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     

一种季铵盐阳离子表面活性剂的合成与性质

以氯丙烯与N,N-二甲基十二烷基胺(DTA)为原料合成了季铵盐阳离子表面活性剂十二烷基二甲基烯丙基氯化铵(DADAC);研究了原料配比、反应温度、反应时间和溶剂等因素对生成物DADAC收率的影响,通过红外光谱、元素分析确定其化学结构。较佳反应条件为:n(氯丙烯)∶n(DTA)=3∶1,无水乙醇为溶剂,50℃下反应24 h,DADAC收率为93.76%。最后测定了产物的表面性能,得到25℃下,DADAC的cmc为5.76 mmol/L,在cmc时的γ=34.2 mN/m,Krafft点<0℃。     

Effect of epoxy–amine stoichiometry on cured resin material properties

Sizings and/or surface treatments are commonly employed to enhance the interaction of fiber reinforcements in polymer matrix composites. These modifications can induce physical and chemical interactions that cause local stoichiometric imbalances to occur that can affect the properties of the polymer matrix in the vicinity of the fiber surface. This work reports the results of an experimental study of the influence of stoichiometric imbalance on the thermoelastic properties of an epoxy–amine resin. It is shown that the modulus and glass transition temperature are significantly affected by relatively small variations in stoichiometry. These results suggest that a fiber-induced interphase region in thermosetting composites can exhibit material properties that are significantly different from those of the bulk resin. © 1992 John Wiley & Sons, Inc.     

季铵盐类荧光增白剂的合成及性能

三聚氯氰与4,4′-二氨基二苯乙烯-2,2′-二磺酸和两种氨基化合物经过三步缩合反应得到三嗪基氨基二苯乙烯型荧光增白剂,用三乙醇胺和三乙胺分别替代二乙醇胺和二乙胺,合成新型两性季铵盐类荧光增白剂,研究其与对比的非季铵盐类荧光增白剂的应用性能和在水溶液中的紫外吸收性能、光致异构化现象、荧光发射性能及其应用性能.结果表明：该季铵盐类增白剂耐酸碱性能明显提高,使用范围扩大,但其紫外吸收和荧光发射性能下降,且同样存在较为明显的光致异构化现象,耐光性也较差.     

Synthesis and properties of a polymerizable quaternary ammonium salt

Novel polymerizable monomer N,N‐dimethyl‐2‐[(2‐methylacryloyl)oxy] ethanaminium 5‐carboxy‐2,4‐bis benzoate (DMAEMA‐PMDPM salt) was synthesized by acid‐alkali neutralizing reaction and was proved to be successful by Fourier transform infrared spectroscopy. The antibacterial activity and cytotoxicity of monomer were assessed by determination of the minimal inhibitory concentration and minimal bactericidal concentration, time–kill study and methyltetrazolium test assay. Polymerizable efficiency was determined by measurement of degree of conversion. The results indicated that DMAEMA‐PMDPM salt which is a kind of liquid polymerizable has some antimicrobial activity and similar cytotoxicity to common dental resin monomers. The new monomer also has a high polymerizable ability. Therefore it might have a great potential to prepare antimicrobial coatings on denture base and soft lining materials, as well as some biomedical applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41002.     

一种有机硅季铵盐抗菌剂的合成和性能

利用γ-氯丙基三甲氧基硅烷(CTS)与N,N-二甲基十二烷基胺(DDA)反应,合成了N,N-二甲基-N-十二烷基氨丙基三甲氧基硅烷氯化铵(DDATAC)。研究了原料配比、反应温度和溶剂等因素对DDATAC收率的影响。较佳反应条件为:n(CTS)∶n(DDA)=1.0∶1.1,二甲亚砜为溶剂,于120℃反应30 h,DDATAC收率为91.37%。通过红外光谱、元素分析确定产物的化学结构,最后测定了产物的抗菌性能和耐洗性能。结果表明,制备得到的有机硅季铵盐具有良好的抗菌性能和一定的抗菌耐洗性。     

