Quaternary Ammonium Groups Research Articles

Synthesis and mechanism of quaternary ammonium salts based on porphyrin as high-performance copper levelers

The molecular structure and energy distribution of organic compounds have a great influence on their adsorption capacity on the metal surface. However, there are still insufficient researches on the influence of energy distribution on adsorption properties of organic molecules. Herein, a family of porphyrin derivatives (TPyP-Et, TPyP-Oct, TPyP-Bn and TPyP-Al) bearing quaternary ammonium groups were synthesized for the first time as promising levelers for through-hole copper electrodeposition. Electrochemical tests revealed that all four TPyP derivatives displayed enhanced electrochemical properties. Theoretical calculations and molecular dynamics simulations were carried out to investigate the physisorption capacity and chemical reaction activity of the TPyP molecules, as well as the adsorption capacity on the surface of the copper layer. Through optical and scanning electron microscopy as well as X-ray diffractometry, it was demonstrated that TPyP molecules are effective electroplating levelers. TPyP-Oct, with its longer carbon chain substituent, exhibited superior hole-filling performance in practical PCB experiments among the four compounds. This study expandes the application range of porphyrin compounds, analyzes the influence of organic molecular adsorption properties in copper electrodeposition, and provides theoretical guidance for the future study of organic compounds adsorbed on metal surfaces.

Remarkably Enhanced Phosphate Sequestration from Waters by Biochar with High-Density Quaternary Ammonium Groups.

A new biochar (N-BC) was fabricated by incorporating high-density positively charged quaternary ammonium groups into the pristine biochar without any adsorption for phosphate. N-BC can highly efficiently remove phosphate with an optimal pH of 5.0, a maximum experimental adsorption capacity of 30 mg of P/g, and an adsorption equilibrium time of 180 min. The predicted pore diffusion coefficient D (the diffused surface area of the adsorbate for unit time) for phosphate adsorption by N-BC was 5.3 × 10-9 cm2/s. N-BC can still capture phosphate in the copresence of anion Cl- with a molar concentration 50 times that of phosphate. The exhausted N-BC was completely regenerated using a 10 wt % NaOH solution and further reused without any observable loss in adsorption capacity. Moreover, N-BC yielded ∼324 bed volumes (BV) of wastewater containing 1 mg P/L phosphate and 50 mg/L Cl- before breakthrough occurring (<0.1 mg P/L in effluent) in a fixed-bed column operation system. The introduced quaternary ammonium groups covalently bound to biochar played a dominant role in phosphate sequestration by N-BC through forming the out-sphere complexation with phosphate. All results imply that it is of promising prospect for N-BC practical application for phosphate purification from waters. The present study provided a new strategy to expand the application of biochar, usually serving as an adsorbent for cationic pollutants, to the purification of anionic pollutants such as phosphate from waters.

Quaternization of porphyrin conjugated organic polymer as an effective photocatalyst for fast degradation of 2,4-D and BPA

Conjugated organic polymers (COPs) originating from porphyrin and perylene bisimide exhibit promising capacity as photocatalysts benefiting from their inherent semiconducting characteristics, but most of them suffer from the hydrophobic properties, which strongly hinder their surface reactions and photocatalytic performance. To solve this problem, the quaternary ammonium groups were introduced into the porous skeleton of a COP-based photocatalyst (PDIN-Py) through Friedel-Crafts alkylation & Menschutkin reactions to yield a super-hydrophilic COP, denoted as PDIN-PyN+. Apart from the hydrophilicity, such post-modification strategy also enhances the visible light utilization, boosts the photogenerated carriers transport and endows PDIN-PyN+ with more positive zeta potential (21.9 mV), thus enhancing the electrostatic interaction with target anionic model pollutants including bisphenol A (BPA) and 2,4-dichlorophenoxyacetic acid (2,4-D) and improving the photocatalytic degradation performance. The removal efficiency (η) of PDIN-PyN+ towards 2,4-D (150 ppm) and BPA (20 ppm) can reach >99 % within 30 min under the irradiation of visible light, and the PDIN-PyN+ also exhibits excellent reusability and withstands various environmental influencing factors, thereby it shows great potential in real-water treatment scenarios.

