Ultrafiltration recovery of alginate: Membrane fouling mitigation by multivalent metal ions and properties of recycled materials

Recovery of alginate extracted from aerobic granular sludge (AGS) has given rise to a novel research direction. However, these extracted alginate solutions have a water content of nearly 100%. Alternately, ultrafiltration (UF) is generally used for concentration of polymers. Furthermore, the introduction of multivalent metal ions into alginate may provide a promising method for the development of novel nanomaterials. In this study, membrane fouling mitigation by multivalent metal ions, both individually and in combination, and properties of recycled materials were investigated for UF recovery of sodium alginate (SA). The filtration resistance showed a significantly negative correlation with the concentration of metal ions, arranged in the order of Mg²⁺ < Ca²⁺ < Fe³⁺ < Al³⁺ (filtration resistance mitigation), and the moisture content of recycled filter cake showed a marked decrease. For Ca²⁺, Mg²⁺, Fe³⁺, and Ca²⁺+ Fe³⁺, the filtration resistances were almost the same when the total charge concentration was less than 5 mmol⋅L^–1. However, when the total charge concentration was greater than 5 mmol⋅L^–1, membrane fouling mitigation increased significantly in the presence of Ca²⁺ or Fe³⁺ and remained constant for Mg²⁺ with the increase of total charge concentration. The filtration resistance mitigation was arranged in the order of Fe³⁺ > Fe³⁺ + Ca²⁺ > Ca²⁺ > Mg²⁺. Three mechanisms were proposed in the presence of Fe³⁺, such as the decrease of SA concentration, change in pH, and production of hydroxide iron colloids from hydrolysis. The properties of recycled materials (filter cake) were investigated via optical microscope observation, dynamic light scattering, Fourier transform infrared, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy. The results provide further insight into UF recoveries of alginate extracted from AGS.     

Investigations of cell immobilization in alginate: rheological and electrostatic extrusion studies

In this study, the process of electrostatic extrusion as a method for cell immobilization was investigated. We have assessed the effects of concentrations of yeast cells (as a model cell type) and Na alginate on the size of the resulting microbeads and attempted to rationalize the obtained findings by rheological characterization of the cell–alginate suspensions. Under the investigated conditions, microbeads, 50–600 µm in diameter, were produced and the increase in both alginate and cell concentrations resulted in larger microbeads with their sizes having higher standard deviations. Rheological characterization revealed non‐Newtonian, pseudoplastic behavior of cell–alginate suspensions with higher viscosities at higher alginate concentrations. However, the presence of cells even at high concentrations (5 × 10⁸ and 1 × 10⁹ cells mL^?1) did not significantly affect the rheological properties of the Na alginate solution. Finally, we have investigated the kinetics of alginate gelation with respect to the quantity of Ca²⁺ ions and the presence of cells. The molar ratio of α‐L ‐guluronic acid units to Ca²⁺ ions of 4:1 provided complete crosslinking. The presence of cells decreased the rate of network formation as well as the strength of the obtained Ca alginate hydrogel. Copyright © 2006 Society of Chemical Industry     

Preparation and evaluation of alginate/chitosan microspheres containing pheromones for pest control of Megaplatypus mutatus Chapuis (Platypodinae: Platypodidae)

This work describes the optimization of an alginate/chitosan microsphere preparation for the encapsulation of a sexual pheromone, 6‐methyl‐5‐hepten‐2‐ol (sulcatol), to realize a slow‐release device for the biological control of the Megaplatypus mutatus pest. To evaluate and select the best encapsulation/release conditions three parameters were studied: alginate concentration, pH of gelling solution and Ca²⁺/COO^? ratio. The preparation was optimized using biopolymers with improved mechanical properties and swelling behavior. The obtained microspheres were characterized using Fourier transform infrared spectroscopy, scanning electron and optical microscopies, swelling degree, mechanical properties and in vitro release of encapsulated pheromone. The microspheres performed best when they were synthesized using an alginate concentration of 4% w/v, at pH = 9 and with a Ca²⁺/COO^? ratio of 3.5. The attractiveness of the alginate/chitosan microspheres towards M. mutatus was demonstrated by behavioral bioassay with the completed pheromonal blend of the species (sulcatol, sulcatone and 3‐pentanol). The formulation can be considered as an efficient slow‐release biological control system, with no negative environmental impact. © 2015 Society of Chemical Industry     

Highly Mechanical and Fatigue‐Resistant Double Network Hydrogels by Dual Physically Hydrophobic Association and Ionic Crosslinking