聚合季铵盐阳离子表面活性剂的合成和性能研究

以氯丙烯与二甲基十八烷基胺(OTA)为原料合成了二甲基十八烷基烯丙基氯化铵(DAOAAC).用红外光谱、元素分析、显微镜以及熔点测定仪对产物进行了理化分析和表征,以溴酚蓝为指示剂、二氯乙烷为分散相的两相化学滴定法测定产品中所含季铵盐的质量分数,最后测定了产品的表面物理性质,并对产品的杀菌和缓蚀性能进行了研究.结果表明,25℃下,DAOAAC的cmc为1.09×10-4mol/L,γcmc33.6mN/m,Krafft点＜0℃,制备得到的季铵盐具有优良的表面性能、抗菌和缓蚀性能.     

琥珀酰壳聚糖季铵盐的合成及絮凝性能

壳聚糖由于水溶性差、电荷密度低等缺点,使其在絮凝应用方面受到限制。对壳聚糖进行化学改性,可以改善其水溶性和絮凝性能。本文采用苯甲醛保护壳聚糖氨基,然后与丁二酸酐反应合成琥珀酰壳聚糖（SACTS）,进一步与二甲基二烯丙基氯化铵（DMDAAC）反应合成琥珀酰壳聚糖季铵盐（SAQCS）。采用FTIR、¹H NMR、XRD、ESEM等方法对SAQCS的结构和形貌进行表征。探讨了引发剂用量、单体配比、反应温度、反应时间对SAQCS阳离子度的影响。结果表明,SAQCS较优合成工艺条件为：引发剂用量（占单体的质量分数） 2%,m（DMDAAC）/m（SACTS）=5.4,反应温度70℃,反应时间7h。此工艺条件下合成的SAQCS的阳离子度为42.26%。将SAQCS、壳聚糖、聚丙烯酰胺与配制的高岭土模拟废水进行絮凝实验,考察了pH、投加量、温度对絮凝效果的影响。结果表明,当絮凝条件为pH=2～5、投加量3~9mg/L、温度25～50℃范围内,使用SAQCS絮凝后上清液浊度去除率均在96%以上。     

Preparation and properties of multiwalled carbon nanotube/epoxy‐amine composites

Different amounts of multiwalled carbon tubes (MWCNTs) were incorporated into an epoxy resin based on diglycidyl ether of bisphenol A and both epoxy precursor and composite were cured with 4,4′‐diamino diphenyl sulfone. Transmission and scanning electron microscopy demonstrated that the carbon nanotubes are dispersed well in the epoxy matrix. Differential scanning calorimetry measurements confirmed the decrease in overall cure by the addition of MWCNTs. A decrease in volume shrinkage of the epoxy matrix caused by the addition of MWCNTs was observed by pressure–volume–temperature measurements. Thermomechanical and dynamic mechanical analysis were performed for the MWCNT/epoxy composites, showing that the T_g was slightly affected, whereas the dimensional stability and stiffness are improved by the addition of MWCNTs. Electrical conductivity measurements of the composite samples showed that an insulator to conductor transition takes place between 0.019 and 0.037 wt % MWCNTs. The addition of MWCNTs induces an increase in both impact strength (18%) and fracture toughness (38%) of the epoxy matrix with very low filler content. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