Turning Polysaccharides into Injectable and Rapid Self-Healing Antibacterial Hydrogels for Antibacterial Treatment and Bacterial-Infected Wound Healing.

Great efforts have been devoted to the development of novel and multifunctional wound dressing materials to meet the different needs of wound healing. Herein, we covalently grafted quaternary ammonium groups (QAGs) containing 12-carbon straight-chain alkanes to the dextran polymer skeleton. We then oxidized the resulting product into oxidized quaternized dextran (OQD). The obtained OQD polymer is rich in antibacterial QAGs and aldehyde groups. It can react with glycol chitosan (GC) via the Schiff-base reaction to form a multifunctional GC@OQD hydrogel with good self-healing behavior, hemostasis, injectability, inherent superior antibacterial activity, biocompatibility, and excellent promotion of healing of methicillin-resistant Staphylococcus aureus (MRSA)-infected wounds. The biosafe and nontoxic GC@OQD hydrogel with a three-dimensional porous network structure possesses an excellent swelling rate and water retention capacity. It can be used for hemostasis and treating irregular wounds. The designed GC@OQD hydrogel with inherent antibacterial activity possesses good antibacterial efficacy on both S. aureus (Gram-positive bacteria) and Escherichia coli (Gram-negative bacteria), as well as MRSA bacteria, with antibacterial activity greater than 99%. It can be used for the treatment of wounds infected by MRSA and significantly promotes the healing of wounds. Thus, the multifunctional antibacterial GC@OQD hydrogel has the potential to be applied in clinical practice as a wound dressing.

Functionalization of PTFE substrates with quaternary ammonium groups – An approach towards anion conducting properties

Hydrogen produced by electrolysis using renewable energy sources offers a zero-emission alternative to fossil-based sources providing high efficiencies in all energy sectors. Anion Exchange Membrane Water Electrolysis (AEM-WE) combines the advantages of the established technologies, alkaline (AEL) and proton exchange membrane (PEM) water electrolysis. However, AEM-WE still requires optimization, especially with regard to the membrane, catalysts and electrode structure. In this contribution we focus on the improvement of PTFE-based binders for AEM-WE membranes, which provide high chemical stability but lack the required ion conductivity. Thus, the functionalization of PTFE towards quaternary ammonium moieties (QAS) was investigated employing two approaches: (i) NH3-plasma treatment and (ii) O2-plasma with subsequent coupling of aminosilanes. Finally, the surface coupled amino groups were converted into QAS via alkylation with iodomethane (CH3-I), introducing ion conductivity. Successful functionalization was proved by X-ray photoelectron spectroscopy (XPS), displaying changes in the surface composition of PTFE surfaces such as the introduction of amino groups at the expense of fluorine, and the increase in surface carbon content upon alkylation. Furthermore, contact angle measurements revealed increased wettability with water due to the introduction of the polar surface functionalities, while zeta potential measurements confirmed the increase of positive surface charges along the modification processes.

Optimized design of quaternary amino-functionalized chitosan fibers for ultra-high diclofenac adsorption from wastewater

The extraction of non-steroidal anti-inflammatory drugs (NSAIDs) from water bodies is imperative due to the potential harm to humans and the ecosystem caused by NSAID-contaminated water. Quaternary amino-functionalized epichlorohydrin cross-linked chitosan fibers (QECFs), an economical and eco-friendly adsorbent, were successfully prepared using a simple and gentle method for efficient diclofenac (DCF) adsorption. Additionally, the optimized factors for the preparation of QECFs included epichlorohydrin concentration, pH, temperature, and (3-chloro-2-hydroxypropyl) trimethylammonium chloride (CHTAC) concentration. QECFs demonstrated excellent adsorption performance for DCF across a broad pH range of 7–12. The calculated maximum adsorption capacity and the amount of adsorbed DCF per adsorption site were determined to be 987.5 ± 20.1 mg/g and 1.2 ± 0.2, respectively, according to the D-R and Hill isotherm models, at pH 7 within 180 min. This performance surpassed that of previously reported adsorbents. The regeneration of QECFs could be achieved using a 0.5 mol/L NaOH solution within 90 min, with QECFs retaining their original fiber form and experiencing only a 9.18% reduction in adsorption capacity after 5 cycles. The Fourier transform infrared spectrometer and X-ray photoelectron spectroscopy were used to study the characterization of QECFs, the preparation mechanism of QECFs, and the adsorption mechanism of DCF by QECFs. Quaternary ammonium groups (R4N+) were well developed in QECFs through the reaction between amino/hydroxyl groups on chitosan and CHTAC, and approximately 0.98 CHTAC molecule with 0.98 R4N+ group were immobilized on each chitosan monomer. Additionally, these R4N+ on QECFs played a crucial role in the removal of DCF.

