Polyelectrolyte Research Articles

Composite polymer electrolyte facilitated by enhanced amorphousity and Li+ conduction using LaFeO3-embedded PVDF-HFP for solid-state lithium metal battery

Composite polymer electrolytes (CPEs) are a promising alternative to flammable conventional liquid electrolytes for high-safety lithium-ion batteries. Establishing low-cost filler that enhances the amorphous nature of polymer in the CPEs and exhibits efficient Lewis acid-base interaction between fillers and anions of lithium salt, leading to improved dissociation of salts for enhanced conduction, is indispensable. In this work, for the first time, we construct a solid composite polymer electrolyte of poly(vinylidene fluoride hexafluoropropylene) embedded LaFeO3 (LFO) particles prepared by solution casting and electrospinning methods and study their performances. The 5 wt% LFO filler embedded CPE made by means of solution casting and electrospinning methods exhibited the highest ionic conductivity of 5.9 × 10-4 and 1.49 × 10-3 S cm−1 at room temperature and electrochemical stability window up to 4.6 and 4.45 V, respectively. Further, as-assembled solid-state lithium-ion batteries using electrospun CPE showed an initial discharge capacity of 166 mAh/g at 0.1C-rate and solution-casted CPE showed excellent cycling stability with 98.6 % capacity retention at 0.3C-rate even at 50th cycle. Such excellent performance originated from the introduction of the LFO particles as filler into the polymer matrix to enhance the ionic conductivity, mechanical strength and lithium metal compatibility of the resulting CPEs.

Porous Morphology of High Grafting Density Mixed Polyelectrolyte Brushes Grown from a Y-Inimer Coating.

Mixed A/B polyelectrolyte (PE) brushes of opposite charges are grown from a Y-shaped initiator-bearing coating to facilitate intimate mixing of the A and B polyelectrolytes in a 1:1 grafting ratio. The design of the Y-shaped inimer includes both ATRP and NMP initiators attached to a common Y-junction. A copolymer of a Y-shaped inimer with glycidyl methacrylate is cross-linked to the substrate resulting in a stable ultrathin coating decorated with Y-shaped initiators. Weak PE A/B mixed brushes based on poly(methacrylic acid)/poly(2-vinylpyridine) (PMAA/P2VP) with a high grafting density of ∼1 chain/nm2 are grown by surface-initiated ATRP and NMP, respectively. Detailed morphological characterization of the PMAA/P2VP brushes in response to pH changes reveals a nanoporous morphology under conditions that maximize complex coacervate formation between oppositely charged brushes. The charge ratio between the A and B brushes is varied via the composition of the brushes to further study the morphology evolution. The effect of intimate contact between the A and B brushes on the morphology is probed by comparing with a mixed A/B PE system with random fluctuations in grafting composition. A quantitative and qualitative study of the pore evolution with pH as well as charge composition is presented using a combination of atomic force microscopy, water contact angle measurement, and image analysis using Gwyddion software. These studies demonstrate that the porous morphology is enhanced and most uniform when the brushes are grown from the Y-inimer, indicating that a 1:1 grafting ratio and intimate contact between A and B brushes are essential.

Self-healing and corrosion-sensing multifunctional coatings containing pH-sensitive TiO2-based composites

Polyelectrolyte-encapsulated nanocontainers can effectively respond to changes of pH and thus control the on-demand release of corrosion inhibitors. A pH-responsive release system (Phen-Tpp@MTNs-PDDA) was developed based on the cationic polyelectrolyte poly dimethyl diallyl ammonium chloride (PDDA) encapsulated mesoporous TiO2 nanocontainers (MTNs) loaded with 1,10-phenanthroline (Phen) and tripolyphosphate ions (Tpp) corrosion inhibitors. The epoxy coating (EP) embedded with Phen-Tpp@MTNs-PDDA (Phen-Tpp@MTNs-PDDA/EP) demonstrates superior self-healing properties and confers long-term protection on the metal substrate through the cooperative effect of Phen and Tpp. Simultaneously, this hybrid coating is endowed with corrosion sensing capability based on the color development originating from the interaction of Phen and carbon steel. This self-healing and corrosion-sensing multifunctional coating provides an effective strategy for the corrosion protection of metals.

