Quaternization Reaction Research Articles

Synthesis and physiochemical performance evaluation of novel sulphobetaine zwitterionic surfactants from lignin for enhanced oil recovery

Lignin sulphobetaine zwitterionic surfactants (LSBA) were successfully synthesized by a cost-effective three-step route containing sulfonation, quaternization and alkylation reaction from renewable alkali lignin. The synthesized surfactants were characterized by FT-IR, UV and 1H NMR analysis. The physicochemical properties of synthesized surfactants had been tested to investigate the effectiveness of LSBA surfactants for enhanced oil recovery (EOR). The hydrophile lipophile balance (HLB) values of LSBA-1, LSBA-2 and LSBA-3 were 14, 11 and 10, respectively. LSBA surfactants exhibited high surface activity with low surface tension and the critical micelle concentration (cmc) of LSBA-1, LSBA-2 and LSBA-3 were 4.36×10−4mg/L, 4.45×10−4mg/L and 1.04×10−3mg/L, respectively. The dynamic interfacial tension (IFT) between the crude oil from Huabei and Xinjiang oilfields (China) and the LSBA solution was measured. Compared with Huabei crude oil, LSBA surfactants showed better interfacial activity on Xinjiang crude oil. LSBA surfactants reduced the IFT between Xinjiang crude oil and brine down to ultra-low (<10−3mN/m) under weak alkaline conditions.

Facile Cellulose Dissolution and Characterization in the Newly Synthesized 1,3-Diallyl-2-ethylimidazolium Acetate Ionic Liquid.

A facile cellulose solvent 1,3-diallyl-2-ethylimidazolium acetate ([AAeim][OAc]) with high electrical conductivity has been designed and synthesized for the first time, via a quaternization reaction and ion exchange method. The dissolution characteristics of cellulose in this solvent were studied in detail. Meanwhile, the co-solvent system was designed by adding an aprotic polar solvent dimethyl sulfoxide (DMSO) in [AAeim][OAc]. The effects of temperature and the mass ratio of DMSO to [AAeim][OAc] on the solubility of cellulose were studied. Furthermore, the effects of regeneration on the molecular structure and thermal stability of cellulose were determined by Fourier transform infrared spectroscopy (FT-IR), thermal gravity analysis (TGA) and X-ray diffraction (XRD). The findings revealed that the synthesized ionic liquid (IL) has a relatively low viscosity, high conductivity and a good dissolving capacity for bamboo dissolving pulp cellulose (Degree of Polymerization: DP = 650). The macromolecular chain of the cellulose is less damaged during the dissolution and regeneration process. Due to the increased number of “free” anions [OAc]− and cations [AAeim]+, the addition of DMSO can significantly increase the solubility of the cellulose up to 12 wt % at the mass ratio of 3:1, indicating that the synthesized IL has a potential application in the electrospinning field.

Synthesis and corrosion inhibition effects of quinazolin-(3H)-4-one derivatives containing long-chain pyridinium salts on carbon steel in 1.5 M HCl

Quinazolin-4(3H)-one derivatives containing long-chain pyridinium salts were synthesized by a quaternization reaction of pyridine. The confirmation of the synthesized compounds structure was performed by FT-IR, 1H NMR and 13C NMR spectroscopy. Corrosion inhibition tests were performed at room temperature for 24 h on carbon steel coupons in 1.5 M HCl using the weight loss measurements. After the corrosion tests of the compounds it has shown that almost all of the prepared pyridinium salts showed efficient corrosion inhibition at higher inhibitor concentrations (100–250 ppm). Nevertheless, the quinazolin-(3H)-4-one derivative with the longest alkyl chain showed fairly good inhibition in acidic media. To support and establish the corrosion inhibition test results several surface imaging and characterization studies (contact angle, optical profilometer and SEM) were also performed.

