Antibacterial materials: structure–bioactivity relationship of epoxy–amine resins containing quaternary ammonium compounds covalently attached

Bifunctional aminoalkyldimethylpropylammonium salts (N‐(3‐aminopropyl)‐N,N‐dimethylpentylammonium chloride, N‐(3‐aminopropyl)‐N,N‐dimethyloctylammonium chloride, N‐(3‐aminopropyl)‐N,N‐dimethyldecylammonium chloride, N‐(3‐aminopropyl)‐N,N‐dimethyldodecylammonium chloride) are synthesized and their structure‐dependent antibacterial effect against Gram‐negative Escherichia coli and Gram‐positive Lactococcus lactis is investigated. To this end, resins prepared from bisphenol A diglycidyl ether (2,2‐bis[4‐(glycidyloxy)phenyl]propane) and diethylenetriamine (2,2′‐diaminodiethylamine) as matrix and the bifunctional aminoalkyldimethylpropylammonium salts in a ratio of 6 mol% compared to epoxy components are used. A dependence of antibacterial effect on alkyl chain length of the quaternary ammonium compounds is observed for both species. Furthermore, resins with N‐(3‐aminopropyl)‐N,N‐dimethyldecylammonium chloride in varying concentrations up to 16 mol% for both organisms show a concentration‐dependent antibacterial effect of the quaternary ammonium salt. The antibacterial materials are characterized by differential scanning calorimetry, infrared spectroscopy and rheological studies. © 2013 Society of Chemical Industry     

Synthesis and Characterization of a Novel Series of Cationic Fumaric Polymerizable Emulsifiers

A series of novel cationic fumaric polymerizable emulsifiers (named as F series emulsifiers) were synthesized. The chemical structures of these emulsifiers were confirmed by ¹H NMR and MS and their minimal inhibitory concentrations to Escherichia coli were determined. Antibacterial tests of latex films showed that [2-(N-benzyl-N,N-dimethylamino)ethyl]dodecyl fumaric ammonium bromide, [2-(N-benzyl-N,N-dimethylamino)ethyl]decyl fumaric ammonium chloride and [2-(N-benzyl-N,N-dimethylamino)ethyl]dodecyl fumaric ammonium chloride can possibly be used as a polymerizable bactericides.     

The use of N-bridgehead heterocyclic indolizinium ylide in the synthesis of aza-cyanine dyes

The reaction of 3-methyl-8-oxime-1-phenylpyrazolo [4,5-d]indolizinium (bezoindolizinium) ylide iodide with 2(4)-methyl substituted heterocyclic quaternary salts give 8[2(4)]-aza-monomethine cyanine dyes. Meanwhile, the reaction with carbonyl compounds followed by reaction with 2-methyl quinolinium methiodide salts afforded 5(2)-aza-trimethine cyanine dyes. On the other hand, the reaction of 5-formyl-2-methyl-4-phenylpyrazolo[4,5-d]indolizinium (benzoindolizinium) ylide iodide with hydroxylamine hydrochloride followed by reaction with N-methyl heterocyclic quaternary salts afforded the corresponding 5[4(1)]-aza-dimethine cyanine dyes. These new compounds are characterized with elemental analyses, visible absorption, IR, ¹³C NMR, ¹H NMR and mass spectroscopy. The correlations between the structure and spectral properties of these dyes have been studied.     

Synthesis,Characterization and Surface-Activity of a Polyoxyethylene Ether Trimeric Quaternary Ammonium Surfactant

A trimeric quaternary ammonium salt surfactant containing polyoxyethylene chains was synthesized from fatty alcohol polyoxyethylene ether, pentamethyldiethylenetriamine and thionyl chloride by a two-step process. Its chemical structure was characterized, and the surface activity in aqueous solution was studied at different temperatures. The results showed that when the concentration attains the CMC (1.0 mmol/L), the surface tension is 38.9 mN m⁻¹ and the conductivity is 105.3μS cm⁻¹ at 25 °C. These show that the trimeric quaternary ammonium salt surfactant containing polyoxyethylene chains exhibits high surface activity and effectively reduces the surface tension of water.     

