Glycidyltrimethylammonium Chloride Research Articles

Salt-free neutral dyeing of cotton fiber with monochlorotriazine type reactive dyes

In this paper, we present the modification of cotton with glycidyltrimethylammonium chloride (GTA), demonstrating its capability not only for salt-free dye adsorption but also for achieving fixation reactions with monochlorotriazine-type reactive dyes under neutral conditions. The results of adsorption kinetics and isotherm experiments indicate that the adsorption of reactive dyes by modified cotton is chemisorption. Color-stripping experiments conducted on modified cotton dyed with different dyes revealed that GTA-modified cotton underwent fixation reactions with monochlorotriazine-type reactive dyes under neutral conditions. The reaction sites of modified cotton with reactive dyes were determined by measuring the 1H NMR of the model reaction products. Mechanism investigation using Density Functional Theory (DFT) on the fixation reaction revealed that the hydroxyl groups on the modification agent chain exhibit a lower pKa value and carry more negative charge, resulting in a lower reaction barrier with monochlorotriazine-type reactive dyes. Our research findings demonstrate that GTA-modified cotton fiber enhance the reactivity of cotton, providing significant guidance for the development of novel modifiers.

Synthesis of base-acid pair based poly(isatin arylene) membranes for HT-PEMFC applications

Phosphoric acid (PA) doped polymer electrolyte membranes are promising high temperature proton exchange membranes (HT-PEMs) for fuel cells. While PA doped polybenzimidazole (PBI) has been considered as a successful HT-PEM, several issues remain, such as the use of carcinogenic monomer, poor solubility in organic solvents and easy PA loss. To develop more cost-effective, readily synthesized and high-performance HT-PEMs, this study focuses on synthesizing high-performance HT-PEMs based on poly(isatin arylene)s (i.e., PIT and PIB) containing a lactam structure and devoid of ether bonds. These polymers are synthesized from isatin and p-terphenyl (or biphenyl) under superacid catalysis. Subsequently, glycidyl trimethyl ammonium chloride (GTA) is employed as a grafting reagent for PIT and PIB. This ring-opening reaction is accomplished through an efficient and environmentally friendly procedure without any alkaline catalysts. The introduced GTA side chains with quaternary ammonium and hydroxyl groups not only produce microphase separation structures that facilitate proton conduction, but also reduce PA loss. Comparing with PIT-GTA with terphenyl units, the PIB-GTA membrane with short biphenyl units exhibits superior properties. For instance, the PIB-GTA/218.5%PA membrane achieves a high conductivity of 0.103 S cm−1 at 180 °C and a tensile strength of 6.6 MPa at room temperature. Without humidification and backpressure, the PIB-GTA/218.5%PA based H2–O2 single cell displays a peak power density of 632 mW cm−2 at 160 °C. This work presents a straightforward approach to synthesizing GTA grafted poly(isatin arylene) membranes for HT-PEM fuel cells.

Quaternary ammonium grafted chitosan hydrogel with enhanced antibacterial performance as tannin acid and deferoxamine carrier to promote diabetic wound healing

The delay of diabetic wound healing puts a huge burden on the society. The key factors hindering wound healing include bacterial infection, unresolved inflammation and poorly generated blood vessels. In this paper, glycidyl trimethyl ammonium chloride (GTA) was grafted to chitosan (CS) to obtain quaternary ammonium grafted chitosan (QCS) with enhanced antibacterial performance, and then cross-linked by dialdehyde terminated poly(ethylene oxide) (PEO DA) to construct QCS/PEO DA hydrogel with tissue adhesion, biodegradation and self-healing properties. The QCS/PEO DA hydrogel is loaded with tannin acid (TA) and deferoxamine (DFO) to enhance antioxidant property and angiogenesis. At the same time, the TA and DFO loaded TA@DFO/hydrogel preserved the biocompatibility and biodegradability of chitosan. Moreover, the multifunctional hydrogel behaved excellent hemostatic properties in mice model and significantly promoted the healing efficacy of diabetic wounds. Overall, the TA@DFO/hydrogel is promising anti-infection dressing material for diabetic wound healing.

Trace Thiol Moieties in the Ligand Layer Induce Superior Catalytic Gold Nanoclusters.