Synthesis and characterization of novel ferrocenyl chalcone ammonium and pyridinium salt derivatives

A novel series of ferrocenyl chalcone ammonium and pyridinium salt derivatives were synthesized in order to improve their solubility in aqueous media. Substituted ferrocenyl chalcones with amines and pyridines were synthesized using the base-catalyzed Claisen-Schmidt reaction, and their corresponding salts were prepared by a nucleophilic quaternization reaction at the nitrogen atom. Most of the synthesized ferrocenyl chalcone salts were soluble in water at room temperature. They were fully characterized by IR, NMR spectroscopy and HRMS spectrometry, and their electrochemistry was studied. The salt derivatives presented chemical reversibility, electrochemical quasi reversibility, and the slope of a plot of LogIpc (or Ipa) versus Log v were almost 0.5 suggesting that their redox process was controlled by diffusion.

The water soluble axially disubstituted silicon phthalocyanines: photophysicochemical properties and in vitro studies.

Two novel silicon(IV) phthalocyanines bearing 1,3-bis[3(dimethylamino)phenoxy]propan-2-ol or 1,3-bis[3(diethylamino)phenoxy]propan-2-ol groups at their axial positions were synthesized. These phthalocyanines were converted into their water soluble derivatives by the quaternization reaction with methyl iodide. The quaternized phthalocyanines show excellent solubility aqueous solutions without any aggregation which makes them potential photosensitizers for use in photodynamic therapy (PDT). For this reason, the photophysical and photochemical properties such as fluorescence quantum yields, lifetimes, singlet oxygen generation and photodegradation of both non-ionic (3 and 5) and quaternized cationic silicon(IV) phthalocyanines were investigated. Furthermore, the cytotoxicity of PDT was determined by colorimetric proliferation assay against to hepatocellular carcinoma (HuH-7) cancer cells. In this study, the cells were incubated with a novel water soluble silicon(IV) phthalocyanine derivatives and thereafter the cells were illuminated using broad-band incoherent light source.

Functionalized Ionic Microgel Sensor Array for Colorimetric Detection and Discrimination of Metal Ions.

A functional ionic microgel sensor array was developed by using 1-(2-pyridinylazo)-2-naphthaleno (PAN)- and bromothymol blue (BTB)-functionalized ionic microgels, which were designed and synthesized by quaternization reaction and anion-exchange reaction, respectively. The PAN microgels (PAN-MG) and BTB microgels (BTB-MG) were spherical in shape with a narrow size distribution and exhibited characteristic colors in aqueous solution in the presence of various trace-metal ions, which could be visually distinguished by the naked eye. Such microgels could be used for the colorimetric detection of various metal ions in aqueous solution at submicromolar levels, which were lower than the U.S. Environmental Protection Agency standard for the safety limit of metal ions in drinking water. A total of 10 species of metal ions in aqueous solution, Ba2+, Cr3+, Mn2+, Pb2+, Fe3+, Co2+, Zn2+, Ni2+, Cu2+, and Al3+, were successfully discriminated by the as-constructed microgel sensor array combined with discriminant analysis, agglomerative hierarchical clustering, and leave-one-out cross-validation analysis.

Synthesis and properties of poly(arylene ether sulfone) anion exchange membranes with pendant benzyl-quaternary ammonium groups

A series of side-chain type poly(arylene ether sulfone)s (sPAE) bearing pendant 3,5-dimethylphenyl groups are prepared via high temperature polycondensation reaction of 4,4’-biphenol, 4,4'-difluorodiphenyl sulfone, and new difluoro aromatic ketone monomer, (2,6-difluorophenyl) [3-[(3,5-dimethylphenyl)methyl]-5-methylphenyl] methanone. The sPAE-based anion exchange membranes (sQPAE(x/y)) containing pendant benzyl-quaternary ammonium groups are obtained by the corresponding bromomethylation of sPAE and subsequent quaternization. The obtained side-chain type membranes sQPAE(x/y) display anisotropic membrane swelling, high alkaline stability and good hydroxide conductivity in the range of 42.7–61.5 mS cm−1 at 80 °C, taking their low IECs of 0.97–1.29 mequiv g−1 into consideration. Their high hydroxide conductivity is attributed to the greater length and dense distribution of the pendant benzyl-quaternary ammonium groups. Besides, the crosslinked membrane sCQPAE(1/4) is prepared via quaternization reaction between brominated sPAE and crosslinker. Compared to the uncrosslinked membrane, sCQPAE(1/4) with same IEC shows lower membrane swelling, better oxidative stability, higher conductivity and chemical stability at 80 °C.

