Divalent Cations Mg2 Research Articles

Design of Point Charge Models for Divalent Metal Cations Targeting Quantum Mechanical Ion–Water Dimer Interactions

Divalent metal cations are of vital importance in biochemistry and materials science, and their structural and thermodynamic properties in aqueous solution have often been used as targets for the development of ion models. This study presented a strategy for designing nonbonded point charge models of divalent metal cations (Mg2+ and Ca2+) and Cl− by targeting quantum mechanics (QM)-based ion–water dimer interactions. The designed models offered an accurate representation of ion–water interactions in the gas phase and showed reasonable performance for non-targeted properties in aqueous solutions, such as the ion–water oxygen distance (IOD), coordination number (CN), and density and viscosity of MgCl2 and CaCl2 solutions at low concentrations. Our metal cation models yielded considerable overestimates of the hydration free energies (HFEs) of the ions, whereas the Cl− model displayed good performance. Together with the overestimated density and viscosity of the salt solutions, these results indicated the necessity of re-optimizing ion–ion interactions and/or including polarization effects in the design of ion models. The designed Mg2+ model was capable of maintaining the crystal metal-binding networks during MD simulation of a metalloprotein, indicating great potential for biomolecular simulations. This work highlighted the potential of QM-based ion models to advance the study of metal ion interactions in biological and material systems.

Simultaneous removal of lead(II) and cadmium(II) from acidic wastewater by Fe-modified sludge biochar

In natural environments, heavy metal water pollution often involves simultaneous presence of various heavy metal ions (HMs), posing significant challenges for their removal. In this study, Fe-modified sludge biochar was synthesized via the co-precipitation method, and the effects of various environmental factors on simultaneously removing lead(II) and cadmium(II) by Fe@SBC were investigated. Batch adsorption experiments showed that Fe@SBC has a higher removal capacities for Pb(II) than for Cd(II) in both single or binary solutions. Increasing solution pH promoted the HMs removal on Fe@SBC. Coexisting divalent cations (Mg2+ and Ca2+) exhibited stronger inhibitory effects on HMs removal by Fe@SBC than monovalent cations (K+ and Na+). The presence of humic acid (HA) did not affect Pb(II) removal on Fe@SBC in either single or binary systems. In single systems, increasing HA concentration enhanced Cd(II) removing on Fe@SBC, while in binary systems, increasing HA concentrations inhibited the Cd(II) removal on Fe@SBC. The sorption of Pb(II) and Cd(II) on Fe@SBC followed the pseudo-second-order kinetic model and the Langmuir model. The removal mechanisms involved electrostatic interactions, complexation with O-containing group, and mineral dissolution-precipitation. After three regenerations, the adsorption capacity of Fe@SBC for Pb(II) and Cd(II) decreased by approximately 5–10 %. In summary, this environmentally friendly composite material has great potential for simultaneously remediating of Pb(II) and Cd(II).

Catalytic Activities of Ir-Based Pyrochlore-Type Oxides Doped with Divalent Cations for Oxygen Evolution Reaction

