Design,Synthesis, Antibacterial,and Antitumor Activity of Linear Polyisocyanide Quaternary Ammonium Salts with Different Structures and Chain Lengths

The development of organic polymer materials for disinfection and sterilization is thought of as one of the most promising avenues to solve the growth and spread of harmful microorganisms. Here, a series of linear polyisocyanide quaternary ammonium salts (L-PQASs) with different structures and chain lengths were designed and synthesized by polymerization of phenyl isocyanide monomer containing a 4-chloro-1-butyl side chain followed by quaternary amination salinization. The resultant compounds were characterized by ¹H NMR and FT-IR. The antibacterial activity of L-PQASs with different structures and chain lengths against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) was evaluated by determining the minimum inhibitory concentrations (MICs). The L-POcQAS-M₅₀ has the strongest antimicrobial activity with MICs of 27 μg/mL against E. coli and 32 μg/mL against S. aureus. When the L-PQASs had the same polymerization degree, the order of the antibacterial activity of the L-PQASs was L-POcQAS-M_n > L-PBuQAS-M_n > L-PBnQAS-M_n > L-PDBQAS-M_n (linear, polyisocyanide quaternary ammonium salt, monomer, n = 50,100). However, when L-PQASs had the same side chain, the antibacterial activity reduced with the increase of the molecular weight of the main chain. These results demonstrated that the antibacterial activity of L-PQASs was dependent on the structure of the main chain and the length of the side chain. In addition, we also found that the L-POcQAS-M₅₀ had a significant killing effect on MK-28 gastric cancer cells.     

In-situ construction of Co(OH)2 nanoparticles decorated biochar for highly efficient degradation of tetracycline hydrochloride via peracetic acid activation

Peracetic acid(CH₃C(O)OOH, PAA)-based heterogeneous advanced oxidation process(AOP) has attacked intensive interests due to production of various reactive species. Herein, Co(OH)₂ nanoparticles decorated biochar(Co(OH)2_/BC) was fabricated by a simple and controllable method, which was used to degrade tetracycline hydrochloride(TTCH) in water through PAA activation. The results indicated that 100% TTCH(C0= 10 μmol/L) degradation efficiency was realized within 7 mi...     

Ion Dynamics in a Mixed‐Cation Alkoxy‐Ammonium Ionic Liquid Electrolyte for Sodium Device Applications

The ion dynamics in a novel sodium‐containing room‐temperature ionic liquid (IL) consisting of an ether‐functionalised quaternary ammonium cation and bis(trifluoromethylsulfonyl)amide [NTf₂] anion with various concentrations of Na[NTf₂] have been characterised using differential scanning calorimetry, impedance spectroscopy, diffusometry and NMR relaxation measurements. The IL studied has been specifically designed to dissolve a relatively large concentration of Na[NTf₂] salt (over 2 mol kg^?1) as this has been shown to improve ion transport and conductivity. Consistent with other studies, the measured ionic conductivity and diffusion coefficients show that the overall ionic mobility decreases with decreasing temperature and increasing salt content. NMR relaxation measurements provide evidence for correlated dynamics between the ether‐functionalised ammonium and Na cations, possibly with the latter species acting as cross‐links between multiple ammonium cations. Finally, preliminary cyclic voltammetry experiments show that this IL can undergo stable electrochemical cycling and could therefore be potentially useful as an electrolyte in a Na‐based device.     

Facile preparation of pH-sensitive poly(acrylic acid-co-acrylamide)/SiO2 hybrid hydrogels with high strength by in situ frontal polymerization

A series of poly(acrylic acid-co-acrylamide) (PAA)/SiO₂ hybrid hydrogels were prepared by in situ frontal polymerization. It was found that the increase in the concentration of SiO₂ nanoparticles could lead to the increase in front velocity (V _f) and the highest front temperature (T _max). This may be attributed to the fact that SiO₂ nanoparticles could increase the liquid viscosity of reaction mixture. The obtained PAA/SiO₂ hybrid hydrogels were characterized by SEM and Fourier transform infrared spectroscopy spectrum and swelling measurements. The pH-sensitive swelling behaviors showed that the prepared PAA/SiO₂ hybrid hydrogel had high pH sensitivity in different pH buffer solutions. Mechanical property test indicated that the PAA/SiO₂ hybrid hydrogels exhibited a high compressive strength while remaining a high swelling radio (SR). The maximum of compressive strength and SR of the hybrid hydrogel may reach 42.6 kPa and 17.8, respectively, which was much higher than that of pure PAA hydrogel.     