Chemical modification of hydroxyl functions: Introduction of hydrolyzable ester function and bactericidal quaternary ammonium groups

Polymers carrying a hydrolyzable ester function and bactericidal quaternary ammonium salts were successfully synthesized in 2 steps. The first one was the modification of hydroxyl functions of poly(vinyl alcohol) by chloroacetic anhydride. The structure of synthesized polymers was confirmed by infrared (IR), ¹H-, and ¹³C- nuclear magnetic resonance (NMR). The kinetic results were consistent with a 1-order reaction, and the activation energy in the case of total modification was found to be 16.8 kJ mol⁻¹. The second step was the quaternization of the pendant chlorine atom with a long alkyl chain or aromatic tertiary amines. The percentage of grafting was almost total, except with 3-diethylaminophenol, probably due to steric hindrance. The thermal degradation of polymers was studied. Side chains carrying quaternary ammonium salts begin to degrade at 168°C with the emission of chloride and amine compounds. At about 250°C, acetic and chloroacetic acid are evolved due to acetate and chloroacetate side chains. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2657–2666, 1998     

Synthesis and Application of Perfluoroalkyl Quaternary Ammonium Salts in Protein-Based Fire-Fighting Foam Concentrates

Nine perfluoroalkyl quaternary ammonium salts containing a perfluorinated tail were synthesized in order to evaluate their properties as additives in protein-based fire-fighting foam concentrates. They were obtained in high yield starting from (perfluoro-n-octyl)methyl oxirane via a two-step reaction scheme. Their structures were identified by Fourier-transform infrared spectroscopy and elemental analysis. Surface tension, interfacial tension, critical micellar concentration, and spreading coefficient of aqueous solutions of the synthesized compounds were first determined. Synthetic perfluoroalkyl quaternary ammonium salts were then added at reduced concentration (0.5 wt.%) to a commercial protein-based fire-fighting foam concentrate and their effects on foam spreading properties were further investigated via five specific laboratory tests: sealing time test, burn back time test, foam expansion test, drain time test, and foam flowing test. Results showed that the perfluoroalkyl quaternary ammonium salts strongly influence surface and extinguishing properties of protein-based fire-fighting foam concentrates, producing stable foams able to spread spontaneously over hydrocarbons and forming aqueous films with enhanced organic-vapor sealing properties.     

Synthesis and Performance of Allyl Dimethyl Dehydroabietyl Ammonium Chloride

Allyl dimethyl dehydroabietyl ammonium chloride (ADMDHA), as a cationic quaternary ammonium polymerizable antibacterial surfactant, was synthesized from dehydroabietylamine and 3‐chloropropene. The structure of ADMDHA was characterized by FT‐IR, NMR, and elemental analysis. The critical micelle concentration (CMC) of ADMDHA and the surface tension at the CMC (γ_CMC) in aqueous solution were about 2.51 × 10^?4 mol L^?1 and 28.5 mN m^?1 at 25 °C, respectively. The emulsion consisting of benzene and water with ADMDHA as an emulsifier maintained its stability for 2 days. Meanwhile, the antimicrobial activities of ADMDHA against Escherichia aerogenes and Pseudomonas aeruginosa were much stronger than those of ampicillin sodium and bromogeramine against the same bacteria.     

Selection of quaternary ammonium groups for optimizing properties of water‐soluble,photosensitive phenolic resins and study of their postcuring mechanism

This article deals with the selection of quaternary ammonium groups for synthesis of water‐soluble, photosensitive phenolic resins, containing acrylate and different quaternary ammonium salt groups (AQSPRs), via ring‐opening reactions of epoxy phenolic resin (EPR) with acrylic acid and with different tertiary amine‐protonic acid salts. Conversion of epoxy groups, solubility, photosensitive properties, and thermal decomposition of the different AQSPRs were compared. Modification of AQSPR with methanol solution of KOH to form phenolic resin containing both quaternary ammonium hydroxide groups and acrylate groups (AQHPR) was also studied. Characterization by IR spectrum, DSC, and thermal gravimetric analysis was carried out. The results showed that in the synthesis of AQSPRs containing different quaternary ammonium salt groups, the efficiency of ring‐opening reaction of epoxy phenolic resin with tertiary amine salt in terms of conversion of epoxy groups decreases in the following order: for the tertiary amine, N,N‐dimethyl benzylamine (DMBA) > triethylamine (TEA) > trimethylamine (TMA) > N,N‐dimethyl aniline (DMA) > triethanolamine (TENA) > tri(n‐butylamine) (TBA); for the protonic acid, HCl > HBr > HCOOH > HI > NaHSO₃ > Cl₃CCOOH > HClO₄ > HBF₄. All the AQSPRs except that from HClO₄ can be dissolved in water, methanol, DMF, or DMSO. The gel content formed during UV exposure decreases in the following order of acids used in forming quaternary ammonium salt groups: HCl > HCOOH > NaHSO₃ > Cl₃CCOOH; or decreases in the following order of tertiary amines or hydrohalic acids used in forming the quaternary ammonium groups: TMA. > TEA > DBMA; HCl > HBr > HI. During thermal decomposition of EPR with about half epoxy groups of EPR ring‐opened with tertiary amine salt at 160°C for 0.5 h, water‐insoluble product was formed. The insoluble content and the % decrease of epoxy groups or halide ions increase in the following order: TMA < TEA < DMBA; HCl < HBr < HI. The % decrease of epoxy groups for the insoluble residue is nearly equal to the % decrease of halide ions. A crosslinking reaction mechanism occurred in the thermal decomposition was thus proposed. During the modification of AQSPR with KOH, conversion of quaternary ammonium chloride groups can reach above 90%. The decomposition temperature of the quaternary ammonium groups was lowered from 204 to 120°C after modification of AQSPR with KOH. The photosensitive properties of the resin after modification became lower. It is better to react DMBA · HCl with EPR so as to obtain a product with higher conversion of epoxy groups, good water solubility, moderate photosensitivity, lower decomposition temperature, and better postcuring. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2914–2922, 2004     