Coordination cages integrated into swelling poly(ionic liquid)s for guest encapsulation and separation

Coordination cages have been widely reported to bind a variety of guests, which are useful for chemical separation. Although the use of cages in the solid state benefits the recycling, the flexibility, dynamicity, and metal-ligand bond reversibility of solid-state cages are poor, preventing efficient guest encapsulation. Here we report a type of coordination cage-integrated solid materials that can be swelled into gel in water. The material is prepared through incorporation of an anionic FeII4L6 cage as the counterion of a cationic poly(ionic liquid) (MOC@PIL). The immobilized cages within MOC@PILs have been found to greatly affect the swelling ability of MOC@PILs and thus the mechanical properties. Importantly, upon swelling, the uptake of water provides an ideal microenvironment within the gels for the immobilized cages to dynamically move and flex that leads to excellent solution-level guest binding performances. This concept has enabled the use of MOC@PILs as efficient adsorbents for the removal of pollutants from water and for the purification of toluene and cyclohexane. Importantly, MOC@PILs can be regenerated through a deswelling strategy along with the recycling of the extracted guests.

Carbon Black Functionalized with Serinol Pyrrole to Replace Silica in Elastomeric Composites.

Elastomer composites for dynamic mechanical applications with a low dissipation of energy are of great importance in view of their application in tire compounds. In this work, furnace carbon black functionalized with 2-2,5-dimethyl-1H-pyrrol-1-yl-1,3-propanediol (SP) was used in place of silica in an elastomer composite based on poly(styrene-co-butadiene) from solution anionic polymerization and poly(1,4-cis-isoprene) from Hevea Brasiliensis. The traditional coupling agent used for silica was also used for the CB/SP adduct: 3,3'-bis(triethoxysilylpropyl)tetrasulfide (TESPT). The composite with the CB/SP + TESPT system revealed a lower Payne effect, higher dynamic rigidity, and lower hysteresis, compared to the composite with CB + TESPT, although the latter composite had a higher crosslinking density. The properties of the silica and the CB/SP + TESPT-based composites appear similar, though in the presence of slightly higher hysteresis and lower ultimate properties for the CB/SP-based composite. The use of CB in place of silica allows us to prepare lighter compounds and paves the way for the preparation of tire compounds with lower environmental impacts.

Collapse and expansion kinetics of a single polyelectrolyte chain with hydrodynamic interactions.

We investigate the collapse and expansion dynamics of a linear polyelectrolyte (PE) with hydrodynamic interactions. Using dissipative particle dynamics with a bead-spring PE model, long-range electrostatics, and explicit ions, we examine how the timescales of collapse tcol and expansion texp depend on the chain length N and obtain scaling relationships tcol ∼ Nα and texp ∼ Nβ. For neutral polymers, we derive values of α = 0.94 ± 0.01 and β = 1.97 ± 0.10. Interestingly, the introduction of electrostatic interaction markedly shifts α to α ≈ 1.4 ± 0.1 for salt concentrations within c = 10-4 to 10-2M. A reduction in the ion-to-monomer size ratio noticeably reduces α. On the other hand, the expansion scaling remains approximately constant, β ≈ 2, regardless of the salt concentration or ion size considered. We find β > α for all conditions considered, implying that expansion is always slower than collapse in the limit of long polymers. This asymmetry is explained by distinct kinetic pathways of collapse and expansion processes.

Enzyme-Triggered Polyelectrolyte Complex for Responsive Delivery of α-Helical Polypeptides to Optimize Antibacterial Therapy.

Responsive nanomaterials hold significant promise in the treatment of bacterial infections by recognizing internal or external stimuli to achieve stimuli-responsive behavior. In this study, we present an enzyme-responsive polyelectrolyte complex micelles (PTPMN) with α-helical cationic polypeptide as a coacervate-core for the treatment of Escherichia coli (E. coli) infection. The complex was constructed through electrostatic interaction between cationic poly(glutamic acid) derivatives and phosphorylation-modified poly(ethylene glycol)-b-poly(tyrosine) (PEG-b-PPTyr) by directly dissolving them in aqueous solution. The cationic polypeptide adopted α-helical structure and demonstrated excellent broad-spectrum antibacterial activity against both Gram-negative and Gram-positive bacteria, with a minimum inhibitory concentration (MIC) as low as 12.5 μg mL-1 against E. coli. By complexing with anionic PEG-b-PPTyr, the obtained complex formed β-sheet structures and exhibited good biocompatibility and low hemolysis. When incubated in a bacterial environment, the complex cleaved its phosphate groups triggered by phosphatases secreted by bacteria, exposing the highly α-helical conformation and restoring its effective bactericidal ability. In vivo experiments confirmed accelerated healing in E. coli-infected wounds.