We here show that the typical poison of thiols, if below a certain level, promotes rather than suppresses the catalytic activity of gold nanoclusters (AuNCs). A few thiol groups functionalized hyperbranched polyethylenimine (PEI, Mn = 2000 Da) patched on a mesoporous polymeric bead aid the direct synthesis of AuNCs. The nucleation efficiency of AuNC is 93-fold favored at a level of 2 thiols per PEI (0.04 equiv of the amino units) than that by neat PEI, and AuNCs (1.3 nm) are obtained up to a gold load of 6.3% on the support. Unexpectedly, the catalytic activity of AuNCs is favored by the thiol up to 2 thiols per PEI, as evaluated from the surface-normalized rate constant of the model reaction of 4-nitrophenol-reduction. The catalytic promotion by thiols probably stems from optimized electron density on AuNC. If the residual NH groups of PEI were further fully treated with glycidyltrimethylammonium chloride, the catalytic activity is again enhanced, where the accelerated mass transfer is responsible for the promotion. Overall, the catalytic activity reaches an unprecedented value (metal-normalized rate constant kc = 29.4 L mmol-1 s-1 and turnover frequency = 1623 h-1, as evaluated with the model reaction of 4-nitrophenol reduction) ever reported for supported AuNCs. Our results suggest that orthogonal ligand optimization is an effective manner of triggering the release of the catalytic potential of AuNCs, among which thiol is unique.

Ionic Lignin Polymers for Controlled CO2 Capture, Release, and Conversion into High-Value Chemicals.

In this study, an innovative and cost-effective ionic polymer for CO2 capture and utilization for the first time, using abundant and nonfood-based biomass lignin is reported. The modified ionic polymer synthesizes through the reaction of glycidyltrimethylammonium chloride with lignin under alkaline conditions to yield quaternary ammonium ionic functionality. Subsequently, the hydroxide-based pure ionic lignin polymer is employed for CO2 capture from both direct air and concentrated CO2 sources at room temperature and atmospheric pressure. Structural characterization of the polymers is accomplished through 1H, 13C, and 2D-heteronuclear single quantum coherence (HSQC)NMR, and FT-IR spectroscopy. The CO2 capture process is established through the formation of bicarbonate ions alongside the presence of CO2. The captured CO2 is precisely quantified by using inverse-gated proton decoupled 13C NMR with an internal standard (trioxane). Remarkably, the captured-CO2 amounts of ionic lignin polymer are 1.06mmol g-1 (47mg g-1) from concentrated-CO2 source and 0.60mmol g-1 (26mg g-1) from direct-air. The captured-CO2 in ionic lignin polymer is released in controlled manner and utilized in the synthesis of cyclic carbonate, showcasing the productive application of the captured carbon. Moreover, the fully controlled recovering of ionic lignin polymer achieves via repeated CO2 release ↔ CO2 capture.

Quaternized Graphene for High-Performance Moisture Swing Direct Air Capture of CO2.

Nowadays, moisture-swing adsorption technology still relies on quaternary ammonium resins with limited CO2 capacity under ambient air conditions. In this work, a groundbreaking moisture-driven sorbent is developed starting from commercial graphene flakes and using glycidyltrimethylammonium chloride for incorporation of CO2-sensitive quaternary ammonium functional groups. Boasting an outstanding CO2 capture performance under ultra-diluted conditions (namely, 3.24mmolg-1 at CO2 400ppm and 20% RH), the functionalized sorbent (fGO) features clear competitive advantages over current technologies for direct air capture. Notably, fGO demonstrated unprecedented moisture-swing capacity, ease of regenerability, versatility, selectivity, and longevity. These distinctive features position the fGO as an advanced and promising solution, showcasing its potential to outperform existing methods for moisture-swing direct air capture of CO2.

Development and Characterization of Modified Gelatin-Based Cling Films with Antimicrobial and Antioxidant Activities and Their Application in the Preservation of Cherry Tomatoes.