Double network (DN) hydrogels with high strength and toughness are considered as promising soft materials. Herein, a dual physically cross‐linked hydrophobic association polyacrylamide (HPAAm)/alginate‐Ca²⁺ DN hydrogel is reported, consisting of a HPAAm network and a Ca²⁺ cross‐linked alginate network. The HPAAm/alginate‐Ca²⁺ DN hydrogel exhibits excellent mechanical properties with the fracture stress of 1.16 MPa (3.0 and 1.7 times higher than that of HPAAm hydrogel and HPAAm/alginate hydrogel, respectively), fracture strain of 2604%, elastic modulus of 71.79 kPa, and toughness of 14.20 MJ m^?3. HPAAm/alginate‐Ca²⁺ DN hydrogels also demonstrate self‐recovery, notch‐insensitivity, and fatigue resistance properties without any external stimuli at room temperature through reversible physical bonds consisting of hydrophobic association and ionic crosslinking. As a result, the dual physical crosslinking would offer an avenue to design DN hydrogels with desirable properties for broadening current applications of soft materials.     

Calcium in Red Blood Cells—A Perilous Balance

Ca²⁺ is a universal signalling molecule involved in regulating cell cycle and fate, metabolism and structural integrity, motility and volume. Like other cells, red blood cells (RBCs) rely on Ca²⁺ dependent signalling during differentiation from precursor cells. Intracellular Ca²⁺ levels in the circulating human RBCs take part not only in controlling biophysical properties such as membrane composition, volume and rheological properties, but also physiological parameters such as metabolic activity, redox state and cell clearance. Extremely low basal permeability of the human RBC membrane to Ca²⁺ and a powerful Ca²⁺ pump maintains intracellular free Ca²⁺ levels between 30 and 60 nM, whereas blood plasma Ca²⁺ is approximately 1.8 mM. Thus, activation of Ca²⁺ uptake has an impressive impact on multiple processes in the cells rendering Ca²⁺ a master regulator in RBCs. Malfunction of Ca²⁺ transporters in human RBCs leads to excessive accumulation of Ca²⁺ within the cells. This is associated with a number of pathological states including sickle cell disease, thalassemia, phosphofructokinase deficiency and other forms of hereditary anaemia. Continuous progress in unravelling the molecular nature of Ca²⁺ transport pathways allows harnessing Ca²⁺ uptake, avoiding premature RBC clearance and thrombotic complications. This review summarizes our current knowledge of Ca²⁺ signalling in RBCs emphasizing the importance of this inorganic cation in RBC function and survival.     

Strontium ion substituted alginate-based hydrogel fibers and its coordination binding model

Sr-alginate and Ca-alginate hydrogel fibers were fabricated via microfluidic spinning technology, and various analytical methods were adopted to characterize fibers and disclose the coordination model of Sr²⁺ binding with alginate molecule chain. For both fibers, the more crosslinking sites of Sr²⁺ with alginate molecule were illustrated in comparison with that of Ca²⁺. The more robust mechanical performance of Sr-alginate fibers than Ca-alginate counterpart was a strong indication of the more strong binding of Sr²⁺ with alginate molecular chain. FTIR and electric conductivity disclosed the chelation type of Sr²⁺ with alginate macromolecule being similar to that of Ca²⁺, which was core-shell of the analogous “egg-box” structure. Circular dichroism spectroscopy further certified the extra coordination sites for Sr²⁺ with alginate molecule than Ca²⁺. Research on the coordination model will be more beneficial to optimizing the physicochemical properties of alginate fibers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48571.     

Electrophysiological Properties of Endogenous Single Ca2+ Activated Cl− Channels Induced by Local Ca2+ Entry in HEK293

Microdomains formed by proteins of endoplasmic reticulum and plasma membrane play a key role in store-operated Ca²⁺ entry (SOCE). Ca²⁺ release through inositol 1,4,5-trisphosphate receptor (IP₃R) and subsequent Ca²⁺ store depletion activate STIM (stromal interaction molecules) proteins, sensors of intraluminal Ca²⁺, which, in turn, open the Orai channels in plasma membrane. Downstream to this process could be activated TRPC (transient receptor potential-canonical) calcium permeable channels. Using single channel patch-clamp technique we found that a local Ca²⁺ entry through TRPC1 channels activated endogenous Ca²⁺-activated chloride channels (CaCCs) with properties similar to Anoctamin6 (TMEM16F). Our data suggest that their outward rectification is based on the dependence from membrane potential of both the channel conductance and the channel activity: (1) The conductance of active CaCCs highly depends on the transmembrane potential (from 3 pS at negative potentials till 60 pS at positive potentials); (2) their activity (NPo) is enhanced with increasing Ca²⁺ concentration and/or transmembrane potential, conversely lowering of intracellular Ca²⁺ concentration reduced the open state dwell time; (3) CaCC amplitude is only slightly increased by intracellular Ca²⁺ concentration. Experiments with Ca²⁺ buffering by EGTA or BAPTA suggest close local arrangement of functional CaCCs and TRPC1 channels. It is supposed that Ca²⁺-activated chloride channels are involved in Ca²⁺ entry microdomains.     