Biomass derived carbon dots with antibacterial and anti-inflammatory properties for the treatment of wound healing

We report the synthesis of multifunctional carbon dots (PAPBCDs) via a one-step hydrothermal method, and evaluated their therapeutic efficacy in wound healing in vivo using a Staphylococcus aureus-infected wound mouse model. The multifunctional carbon dots (CDs) were derived from biomass-based polysaccharide (PAP) and betaine (B), and retained the antioxidant and antibacterial activities, respectively, of their starting precursors. In addition to possessing favorable biocompatibility in cytotoxicity studies, the antibacterial activity of the PAPBCDs was 99.38% against Gram-negative bacteria and 90.80% against Gram-positive bacteria, respectively, suggesting that the betaine-derived quaternary ammonium groups in the PAPBCDs were able to electrostatically disrupt bacterial cell membranes leading to pathogen inactivation. ROS scavenging studies demonstrated that the PAPBCDs could effectively scavenge hydroxyl radicals, suggesting that the PAPBCDs could remove intracellular ROS and protect wound tissue from oxidative stress. In vivo studies using mouse models indicated that PAPBCDs could accelerate S. aureus-infected wound healing. These findings offer some interesting ideas for how to design of effective nanomaterials to treat wound infections, and suggest that multifunctional carbon-dot based materials may play a therapeutic role in tissue regeneration and healing.

Surface modification of nanofiltration membrane using quaternary diethanolamine for efficient antibiotics/salt separation

Nanofiltration plays a crucial role in antibiotic desalination from high salinity water, but the membranes often have low water permeability and insufficient selectivity between antibiotics and salts. In this study, a Gemini-type quaternary diethanolamine monomer (QTDEA) containing quaternary ammonium and hydroxyl groups was synthesized. This monomer had a hybrid spatial structure combining both rigid and flexible components, allowing it to covalently graft to the acyl chloride groups on the nascent polyamide (PA) film. The resulting modified PA-QTDEA membrane exhibited enhanced hydrophilicity, reduced negative charge, and a looser structure. It demonstrated a high water permeance of 18.2 L m−2 h−1·bar−1 for chlortetracycline hydrochloride (CTC) desalination from a NaCl solution of 10 g L−1, and the NaCl/CTC selectivity was 21.2. This research presents an efficient method for improving the performance of antibiotic desalination through surface modification using the novel QTDEA monomer.

Preparation and Characterization of Magnetic Material/Chitosan Composite Modified with Glycidyl-Trimethylammonium Chloride

Glycidyl-trimethylammonium chloride (GTMAC) containing quaternary ammonium (QA) groups is commonly used as a base catalyst for any organic reaction. This research prepared a novel composite of GTMAC attached to chitosan-coated magnetic material (MM/Chi/GTMAC) using a precipitation method. The effect of chitosan and GTMAC contents on MM/chi/GTMAC properties was studied, where the chitosan content varied from 0, 0.3, 0.5, 1.0, and 3.0 mol, and GTMAC varied from 0, 0.3, 0.8, 1.0, 1.5, and 3 mL with the constant mass of MM (0.4640 g). The physicochemical and morphological properties were characterized with FTIR, SEM-EDX, XRD, TGA, UV-vis, AAS, and zeta-sizer, and the magnetic strength was simply tested with an external magnet. The result showed that a mixture containing chitosan and GTMAC of 0.358 g and 1.5 mL was an optimum composition, in which MM/chi(0.5)/GTMAC(1.5) has high thermal stability, low chitosan and Fe solubility, and optimum content of QA (0.284 mol/g) without loss of magnetic strength. The higher the amount of chitosan, the lower the magnetic properties, and the higher the GTMAC did not increase the QA content. Therefore, the composite produced has the potential to be a novel heterogeneous base catalyst that is quickly recovered from any organic reaction media.