The utilization of functional cling films presents a promising approach to alleviate post-harvest spoilage caused by microbial activity, oxidative metabolism, and moisture loss in agricultural products. To overcome the environmental problems of conventional packaging materials, in this study, we developed functional fruit and vegetable cling films based on glycidyltrimethylammonium chloride and rosemarinic acid cross-linked gelatin (RQ-GEL). The results indicate that the prepared RQ-GEL film possesses excellent UV light barrier properties and mechanical performance. RQ-GEL inhibited S. aureus and E. coli by 93.79% and 92.04%, respectively. DPPH and ABTS free radical scavenging activities were as high as 87.69% and 84.6%. In the cherry tomato preservation experiment, when compared to uncovered samples, the RQ-GEL group had a 29.77% reduction in weight loss and a significant 26.92% reduction in hardness. Meanwhile, the RQ-GEL group delays the decline of fruit total soluble solids and titratable acidity content, and prolongs the preservation period of cherry tomatoes. Hence, RQ-GEL cling film is poised to emerge as a promising packaging material for the post-harvest preservation of agricultural products.

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.

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.

Synthesis of Raspberry-like Nanoparticles via Surface Grafting of Positively Charged Polyelectrolyte Brushes: Colloidal Stability and Surface Properties.

A method to synthesize stable, raspberry-like nanoparticles (NPs), using surface grafting of poly(glycidyl methacrylate) (PGMA) brushes on a polystyrene (PS) core with varying grafting densities, is reported. A two-step functionalization reaction of PGMA epoxide groups comprising an amination step first using ethylene diamine and then followed by a quaternization using glycidyltrimethylammonium chloride generates permanently and positively charged polyelectrolyte brushes, which result in both steric and electrostatic stabilization. The dispersion stability of the brush-bearing NPs is dramatically improved compared to that of the pristine PS core in salt solutions at ambient (25 °C) and elevated temperatures (60 °C). Additionally, the grafted polyelectrolyte chains undergo a reversible swelling in the presence of different ionic strength (IS) salts, which modulate the surface properties, including roughness, stiffness, and adhesion. An atomic force microscope under both dry and wet conditions was used to image conformational changes of the polyelectrolyte chains during the swelling and deswelling transitions as well as to probe the nanomechanical properties by analyzing the corresponding force-sample separation curves. The quaternized polyelectrolyte brushes undergo a conformational transition from a collapsed state to a swelled state in the osmotic brush (OB) regime triggered by the osmotic gradient of mobile ions to the interior of the polymer chain. At IS ∼ 1 M, the brushes contract and the globules reform (salted brush state) as evidenced by an increase in the surface roughness and a reduction in the adhesion of the brushes. Beyond IS ∼ 1 M, quartz crystal microbalance with dissipation monitoring measurements show that salt uptake continues to take place predominantly on the exterior surface of the brush since salt adsorption is not accompanied by a size increase as measured by dynamic light scattering. The study adds new insights into our understanding of the behavior of NPs bearing salt-responsive polyelectrolyte brushes with adaptive swelling thresholds that can ultimately modulate surface properties.

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.

Sunflower-like missing-linker covalent organic framework for efficient extraction of non-steroidal anti-inflammatory drugs.

As excellent crystalline materials, covalent organic frameworks (COFs) are widely used in drug adsorption. In this work, a defective engineering strategy was proposed for designing and preparing the functionalized end-capping monomer and missing-linker COFs. The missing-linker COF 2,4,6-trihydroxybenzene-1,3,5-tricarbaldehyde compound with glycidyltrimethyl ammonium chloride modified benzene-1,4-diamine (TpPa-GTA) was synthesized through Schiff base reaction with wide pore size distribution for adsorption of four nonsteroidal anti-inflammatory drugs (NSAIDs). The adsorption process follows pseudo-second-order kinetics, and the four drugs reached adsorption equilibrium within 10 min. The sunflower-like structure helps to promote intraparticle diffusion during the adsorption process, thereby realizing the rapid adsorption of TpPa-GTA. The equilibrium isotherms fit well with both the Freundlich and Langmuir models, with a maximum adsorption capacity of 83.3-315 mg g-1 calculated from the Langmuir model. Based on the detection results of Zeta potential and XPS, the adsorption mechanism was inferred, and the rapid capture of NSAIDs in the wide pH range of 4.0 to 7.5 was realized under electrostatic interaction, hydrogen bonding, and π-π interaction. The detection of lake and river samples using the missing adapter TpPa-GTA has a recovery rate of 84.2-117%, which provides a new approach to the adsorption of pollutants with COFs.