Alternative energy sources to fossil fuels are essential for a sustainable society, and hydrogen energy is expected to be a solution to environmental and energy problems. Currently, proton exchange membrane water electrolyzers are becoming widely used for the electrochemical production of hydrogen due to their advantages such as high efficiency. However, the highly acidic conditions and the large overpotentials of oxygen evolution reaction (OER) at the anode are problems, and the development of catalysts that are stable and highly active in acidic aqueous solutions is important for further popularization.Ir-based oxides with pyrochlore structure (A2B2O7) are known to exhibit high catalytic activities in acidic aqueous solutions. Recently, it has been reported that the improved catalytic activities of Pr2Ir2O7 by Zn doping, which controlled the composition of A-site elements in the pyrochlore structure [1]. In this study, we synthesized Pr2-x MgxIr2O7 (x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5), in which a part of trivalent cation Pr3+ was replaced by divalent cation Mg2+ and improved the OER catalytic activity in acidic aqueous solutions.Pr2-x MgxIr2O7 was synthesized by the hydrothermal method. The catalyst was mixed with a conductivity aid carbon (Vulcan XC-72) and a cationic conductive ionomer (Nafion) at a weight ratio of 5:1:1 and dispersed in 2-propanol to form a catalyst ink. The catalytic activity was evaluated by cyclic voltammetry (CV) using a glassy carbon rotating disk electrode (RDE) as a working electrode, a reversible hydrogen electrode (RHE) as a reference electrode, and a platinum wire as a counter electrode. The electrolyte was a 0.1 mol dm-3 HClO4 solution saturated with oxygen, and the CV scanning range was 1.1 to 1.7 V with respect to the RHE, scanning speed was 20 mV s-1, and the RDE rotation speed was 1200 rpm. The stability of the catalyst in acidic aqueous solutions was evaluated by chronopotentiometry (CP) using the same cell.X-ray diffraction and energy-dispersive X-ray analysis measurements of the synthesized materials confirmed that the desired compounds were obtained, and CV measurements showed that the OER activity of Pr2-x MgxIr2O7 increased in the first 20 cycles for all compositions, and then stabilized over several tens of cycles. The cycle change was similar to that of Pr2Ir2O7, suggesting that the surface rearrangement proceeds in acidic aqueous solutions [2]. Linear sweep voltammogram (LSV) and OER activity normalized by Brunauer-Emmett-Teller (BET) specific surface area were measured at the 20th cycle, and the catalytic activity stabilized at a high value. The OER activity was enhanced by Mg substitution in the catalysts of Pr2-x Mg x Ir2O7.References L. Zhu, C. Ma, Z. Wang, X. Gong, L. Cao, and J. Yang, Appl. Surf. Sci., 31, 151840 (2022).C. Shang, C. Cao, D. Yu, Y. Yan, Y. Lin, H. Li, T. Zheng, X. Yan, W. Yu, S. Zhou, and J. Zeng, Adv. Mater., 31, 1805104 (2018).

Diffusion and structure of propylene carbonate-metal salt electrolyte solutions for post-lithium-ion batteries: From experiment to simulation.

The diffusion of cations in organic solvent solutions is important for the performance of metal-ion batteries. In this article, pulsed field gradient nuclear magnetic resonance experiments and fully atomistic molecular dynamic simulations were employed to study the temperature-dependent diffusive behavior of various liquid electrolytes representing 1M propylene carbonate solutions of metal salts with bis(trifluoromethylsulfonyl)imide (TFSI-) or hexafluorophosphate (PF6-) anions commonly used in lithium-ion batteries and beyond. The experimental studies revealed the temperature dependence of the diffusion coefficients for the propylene carbonate (PC) solvent and for the anions following an Arrhenius type of behavior. It was observed that the PC molecules are the faster species. For the monovalent cations (Li+, Na+, K+), the PC solvent diffusion was enhanced as the cation size increased, while for the divalent cations (Mg2+, Ca2+, Sr2+, Ba2+), the opposite trend was observed, i.e., the diffusion coefficients decreased as the cation size increased. The anion diffusion in LiTFSI and NaTFSI solutions was found to be similar, while in electrolytes with divalent cations, a decrease in anion diffusion with increasing cation size was observed. It was shown that non-polarizable charge-scaled force fields could correspond perfectly to the experimental values of the anion and PC solvent diffusion coefficients in salt solutions of both monovalent (Li+, Na+, K+) and divalent (Mg2+, Ca2+, Sr2+, Ba2+) cations at a range of operational temperatures. Finally, after calculating the radial distribution functions between cations, anions, and solvent molecules, the increase in the PC diffusion coefficient established with the increase in cation size for monovalent cations was clearly explained by the large hydration shell of small Li+ cations, due to their strong interaction with the PC solvent. In solutions with larger monovalent cations, such as Na+, and with a smaller solvation shell of PC, the PC diffusion is faster due to more liberated solvent molecules. In the salt solutions with divalent cations, both the anion and the PC diffusion coefficients decreased as the cation size increased due to an enhanced cation-anion coordination, which was accompanied by an increase in the amount of PC in the cation solvation shell due to the presence of anions.

Competition between Stacking and Divalent Cation-Mediated Electrostatic Interactions Determines the Conformations of Short DNA Sequences.