Zwitterionic functionalization of polysaccharide gum by graft copolymerization to develop 3-D network materials for anticancer drug delivery applications

Herein, functionalization of polysaccharide gum has been carried out to develop network copolymeric materials for use in sustained anticancer drug delivery. Grafting reaction of poly[2-(methacryloyloxy)ethyl] dimethyl-(3-sulfopropyl)ammonium hydroxide (MEDSAH) onto sterculia gum has been done in the presence of crosslinker. Copolymeric materials were characterized by scanning electron micrographs (SEMs), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), 13C-nuclear magnetic resonance (NMR), and thermogravimetric analysis (TGA). SEM, AFM and XRD displayed heterogeneous morphology with a rough surfaces of amorphous copolymeric materials. Peaks at 173.822 ppm (carbonyl carbon) and at 60.653 ppm (methylene carbon attached to a quaternary ammonium group) confirmed the addition of poly(MEDSAH) during the grafting reaction. Mesh size in network hydrogel was found between 14.54 nm to 36.32 nm. Sustained release of doxorubicin was found with non-Fickian diffusion and was best demonstrated by the kinetic model Hixson Crowell. The biocompatibility of material was revealed in a haemolytic index (1.74 ± 0.26%) less than two percent during the copolymer-blood interaction. The material exhibited antioxidant and mucoadhesion properties. Free radical scavenging ability of copolymers was 49.41 ± 0.97% in 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay of the antioxidant test. These properties of copolymeric hydrogels demonstrated their suitability for use in sustained drug delivery systems for cancer chemotherapy.

Functionalization of rubbery domains in SBS triblock copolymers for anion exchange membrane applications with enhanced robustness

A series of anion exchange membranes (AEMs) based on hydrogenated poly (styrene-b-butadiene-b-styrene) (h-SBS) triblock copolymers were prepared via thiol-ene click reaction of the mid-block polybutadiene with 6-mercapto-1-hexanol, followed by hydrogenation of the remaining double bonds, direct bromination of the pendant alcohol group, and substitution of with trimethylamine (TMA). The thiol-ene click reaction provided a facile and effective control of degree of functionalization up to 50 mol% of total CC bonds in the polymer. Membrane properties of the TMA-functionalized h-SBS for AEM applications were investigated by measuring ion exchange capacity (IEC), water uptake, and ion conductivity. h-SBS-TMA-1.83 with 24% degree of functionalization of polybutadiene block exhibited an IEC of 1.83 mequiv./g and the highest hydroxide ion conductivity of 93 mS/cm at 80 °C. IEC and hydroxide ion conductivity of all h-SBS AEMs were preserved after treatment with aq. 1 M NaOH solution at 80 °C for 4 weeks, demonstrating good alkaline stability. The h-SBS AEMs with quaternary ammonium groups tethered to the rubbery polybutadiene block of SBS showed better mechanical properties, lower water uptake, less water swelling under humidified conditions, and higher and more stable hydroxide conductivity at 80 °C than the ones tethered to the rigid polystyrene block of hydrogenated SBS AEMs. These results suggest that ionic group functionalization at the rubbery block of SBS provides mechanically more robust AEMs and is better AEM material design than that of glassy block functionalized AEM.