Controlled mechanical and swelling properties of poly(vinyl alcohol)/sodium alginate blend hydrogels prepared by freeze–thaw followed by Ca2+ crosslinking

Poly(vinyl alcohol) (PVA)/sodium alginate (SA) blend hydrogels have immense potential for use as functional biomaterials. Understanding of influences of processing parameters and compositions on mechanical and swelling properties of PVA/SA blend hydrogels is very important. In this work, PVA/SA blend hydrogels with different SA contents were prepared by applying freeze–thaw method first to induce physical crosslinking of PVA chains and then followed by Ca²⁺ crosslinking SA chains to form interpenetrating networks of PVA and SA. The effects of number of freeze–thaw cycles, SA content and Ca²⁺ concentration on mechanical properties, swelling kinetics, and pH‐sensitivity of the blend hydrogels were investigated. The results showed that the blend hydrogels have porous sponge structure. Gel fraction, which is related to crosslink density of the blend hydrogels, increased with the increase of freeze–thaw cycles and strongly depended on SA content. The SA content exerts a significant effect on mechanical properties, swelling kinetics, and pH‐sensitivity of the blend hydrogels. The number of freeze–thaw cycles has marked impact on mechanical properties, but no obvious effect on the pH‐sensitivity of the PVA/SA blend hydrogels. Concentration of CaCl₂ aqueous solution also influences mechanical properties and pH‐sensitivity of the blend hydrogel. By altering composition and processing parameters such as freeze–thaw cycles and concentration of CaCl₂ aqueous solution, the mechanical properties and pH‐sensitivity of PVA/SA blend hydrogels can be tightly controlled. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of Ca2+ induced crosslinking on the mechanical and barrier properties of cast alginate films

The use of alginate as a coating material for packaging applications is currently limited due to its difficult processability and high moisture sensitivity. Therefore, this study addresses the crosslinking and scale‐up to a continuous application. Three different crosslinking agents were applied: CaCl₂ with ethylene diamine tetraacetic acid and two low soluble salts (CaHPO₄ and CaCO₃). Those were incorporated by internal setting in an alginate matrix with varying Ca²⁺ concentration ( ) and ratio. With the addition of Ca²⁺, the tensile strength and elongation at break of the cast alginate films increased. This was optimal for a of 0.010–0.015 g (g alginate)^?1 dependent on the crosslinking agent. The decrease in water vapor and oxygen permeability due to crosslinking was independent of the crosslinking agent. However, the optimal aiming to decrease permeability was different for the crosslinking agents: CaHPO₄ showed best results at a of 0.010 g (g alginate)^?1, CaCl₂ at 0.012 g (g alginate)^?1, and CaCO₃ at 0.027 g (g alginate)^?1. Upon all analyzed properties CaHPO₄ was the most promising crosslinking agent for alginate. Moreover, selected alginate formulations were successfully processed in a continuous lacquering plant. The produced two‐layer systems have very low oxygen permeabilities which can be further reduced by crosslinking. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45754.     

Calcium alginate gel fibers: Influence of alginate source and gel structure on fiber strength

The low-deformation extension modulus was measured for Ca–alginate gel fibers prepared from alginates of different compositions and molecular weights. The modulus showed an increase with increasing molecular weight for alginates of the same composition and sequence parameters. Fibers prepared with an inhomogeneous polymer concentration profile showed higher moduli than did fibers with a homogeneous polymer concentration profile. The higher modulus observed for fiber prepared from an alginate with low Ca²⁺ affinity is tentatively explained as resulting from a higher degree of polymer chain alignment. © 1994 John Wiley & Sons, Inc.     