Interplay between divalent cations (Mg2+ and Ca2+) and single-stranded DNA (ssDNA) and double-stranded DNA (dsDNA), as well as stacking interactions, is important in nucleosome stability and phase separation in nucleic acids. Quantitative techniques accounting for ion-DNA interactions are needed to obtain insights into these and related problems. Toward this end, we created a sequence-dependent computational TIS-ION model that explicitly accounts for monovalent and divalent ions. Simulations of the rigid 24 base-pair (bp) dsDNA and flexible ssDNA sequences, dT30 and dA30, with varying amounts of the divalent cations show that the calculated excess number of ions around the dsDNA and ssDNA agree quantitatively with ion-counting experiments. Using an ensemble of all-atom structures generated from coarse-grained simulations, we calculated the small-angle X-ray scattering profiles, which are in excellent agreement with experiments. Although ion-counting experiments mask the differences between Mg2+ and Ca2+, we find that Mg2+ binds to the minor grooves and phosphate groups, whereas Ca2+ binds specifically to the minor groove. Both Mg2+ and Ca2+ exhibit a tendency to bind to the minor groove of DNA as opposed to the major groove. The dA30 conformations are dominated by stacking interactions, resulting in structures with considerable helical order. The near cancellation of the favorable stacking and unfavorable electrostatic interactions leads to dT30 populating an ensemble of heterogeneous conformations. The successful applications of the TIS-ION model are poised to confront many problems in DNA biophysics.

A comparative study on the Cs adsorption/desorption and structural changes in different clay minerals.

We investigated the structural changes in clay minerals after Cs adsorption and understood their low desorption efficiency using an ion-exchanger. We focused on the role of interlayers in Cs adsorption and desorption in 2:1 clay minerals, namely illite, hydrobiotite, and montmorillonite, using batch experiments and XRD and EXAFS analyses. The adsorption characteristics of the clay minerals were analyzed using cation exchange capacity (CEC), maximum adsorption isotherms (Qmax), and radiocesium interception potential (RIP) experiments. Although illite showed a low CEC value, it exhibited high selectivity for Cs with a relatively high RIP/CEC ratio. The Cs desorption efficiency after treatment with a NaCl ion exchanger was the highest for illite (74.3%), followed by hydrobiotite (45.5%) and montmorillonite (30.3%); thus, Cs adsorbed onto planar sites, rather than on interlayers or frayed edge sites (FESs), is easily desorbed. After NaCl treatment, XRD analysis showed that the low desorption efficiency was due to the collapse of the interlayer-fixed Cs, which tightly narrowed the interlayers' hydrobiotite due to the ion exchange of divalent cations (Mg2+ or Ca2+) into the monovalent cation (Na+). Moreover, EXAFS analysis showed that hydrobiotite formed inner-sphere structures after NaCl desorption, indicating that it was difficult to remove Cs from NaCl desorption due to the collapsed hydrobiotite and montmorillonite interlayers as well as the strong bonding in FESs of illite. In contrast, chelation desorption using oxalic acid effectively dissolved the narrowed interlayers of hydrobiotite (98%) and montmorillonite (85.26%), enhancing the desorption efficiency. Therefore, low desorption efficiency for Cs clays using an ion exchanger was caused by the collapsed interlayer due to the exchange between monovalent cation and divalent cation.

Fine Tuning of Hierarchical Zeolite Beta Acid Sites Strength

Two different synthesis methods to obtain hierarchical Beta zeolite are investigated: direct synthesis using cetyltrimethylammonium bromide (CTAB) as a mesoporous template and post-synthesis desilication by etching with NaOH and TPAOH. The main focus of this study is to show the possibility of fine tuning of the acid site (OH) strength (Brønsted and Lewis acid sites) through wet impregnation of these hierarchical Beta zeolites with divalent metal cations (Mg2+, Co2+, Ni2+, Cu2+, and Zn2+), which are important for various applications. Fourier transform infrared spectroscopy (FTIR) and deuterated acetonitrile as the probe molecule were used as a powerful technique to analyze the quantity and number of Brønsted/Lewis acid sites in the modified zeolite Beta structure. Investigating the influence of different divalent metal cations with a comparable ionic radius on the acidity of the hierarchical Beta zeolites, the present research aims to shed light on the structure–activity relationship that determines their catalytic behavior, for the development of efficient and environmentally friendly catalysts for various industrial applications.