The System Polyacrylamide—Water

The system polyacrylamide (PAA) — water at 0<n<25 (n=H₂O/(-C(O)NH₂)) was investigated. In air of 100% humidity at 292 K, at equilibrium n≈18. The differential heat of water vapour sorption decreases from 56 kJ mol¹ (initial heat) to the heat of water vaporization (Q _L) at n≈0.5, and then up to n=18 it passes through several maxima and minima in the vicinity of Q _L; at n>18, it is equal to Q _L. The mechanism of the gradual solution of PAA is proposed. As the system sorbs water, it passes through the consecutive stages of formation of the clathrate-like compounds AG·2H₂O and AG·(17?18)H₂O (AG is an amido group of PAA) with subsequent formation of a perfect aqueous solution of compound I.     

Recyclable,non-leaching antimicrobial magnetic nanoparticles

Pathogenic bacterial contaminations in water cause serious or even lethal threats. Strategies that effectively kill bacteria without causing environmental contamination are urgently needed in a wide range of applications. We prepared recyclable antimicrobial magnetic nanoparticles, Fe₃O₄@P(St-co-AcQAC), through surfactant-free seeded emulsion polymerization involving a polymerizable, hydrophobic quaternary ammonium compound (QAC). Fe₃O₄ particles were first synthesized by a solvothermal reaction, followed by functionalization with a methacrylic silane (MPS), and then copolymerized with a QAC-containing acrylic monomer (AcQAC), leading to Fe₃O₄ @P(St-co-AcQAC) nanoparticles. As confirmed by antibacterial assays, these Fe₃O₄@P(St-co-AcQAC) nanoparticles exhibited strong antimicrobial action against both Gram-positive Staphylococcus epidermidis and Gram-negative Escherichia coli, without leaching out any bactericidal agent. An additional benefit of antimicrobial magnetic particles is that they can be easily recycled while maintaining excellent antimicrobial efficacy.     

Liquid—liquid distribution of ion associates of tetraiodopalladate(II) with quaternary ammonium counter ions

The distribution behaviour of ion association of Pdl^2?₄ with ten quaternary ammonium cations between chloroform and an aqueous phase was examined and extraction constants (log K_ex) were determined. Linear relationships between log K_ex and the number of methylene groups in the quaternary ammonium ions were observed. Quantitative extraction of palladium was achieved with Zeph⁺ or TBA⁺; the molar absorptivity was 2.5 × 10⁴ l mol^?1 cm^?1 at 344 nm. The effect of other ions on the spectrophotometric determination of palladium, based on their extraction, is reported.     

Synthesis,characterization, and swelling behaviors of chitosan‐g‐poly(acrylic acid)/poly(vinyl alcohol) semi‐IPN superabsorbent hydrogels

A series of granulated semi‐interpenetrating polymer network (semi‐IPN) superabsorbent hydrogels composed of chitosan‐g‐poly(acrylic acid) (CTS‐g‐PAA) and poly(vinyl alcohol) (PVA) were prepared by solution polymerization using ammonium persulfate (APS) as an initiator and N,N′‐methylenebisacrylamide (MBA) as a crosslinker. The effects of reaction conditions such as the concentration of MBA, the weight ratio of AA to CTS, and the content of PVA on water absorbency were investigated. Infrared (IR) spectra and differential scanning calorimetry (DSC) analyses confirmed that AA had been grafted onto CTS backbone, and PVA semi‐interpenetrating into CTS‐g‐PAA networks. SEM analyses indicated that CTS‐g‐PAA/PVA has improved porous surface and PVA was uniformly dispersed in CTS‐g‐PAA network. The semi‐IPN hydrogel containing 10 wt% PVA shows the highest water absorbency of 353 and 53 g g^?1 in distilled water and 0.9 wt% NaCl solution, respectively. Swelling behaviors revealed that the introduction of PVA could improve the swelling rate and enhance the pH stability of the superabsorbent hydrogel. Copyright © 2009 John Wiley & Sons, Ltd.     