Molecular insight into sequence-defined polyelectrolytes for energy storage devices

Polyelectrolyte (PE) adsorption on charged surfaces is a complex phenomenon that has an array of applications ranging from healthcare to designing energy storage devices. PE adsorption on surfaces involves surface charge polarization effects which arise due to the dielectric dissimilarities between the PE and the charged surface. PEs owing to their high potential window, and leakage-resistant behavior are used as supercapacitor electrolytes. Recent experimental evidence suggests co-block polymers as potential design materials for energy storage devices (ESDs). It is imperative to mention that the structural variation of the co-block polymers under spatial confinements will have a key role in designing electrodes and electrolytes for ESDs which demands a detailed investigation. This study reveals that the spatial orientations of the charged groups have an impressive impact on the changes in PE charge density peaks, charge amplification peaks, PE adsorption, counter-ion adsorption, and differential and integral capacitance while confined by graphene electrodes. It is startling to observe that the counter-ion distribution within the electrical double layer of the positively charged surface significantly depends on the orientation of the PEs. However, with increasing solvent dielectric constant the variations in the above-mentioned properties subside due to reduced electrostatic interactions. The differential capacitance and the integral capacitance are also found to be dependent on the dielectric constants of the solvent. These findings will be immensely useful in determining the key factors needed to describe the preferred spatial configuration of a PE suitable for various ESDs and applications involving PEs in a confined system.

Effect of Counterion Size on Knotted Polyelectrolyte Conformations.

Using Langevin dynamics simulations and a coarse-grained primitive model of electrolytes, we show that the behavior of knotted circular strong polyelectrolytes (PEs) in diluted aqueous solution is largely affected by the diameter of the counterions (CIs), σCI. Indeed, we observe that both gyration radius and knot length vary nonmonotonically with σCI, with both small and bulky CIs favoring knot localization, while medium-sized ones promote delocalized knots. We also show that the conformational change from delocalized to tight knots occurs via the progressive coalescence of the knot's essential crossings. The emerging conformers correspond to the minima of the free energy landscape profiled as a function of the knot length or PE size. We demonstrate that different conformational states can coexist, the transition between them appearing first-order-like and controlled by the enthalpic and entropic trade-off of the amount of CIs condensed on the PE. Such balance can be further altered by varying CI concentrations, thus providing an additional and more convenient tuning parameter for the system properties. Our results lay the foundation for achieving broader and more precise external adjustability of knotted PE size and shape by choosing the nature of its CIs. Thus, they offer new intriguing possibilities for designing novel PE-based materials that are capable of responding to changes in ionic solution properties.

Anion-mediated interphase construction enabling high-voltage solid-state lithium metal batteries

Enhancing the interphase stability of polymer electrolytes with high-voltage cathodes is crucial for the development of high-energy-density lithium metal batteries (LMBs), especially in wearable devices area. Herein, lithium difluorophosphate (LiDFP) is incorporated into the solid polymer electrolyte of poly(ethylene oxide) (PEO) to enhance the formation of a robust cathode-electrolyte interphase (CEI) in high-voltage LiCoO2 LMBs. Through combining electrochemical measurements, spectroscopic techniques and theoretical calculations, the underlying modification mechanism is revealed. Due to its stronger anionic coordination with both polymer electrolyte chain and proton, and more oxidation-active resultant anion-coordinated polymer compared with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiDFP suppresses the formation of the strong acid HTFSI deriving from the deprotonated process of the terminal O-H group thus avoiding the further oxidative attack to the polymeric framework. Furthermore, under the synergetic decomposition of HDFP intermediate, the polymer-derived radical helps to reconstruct a chemo-mechanically stable and Li-conductive CEI layer, which consists of abundant LiF/Li3PO4/LixPOyFz inorganic species distributed in lithiated organic macromolecules. The in-situ constructed CEI effectively passivates catalytic sites on LiCoO2 directly against PEO, resulting in well-maintained layered structure during high-voltage cycling. The proposed interphasial chemistry that regulates CEI formation provides directive knowledge of electrolyte optimization for high-voltage solid-state batteries.