Modification of chitosan-coated magnetic material with glycidyltrimethylammonium chloride and its application as heterogeneous base catalyst for levulinic acid esterification

A magnetically separable solid Lewis base catalyst composed of natural magnetic material, chitosan, and glycidyltrimethylammonium chloride was developed. The catalyst is effective for esterification of levulinic acid to produce ethyl levulinate.

Cationic lignin as an efficient and sustainable homogenous catalyst for aqueous Knoevenagel condensation reactions.

Knoevenagel condensation is a chemical reaction between aldehydes and active methylene-containing compounds in the presence of heterogeneous, basic homogenous organic or inorganic catalysts and solvent or neat systems. Herein, we introduced a new strategy for this synthesis by using the aqueous solution of cationic kraft lignin (CKL) as a catalyst. The CKL was synthesized through the reaction of kraft lignin (KL) with glycidyltrimethylammonium chloride (GTMAC) in a basic medium. The optimal reaction conditions for the Knoevenagel reaction were 5% catalyst load (weight of catalyst to the weight of benzaldehyde), water as the solvent, and at room temperature, which generated the products with a yield of 97%, illustrating that the CKL was an effective homogenous and green catalyst. The results confirmed that the increase in CKL charge density improved the product yield. The water-insoluble products were easily separated by filtration, and the filtrate containing the catalysts was reused effectively for 5 cycles without a significant decrease in the production yield, which would confirm the advantages of this catalyst for this reaction system. The CKL catalyst exhibited biodegradability comparable to KL. This paper discusses a novel method for Knoevenagel condensation reactions for different aldehydes in a green system utilizing a sustainable, biodegradable catalyst at room temperature and in an aqueous system.

A novel scalable polycationic melamine sponge-based filtration matrix for continuous ultrafast adsorption of anionic pollutants

Effective capturing of anionic pollutants from wastewater under industrial operating conditions, which requires high processing flux and fast adsorption rate remains a challenge. Here, a commercially available melamine sponge (MS) with reticulated 3D macroporous structures was covalently modified with positively charged moieties using a single step functionalization under mild conditions. The developed novel polycationic melamine sponge (MS+) was formed by a nucleophilic addition reaction between glycidyltrimethylammonium chloride (GMTA) and MS, followed by a self-propagation of GMTA. The produced MS+ possessed strong electrostatic interactions with different anions such as Rose Bengal (RB) and phosphates (P) under a wide pH range (3–11). The MS+ exhibited promoted static adsorption efficiencies of 400 mg g−1 (P) and 600 mg g−1 (RB), within 5 min and 60 s, respectively. Furthermore, the MS+ showed high stability and recyclability for up to 15 cycles of uses, and the recycling process was environmentally friendly by using 1 M NaCl as a releasing solution. Benefiting from fast flow through the macroporous MS+ and highly positive charged skeleton, the MS+ was applied for rapid dynamic enrichment process of P from real manure wastewater with an enrichment factor of 4.4. Utilization of the MS+ as the substrate brings additional advantages such as low cost, availability, and flexibility to fit into existing filtration devices. The developed MS+ could be expanded for enrichments of other anionic species from various polluted water sources.

Construction of Janus structures on thin silk fabrics via misting for wet–thermal comfort and antimicrobial activity

Owing to their small fiber diameter (10–15 μm), silk fabrics are always thin (32–90 g m−2). Therefore, construction of the Janus surfaces of silk fabrics that possess excellent multifunctionality remains a formidable challenge. Herein, first, silk fabrics were grafted using glycidyltrimethylammonium chloride to form a superhydrophilic surface (G-side). Then, a unilateral hydrophobic surface (O-side) was readily fabricated by mist coating octadecyltrichlorosilane-functionalized SiO2 nanoparticles (NPs) to produce hierarchical surface textures. To prevent NP penetration from the G-side to the O-side, a “fireproof isolation” method was employed. Consequently, Janus silk fabrics (JanSFs) bearing asymmetric wettability were prepared, and their wetting gradient could be conveniently regulated. With the mist time ranging from 4 to 7 min, the unidirectional transport index and efficiency of the unidirectional water transport increased and decreased by 13.2 and 10.4 times, respectively. Sweat could be effectively drained away from human skin to ensure that the skin was dry and comfortable. Compared with the surface temperature of the raw fabric, the raw fabric of JanSFs increased by 2.7 °C. Furthermore, the breathability of JanSF was negligibly affected, and the outer O-side of the JanSF showed substantial antibacterial activity. This study is important for designing JanSFs that exhibit unidirectional water transport.

