiently remove both HCl and SO2 at temperatures below 550 °C, with HCl dominating the adsorption process at higher temperatures. This dual-action capability is attributed to several mechanisms through which HTL sorbents interacted with HCl, including pore filling, ion exchange, and cation exchange. Initially, HCl absorbed onto specific sites created by water and CO2 removal due to the surface's polarity. Subsequently, HCl reacted with CaCO3 and CaO formed during HTL decomposition.

Site-specific mutagenesis on Mnemiopsin 2: Calcium coordination and substrate binding properties of new variants.

We used site-specific mutagenesis by targeting E179 and F190 on the structure of photoprotein Mnemiopsin 2 (Mn2) from Mnemiopsis leidyi. The tertiary structure of E179S and F190L mutants was made by the MODELLER program. Far-ultraviolet circular dichroism data showed that the overall secondary structural content of photoprotein is not changed upon mutation, however the helicity and stabilizing interactions in helical structure decreases in mutants as compared with the wild-type (WT) photoprotein. Fluorescence spectra data revealed that the tertiary structure of the mutants is more compact than that of WT Mn2. According to the heat-induced denaturation experiments data, the melting temperature (Tm ) for the unfolding of tertiary structure of the F190L variant increases by 3°C compared with that of the WT and E179S mutant. Interestingly, the conformational enthalpy of the F190L mutant (86 kcal mol-1 ) is considerably lower than those in the WT photoprotein (102 kcal mol-1 ) and E179S mutant (106 kcal mol-1 ). The significant difference in the enthalpy of the thermal unfolding process could be explained by considering that the thermally denatured state of the F190L mutant is structurally less expanded than the WT and E179S variants. Bioluminescence activity data showed that the maximum characteristic wavelengths of the mutants undergo blue shift as compared with the WT protein. Initial intensity of the F190L and E179S variants was recorded to be 137.5% and 55.9% of the WT protein, respectively.

Anionic species from multivalent metal salts are differentially retained during aqueous ionic gelation of sodium alginate and could fine-tune the hydrogel properties.

The role of anionic counterions of divalent metal salts in alginate gelation and hydrogel properties has been thoroughly investigated. Three anions were selected from the Hofmeister series, namely sulphate, acetate and chloride, paired in all permutations and combinations with divalent metal cations like calcium, zinc and copper. Spectroscopic analysis revealed the presence of anions and their interaction with the respective metal cations in the hydrogel. The data showed that the gelation time and other hydrogel properties were largely controlled by cations. However, subtle yet significant variations in viscoelasticity, water uptake, drug release and cytocompatibility properties were anion dependent in each cationic group. Computational modelling based study showed that metal-anion-alginate configurations were energetically more stable than the metal-alginate models. The in vitro and in silico studies concluded that acetate anions preceded chlorides in the drug release, swelling and cytocompatibility fronts, followed by sulphate anions in each cationic group. Overall, the data confirmed that anions are an integral part of the metal-alginate complex. Furthermore, anions offer a novel option to further fine-tune the properties of alginate hydrogels for myriads of applications. In addition, full exploration of this novel avenue would enhance the usability of alginate polymers in the pharmaceutical, environmental, biomedical and food industries.