Responses of assembled structures of block polyelectrolytes to electrostatic interaction strength.

In this paper, the responses of assembled behaviors of block polyelectrolytes (PEs) to the strength of electrostatic interactions are studied through molecular dynamic simulations. The results show that the assembled structures closely depend on the electrostatic strength. It should be noted that PE coacervation can outweigh the nucleation of hydrophobic blocks and invert the micelle structures at strong electrostatic strengths, leading to the formation of inverted micelles of PE cores and hydrophobic coronas. In the poor solvent condition for neutral block, diverse anisotropic micelles are presented; candy-like conventional micelles of hydrophobic cores and PE patches coexist with inverted candy-like micelles of PE cores and hydrophobic patches and with Janus micelles of semi-neutral aggregate and semi-PE cluster in the presence of divalent and trivalent counterions. The formation of conventional or inverted micelle is largely determined by the type of micellar fusion, which results from the nucleation competition between electrostatic correlation and hydrophobic interaction. The merge of micelles mediated by hydrophobic attraction leads to conventional hydrophobic cores, and the fusion induced by electrostatic correlations results in PE cores micelles. At strong electrostatic strengths, the PE chains exhibit rich conformations at trivalent counterions, ranging from a fully collapsed state to a rod-like state, and parallel alignment of PE chains is found.

Polyelectrolyte-protein synergism: pH-responsive polyelectrolyte/insulin complexes as versatile carriers for targeted protein and drug delivery

The co-assembly of polyelectrolytes (PE) with proteins offers a promising approach for designing complex structures with customizable morphologies, charge distribution, and stability for targeted cargo delivery. However, the complexity of protein structure limits our ability to predict the properties of the formed nanoparticles, and our goal is to identify the key triggers of the morphological transition in protein/PE complexes and evaluate their ability to encapsulate multivalent ionic drugs. A positively charged PE can assemble with a protein at pH above isoelectric point due to the electrostatic attraction and disassemble at pH below isoelectric point due to the repulsion. The additional hydrophilic block of the polymer should stabilize the particles in solution and enable them to encapsulate a negatively charged drug in the presence of PE excess. We demonstrated that diblock copolymers, poly(ethylene oxide)-block-poly(N,N-dimethylaminoethyl methacrylate) and poly(ethylene oxide)-block-poly(N,N,N-trimethylammonioethyl methacrylate), consisting of a polycation block and a neutral hydrophilic block, reversibly co-assemble with insulin in pH range between 5 and 8. Using small-angle neutron and X-ray scattering (SANS, SAXS), we showed that insulin arrangement within formed particles is controlled by intermolecular electrostatic forces between protein molecules, and can be tuned by varying ionic strength. For the first time, we observed by fluorescence that formed protein/PE complexes with excess of positive charges exhibited potential for encapsulating and controlled release of negatively charged bivalent drugs, protoporphyrin-IX and zinc(II) protoporphyrin-IX, enabling the development of nanocarriers for combination therapies with adjustable charge, stability, internal structure, and size.

Photonic Interpenetrating Polymer Network Fibers Comprising Intertwined Solid-State Cholesteric Liquid Crystal and Polyelectrolyte Networks for Sensor Applications.

Uniform-sized photonic interpenetrating polymer network (IPN) fibers comprising intertwined solid-state cholesteric liquid crystal (CLCsolid) and anionic poly(acrylic acid) (PAA) or cationic poly(2-dimethylaminoethyl methacrylate) (PDMAEMA) networks (photonic IPNPAA or IPNPDMAEMA fibers) were developed for sensor applications. IPNPAA or IPNPDMAEMA fibers with a perfect photonic structure were fabricated inside Teflon tube templates without any treatments for realizing a planar orientation in those fibers. The dominant wavelength of the photonic color from a photograph taken with a cellular phone was used to measure the photonic color change. Photonic IPNPAA fibers treated with KOH (IPNKOH fibers) were used for sensing humidity and divalent metal ions. The linear ranges for relative humidity and Ca2+ detection were 21-92% and 0.5-3.5 mM, and their limits of detection (LODs) were 7.86% and 0.07 mM, respectively. The photonic IPNPAA (or IPNPDMAEMA) fiber immobilized with urease (IPNPAA-urease) (or glucose oxidase (IPNPDMAEMA-GOx)) was used for urea (or glucose) biosensor application. The photonic IPNPAA-urease (or IPNPDMAEMA-GOx) fiber was red-shifted in response to urea (or glucose) in the linear range of 10-60 mM (or 2-16 mM) with an LOD of 2.54 mM (or 0.76 mM). These photonic IPN fibers are promising because of their easy fabrication and miniaturization, battery-free device, cost-effectiveness, and visual detection without using sophisticated analytical instruments. The developed photonic IPN fibers provide new possibilities for the widespread use of photonic sensors in cutting-edge wearable technology and beyond.