Removal of heavy metal ions from acidic wastewater by constructing positively charged hollow fiber nanofiltration separating-layer based on Fe (III)/co deposition-quaternization

A surface positively charged nanofiltration (NF) membrane was successfully constructed to effectively remove heavy metal ions by co-deposition and quaternization strategy. The combination between Fe3+ and H2O2 accelerated the co-deposition of tannic acid (TA) and polyvinyl amine (PVAM) on the membrane surface. The mechanism by which metal ions accelerated co-deposition process to regulate membrane surface structure was elucidated. The convenient quaternary ammonium modification was carried out by reacting glycidyl trimethyl ammonium chloride (GTMAC), which significantly increased the potential and density of the membrane surface. The membrane had a high retention rate for heavy metal ions (1000 ppm (mg· L−1), Cr3+ (94.6 %), Fe3+ (93.7 %), Cu2+ (92.1 %), Ni2+ (90.2 %)), while maintaining an excellent water permeance (27.8 L m−2 h−1 bar−1). The membrane also presented outstanding separation performance for rare earth metal ion. In particular, the retention rate for 500 ppm (mg·L−1) Ce3+ was 95.3 %. The relationship between membrane surface potential, pore size and rejection of heavy metal revealed the removal mechanism. Furthermore, the membrane exhibited excellent acid-base resistance and long-term operation stability. This study supplies an effective surface modification method for preparing hollow fiber NF membranes used for removing heavy metal and recovering rare earth metal from wastewater.

A highly efficient and green adsorbent for anionic dyes synthesized from whole pine needles modified with glycidyltrimethylammonium chloride: synthesis, kinetic, and thermodynamic investigation

A highly efficient and green adsorbent for anionic dyes synthesized from whole pine needles modified with glycidyltrimethylammonium chloride: synthesis, kinetic, and thermodynamic investigation

Synthesis of cellulose graft cyclic anhydride and epoxide alternating copolyesters in a DBU/ DMSO/CO2 solvent system

A series of cellulose grafted alternating cyclic anhydride (CA) and epoxide (EPO) copolyesters (cell-g-P(CA-alt-EPO)) have been prepared in the novel DBU/DMSO/CO2 cellulose solvent system. The DBU acted both as a reagent for cellulose dissolution and as a catalyst for ring-opening copolymerization (ROCOP) of cellulose with EPO and CA. The structural features and thermal performances of cell-g-P(CA-alt-EPO) were characterized via MALDI-TOF, FT-IR NMR, TGA, DSC and XPS. Perfectly alternating sequence distributions and controlled molecular weights of a series of cell-g-P(CA-alt-EPO) were easily achieved by a variation of the CA or EPO. The cell-g-P(CA-alt-EPO) also had satisfactory UV-absorbing properties and cellulose grafted phthalic anhydride and glycidyltrimethylammonium chloride exhibited outstanding antibacterial behavior. Antibacterial activity against Escherichia coli and Staphylococcus aureus were 96.7% and 99.4% respectively. Thus, cell-g-P(CA-alt-EPO) with good solubility, melt processability, UV absorption and antibacterial properties have potential applications in UV-shielding and antibacterial agent fields.

A mussel-inspired coating for cost-effective and environmentally friendly CO2 capture

Nowadays, finding innovative technologies to efficiently adsorb/desorb CO2 over several cycles with low energy consumption is a pressing environmental concern. In this work, a new bioionspired coating based on the copolymerization of benzene-1,2-diol and hexamethylenediamine, with a CO2 uptake of 7.28 mmol/g under humidified conditions with an outstanding chemical stability and regenerability process is reported. Further functionalization with glycidyltrimethylammonium chloride increases the uptake capacity up to 9.96 mmol/g while lowering the desorption temperature down to 50 °C for 20 min. Moreover, the coating shows strong adhesion on cotton and paper, without modifying their intrinsic permeability and mechanical properties, allowing for the recycling of fully available and environmentally friendly biomass. These results demonstrate the competitive advantages of this bioinspired coating compared with current technologies to capture CO2 while accomplishing the resource efficiency of bioeconomy policies.