Synthesis and characterisation of magnesium-wrapped hydroxyapatite nanomaterials for biomedical applications

The advancement of novel nanobiomaterials holds significant importance in the fields of drug delivery and environmental remediation. Hydroxyapatite, which falls under the category of bioceramic materials, has demonstrated efficacy as a bone graft material. The substitution of cations in hydroxyapatite has been found to enhance its biological properties, making it a promising material for various biomedical applications. In this study, the synthesis of Mg2+ substituted hydroxyapatite nanostructures was conducted through the sol-gel method employing different surfactants, namely polyethylene glycol and cetyltrimethylammonium bromide. The resulting nanoparticles were subjected to analysis to evaluate their structural, morphological, and optical characteristics. The antimicrobial and antioxidant behavior of the Mg2+ doped hydroxyapatite nanoparticles were also studied. The XRD analysis showed a hexagonal crystal structure for Mg2+ doped hydroxyapatite nanostructures for all samples. The Raman and FTIR results also confirmed the successful substitution of divalent cation Mg2+ in hydroxyapatite. EDAX results exhibited the qualitative elemental composition and stoichiometric nature of synthesized hydroxyapatite. The optical study showed higher transmission in the visible region for the Mg2+ doped hydroxyapatite prepared using various surfactants. The microbial restriction efficacy of Mg2+ doped hydroxyapatite prepared using various surfactants was examined against human pathogenic bacterias Shigella flexneri (MTCC-2197), Escherichia coli (MTCC-4213), Pseudomonas aeruginosa (MTCC-3131), Klebseilla pneumoniae (MTCC-1214), and Staphylococcus aureus (MTCC-3123). The hydroxyapatite nano biomaterial doped with Mg2+ demonstrates remarkable antibacterial, antifungal, and antioxidant properties. The HeLa cell lines exhibited significant cytotoxicity when exposed to magnesium ion-doped hydroxyapatite nanoparticles.

Vibrational properties of OH groups associated with divalent cations in corundum (α-Al2O3)

Abstract. The infrared spectra of synthetic corundum (α-Al2O3) samples either doped directly with divalent cations (Mg2+) or containing divalent cations formed by reduction of trivalent cations in H2 gas (Co2+, Ni2+) may display broad OH stretching bands at ∼3000 cm−1 due to the structural incorporation of trace amounts of hydrogen. Experimental spectra recorded from some natural sapphires display a similar absorption band associated with a dominant absorption at 3161 cm−1, and some beryllium-diffused corundum crystals show a band at 3060 cm−1. All of these also display smaller and generally narrower bands between 1900 and 2700 cm−1, whose natures are poorly defined. In this work, the atomic-scale structure, relative stability and infrared spectroscopic properties of a series of OH defects in corundum (α-Al2O3) are theoretically investigated at the density-functional-theory level. The investigated defects consist of interstitial H+ ions forming OH groups and compensating for the charge imbalance related to the presence of divalent cations (Be2+, Mg2+, Cr2+, Mn2+, Fe2+, Co2+, Ni2+) substituted for Al3+ at nearby octahedral sites. Bands occurring at ∼3000 cm−1 in experimental spectra are assigned to the OH stretching modes of some of these defects, with bands observed around 1900 and 2700 cm−1 being assigned to overtones of corresponding OH bending modes. The results also support the assignment of the so-called “3161 cm−1 series”, observed in experimental spectra of some rubies and yellow sapphires, to structural OH groups in association with Fe2+ ions, rather than Si4+, as has been previously proposed. These inferences are also supported by analysis of correlations between band areas in experimental infrared spectra extracted from a database of corundum gemstones. A qualitative explanation relating the anomalous intensity and the polarisation properties of the OH bending overtone bands to the electrical anharmonicity of OH groups involved in medium-strength H bonds is proposed.

Experimental investigation of wettability alteration, IFT reduction, and injection schemes during surfactant/smart water flooding for EOR application

In recent years, the application of smart water and surfactant in order to improve oil recovery has attracted special attention in carbonate reservoirs. In this research, the effects of various salts in smart water and two surfactants of Cetyl Trimethyl Ammonium Bromide (CTAB) and Sodium Dodecyl Sulfate (SDS) on the wettability alteration of carbonate rock and IFT were studied. Besides, along with micromodel flooding, core flooding tests were conducted to assess the amount of oil recovery at reservoir conditions as an injection scheme was used. In this regard, the results illustrated that the presence of CTAB or SDS in seawater (SW) can act better in contact angle reduction compared to smart water. Also, a four times increase in the concentration of SO42− and removing Na+ from SW reduced the contact angle to 68° and 71°, respectively, being the best possible options to alter the carbonate surface wettability to more water-wet states. Moreover, in the second-order process in which the rock section was first placed in SW, and then was put in the smart solution (with or without surfactant), CTAB had a great effect on the wettability alteration. In the case of IFT reduction, although SW4Mg2+, compared to other ions, better decreased the IFT to 17.83 mN/m, SW + SDS and SW + CTAB further declined the IFT to 0.67 and 0.33 mN/m, respectively. Concerning different ions, divalent cations (Mg2+ and Ca2+) show better results in improving oil recovery factor. However, the combination of SW and surfactants has a more positive effect on boosting oil recovery, as compared to smart water flooding. It should be mentioned that the first-order injection is better than the second-order one since SW is flooded at first, and then, after the breakthrough, smart water is injected into the micromodel. In addition, the core flooding tests showed that SW + CTAB and SW + SDS in tertiary injection increased the oil recovery to about 59 and 57%, respectively, indicating that the presence of CTAB could be more effective than that of SDS.