Efficient self healable blended cationic and anionic poly(ionic liquids) under ambient conditions

AbstractPoly(ionic liquid)‐based self‐healable electrolytes are getting tremendous attention owing to their quick self‐healing ability at ambient conditions without external stimulus, prominent safety, high mechanical strength, appreciably good conductivity, and no electrolyte leakage. Ionic interactions are much stronger and more dynamic, capable of imparting faster healing ability to the electrolyte. To exploit ionic interactions and non‐covalent hydrogen bonding simultaneously for faster self‐healing at ambient conditions. In the present work, free radical promoted copolymerization of 3‐methyl‐1‐vinylimidazolium iodide and sodium 4‐vinyl benzenesulfonate (VMeImI/SS) with poly(ethylene glycol) methyl ether acrylate and ureidopyrimidinone methacrylate to obtain cationic poly (PEG‐UPy‐Im) and anionic poly (PEG‐UPy‐SS) poly ionic liquid (PIL), respectively, as polymer electrolytes (PEs) have been achieved. The complete structural analysis of the copolymers by FTIR, 1H NMR, 13C NMR, DOSY‐NMR, and GPC was done. The ionic conductivity and self‐healing properties of the synthesized PEs, poly (PEG‐UPy‐Im) and poly (PEG‐UPy‐SS) were investigated, which gave encouraging results. For further enhancement of hydrogen bonding and ionic interactions, poly (PEG‐UPy‐Im) and poly (PEG‐UPy‐SS) were blended in the ratio of 1:1, referred to as poly (Im‐SS), a binary blend, as a self‐healable oppositely charged polyelectrolyte. Poly(Im‐SS) exhibited self‐healing behavior in 15 min and 5 min at 25 and 60°C, respectively, without any external stimulus. Poly(Im‐SS) also exhibited exceptionally high ionic conductivity of 2.04 × 10−5 and 11.48 × 10−5 Scm−1 at 30 and 80°C, respectively. This unique approach of blending two oppositely charged PEs to create a binary blend has improved ionic conductivity and self‐healing capabilities. Because a poly‐ionic network forms in poly(Im‐SS) as a binary blend, the physical and chemical properties in terms of mechanical and thermal stability as well as water contact angle point to a synergistic effect of ion–ion, ion–dipole, and quadruple Hbonding. Thus, the designed copolymer electrolytes and their blend, present a new perspective to develop innovative and rapid self‐healable polyelectrolytes with significant ionic conductivity for advanced electrochemical devices such as fuel cells, batteries, and supercapacitors.

Numerical analysis of scaffold degradation in cryogenic environment: impact of cell migration and cell apoptosis

The analysis of degradation in the presence of cell death and migration is a critical aspect of research in various biological fields, such as tissue engineering, regenerative medicine, and disease pathology. In present study, numerical study of degradation of scaffold were performed in present of cells, cell apoptosis and cell migration. A poly electrolyte complex (PEC) silk fibroin scaffold was used for degradation study. Degradation study in the presence of cells and migration were performed at fixed pH concentration 7.2. Similarly, degradation study of scaffold were performed at different pH cell apoptosis. A transient analysis of scaffold was evaluated in COMSOL 5.5 in presence of cryogenic temperature at different temperature gradient. The parameters; temperature, stress, strain tensor and deformation gradient associated with the degradation of polyelectrolyte complex scaffold were evaluated. Result shows that in both geometries minimum temperature had been achieved as 230.051 K at point P4 in series view and parallel view and at a point P3 for cell migration study for −5 k min−1 and −1 k min−1, respectively. The maximum stress had been generated for 5.57 × 107 N m−2 for the temperature gradient of −2 K min−1 at T cycle in the case of cell migration study. In contrast in series view the maximum stress 2.9 × 107 N m−2 were observed at P4 which was higher as compare to P3. Similarly, for a parallel view, maximum stress (3.93 × 107 N m−2) was obtained for point P3. It had been observed that the maximum strain tensor 5.21 × 10−3, 5.15 × 10−3 and 5.26 × 10−3 was generated in series view at 230 k on a point P3 for − 1, −2 and −5 K min−1, respectively. Similarly, the maximum strain tensor 8.16 × 10−3, 8.09 × 10−3 and 8.09 × 10−3 was generated in parallel view at 230 k on a point P3 for −1, −2 and −5 K min−1, respectively. In the presence of cells, at a point P4 for temperature gradient of −1 and −2 K min−1, it had been closed to the scaffold wall, which had a different temperature profile than the point P3 and scaffold comes to the contact with the cells. The analysis of PEC scaffold degradation in the presence of cells, including cell apoptosis and migration, offers significant insights into the relationship between scaffold properties, cell behaviour, and tissue regeneration.