Cationic amphiphilic copolymers: synthesis, characterization, self‐assembly and drug‐loading capacity

AbstractAmphiphilic copolymers with cationic hydrophilic moieties and different ratios of hydrophobic portion to hydrophilic portion were designed and synthesized via the combination of hydrosilylation reactions and quaternization reactions. The structures were characterized through Fourier transform infrared spectroscopy, 1H NMR, 13C NMR and gel permeation chromatography. The measurements of critical micelle concentrations, electrical conductivities and zeta potentials indicated that the copolymers could self‐assemble into nanoparticles with charges around the surface in aqueous solution. The sizes of the micelles were between 67 nm and 104 nm detected by dynamic light scattering. The self‐assembled micelles were used as drug carriers to encapsulate a model drug (tocopherol), and their drug‐loading content (DLC) and efficiency (DLE) were determined by UV−visible spectra, resulting in considerable drug‐loading capacity to a tocopherol maximum up to 17.2% (DLC) and 80.3% (DLE) with a size of 90 nm. The blank micelles and drug‐loaded micelles displayed a spherical shape detected by transmission electron microscopy, which demonstrated not only the self‐assembly behaviors but also the drug‐loading performances of the cationic amphiphilic copolymers. All the results demonstrated that the cationic amphiphilic copolymers could be used as potential electric‐responsive drug carriers. © 2017 Society of Chemical Industry

Pyrrolidinium-functionalized poly(arylene ether sulfone)s for anion exchange membranes: Using densely concentrated ionic groups and block design to improve membrane performance

To design and construct high ionic conductive anion exchange membranes (AEMs), tetra-pyrrolidinium-based block poly(arylene ether sulfone)s were synthesized. Pyrrolidinium groups were densely and controllably introduced into the polymer scaffold using a novel tetra-functionalized monomer, 4, 4′-oxybis (2,6-bis(pyrrolidinyl-1-methyl) phenol) (OBBPYP), which was synthesized via the Mannich reaction. To obtain chemically stable pyrrolidinium cations, the alkaline stabilities of pyrrolidinium-based cationic model compounds with various N-substituted alkyl chains (methyl, ethyl, butyl) were studied using 1H nuclear magnetic resonance (1H NMR) spectroscopy, in which methyl as the N-substituent group exhibited the highest alkaline stability. Based on the results above, a targeted, well-controlled, multiblock structure AEM (QQBPES-2.4OH) with densely concentrated pyrrolidinium cations was obtained via an iodomethane quaternization reaction. The densely concentrated ionic groups provide ionic nanochannels for hydroxide conduction, and the hydrophobic polymer backbone is responsible for the critical membrane mechanical support. As confirmed by transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS), the QQBPES-2.4OH membrane exhibited a more obvious hydrophilic-hydrophobic microphase structure, compared to the random di-pyrrolidinium cation-based AEM (DQRPES-2.4OH) and tetra-pyrrolidinium cation-based AEM (QQRPES-2.4OH). Moreover, the QQBPES-2.4OH membrane exhibited considerably higher hydroxide conductivity, up to 68.0mScm−1 at 80°C, better flexibility and lower water swelling. The results of this work suggest a novel and scalable approach to the functionalization of polymers for AEMs.

Chemoenzymatic Synthesis of Cholesterol-g-Poly(amine-co-ester) Amphiphilic Copolymer as a Carrier for miR-23b Delivery.

The lipase-catalyzed polymerization of N-methyldiethanolamine, diethyl sebacate and ω-pentadecanolide was performed to construct a cationic poly(amine-co-ester), and a hydrophobic N-(2-bromoethyl)carbamoyl cholesterol was then grafted onto its main chain through a quaternization reaction to prepare the amphiphilic copolymer Chol-g-PMSC-PPDL. The copolymer efficiently bound and condensed miR-23b to form stable nanocomplexes, which showed favorable cellular uptake and miR-23b transfection efficacy due to the introduction of the hydrophobic segment. After miR-23b delivery, an obvious inhibition of cell proliferation could be induced, which was attributed to the induction of cell apoptosis and cell cycle arrest. Moreover, the carrier-mediated miR-23b delivery could inhibit the migration and invasion of tumor cells. Overall, the work provides a novel chemoenzymatic strategy for constructing biodegradable and biocompatible poly(amine-co-ester) derivatives, which are promising carriers for oligonucleotide delivery to achieve tumor gene therapy.