The influence of divalent cations on the dynamic surface tension of sodium dodecylbenzenesulfonate solutions

The kinetics of surfactant adsorption at interfaces is crucial in many industrial settings. Maximum bubble pressure tensiometry allows accessing the adsorption at time scales of tens of ms to uncover the initial stages of surfactant diffusion to the interface. This method was used to investigate electrolyte solutions of sodium dodecylbenzenesulfonate (SDBS), specifically targeting how the presence of small amounts of divalent cations (Mg2+, Ca2+, Sr2+ and Ba2+) influenced the adsorption kinetics and equilibrium. The dynamic surface tensions revealed that the adsorption of SDBS was strongly influenced by the presence of divalent cations due to strong interactions with the anionic surfactant. In addition, the type (i.e. size) of cations played a role. The strong divalent cation-surfactant interactions lead to distinct lowering of surfactant diffusion coefficients, calculated using the short-time approximation solution of the Ward-Tordai equation. The diffusion coefficients were slightly and similarly lowered for all types of divalent cations when the surfactant concentration was increased up to the critical micelle concentration (CMC). Above CMC, the diffusion coefficients increased steadily depending on the divalent cation. It was speculated that this could be due to differences in structure and aggregation numbers of micelles and slower disassembly of micelles to supply monomers for adsorption. Furthermore, CMC of SDBS was reduced according to the Hofmeister series in the presence of divalent cations.

Impacts of divalent cations (Mg2+ and Ca2+) on PFAS bioaccumulation in freshwater macroinvertebrates representing different foraging modes

Per- and polyfluoroalkyl substances (PFAS) have extensively contaminated freshwater aquatic ecosystems where they can be transported in water and partition to sediment and biota. In this paper, three freshwater benthic macroinvertebrates with different foraging modes were exposed to environmentally relevant concentrations of eight perfluoroalkyl carboxylates (PFCA), three perfluoroalkyl sulfonates (PFSA), and three fluorotelomer sulfonates (FTS) at varying divalent cation concentrations of magnesium (Mg2+) and calcium (Ca2+). Divalent cations can impact PFAS partitioning to solids, especially to sediments, at higher concentrations. Sediment dwelling worms (Lumbriculus variegatus), epibenthic grazing snails (Physella acuta), and sediment-dwelling filter-feeding bivalves (Elliptio complanata) were selected due to their unique foraging modes. Microcosms were composed of synthetic sediment, culture water, macroinvertebrates, and PFAS and consisted of a 28-day exposure period. L. variegatus had significantly higher PFAS bioaccumulation than P. acuta and E. complanata, likely due to higher levels of interactions with and ingestion of the contaminated sediment. “High Mg2+” (7.5 mM Mg2+) and “High Ca2+” (7.5 mM Ca2+) conditions generally had statistically higher bioaccumulation factors (BAF) than the “Reference Condition” (0.2 mM Ca2+ and 0.2 mM Mg2+) for PFAS with perfluorinated chain lengths greater than eight carbons. Long-chain PFAS dominated the PFAS profiles of the macroinvertebrates for all groups of compounds studied (PFCA, PFSA, and FTS). These results indicate that the study organism has the greatest impact on bioaccumulation, although divalent cation concentration had observable impacts between organisms depending on the environmental conditions. Elevated cation concentrations in the microcosms led to significantly greater bioaccumulation in the test organisms compared to the experimental reference conditions for long-chain PFAS.