A double network facilitated ion-electron conductor for thermoelectric harvesting with high energy density

As a young member of the thermoelectric (TE) family, ionic thermoelectric (i-TE) technology stands out due to its exceptionally high thermopower. However, the intermittent nature of its heat utilization results in a weak power output, thus limiting its practical application. To tackle this issue, combining i-TE with electronic thermoelectric (e-TE) materials that exhibit stable heat-to-electricity conversion capabilities presents itself as a promising solution. With this aim, we introduced interpenetrating network (IPN) structure in the fabrication process of mixed ionic-electronic TE (MIETE) materials. Specifically, we created a double network MIETE converter through the in-situ polymerization of ionic poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS) on a loosely structured poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS)/lithium bis(trifluoromethane)sulfonimide (LiTFSI) electronic conductive framework. This subsequent construction of the inert network ensures uninterrupted electronic conductivity and boosts density for improved conductivity (σ). The innovative structural design effectively amalgamates thermodiffusion and Seebeck effects, facilitating continuous electricity generation. The resulting hybrid PEDOT:PSS/LiTFSI/PAMPS-LiCl (PLiP) hydrogels exhibit exceptional TE performance, showing a thermopower of 7.86 mV K−1 and σ of 33.3 mS cm−1. It is worth noting that the PLiP hydrogel illustrates a power generation time of over 4 h and an ultra-high energy density of 93.7 J m−2, which exceeds other TE hydrogels based on the thermodiffusion principle.

Effect of counterion size on polyelectrolyte conformations and thermodynamics.

We present a theoretical model to study the effect of counterion size on the effective charge, size, and thermodynamic behavior of a single, isolated, and flexible polyelectrolyte (PE) chain. We analyze how altering counterion size modifies the energy and entropy contributions to the system, including the ion-pair free energy, excluded volume interactions, entropy of free and condensed ions, and dipolar attraction among monomer-counterion pairs, which result in competing effects challenging intuitive predictions. The PE self-energy is calculated using the Edwards-Muthukumar Hamiltonian, considering a Gaussian monomer distribution for the PE. The condensed ions are assumed to be confined within a cylindrical volume around the PE backbone. The dipolar and excluded volume interactions are described by the second and third virial coefficients. The assumption of freely rotating dipoles results in a first-order coil-globule transition of the PE chain. A more realistic, weaker dipolar attraction, parameterized in our theory, shifts it to a second-order continuous transition. We calculate the size scaling-exponent of the PE and find exponents according to the relative dominance of the electrostatic, excluded volume, or dipolar effects. We further identify the entropy- and energy-driven regimes of the effective charge and conformation of the PE, highlighting the interplay of free ion entropy and ion-pair energy with varying electrostatic strengths. The crossover strength, dependent on the counterion size, indicates that diminishing sizes favor counterion condensation at the expense of free ion entropy. The predictions of the model are consistent with trends in simulations and generalize the findings of the point-like counterion theories.