Piezoelectric and mechanical properties of CaO reinforced porous PZT ceramics with one-dimensional pore channels

The formation of capillaries in sodium alginate gels is a dissipative process driven by unidirectional diffusion of divalent cations into sodium alginate sols. In the present work, we have prepared 3-1 type porous lead zirconate titanate (PZT) ceramics with oxides (CaO) being doped on a molecular level from the dissipative process by incorporating PZT particles into the sodium alginate gel matrix. By varying the concentration of cation solutions (CaCl₂) from 0.5 mol/L to 2.5 mol/L, both the microstructure, doping amount of oxides (CaO) and crystalline phase of the porous PZT ceramics were tailored. Accordingly, increase in the concentration of Ca²⁺ has led to a reduction in the relative permittivity (ε_r) first, and then an increase, while the piezoelectric coefficient (d₃₃ and d₃₁) demonstrated an opposite variation tendency. The prepared samples possessed a maximal HFOM value of 4755×10^–15 Pa⁻¹ when the concentration of Ca²⁺ was 1.0 mol/L. Addition of CaO was found to improve the compressive strength of porous PZT ceramics, which was preferential to promoting the stability and reliability for application.     

Characterization of the structure and diffusion behavior of calcium alginate gel beads

A simple and novel method using gel shrinkage to indirectly characterize the structure of calcium alginate gel (CAG) beads during the calcium alginate gelation process was presented in this study. The effect of preparation process parameters (gelling cations, bead diameter, and alginate M _w and concentration) on the structure of the CAG bead formation process was thoroughly investigated. It was found that (a) the concentration of the Na⁺ and Ca²⁺ ion in gel bath was found to be the determining factor in the gel structure formation process by regulating the dissociation of alginate and the complexation of the calcium; (b) Na⁺ acts as a competitor with calcium and a screen in the electrostatic repulsion; (c) the effect of beads size below 700 μm on the structure of CAG beads can be neglected; and (d) the sodium alginate concentration has no significant effect on the gel formation process. Furthermore, the diffusion of bovine serum albumin (BSA) was controlled by the density of CAG bead. Consequently, a faster diffusion rate of BSA within the looser structure of beads can be observed. These results are keys to understanding the behavior and performance of beads in their utilization medium. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48923.     

Production of bioethanol by immobilized Saccharomyces Cerevisiae onto modified sodium alginate gel

BACKGROUND: Microbial bioethanol production is an important option in view of the finite global oil reserves. Bioethanol fermentation was carried out using immobilized microorganisms (Saccharomyces cerevisiae, Zymomonas mobilis, Pichia stipitis, etc.), which has many advantages compared with the use of free cells. Various support materials have been used for bioethanol fermentation, and alginate gels have been one of the most widely used matrices for cell entrapment. The aim of this study was increased bioethanol production by Saccharomyces cerevisiae immobilized on alginate gels. First, N‐vinyl‐2‐pyrrolidone was grafted onto sodium alginate. Then, the properties of ethanol production were investigated using the matrix obtained. RESULTS: The performance of ethanol fermentation was affected by calcium chloride concentration, N‐vinyl‐2‐pyrrolidone grafted onto the sodium alginate, sugar concentration and the percentage of immobilized cell beads. These effects were optimized to give maximum ethanol production. Ethanol production was accelerated when sodium alginate polymer was modified with N‐vinyl‐2‐pyrrolidone. The maximum concentration, productivity and yield of ethanol were 69.68 g L^?1, 8.71 g L^?1 h^?1 and 0.697 g g^?1, respectively. CONCLUSION: The new polymeric matrix, when compared with sodium alginate, showed better ethanol production due to the hydrophilic property of N‐vinyl‐2‐pyrrolidone. The results suggest that the proposed method for immobilization of Saccharomyces cerevisiae has potential in industrial applications of the ethanol production process. Copyright © 2011 Society of Chemical Industry     

Effect of different fermentation parameters on bioethanol production from corn meal hydrolyzates by free and immobilized cells of Saccharomyces cerevisiae var. ellipsoideus

BACKGROUND: Bioethanol produced from renewable biomass, such as corn meal, is a biofuel that is both renewable and environmentally friendly. Significant scientific and technological investments will be needed to achieve substitution of conventional fossil fuels with alternative fuels. The ethanol fermentation of enzymatically obtained corn meal hydrolyzates by free and immobilized cells of Saccharomyces cerevisiae var. ellipsoideus yeast in a batch system was studied. The initial glucose and inoculum concentration and the time required for the efficient ethanol production were optimized taking into account parameters such as ethanol concentration, ethanol yield, percentage of the theoretical yield of ethanol and volumetric productivity in both immobilized and free cell systems. RESULTS: The yeast cells were immobilized in Ca–alginate by an electrostatic droplet generation method. An optimal initial inoculum concentration of 2% (v/v) and optimal fermentation time of 38 h for both immobilized and free yeasts were determined. An optimal initial glucose concentration of 150 g L^?1 for free system was achieved. At the initial glucose concentration of 176 g L no substrate or product inhibition were achieved with immobilized yeast. CONCLUSION: By immobilization of the yeast into Ca–alginate using the method of electrostatic droplet generation a superior system was realized, which exhibited lower substrate inhibition and higher tolerance to ethanol. The cells of S. cerevisiae var. ellipsoideus yeast entrapped in Ca–alginate showed good physical and chemical stability, and no substrate and product diffusion restrictions were noticed. Copyright © 2008 Society of Chemical Industry     