Synthesis, Characterization and Properties of New Lauryl Amidopropyl Trimethyl Ammoniums

A new lauryl amidopropyl trimethyl ammonium methyl carbonate with the formula CH₃(CH₂)₁₀CONH(CH₂)₃N⁺(CH₃)₃CH₃CO₃ ^? was synthesized via a high pressure process with tertiary amines and dimethyl carbonate, and its chemical structure was confirmed using ¹H-NMR spectra, mass spectral fragmentation, and FTIR spectroscopic analysis. In addition, several quaternary ammonium salts with new counterions X^? (X^?=HCO₃ ^?, HCOO^?, CH₃COO^?, CH₃CH(OH)COO^?) were also synthesized by the ion exchange reaction of methyl carbonate quaternary ammoniums with corresponding acids. The surface activities of these compounds were measured, including surface tension (??), critical micelle concentration and minimum surface area (A _min) at 25?°C. Adsorption and micellization free energies of these quaternary ammonium salts in their solutions showed a good tendency towards adsorption at interfaces. The antimicrobial activities are reported for the first time against representative bacteria and fungi for lauryl amidopropyl trimethyl ammoniums. It was found that the antimicrobial potency was Gram-positive bacteria?>?fungi?>?Gram-negative bacteria.     

Quaternarized cationic poly[(vinyl chloride)-co-(vinyl chloroacetate)] binary copolymer as non-migration antibacterial additive in PVC matrix

Antibacterial polyvinyl chloride (PVC) materials have drawn considerable attention since their wide application in medical devices. The objective of this study is to develop a novel quaternary ammonium cationic vinyl chloride copolymer, which can be potentially used as antibacterial additive in PVC matrix. Initially, the low average-number molecular weight poly[(vinyl chloride)-co-(vinyl chloroacetate)] (PVC-co-PVCA) is synthesized by precipitation copolymerization. Subsequently, quaternary ammonium cationic moieties with different lengths of alkyl chains are introduced into the copolymers via quaternization reaction between alkyl-dimethyl tertiary amines with acyl chloride groups. The successful synthesis of PVC-co-PVCA and quaternarized copolymers are carefully confirmed by Fourier transform infrared spectroscopy, nuclear magnetic resonance (1H NMR), and x-ray photoelectron spectroscopy. The antibacterial behaviors of the quaternarized copolymers and its blends with PVC are investigated. The results reveal that all the PVC blends containing at least 5% by weight of quaternarized copolymer have superior bacteriostasis ratio (>99.6%) against both Escherichia coli (E.coli) and Staphylococcus aureus (S. aureus) due to the incorporation of quaternary ammonium groups. Meanwhile, the cationic copolymer exhibits excellent antifouling and much lower migration rate (<0.4%). These interesting consequences endow the quaternarized copolymers as alternative antibacterial agents possess a great deal of potential for use in PVC materials.     