Long-chain ammonium fluoride salts as universal analytical reagents for total anion determination

Lipophilic quaternary ammonium cations are insoluble in water when paired with any anion except fluoride or hydroxide. This phenomenon is the basis for a novel method for total anion determination. Tetra-n-octylammonium fluoride (TOAF) is used for the direct titration of any anion or mixture of anions with the exception of hydroxide. Anions for which no direct analytical method exists, e.g., nitrate or hydrogenfluoride (HF₂^?), are simply assayed by conductimetric titration with TOAF reagent.     

Novel polyamidoamine‐based hydrogel with an innovative molecular architecture as a Co2+‐, Ni2+‐, and Cu2+‐sorbing material: Cyclovoltammetry and extended X‐ray absorption fine structure studies

An amphoteric polyamidoamine (PAA)‐based hydrogel, named INT‐PAA1, with a novel molecular architecture was prepared and studied as a Co²⁺‐, Ni²⁺‐, and Cu²⁺‐sorbing material. This hydrogel was obtained by the synthesis of a PAA in the presence of a second presynthesized PAA carrying many primary amino groups as side substituents, which acted as a macromolecular crosslinking agent. Therefore, it had an intersegmented structure. INT‐PAA1 exhibited a remarkable sorption capacity and sorption rate for Co²⁺, Ni²⁺, and Cu²⁺ that were advantageously in situ monitored by cyclic voltammetry. An extended X‐ray absorption fine structure spectroscopy characterization of the Co²⁺/INT‐PAA1 complex was also performed. The very fast and quantitative metal‐ion uptake, made apparent by an intense coloring of the hydrogel, showed remarkable potential for environmental applications such as heavy‐metal detection, recovery, and elimination. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2316–2327, 2006     

First colorimetric sensor array for the identification of quaternary ammonium salts

A colorimetric sensor array based on supramolecular host-guest complexes has been developed for the identification and quantification of quaternary ammonium salts (QAS). QAS are ubiquitous undesirable compounds for which the identification of the individual compounds is not trivial and needs instrumental techniques. The sensor array developed by us is constituted by host-guest complexes formed by the inclusion of tricyclic basic dyes such as proflavine, acridine orange, thionin, and methylene blue inside the hollow space defined by cucurbit[n]urils with n = 7 and 8. The operation of the sensor array has been demonstrated by differentiating 14 quaternary ammonium salts, some of them differing by a single carbon atom in the alkyl group. The detection limit concentration was 10⁻⁵ M and the system can also be used to quantify the concentration of the quaternary ammonium ion.     

Bi-ionic membrane potential across a liquid anion-exchange membrane containing triphenyltin chloride

Potentiometric selectivities of a liquid anion-exchange membrane containing triphenyltin chloride (TPTCl) to several inorganic anions were evaluated via measurements of the membrane potential of a bi-ionic system, also called bi-ionic membrane potential. Addition of TPTCl to the liquid anion-exchange membrane, based on the quaternary ammonium salt, gave rise to a quite different selectivity pattern from the so-called Hofmeister anion series observed for the liquid anion-exchange membrane. An additivity rule of the bi-ionic membrane potential was observed to hold for the liquid anion-exchange membrane containing TPTCl. Thus, the following multiple chain rule was derived for selectivity coefficients; k_1,n^pot = k_1,2^pot · k_2,3^pot … k_i,(i+1)^pot … k_n−1,n^pot where k_i,i+1^pot is the selectivity coefficient of the membrane for the (i + 1)th ion over the ith ion.     

Functional membranes prepared by layer‐by‐layer assembly and its metal ions adsorption property

PVDF/(PEI‐C/PAA)_n functional membranes were prepared by layer‐by‐layer (LbL) assembly, and their heavy metal ions adsorption capability was investigated. The changes in the chemical compositions of membrane surfaces were determined by X‐ray photoelectron spectroscopy (XPS). XPS results show that the surface of the PVDF membrane can be alternatively functionalized by PEI‐C and PAA. The membrane surface hydrophilicity was evaluated through water contact angle measurement. Contact angle results show that the surface hydrophilicity of the membrane surface depends on the outermost deposited layer. Morphological changes of membrane surfaces were observed by scanning electron microscopy (SEM). The water fluxes for these membranes were elevated after modification. The performances of the PVDF/(PEI‐C/PAA)_n membranes on the adsorption of copper ions (Cu²⁺) from aqueous solutions were investigated by inductively coupled plasma (ICP). The results indicate that the PVDF/(PEI‐C/PAA)_n functional membranes show high copper ions adsorption ability. Copyright © 2010 John Wiley & Sons, Ltd.     