P2X4 Receptors Mediate Ca2+ Release from Lysosomes in Response to Stimulation of P2X7 and H1 Histamine Receptors

The P2X4 purinergic receptor is targeted to endolysosomes, where it mediates an inward current dependent on luminal ATP and pH. Activation of P2X4 receptors was previously shown to trigger lysosome fusion, but the regulation of P2X4 receptors and their role in lysosomal Ca²⁺ signaling are poorly understood. We show that lysosomal P2X4 receptors are activated downstream of plasma membrane P2X7 and H₁ histamine receptor stimulation. When P2X4 receptors are expressed, the increase in near-lysosome cytosolic [Ca²⁺] is exaggerated, as detected with a low-affinity targeted Ca²⁺ sensor. P2X4-dependent changes in lysosome properties were triggered downstream of P2X7 receptor activation, including an enlargement of lysosomes indicative of homotypic fusion and a redistribution of lysosomes towards the periphery of the cell. Lysosomal P2X4 receptors, therefore, have a role in regulating lysosomal Ca²⁺ release and the regulation of lysosomal membrane trafficking.     

Humic acid fouling in the membrane distillation process

This work investigates the extent of humic acid fouling during the membrane distillation process for water treatment. The effects of pH, ionic strength, and divalent ion on fouling were studied. The experiments were performed with a 0.22-μm PVDF flat-sheet membrane in a direct contact membrane distillation unit. Flux declines were negligible (less than 6%) for the ranges of humic acid concentration, ionic strength, and pH studied. The examination of the membrane surface by SEM revealed a thin deposit layer. The addition of divalent cations (Ca²⁺) into the solution considerably reduced flux when Ca²⁺ concentration exceeded the critical coagulation concentration. Ca²⁺ affected flux by forming complexes with humic acids and resulted in coagulation on the membrane surface. The normalized flux, J/J₀, was 0.57 after 18 h of operation when the CaCl₂ concentration was 3.775 mM. However, the deposit of humic acid coagulate on the membrane surface was loosely packed, and was rather easily removed. Rinsing of the fouled membrane with clean water and a 0.1 M NaOH solution gave 100% of flux recovery.     

Swelling and drug release behavior of calcium alginate/poly (sodium acrylate) hydrogel beads

In the present work calcium alginate/poly (sodium acrylate) composite beads have been prepared by in situ formation of cross-linked poly (sodium acrylate) network, within the calcium alginate (CA) beads. The CA/poly (SA) beads have been found to be stable for more than 48 h, in the physiological fluid (PF) of pH 7.4, while the plain alginate beads disintegrated within a couple of hours. The water uptake of beads was investigated under various composition parameters such as the amount of alginate, concentration of ionic cross-linker Ca⁺⁺ ions, monomer sodium acrylate (SA) contents, and degree of cross-linking. The beads also exhibited fair stability in the media of varying pH. Finally the release of model drug methylene blue (MB) was investigated. It was found that plain CA and CA/poly (SA) composite beads exhibited different release mechanisms.     

High energy storage performance in Ca-doped PbZrO3 antiferroelectric films

In this work, antiferroelectric Pb_1-xCa_xZrO₃ (PCZ) thin films with different concentrations of Ca²⁺ were prepared by chemical solution deposition, and the effects of Ca²⁺ concentration on the antiferroelectric properties and energy storage performance were investigated. The results show that the optimal Ca²⁺ concentration in the PCZ thin films is x = 0.12 for electric properties and energy storage performance. The recoverable energy storage density and energy storage efficiency is 50.2 J/cm³ and 83.1 % at 2800 kV/cm, which is 261 % and 44.8 % higher than those of the PbZrO₃ (PZ) films. These effects are attributed to the enhancement of stability of antiferroelectric phase, diffuseness in the field-induced phase transition and electric breakdown strength by Ca²⁺-doping in the PZ films. Our results demonstrate that doping an appropriate amount of Ca²⁺ ions in antiferroelectric thin films is an effective way to improve their energy storage performance.