Evaluation of Function and Features of Human Induced Pluripotent Stem Cell-Derived Small Intestinal Epithelial Cells for Analyzing Peptide Drug Intestinal Absorption Profiles

Caco-2 cell monolayers are widely employed as an in vitro model of the intestinal barrier, capable of accurately predicting the absorption of conventional small-molecule drugs. However, this model may not be applicable to all drugs, and the accuracy of absorption prediction is typically poor for high molecular weight drugs. Recently, human induced pluripotent stem (iPS) cell-derived small intestinal epithelial cells (hiPSC-SIECs), exhibiting properties similar to those of the small intestine when compared with Caco-2 cells, have been developed and are considered a novel candidate model for in vitro evaluation of intestinal drug permeability. Therefore, we evaluated the utility of human hiPSC-SIECs as a new in vitro model to predict the intestinal absorption of middle-molecular weight drugs and peptide drugs. Firstly, we showed that the hiPSC-SIEC monolayer allowed faster transport of peptide drugs (insulin and glucagon-like peptide-1) than the Caco- 2 cell monolayer. Second, we revealed that hiPSC-SIECs require divalent cations (Mg2+ and Ca2+) to maintain barrier integrity. Third, we demonstrated that experimental conditions established for Caco-2 cells are not persistently applicable to hiPSC-SICEs when analyzing absorption enhancers. Comprehensively clarifying the features of hiPSC-SICEs is essential to establish a new in vitro evaluation model.

Self-assembly of shell protein and native enzyme in a crowded environment leads to catalytically active phase condensates.

The self-assembly of bacterial microcompartments is the result of several genetic, biochemical, and physical stimuli orchestrating inside the bacterial cell. In this work, we use 1,2-propanediol utilization microcompartments as a paradigm to identify the factors that physically drive the self-assembly of MCP proteins in vitro using its major shell protein and major encapsulated enzyme. We find that a major shell protein PduBB' tends to self-assemble under macromolecular crowded environment and suitable ionic strength. Microscopic visualization and biophysical studies reveal phase separation to be the principle mechanism behind the self-association of shell protein in the presence of salts and macromolecular crowding. The shell protein PduBB' interacts with the enzyme diol-dehydratase PduCDE and co-assemble into phase separated liquid droplets. The co-assembly of PduCDE and PduBB' results in the enhancement of catalytic activity of the enzyme. The shell proteins that make up PduBB' (PduB and PduB') have contrasting self-assembly behavior. While N-terminal truncated PduB' has a high self-associating property and forms solid assemblies that separates out of solution, the longer component of the shell protein PduBM38L is more soluble and shows least tendency to undergo phase separation. A combination of spectroscopic, imaging and biochemical techniques shows the relevance of divalent cation Mg2+ in providing stability to intact PduMCP. Together our results suggest a combination of protein-protein interactions and phase separation guiding the self-assembly of Pdu shell protein and enzyme in the solution phase.

Riemerella anatipestifer Endonuclease I displays enzymatic activity and is associated with bacterial virulence

Riemerella anatipestifer is an important pathogen of waterfowl, causing septicemic and exudative diseases. We previously reported that the R. anatipestifer AS87_RS02625 is a secretory protein of the type IX secretion system (T9SS). In this study, R. anatipestifer T9SS protein AS87_RS02625 was determined to be a functional Endonuclease I (EndoI), which has DNase and RNase activities. Optimal temperature and pH of the recombinant R. anatipestifer EndoI (rEndoI) to cleave λDNA were determined as 55–60 °C and 7.5 respectively. The DNase activity of the rEndoI was dependent on the presence of divalent metal ions. Presence of Mg2+ at a concentration range of 7.5–15 mM in the rEndoI reaction buffer displayed the highest DNase activity. In addition, the rEndoI displayed RNase activity to cleave MS2-RNA (ssRNA), either in the absence or presence of divalent cations Mg2+, Mn2+, Ca2+, Zn2+ and Cu2+. The DNase activity of the rEndoI was significantly enhanced by Mg2+, Mn2+ and Ca2+ but not Zn2+ and Cu2+. Moreover, we indicated that R. anatipestifer EndoI functioned on the bacterial adherence, invasion, in vivo survival and inducing inflammatory cytokines. These results indicate that the R. anatipestifer T9SS protein AS87_RS02625 is a novel EndoI, displays endonuclease activity and plays an important role in bacterial virulence.