Intramolecular Quaternization as Folding Strategy for the Synthesis of Catalytically Active Imidazolium-Based Single Chain Nanoparticles.

A novel synthetic strategy to single chain nanoparticles (SCNP) based on a previously unexplored intramolecular reaction as a means to autonomously fold a parent copolymer precursor is reported. The latter is a statistical styrenic-type copolymer synthesized by RAFT polymerization and is composed of four different comonomer units, including styrene, grafted poly(ethylene oxide) chains, and antagonist benzimidazol- and chlorobenzyl-based units. The two latter functions are reacted together by a quaternization reaction to spark the folding process, creating imidazolium-based cross-link points. Formation of SCNP with a hydrodynamic diameter <10 nm is established by a combination of different characterization techniques. A subsequent metathesis step for exchanging chloride anions by acetate ones of imidazolium moieties enables a use of SCNP for the organocatalyzed benzoin condensation, thanks to the ability of imidazolium acetate to generate SCNP-supported N-heterocyclic carbenes as organocatalysts.

Synthesis of three gemini betaine surfactants and their surface active properties

Abstract Three Gemini betaine surfactants bis [N-methylene-N-dimethyl (1-alkyl-1-sodium formate) methine] ammonium bromides (n = 10, 12, 14) were synthesized by substitution reaction, quaternization and neutralization reaction with tetramethylethylenediamine, bromine (Br2), sodium hydroxide (NaOH) and long chain alkyl acid as main raw materials. The chemical structures of the prepared compounds were confirmed by FTIR, 1H NMR, MS spectroscopy and element analysis. With the increasing length of the carbon chain, the values of their CMC (critical micellar concentration) initially decreased. These compounds were superior in surface active properties to single chain betaine surfactant such as decyl dimethyl betaine surfactant. The efficiency of adsorption at the water/air interface (pC20) of these surfactants was very high. The shorter the hydrocarbon chain length of Gemini betaine surfactants, the faster the rate of reduction of surface tension, and smaller the aggregation number of Gemini betaine surfactants. Micelle diameter and maximum wetting angle of pure water drop/air increased, but maximum wetting angle of water phase/n-decane decreased with the increase of the hydrophobic chain length. Their foaming properties toward a felt chip and lime-soap dispersing ability were investigated.

Partially fluorinated and ammonium-functionalized terpolymers: Effect of aliphatic groups on the properties of anion conductive membranes

Synthesis and properties of a series of ammonium-containing terpolymers (QPAF-3) as anion conductive membranes are reported. The QPAF-3s composed of perfluoroalkylene, alkylene, and ammonium-functionalized phenylene groups without heteroatom linkages in the main chain were synthesized via nickel-mediated polycondensation reaction, followed by chloromethylation, quaternization, and ion exchange reactions. Self-standing, bendable membranes were obtained by solution casting. The QPAF-3 membrane with optimized terpolymer composition and ion exchange capacity (1.46 meq g−1) showed high hydroxide ion conductivity (123 mS cm−1 in water at 80 °C). The alkaline stability test in 1 M KOH for 1000 h at 80 °C and the post-test analysis with IR spectra and tensile strength suggested that ammonium groups were likely to be decomposed while the polymer main chain was chemically more robust. The presence of the alkylene groups in the terpolymers lowered solubility, glass transition temperature, and elongation property of the resulting membranes. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1442–1450

Preparation and Properties of Novel Asymmetric Gemini Alkyl Polyglycosides

AbstractIn order to obtain higher surface activity and lower foaming ability, novel asymmetric Gemini alkyl polyglycosides were synthetized based on tertiary dodecyl dimethyl amine and epoxy chloropropane by adopting chlorination, substitution, and quaternization reactions. The structure of synthesis product was characterized by using Fourier transform infrared spectroscopy, 1H nuclear magnetic resonance spectroscopy and elemental analysis. It was confirmed that the synthesis product was an asymmetric glycoside quaternary ammonium salt with double ionic head groups. The critical micelle concentration of the resulting product was 0.025 g/mL at 20°C and its surface tension was low to 22.8 mN/m. The emulsifying ability and wettability of the product were the same as or even better than those of the commonly used surfactants. Moreover, the product revealed low foaming ability.