Detection of Quaternary Ammonium Drugs in Equine Urine by Liquid Chromatography-Mass Spectrometry

Quaternary ammonium drugs are anticholinergic agents and some of which have been known to be abused in equine sports. A general screening method for this class of drugs in equine urine by liquid chromatography-mass spectrometry (LC-MS) has not been reported. The paper describes an efficient LC-MS-MS method for the simultaneous detection and confirmation of twenty quaternary ammonium drugs at low ng mL^?1 in equine urine after solid-phase extraction. Quaternary ammonium drugs were extracted from equine urine by solid-phase extraction using ISOLUTE^® CBA SPE Columns and analysed by LC-MS-MS in the positive electrospray ionisation mode. Separation of twenty quaternary ammonium drugs (the quaternary ammonium ions of edrophonium chloride, pyridostigmine bromide, neostigmine bromide, bretylium tosylate, ipratropium bromide, tubocurarine chloride, N-butylscopolammonium bromide, mepenzolate bromide, rocuronium bromide, clidinium bromide, pipenzolate bromide, isopropamide iodide, glycopyrronium bromide, alcuronium chloride, oxyphenonium bromide, propantheline bromide, tridihexethyl chloride, vecuronium bromide, mivacurium chloride and pancuronium bromide) was achieved in a reversed phase column with a mixture of aqueous ammonium formate (pH 3.0, 10 mM) and acetonitrile as the mobile phase. Detection and confirmation of the twenty quaternary ammonium drugs at about 5 ng mL^?1 in equine urine could be achieved within 22 min using product-ion scan MS-MS. The target analytes were detected by examination of extracted-ion chromatograms of their product ions. Drugs spiked in different equine urine (n = 15) were consistently detected. Negative samples (n = 30) of normal post-race equine urine have also been analysed, no matrix interference at the targeted masses and retention times was observed. The method was successfully applied to the analyses of drug-administration samples. Other method validation data including reproducibility and recovery will also be presented. An LC-MS-MS method for the simultaneous detection and confirmation of twenty quaternary ammonium drugs in equine urine was developed. The methodology should be applicable to other biological matrices such as human urine.     

ChemInform Abstract: Polychloride Monoanions from [Cl3]‐ to [Cl9]‐: A Raman Spectroscopic and Quantum Chemical Investigation.

Polychloride monoanions [Cl_n]^‐ (n = 3, 5, 7, 9) stabilized by quaternary ammonium salts are obtained through the addition or condensation of an excess of dry chlorine to [NMe₄]Cl, [NEt₄]Cl, [NPr₄]Cl, or [NBu₄]Cl and characterized by Raman spectroscopy and state‐of‐the‐art quantum chemical calculations up to the CCSD(T) level.     

Quaternary ammonium salt-catalyzed carboxylative cyclization of propargylic amines with CO2

By employing quaternary ammonium salts as catalysts, the carboxylative cyclization of the propargylic amines with CO₂ proceeded to afford the corresponding 2-oxazolidinones. In particular, tetra-n-butylammonium fluoride was the most effective catalyst for the reaction, providing a 2-oxazolidinone derivative in a maximum chemical yield of 99%. From a screening of the structure of a catalyst, it was found that both a quaternary ammonium cation and a basicity of the counter anion were essential to catalyze the carboxylative cyclization of the propargylic amines with CO₂.     

Swelling behaviour of thermo-sensitive hydrogels based on oligo(ethylene glycol) methacrylates

The thermo-sensitive swelling behaviour of hydrogels based on 2-(2-methoxyethoxy)ethyl methacrylate (MEO₂MA) and synthesized by free radical polymerization has been investigated. The homopolymer hydrogel presents a low critical solution temperature (LCST) close to room temperature, which can be modulated by copolymerization with longer oligo(ethylene glycol) side chain methacrylates (OEG_xMA). Then, three series of copolymeric hydrogels synthesized with MEO₂MA and several low ratios of OEG_xMA with M_n = 475 g mol⁻¹ (OEG₈MA), M_n = 1100 g mol⁻¹ (OEG₂₃MA) and M_n = 2080 g mol⁻¹ (OEG₄₅MA) were studied. In addition to conventional tetra(ethylene glycol) dimethacrylate (TEGDMA) crosslinker, the use of biodegradable oligo(caprolactone) dimethacrylate (OCLDMA) was also tested. The hydrophilic/hydrophobic balance, function of the short and the long OEG side chains, establishes a swelling behaviour depending on monomer composition, side chain length and temperature. The swelling at equilibrium increases with increasing the amount of OEG_xMA in the copolymer and, at the same time, the collapsing moves progressively to higher temperature. The temperature dependent volumetric response of some of these hydrogels can be compare with the most extended thermo-sensitive hydrogel, which is based on poly(N-isopropylacrylamide) (P(N-iPAAm)). Therefore, they are potential candidates to replace it in applications where biocompatibility is required.     