Poly(ethylene glycol)s catalyzed two-phase dehydrochlorination of poly(vinyl chloride) with potassium hydroxide

Poly(ethylene glycol)s [HO(CH₂CH₂O)_nH, where n > 3] are highly active and selective in catalyzing dehydrochlorination of poly(vinyl chloride) in organic–aqueous hydroxide two-phase systems. Their catalytic activity and stability are much higher than those of widely used quaternary ammonium or phosphonium compounds. Poly(vinyl chloride) can be extensively dehydrochlorinated within half an hour at room temperature. The products are polyacetylene-like and have long polyene sequences according to their UV/visible, FT-Raman, and FT-infrared spectra. They can be doped by iodine to conductive states, with conductivities of 1–4 S cm⁻¹. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2463–2469, 1998     

Synthesis and Characterization of Lauryl Trimethyl Ammonium Surfactants with New Counteranion Types

A new family of lauryl trimethyl ammonium surfactants of the general formula CH₃(CH₂)₁₁ N⁺(CH₃)₃X^? (X = CH₃OCOO, HCOO, CH₃COO, CH₃CHOHCOO) were prepared and characterized both structurally and as aqueous surfactants. Lauryl trimethyl ammonium mono-methyl carbonate was synthesized by using dimethyl carbonate (DMC) as the alkylating agent and lauryl dimethyl amine as the starting material. The latter compound was reacted with formic acid, acetic acid, and lactic acid, respectively, to give the corresponding quaternary ammonium salts with other counteranions. They were structurally characterized by IR, ¹H NMR, MS. Members of this family reduced the surface tension of water to 32–38 mN/m at concentration levels of 10^?2 mol/L.     

Polymerization by phase transfer catalysis

Poly(amide-carbonate)s and poly(amide-thiocarbonate)s derived from the diphenol-amides N-(2,6-dichloro-4-nitrophenyl)-2,2-bis(hydroxyphenyl)-propylamide (I), N-(2,6-dichloro-4-nitrophenyl)-3,3-bis(hydroxyphenyl)-butylamide (II), and N-(2,6-dichloro-4-nitrophenyl)-4,4-bis(hydroxyphenyl)-pentylamide (III), and phosgene or thiophosgene, have been synthesized under phase transfer conditions using several quaternary ammonium salts as phase transfer catalysts. Benzyltriethylammonium chloride (BTEAC) was effective in practically all cases due the hydrophilicity of this catalysts. Received: 21 February 1997/Revised: 28 April 1997/Accepted: 30 April 1997     

木质素阳离子乳化剂的制备及其表面活性

先用环氧氯丙烷和三乙胺反应制备环氧丙基三乙基氯化铵中间体,再与木质素反应制得木质素季铵盐。中间体制备条件是温度45～50℃,时间3h,n(三乙胺)/n(环氧氯丙烷)=1～1 1。木质素季铵盐制备条件为温度50～55℃,时间2h,n(木质素)/n(中间体)=0 6～0 8,pH>10 5。产物的表面活性测定表明,不同接枝率的木质素季铵盐降低水溶液表面张力的能力相差不大,最低表面张力约为40mN/m。     

Biologically active polymers. IV. Synthesis and antimicrobial activity of tartaric acid polyamides

New bactericidal polyamides with quaternary ammonium or phosphonium salts were prepared, and their antimicrobial activities were explored. The polyamides were synthesized by the polycondensation of diethyl‐l‐tartrate or chloromethylated diethyl‐l‐tartrate with ethylenediamine in dry absolute ethanol. The polyamides were modified to yield polymers with either quaternary ammonium or phosphonium salts. The polymers were characterized with elemental microanalysis and ¹H‐NMR and IR spectra. The antimicrobial activity of the polymers bearing onium salts was studied against Gram‐negative bacteria (Escherichia coli, Pseudomones aeruginosa, Shigella sp., and Salmonella typhae), Gram‐positive bacteria (Bacillus subtilis and Bacillus cereus), and a fungus (Trichophytum rubrum) by the cut‐plug and viable‐cell‐count methods. Although all the polymers showed high antibacterial activity, some had no antifungal activity. The tributyl phosphonium salt of the polyamide was more effective against both Gram‐negative and Gram‐positive bacteria than the triethyl ammonium and triphenyl phosphonium salts of the polyamide. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4780–4790, 2006     

Synthesis of poly[(2‐oxo‐1,3‐dioxolan‐4‐yl)methyl vinyl ether‐co‐N‐phenylmaleimide] and its miscibility in blends with styrene‐acrylonitrile or poly(vinyl chloride)