Polymerised ionic liquid crystals bearing imidazolium and bipyridinium groups

ABSTRACTNovel kinds of polymerised ionic liquid crystals (PILCs) bearing imidazolium and bipyridinium groups were synthesised and characterised in this work. Some bromo-polyesters were synthesised in an esterification chain reaction using 2,3-dibromosuccinyl dichloride, isophthaloyl chloride and 4,4′-biphenol. The polyester imidazolium bromides (PIBs) and polyester dipyridinium bromides (PDBs) were obtained by a quaternisation reaction between the bromo-polyesters, N-methylimidazole and 4-4′-bipyridine, respectively. The polyester imidazolium tetrafluoroborates (PITs) and polyester dipyridinium tetrafluoroborates (PDTs) were synthesised using the corresponding PIBs and PDBs in an anion-exchange reaction. The chemical structures, liquid crystalline properties and molecular weights of these polymers were characterised by multiple experimental techniques. All the PILCs including PIBs, PDBs, PITs and PDTs display smectic A phase on heating and cooling cycles. The liquid-crystalline properties of bromo-polyesters are influenced by the length of flexible spacer and composition of polyester backbones, while those of PILCs are determined by the ionic groups as additional important influent factors. In comparison with those of the mother bromo-polyesters, the d-spacing of PILCs reduced slightly due to Im+–Br−, Dp+–Br−, Im+–BF4− and Dp+–BF4− ion pairs in the polymer systems. Monocationic imidazolium salts display weaker interionic and intermolecular interaction, higher mobility and lower viscosity than dicationic dipyridinium salts.

Original method for synthesis of chitosan-based antimicrobial agent by quaternary ammonium grafting

Functionalized high molar mass chitosan derivatives with increased antibacterial properties were prepared by the reaction of chitosan with different quaternary ammonium salts. Benzalkonium bromide, pyridinium bromide and triethyl ammonium bromide were synthesized by a quaternization reaction between 1,4-dibromobutane and the respective tertiary amines (N, N-dimethylbenzylamine, triethylamine and pyridine) to obtain three ammonium salts with a bromide end-group capable of reacting with a functional group from the chitosan backbone. The ammonium salts were chemically grafted along the chitosan macromolecular chains. Four different chitosan derivatives were obtained and their chemical structures analyzed and confirmed by 1H NMR and FT-IR. The corresponding thermal stability was analyzed by TGA. Antibacterial activity has been assessed by determining their minimal inhibitory concentration upon Escherichia coli and Staphylococcus aureus. Furthermore, the antibiogram method was used to complement the antibacterial analysis. The bacteria inhibitory property of the chitosan derivatives exhibited a remarkable improvement compared to unmodified chitosan.

Synthesis and Characterization of Stable Anion Exchange Membranes: The Addition of Electron-withdrawing Group

Anion exchange membranes (AEM) based on poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) were used as polymer electrolyte membrane for fuel cell applications. The membranes were prepared via bromination, quaternization and nitration reactions and their fuel cell-related properties (water uptake, ion exchange capacity, ionic conductivity) were determined. Also, the structures and thermal properties were studied with Fourier transform infrared spectroscopy (FTIR), Size exclusion chromatography (SEC) and Differential scanning calorimetry (DSC). Nitration of quaternized PPO (Q-PPO) leaded to a decrease in water uptake and ion exchange capacity of the AEM. However, Q-PPO membrane treated with nitration reaction (NO 2 -Q-PPO) exhibited a significant alkaline stability compared to quaternized PPO (Q-PPO). The results indicated that the addition of electron-withdrawing group, such as nitro, into the structure in order to improve in alkaline stability is a promising new route for preparation alkaline stable AEM membranes.