Quaternization of cassava starch and determination of antimicrobial activity against bacteria and coronavirus

This study describes the novel development of quaternized cassava starch (Q-CS) with antimicrobial and antiviral properties, particularly effective against the MHV-3 coronavirus. The preparation of Q-CS involved the reaction of cassava starch (CS) with glycidyltrimethylammonium chloride (GTMAC) in an alkaline solution. Q-CS physicochemical properties were determined by FTIR, NMR, elemental analysis, zeta potential, TGA, and moisture sorption. FTIR and NMR spectra confirmed the introduction of cationic groups in the CS structure. The elemental analysis revealed a degree of substitution (DS) of 0.552 of the cationic reagent on the hydroxyl groups of CS. Furthermore, Q-CS exhibited a positive zeta potential value (+28.6 ± 0.60 mV) attributed to the high positive charge density shown by the quaternary ammonium groups. Q-CS demonstrated lower thermal stability and higher moisture sorption compared to CS. The antimicrobial activity of Q-CS was confirmed against Escherichia coli (MIC = 0.156 mg mL−1) and Staphylococcus aureus (MIC = 0.312 mg mL−1), along with a remarkable ability to inactivate 99% of MHV-3 coronavirus after only 1 min of direct contact. Additionally, Q-CS showed high cell viability (close to 100%) and minimal cytotoxicity effects, guaranteeing its safe use. Therefore, these findings indicate the potential use of Q-CS as a raw material for antiseptic biomaterials.

A quaternary ammonium cyclodextrin polymer for efficient photocatalytic production of hydrogen peroxide from pure water

A photocatalytic system can be used to efficiently produce hydrogen peroxide (H2O2) without introducing a sacrificial agent or oxygen (O2). This system has practical application potential but remains challenging to implement. To increase the H2O2 yield of this system, a quaternary ammonium cyclodextrin polymeric photocatalyst QCD36A1-1350 is successfully synthesized using quaternization modification and low-temperature polycondensation. The photocatalyst is used to produce H2O2 from pure water and air by the one-step two electron oxygen reduction reaction. Under irradiation by visible light, QCD36A1-1350 produces a higher H2O2 yield (of up to 2.51 mmol g−1h−1) than unquaternized polymers and reported metal-free catalysts under similar conditions. Experimental and theoretical studies clearly show that the introduction of quaternary ammonium groups can effectively broaden the visible light absorption of polymer catalysts, while increasing the hydrophilicity, charge transfer efficiency and surface stability. The practicability of efficient photocatalytic production of H2O2 is realized by increasing the activity and selectivity of the polymer photocatalyst.

Cationic cellulose nanofiber solid electrolytes: A pathway to high lithium-ion migration and polysulfide adsorption for lithium-sulfur batteries

Polyethylene oxide (PEO) solid electrolytes, acknowledged for their safety advantages over liquid counterparts, confront inherent challenges, including low ionic conductivity, restricted lithium ion migration, and mechanical fragility, notably pronounced in lithium‑sulfur batteries due to the polysulfide shuttling phenomenon. To address these limitations, we integrate a quaternary ammonium cation-modified cellulose (QACC) nanofiber, electrospun with cellulose acetate (CA) from recycled cigarette filters, into the PEO electrolyte matrix. The nitrogen atom within the quaternary ammonium group exhibits a pronounced affinity for polysulfide compounds, effectively curtailing polysulfide migration. Concurrently, Lewis acid-base interactions between quaternary ammonium groups and lithium salt anions facilitate the release of additional Li+, achieving a lithium-ion transference number 1.5 times higher than its pure PEO counterpart. Furthermore, the introduction of a larger trifluoromethanesulfonimide (TFSI) group on the QACC macromolecule (TFSI-QACC) disrupts the ordered arrangement of PEO macromolecules, resulting in a noteworthy enhancement in ionic conductivity, reaching 2.07 × 10−4 S cm−1 at 60 °C, thus addressing the challenge of low PEO electrolyte conductivity. Moreover, the nanofiber enhances the mechanical strength of the PEO electrolyte from 0.49 to 7.50 MPa, mitigating safety concerns related to lithium dendrites puncturing the electrolyte. Consequently, the composite PEO demonstrates exemplary performance in lithium symmetrical batteries, enduring 500 h of continuous operation and completing 100 cycles at both room and elevated temperatures. This integrated approach, transitioning from waste to wealth, adeptly addresses a spectrum of challenges in the efficiency of solid-state electrolytes, holding considerable promise for advancing lithium‑sulfur battery technology.

Anion Competition at Positively Charged Surfactant Monolayers.