Kinetics of Cu<Superscript>2+</Superscript> binding to the poly(acrylic acid) hydrogel

Isothermal kinetics of copper (ion) binding to poly(acrylic acid) (PAA) hydrogel at 20, 25, 35 and 45°C was investigated. Isothermal conversions and kinetic curves of Cu²⁺ binding to the PAA hydrogel were determined. It was found that the well-known kinetic models of Peppas cannot be applied to describing the entire process of Cu²⁺ binding. The new method for the determination of the kinetic model of the Cu²⁺ binding process, as well as the activation energy density distribution functions of PAA hydrogel interaction with Cu²⁺, were established. It was found that Cu²⁺ diffusion to the active centers (with E _a = 9 kJ/mol) has a dominant influence on the kinetics of the process at temperatures T ≥ 30°C, but at T ≥ 30°C and for the degree of bound Cu²⁺ α ≥ 0.2, the interaction of Cu²⁺ from the adsorption center with E _a = 26 kJ/mol is dominant. The text was submitted by the authors in English.     

Sustainable Triazine-Based Dehydro-Condensation Agents for Amide Synthesis

Conventional methods employed today for the synthesis of amides often lack of economic and environmental sustainability. Triazine-derived quaternary ammonium salts, e.g., 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM(Cl)), emerged as promising dehydro-condensation agents for amide synthesis, although suffering of limited stability and high costs. In the present work, a simple protocol for the synthesis of amides mediated by 2-chloro-4,6-dimethoxy-1,3,5-triazine (CDMT) and a tert-amine has been described and data are compared to DMTMM(Cl) and other CDMT-derived quaternary ammonium salts (DMT-Ams(X), X: Cl⁻ or ClO₄⁻). Different tert-amines (Ams) were tested for the synthesis of various DMT-Ams(Cl), but only DMTMM(Cl) could be isolated and employed for dehydro-condensation reactions, while all CDMT/tert-amine systems tested were efficient as dehydro-condensation agents. Interestingly, in best reaction conditions, CDMT and 1,4-dimethylpiperazine gave N-phenethyl benzamide in 93% yield in 15 min, with up to half the amount of tert-amine consumption. The efficiency of CDMT/tert-amine was further compared to more stable triazine quaternary ammonium salts having a perchlorate counter anion (DMT-Ams(ClO₄)). Overall CDMT/tert-amine systems appear to be a viable and more economical alternative to most dehydro-condensation agents employed today.     

Insoluble polystyrene-bound quaternary onium salt catalysts for the synthesis of cyclic carbonates by the reaction of oxiranes with carbon dioxide

The addition reaction of oxiranes ( 26a—e ) with carbon dioxide (CO₂) was performed using insoluble polystyrene beads containing pendant quaternary ammonium or phosphonium salts as catalysts under atmospheric pressure. The reaction of 26a—e with CO₂ proceeded smoothly catalyzed by 1–2 mol % of the polymer-supported quaternary onium salts to give the corresponding cyclic carbonates ( 27a—e ) in high yields at 80–90°C. In this reaction system, the catalytic activity of the polymer-supported quaternary onium salts was strongly affected by the following factors: degree of ring substitution (DRS) of the onium salt residues to the polymer, degree of crosslinking (DC) of the polystyrene beads, chain length of the alkylene spacer between the polymer back-bone and the onium salt, hydrophobicity of the alkyl group on the onium salts, and kind of onium salts. That is, the polymer-supported quaternary phosphonium salts with low DRS and DC and with long alkylene spacer chain were found to have higher catalytic activity than low molecualr weight quaternary onium salts. The above polymer-supported catalysts can easily be separated at the end of a reaction by filtration and can be reused for at least seven runs. It was also found that the rate of reaction was proportional to the products of catalyst concentration and oxirane concentration. © 1993 John Wiley & Sons, Inc.