Electrochemical Reaction of Bis(acetylacetonato)Palladium in an Amide-Type Ionic Liquid

Palladium is well known as a useful metal for such as catalytic reaction, hydrogen absorption and improvement of corrosion resistance. Although the electrochemical reaction and deposition of palladium has been researched in some ionic liquids so far, the palladium sources have been limited to halogeno complexes such as [PdBr4]2− or [PdCl4]2−.1,2 We have already reported electrodeposition of Pd from 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (BMPTFSA) containing bis(acetylacetonato)palladium (Pd(acac)2).3 In the present study, the electrochemical reaction of Pd(acac)2in BMPTFSA was investigated using a rotating ring-disk electrode. BMPTFSA was prepared by metathesis reaction of LiTFSA and BMPBr, which was synthesized by quaternization reaction of 1-methylpyrrolidinium with n-butyl bromide in acetonitrile, followed by recrystallization with ethyl acetate. Pd(acac)2 was used as received. Electrochemical measurements were conducted in a glovebox of dry Ar atmosphere. A ring-disk electrode (Pt ring: 1.2 cm2; Pt disk: 0.79 cm2) was used as a working electrode. A Pt wire was used for a counter electrode. A silver wire immersed in BMPTFSA containing 0.1 M AgCF3SO3was used as a reference electrode. The counter electrode was separately set from the working and reference electrode by a glass filter. The UV-vis spectrum of BMPTFSA containing 0.25 mM Pd(acac)2 was well accorded with that of ethanol solution, suggesting that Pd(acac)2 exists as a tetra-coordinated Pd complex coordinated by the oxygen atoms of acetylacetonate in BMPTFSA. The deposition of metallic palladium was confirmed on the electrode after the potentiostatic cathodic redction at −1.9 V. An anodic current was observed at the ring electrode kept at −1.25 V when the cathodic current corresponding to reduction of Pd(acac)2 was observed on the disk electrode at the potentials more positive than –1.9 V. It has been reported that some intermediate species were detected by polarogram in N, N-dimethylformamide solution containing Pd(acac)2.4 The obtained result indicated that the intermediate species, [Pd(acac)2]−, also formed by the reduction of Pd(acac)2 in this study. Thus, it is considered that the metallic palladium may be formed by the disproportionation reaction of [Pd(acac)2]−. Acknowledgments Part of this study was financially supported by MEXT-Supported Program for the Strategic Research Foundation at Private Universities, 2012–2016.

Surface-Anchored Poly(4-vinylpyridine)–Single-Walled Carbon Nanotube–Metal Composites for Gas Detection

A platform for chemiresistive gas detectors based upon single-walled carbon nanotube (SWCNT) dispersions stabilized by poly(4-vinylpyridine) (P4VP) covalently immobilized onto a glass substrate was developed. To fabricate these devices, a glass substrate with gold electrodes is treated with 3-bromopropyltrichlorosilane. The resulting alkyl bromide coating presents groups that can react with the P4VP to covalently bond (anchor) the polymer–SWCNT composite to the substrate. Residual pyridyl groups in P4VP not consumed in this quaternization reaction are available to coordinate metal nanoparticles or ions chosen to confer selectivity and sensitivity to target gas analytes. Generation of P4VP coordinated to silver nanoparticles produces an enhanced response to ammonia gas. The incorporation of soft Lewis acidic Pd2+ cations by binding PdCl2 to P4VP yields a selective and highly sensitive device that changes resistance upon exposure to vapors of thioethers. The latter materials have utility for odorized fuel l...

Novel conjugated polyelectrolytes based on polythiophene bearing phosphonium side groups

The synthesis and photophysical properties of poly{3-[6-(triethylphosphonium)hexyl]-thiophene-2,5-diyl bromide} and poly{3-[6-(triphenylphosphonium)hexyl]-thiophene-2,5-diyl bromide} are reported in the present contribution. Three various polymer precursors (poly[3-(6-bromohexyl)thiophene-2,5-diyl]s) with molecular weights 7.2, 11.8 and 13.2kgmol−1 respectively and head to tail regioregularity from 62% to 94% were prepared and consecutively transformed into the corresponding polyelectrolytes by a simple quaternization reaction with appropriate phosphines. Synthesized polyelectrolytes exhibited solvatochromism. Detailed aggregation experiments via changing water/DMSO ratio have been performed. Photoluminiscence spectra of the polyelectrolyte solutions indicate that the emission maxima are red-shifted gradually with the increasing solvent polarity. Fluorescence quenching has been studied by interaction with model quenchers: K4[Fe(CN)6] and K3[Fe(CN)6] in water using Stern-Volmer methodology.