HMM-based profiling identifies the binding to divalent cations and nucleotides as common denominators of suramin targets

Introduction: Suramin is one of the pharmacopeia’s most promiscuous drugs. Originally developed for African trypanosomiasis, suramin was also used for onchocerciasis and it has been proposed as an anticancer agent, antiviral drug, therapy for arthritis, autism, and antidote for snake bites. Target proteins of suramin have been described from different species. Here we identify the common motifs among these various targets, aiming to explain the promiscuous nature of suramin.Methods: We have searched for suramin target proteins in the literature and in chemical databases. Applying rigorous inclusion criteria, a list of 44 diverse proteins was assembled with experimental evidence for direct interaction with, and inhibition by, suramin. Hidden Markov model-based target profiling was performed by running the full set of Pfam protein family domains against these proteins.Results: Common denominators were identified by mapping the identified Pfam domains to molecular function gene ontology terms. This in silico pipeline identified nucleotide binding, nucleic acid binding, and binding to divalent cations as the most common denominators of the suramin targets.Discussion: Our results suggest that the extraordinary polypharmacology of suramin may be caused by its ability to inhibit the interaction of proteins with nucleotides or nucleic acids and with divalent cations (Mg2+, Ca2+, Zn2+). Suramin is well known to inhibit nucleotide receptors and nucleic acid-binding enzymes. The association with divalent cations is new and might be key towards the design of better, more selective inhibitors.

Rheological behavior and molecular dynamics simulation of κ-carrageenan/casein under simulated gastrointestinal electrolyte conditions

In this study, we investigated the effects of gastrointestinal electrolytes (including simulated gastric fluid (SGF) and simulated intestinal fluid (SIF)) on the conformational transition and exposed sulfate groups of κ-carrageenan (κ-CGN) and κ-CC (κ-carrageenan/casein) during digestion, which might contribute to the colitis. The conformational transition of κ-CGN and κ-CC were assessed through zeta-potential measurements, rheological analysis, differential scanning calorimetry, Fourier-transform infrared spectroscopy, and scanning electron microscopy. The sulfate group content measurement and molecular dynamics simulation were applied to investigate the exposed quantity of free sulfate groups. The results showed that SGF and SIF promoted the formation of a helical structure of κ-CGN and enhanced the intermolecular interactions of κ-CC. The κ-CGN self-helix formation in the presence of monovalent cations (Na+ and K+), and the helix-helix association of the neighboring κ-CGN chain in the presence of divalent cations (Mg2+ and Ca2+). In κ-CC system, the stability of helix conformation was enhanced by SGF and SIF, a greater number of hydrogen bonds were detected in Na+ and K+ solvent boxes, and Mg2+ and Ca2+ not only improved the number of hydrogen bonds through salt bridges but enhanced the electrostatic interaction of κ-CC, which were in accordance with the lower zeta-potential values, greater thermal hysteresis, and intensified binding energy results. There was an increase in hydrogen bonding sites on –SO3- groups and OH- groups of κ-CGN with the effects of electrolyte cations so that decreased the content of free sulfate groups. In conclusion, SGF and SIF enhanced the binding stability and reduced the contents of free sulfate groups of κ-CC. Our study findings provided value information for the safe processing of carrageenan.

Formation and stability of electrostatic complexes formed between scallop female gonad protein isolates and sodium alginate: Influence of pH, total concentration, blend ratio, and ionic strength.

The complex coacervation between scallop (Patinopecten yessoensis) female gonad protein isolates (SFGPIs) and sodium alginate (SA) was determined by the turbidimetric method. The impact of pH, total biopolymer concentration, biopolymer blend ratio, and various salt ionic on the mechanisms governing the complex coacervation of SFGPIs-SA complexes were also investigated. For the SFGPIs:SA ratio of 2:1 without adding NaCl, insoluble and soluble complexes were observed at pH 5.8 (pHφ1 ) and pH 8.2 (pHc ) with the optimum biopolymer interactions appearing at pH 2.6 (pHopt ). The maximum turbidity value increased with the increment of the total biopolymer concentration from 0.37 to 1.83 until attaining the critical value (0.75%). As the blend ratios rose from 1:3 to 12:1, the critical pH values (pHc , pHφ1 , and pHopt ) moved to higher pH. Furthermore, the addition of NaCl led to a remarkable decrease in turbidity over the whole pH region in SFGPIs-SA complexes. Moreover, monovalent ions (Na+ and K+ ) had the same effect on the formation of the SFGPIs-SA complex, whereas the divalent cations (Mg2+ and Ca2+ ) lessened the complex formation in comparison with the monovalent ions. This study offers a methodological and theoretical basis for the design of complex SFGPIs-SA systems by understanding the complex coacervation under different conditions. PRACTICAL APPLICATION: In recent years, several protein-polysaccharides complexes have been widely applied in food and biological systems. Scallop (Patinopecten yessoensis) female gonads are deemed as good marine sources for developing protein matrices on account of their high protein content and nutrients. In our study, the effects of different conditions on the mechanisms governing the complex coacervation of SFGPI-SA mixtures were investigated, and the instability of the system could be overcome by understanding the conditions for SFGPIs/SA complex formation, which have a feasible role in developing marine source-protein as afunctional food base such as kamaboko gels, can, sausage, fat substitutes, and delivery vehicles for bioactive compounds.