The aim of the study was to investigate the synthesis of a copolymer bearing cyclic carbonate and its miscibility with styrene/acrylonitrile copolymer (SAN) or poly(vinyl chloride) (PVC). (2‐Oxo‐1,3‐dioxolan‐4‐yl)methyl vinyl ether (OVE) as a monomer was synthesized from glycidyl vinyl ether and CO₂ using quaternary ammonium chloride salts as catalysts. The highest reaction rate was observed when tetraoctylammonium chloride (TOAC) was used as a catalyst. Even at the atmospheric pressure of CO₂, the yield of OVE using TOAC was above 80% after 6 h of reaction at 80°C. The copolymer of OVE and N‐phenylmaleimide (NPM) was prepared by radical copolymerization and was characterized by FTIR and ¹H‐NMR spectroscopies and differential scanning calorimetry (DSC). The monomer reactivity ratios were given as r₁ (OVE) = 0.53–0.57 and r₂ (NPM) = 2.23–2.24 in the copolymerization of OVE and NPM. The films of poly(OVE‐co‐NPM)/SAN and poly(OVE‐co‐NPM)/PVC blends were cast from N‐dimethylformamide. An optical clarity test and DSC analysis showed that poly(OVE‐co‐NPM)/SAN and poly(OVE‐co‐NPM)/PVC blends were both miscible over the whole composition range. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1809–1815, 2000     

Synthesis of water-soluble cellulose esters applying carboxylic acid imidazolides

Water-soluble, non-ionic cellulose esters with a degree of substitution in the range from 0.11 to 3.0 were synthesized homogeneously using ionic liquids (1-butyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium chloride, and 1-allyl-3-methylimidazolium chloride) as reaction medium. Highly substituted 3,6,9-trioxadecanoic acid esters and 3,6-dioxaheptanoic acid esters of cellulose were obtained via the activation of the carboxylic acids with N,N’-carbonyldiimidazole. The products were characterized by the means of FTIR-, ¹H- and ¹³C NMR spectroscopy.     

Synthesis and Application of a Hyperbranched Polyester Quaternary Ammonium Surfactant

In the presence of the alkaline catalyst sodium hydroxide, the intermediate of hyperbranched polyester (H20Cl) was prepared by the modification of the hyperbranched polyester Boltorn H20 with epichlorohydrin. Then a new kind of quaternary ammonium functionalized hyperbranched polyester (H20C16 N) was synthesized by the reaction of H20Cl and hexadecyldimethylamine. The characteristics of H20C16 N were determined by FT‐IR, ¹H NMR and TGA. The molecular and molecular weight distribution of H20C16 N were determined by Gel Permeation Chromatography (GPC) and the surface activities of H20C16 N including surface tension (γ) and the critical micelle concentration (CMC) were measured at 25 °C. The H20C16 N reduced the surface tension of water to 30.81 mN/m at concentration levels of 7.94 × 10^?5 mol L^?1 and micellization free energies of the quaternary ammonium salt in its solution showed a good tendency towards adsorption at interfaces. The H20C16 N was applied to the silk fabric. An antimicrobial test of the treated fabrics against Escherichia coli and Staphylococcus aureus was carried out. SEM and XPS analysis were performed to study the dispersion of H20C16 N onto the fabric. All results exhibited excellent antibacterial properties of the hyperbranched polyester quaternary ammonium salt.     

季铵盐-季戊四醇低共熔混合物中合成磷酸铝分子筛

在4种季铵盐和季戊四醇的低共融混合物中合成了磷酸铝分子筛,并通过X射线衍射、扫描电子显微镜、热重分析以及核磁共振技术进行表征。结果表明,在氯化胆碱和四乙基氯化铵的低共熔混合物中分别合成了AlPO4-16和AlPO4-5分子筛,而在四丙基溴化铵和四丁基溴化铵低共熔混合物中仅得到方石英致密相。表明在实验条件下,季铵盐阳离子的电荷密度影响结构导向能力,电荷密度越小,结构导向能力越弱。     

Novel biocidal polymers based on branched and linear poly(hydroxystyrene)

New biocidal polymers based on branched as well as linear poly(p-hydroxystyrene) were synthesized. Biocidal polymers were synthesized in two steps by creation of active centers via chloroacetylation of linear and branched poly(p-hydroxystyrene) using chloroacetyl chloride. The second step involves the immobilization of onium salts onto the chloroacetylated polymers. All the prepared polymers were characterized using elemental microanalysis, FT-IR, ¹H NMR spectra, and TGA. Antimicrobial activity of the prepared polymers was tested against various pathogenic microorganisms. The antimicrobial activity was found to be affected by the active group and the tested microorganism. The phosphonium salts showed higher activity than ammonium salts.