Capillary electrophoresis using triple layer modified capillary facilitating salivary ion analyses: Application to search for potential stress markers induced by cold pressure test

In this study, we introduce a novel approach for the analysis of salivary ions using capillary electrophoresis (CE) with a triple-layer coated capillary. The capillary is sequentially coated with cationic silylating reagents, poly(vinylsulfonate), and polybrene to form a custom designed surface that effectively inhibits adsorption of protein matrix on the capillary inner wall and allows for reproducible ion analysis. For the CE with capacitively coupled contactless conductivity detection, we used suitable background electrolytes (BGEs) for salivary ion analysis. Anions were separated using a mixture of 2-(N-morpholino)ethanesulfonic acid and l-arginine, and cations were separated using that with 18-crown-6. This setup enabled rapid separation, within 4 min, together with sensitive detection. We quantified nine common anions and five cations typically found in saliva samples using this CE method, both before and after a cold pressure test (CPT, a standard stress test). The CE system demonstrated consistent ion separation across 30 consecutive measurements without requiring capillary replacement. Notably, the salivary ion balance remained predominantly anion-rich, regardless of the CPT. Cold water exposure induced greater variation in the total anion concentration than in the total cation concentration. Further analysis using multiple regression analysis revealed strong relationships between nitrate and nitrite, formate and phosphate, and potassium and nitrate, before and after the CPT. Notably, potassium and nitrate ions exhibited variations in response to stress. These results provided a method for assessing salivary ion composition and insights into the potential of salivary ions as biomarkers for stress.

Surface characterization and Remazol Red adsorption by asymmetric polyethersulfone membranes modified by polyelectrolyte complexes

AbstractPolyethersulfone (PES) membranes containing 4‐fluorophenyl sulfone‐terminated poly(diallylpiperidinium hexafluorophosphate)‐sulfonated poly(ethylene terephthalate) polyelectrolyte complexes (PECs) were obtained via phase inversion using three different methods that enabled the complexation of polyelectrolytes (PELs) to occur before, after, and during membrane formation. Atomic force microscopy‐infrared spectroscopy analysis revealed varying concentrations of the polyanion depending on the preparation method and confirmed the presence of PECs in the membranes, highlighting an increase in surface roughness. Zeta potential measurements demonstrated positive surface charges for the membrane comprising PES and the polycation. The reduction in zeta potential in PEC membranes corresponded with the neutralization of positive groups by sulfonated poly(ethylene terephthalate. Scanning electron microscopy micrographs depicted surface imperfections in PEC membranes, emphasizing the influence of PECs on membrane surfaces. The water contact angle decreased, indicating increased hydrophilicity in PEC membranes. Additionally, dye adsorption results showcased significant adsorption, with the membranes absorbing at least 60% of Remazol Red from an aqueous solution. Notably, the Blend membrane outperformed others, exhibiting an exceptional adsorption rate exceeding 92%.

Pyrrole Compounds from the Two-Step One-Pot Conversion of 2,5-Dimethylfuran for Elastomer Composites with Low Dissipation of Energy.

A one-pot, two-step process was developed for the preparation of pyrrole compounds from 2,5-dimethylfuran. The first step was the acid-catalyzed ring-opening reaction of 2,5-dimethylfuran (DF), leading to the formation of 2,5-hexanedione (HD). A stoichiometric amount of water and a sub-stoichiometric amount of sulfuric acid were used by heating at 50 °C for 24 h. Chemically pure HD was isolated, with a quantitative yield (up to 95%), as revealed by 1H-NMR, 13C-NMR, and GC-MS analyses. In the second step, HD was used as the starting material for the synthesis of pyrrole compounds via the Paal-Knorr reaction. Various primary amines were used in stoichiometric amounts. 1H-NMR, 13C-NMR, ESI-Mass, and GC-Mass analyses confirmed that pyrrole compounds were prepared with very good/excellent yields (80-95%), with water as the only co-product. A further purification step was not necessary. The process was characterized by a very high carbon efficiency, up to 80%, and an E-factor down to 0.128, whereas the typical E-factor for fine chemicals is between 5 and 50. Water, a co-product of the second step, can trigger the first step and therefore make the whole process circular. Thus, this synthetic pathway appears to be in line with the requirements of a sustainable chemical process. A pyrrole compound bearing an SH group (SHP) was used for the functionalization of a furnace carbon black (CB). The functionalized CB (CB/SHP) was utilized in place of silica, resulting in a 15% mass reduction of reinforcing filler, in an elastomeric composite based on poly(styrene-co-butadiene) from solution anionic polymerization and poly(1,4-cis-isoprene) from Hevea Brasiliensis. Compared to the silica-based composite, a reduction in the Payne effect of about 25% and an increase in the dynamic rigidity (E' at 70 °C) of about 25% were obtained with CB/SHP.