Interactions of anions with hydrophobic surfaces of proteins and water-soluble polymers depend on the ability of the ions to shed their hydration shells. At positively charged surfactant monolayers, the interactions of anions are less well understood. Due to the interplay of electrostatic surface forces, hydration effects, and ion-ion interactions in the electrostatic double layer, a comprehensive microscopic picture remains elusive. Herein, we study the interactions of chloride, bromide, and a mixture of these two anions at the aqueous interface of dihexadecyldimethylammonium (DHDA+) and dioctadecyldimethylammonium (DODA+) cationic monolayers. Using molecular dynamics simulations and three surface-sensitive X-ray scattering techniques, we demonstrate that bromide interacts preferentially over chloride with both monolayers. The structure of the two monolayers and their interfacial electron density profiles obtained from the simulations quantitatively reproduce the experimental data. We observe that chloride and bromide form contact ion pairs with the quaternary ammonium groups on both monolayers. However, ion pairing with bromide leads to a greater reduction in the number of water molecules hydrating the anion, resulting in more energetically stable ion pairs. This leads to long-range (>3 nm) lateral correlations between bromide ions on the structured DODA+ monolayer. These observations indicate that ion hydration is the dominant factor determining the interfacial electrolyte structure.

Positive Charge Influences on the Surface Interactions and Cohesive Bonding of a Catechol-Containing Polymer.

Achieving robust underwater adhesion remains challenging. Through generations of evolution, marine mussels have developed an adhesive system that allows them to anchor onto wet surfaces. Scientists have taken varied approaches to developing mussel-inspired adhesives. Mussel foot proteins are rich in lysine residues, which may play a role in the removal of salts from surfaces. Displacement of water and ions on substrates could then enable molecular contact with surfaces. The necessity of cations for underwater adhesion is still in debate. Here, we examined the performance of a methacrylate polymer containing quaternary ammonium and catechol groups. Varying amounts of charge in the polymers were studied. As opposed to protonated amines such as lysine, quaternary ammonium groups offer a nonreactive cation for isolating effects from only charge. Results shown for dry bonding demonstrated that cations tended to decrease bulk cohesion while increasing surface interactions. Stronger interactions at surfaces, along with weaker bulk bonding, indicate that cations decreased the cohesive forces. When under salt water, overall bulk adhesion also dropped with higher cation loadings. Surface attachment under salt water also dropped, indicating that the polymer cations could not displace surface waters or sodium ions. Salt did, however, appear to shield bulk cation-cation repulsions. These studies help to distinguish influences upon bulk cohesion from attachment at surfaces. The roles of cations in adhesion are complex, with both cohesive and surface bonding being relevant in different ways, sometimes even working in opposite directions.

Microenvironment-Modulating Adsorption Enables Highly Efficient Lithium Extraction under Natural pH Conditions.

Ion-sieve adsorbents are effective materials in practical applications for extracting liquid lithium. However, it is greatly suppressed in adsorption capacity and selectivity (Li/Mg) under natural near-neutral conditions of seawater or salt lakes, due to the interference of in situ released H+ and Mg2+ impurity. This paper proposes an adsorbent with a microenvironment-modulating function as a solution. The introduction of quaternary ammonium groups into the carrier accelerates the migration of H+, while preventing the diffusion of Mg2+ by electrostatic repulsion. Besides, it can also prestore OH-, effectively consuming the generated hydrogen ions in situ. Based on the rational design, the alkali consumption of the microenvironment-modulating strategy is dramatically reduced to 1/144 of the traditional alkali-adding method. Additionally, adsorption performance is significantly promoted under natural pH conditions, with a maximum 33 times higher separation factor (selectivity) and 4 times higher adsorption capacity than commercial ion-sieve adsorbents. This development indicates the feasibility of using microenvironment modulation for effective lithium extraction and inspires the development of next-generation high-performance adsorbents.

Self-Assembled Tetraphenylethene-Based Nanoaggregates with Tunable Electrochemiluminescence for the Ultrasensitive Detection of E. coli.