Stability, aggregation, and sedimentation behaviors of typical nano metal oxide particles in aqueous environment

The wide use of nano metal oxide particles (NMOPs) brings about their inevitable release into the water environment, affecting the environment and human health. Therefore, the stability, aggregation, and sedimentation process of four typical NMOPs (ZnO NPs, CeO2 NPs, TiO2 NPs, and CuO NPs) were investigated in artificial water and real municipal sewage to reveal their complicated behavior. Results showed that NMOPs aggregated at the pH of zero-charge point, and their hydrodynamic diameters and aggregation rates could reach the maximum values. The hydrodynamic diameters and aggregation rates of ZnO NPs, CeO2 NPs, TiO2 NPs, and CuO NPs at the zero-charge point were 617, 1760, 870, 1502 nm, and 31.7, 1158.1, 48.3, 115.7 nm/min, respectively. In addition, the dissolution of NMOPs led to the sedimentation rates under acidic conditions being much lower than those under neutral and alkaline conditions. The aggregation and sedimentation performance of NMOPs were affected by not only pH but also ionic strength (IS) and species. The aggregation rates of NMOPs increased with the increase of IS (0–10 mM), and the maximum aggregation rate of CeO2 NPs was 470.1 nm/min (pH = 7 and CaCl2 = 10 mM). According to Coulomb's law, divalent cations (Mg2+, Ca2+) were more competitively adsorbed on the surface of NMOPs than monovalent cations (K+, Na+), which increased the zeta potential and aggregation rate of NMOPs. Furthermore, the NMOPs were easier to aggregate in municipal sewage because of the homogeneous aggregation between nanoparticles and heterogeneous aggregation with natural colloids. The total interaction energy between NMOPs was calculated by the classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theoretical formula, which was consistent with the experimental results.

Biocontrol activity of anti-salinity Bacillus mesonae H20-5 against Bacterial wilt in different tomato cultivars

Bacterial wilt caused by Ralstonia solanacearum and soil salinity are critical problems associated with the cultivation of tomato plants in Korea. In our previous study, we demonstrated the alleviation of salinity stress by Bacillus mesonae H20-5 in tomato plants. In this study, we investigated the effects of strain H20-5 on disease suppression and salinity stress in two different cultivars, which are susceptible (‘Juiken’) and moderately resistant (‘Mairokku’) to bacterial wilt. The results showed that H20-5 exhibited antibacterial activity against R. solanacearum, where the strain significantly suppressed bacterial wilt only in moderately resistant (‘Mairokku’) but not in susceptible cultivar (‘Juiken’). Moreover, only H20-5-treated moderate resistant cultivar (‘Mairokku’) plants observed an increase in the expression levels of defense-related genes, phenylalanine ammonia-lyase (PAL) and polyphenol oxidase (PPO), and accumulated polyphenols and lawsone after R. solanacearum inoculation. In contrast, under salinity condition, the H20-5-treated two cultivars mitigated the decrease in plant growth and pigment content, and regulated the concentration of the major divalent cation Mg2+. These findings demonstrated that B. mesonae H20-5 could alleviate salinity stress in cultivars regardless of their resistance to R. solanacearum; however, the biocontrol activity was seemingly dependent on cultivar resistance by strongly enhancing resistance related responses, such as regulating expression of PAL and PPO, and accumulating polyphenol and lawsone in the moderately resistant cultivar (‘Mairokku’) compared to susceptible cultivar (‘Juiken’). Therefore, the strain H20-5 could improve the resistance of the cultivar against R. solanacearum, whereas it alleviated salinity stress regardless of the resistance of tomato cultivars.