As an effective ECL emitter, tetraphenylethene (TPE)-based molecules have recently been reported with aggregation-induced electrochemiluminescence (AIECL) property, while it is still a big challenge to control its aggregation states and obtain uniform aggregates with intense ECL emission. In this study, we develop three TPE derivatives carrying a pyridinium group, an alkyl chain, and a quaternary ammonium group via the Menschutkin reaction. The resulting molecules exhibit significantly red-shifted FL and enhanced ECL emissions due to the tunable reduction of the energy gap between the highest occupied molecular orbitals (HOMOs) and the lowest unoccupied molecular orbitals (LUMOs). More importantly, the amphiphilicity of the as-developed molecules enables their spontaneous self-assembly into well-controlled spherical nanoaggregates, and the ECL intensity of nanoaggregates with 3 -CH2- (named as C3) is 17.0-fold higher compared to that of the original 4-(4-(1,2,2-triphenylvinyl)phenyl)pyridine (TPP) molecule. These cationic nanoaggregates demonstrate a high affinity toward bacteria, and an ECL sensor for the profiling of Escherichia coli (E. coli) was developed with a broad linear range and good selectivity in the presence of an E. coli-specific aptamer. This study provides an effective way to enhance the ECL emission of TPE molecules through their derivatization and a simple way to prepare well-controlled AIECL nanoaggregates for ECL application.

Kinetic, Isothermal, and Thermodynamic Analyses of Adsorption of Humic Acid on Quaternized Porous Cellulose Beads

Porous cellulose beads were quaternized with glycidyltrimethylammonium chloride (GTMAC), and the potential use of the quaternized cellulose beads as an adsorbent was explored for the removal of humic acid (HA) from aqueous media. The introduction of quaternary ammonium groups was verified by FT-IR and XPS analyses, and their content increased to 0.524 mmol/g-Qcell by increasing the GTMAC concentration. The adsorption capacity of the HA increased with decreasing initial pH value and/or increasing content of quaternary ammonium groups, and a maximum adsorption capacity of 575 mg/g-Qcell was obtained for the quaternized cellulose beads with a content of quaternary ammonium groups of 0.380 mmol/g-Qcell. The removal % value increased with increasing dose of quaternized cellulose beads, and HA was highly removed at higher quaternary ammonium groups. The kinetics of the HA adsorption in this study followed a pseudo-second-order equation, and the process exhibited a better fit to the Langmuir isotherm. In addition, the k2 value increased with increasing temperature. These results emphasize that HA adsorption is limited by chemical sorption or chemisorption. The quaternized cellulose beads were repetitively used for the adsorption of HA without appreciable loss in the adsorption capacity. The empirical, equilibrium, and kinetic aspects obtained in this study support that the quaternized cellulose beads can be applied to the removal of HA.

Asymmetrically charged polyamide nanofilm of intrinsic microporosity containing quaternary ammonium groups for heavy metal removal

High-performance nanofiltration (NF) is a highly hopeful approach for removing heavy metals from water, which can effectively solve the hazards of heavy metals to the public health and environment security. In this study, a polyamide (PA) nanofilm of intrinsic microporosity was fabricated through interfacial polymerization of the novel spirocyclic diamine monomer (SBI) with trimesoyl chloride (TMC). The PA nanofilm demonstrated high microporosity due to the porous structure formed by the covalent cross-linking of SBI with TMC and the stacking of the SBI monomers due to its rigidly-contorted structure. Consequently, its free volume was high with the water permeance of 19.3 L m−2 h−1·bar−1. Meanwhile, the PA nanofilm exhibited asymmetrical charges on both sides with a positively charged bottom and a negatively charged top. The quaternary ammonium moieties in SBI produced positively charged nanochannels in the PA nanofilm, reinforcing the Donnan exclusion against multivalent cations. The proposed SBI-TMC membrane was able to effectively remove heavy metals from water, with rejections of Cu2+, Ni2+, Zn2+, and Pb2+ at 93.3%, 93.0%, 91.8%, and 88.3%, respectively. This study confirmed that the fit-for-purpose design of monomer with rigidly-contorted structure is a feasible approach to fabricate NF membrane with enhanced separation performance.