壳聚糖季铵盐的制备及性能测试

以壳聚糖(CTS)作为季铵盐化改性原料,以环氧丙基三甲基氯化铵(GTA)作为改性剂,在CTS的C-2位氨基上定位接上季铵盐基团得到壳聚糖季铵盐(CTS-QTS)。采用FTIR、13C NMR、H1NMR、热分析(TG)表征产物CTS-QTS的结构,采用莫尔滴定法研究CTS-QTS的DS,采用凝胶渗透色谱法测定CTS和CTS-QTS的分子量,采用琼脂平板法测定CTS和CTS-QTS对金黄色葡萄球菌(S.aureus)和大肠杆菌(E.coli)的最小抑菌浓度和杀菌率,通过测试CTS-QTS对雄性小鼠和雌性小鼠急性经口毒性试验来验证CTS-QTS是否毒性类材料。研究结果表明:在p H值为7的条件下,CTS和GTA可发生温和的取代反应生成CTS-QTS,其最优反应条件为反应时间8 h、反应温度80℃、CTS与GTA的摩尔比为3。CTS改性生成CTS-QTS后分子链发生了降解,分子量下降。CTS-QTS在低于200℃时分子链几乎不发生降解,具有优良的高温稳定性。CTS-QTS对S.aureus和E.coli均有抑菌和杀菌作用,对S.aureus的抑菌和杀菌作用强于对E.coli。由CTS-QTS和CTS对S.aureus和E.coli的最低抑菌浓度可知,CTSQTS对S.aureus和E.coli的抑菌活性大于CTS。CTS-QTS对雄性小鼠和雌性小鼠急性经口毒性试验结果显示,CTS-QTS属于无毒性类材料。     

聚硅氧烷季铵盐的合成及其抗菌性

以六甲基二硅氧烷(MM)为封头剂，氢氧化四甲铵的硅醇盐为催化剂，使N，N-二乙基-氨丙基甲基二甲氧基硅烷通过水解再和八甲基环四硅氧烷(D4)制得叔胺基硅油，再以氯化苄为季铵化试剂．合成了聚硅氧烷季铵盐。应用IR和^1NMR对产品结构进行了表征，结果与预期值基本吻合。该产品具有明显的表面活性剂性能，测得其临界胶束浓度cmc为0．05％，最小表面张力σcmc为44．8mN／m。抑菌圈实验表明：产品对大肠杆菌有优良的抗菌性，对霉菌有一定的抑制作用。AATCC100抗菌实验表明：质量分数大于0．5％的聚硅氧烷季铵盐水溶液对大肠杆菌的抑菌率达到了100％。     

酯基三甲氧基有机硅季铵盐的性能研究

研究了酯基三甲氧基有机硅季铵盐(ETOQAS)的表面活性、润湿铺展性和生物降解性。结果表明:25℃时采用表面张力法测得ETOQAS的cmc=0.01 g/L,γ_(cmc)=15.72 mN/m;随着体系中NaCl浓度的增加,通过稳态荧光法测得的ETOQAS水溶液的cmc呈减小的趋势;随着ETOQAS水溶液质量浓度的增加,其在铁块和石蜡上的接触角逐渐减小;ETOQAS能够在3 d内降解完全。     

Gas and water transport properties of epoxy–amine networks: Influence of crosslink density

The gas and water transport properties were studied on seven epoxy–amine networks that differ by their di/mono epoxy composition and their cure cycle. The characteristic parameters of transport M_∞ and D were determined in each case, and they show that the solubility and diffusion coefficients are influenced by their composition. The solubility increases with the extend of cure and with the decrease of dangling chains, and in both cases the evolution of the diffusivity is inverse. The variations of the solubility and diffusivity have been discussed as a function of two parameters: polar groups and unrelaxed holes of the glassy networks. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2058–2066, 2001     

微孔聚丙烯膜表面壳聚糖季铵盐的共价修饰及其抗菌性能

为了赋予微孔聚丙烯膜（MPPM）抗菌能力,增强其抗污染性能,本文通过丙烯酸的光引发接枝聚合、壳聚糖与聚丙烯酸的酰胺化反应、壳聚糖胺基与2,3-环氧丙基三甲基氯化铵的开环加成,成功地在MPPM膜表面通过共价修饰技术构建了壳聚糖季铵盐修饰层。构建过程通过FTIR、XPS和荧光素二钠盐染色分析得到了证实。静态水接触角和吸水量实验结果表明,制得的修饰膜具有优异的表面润湿性和吸水性,吸水量可达11.23mg/cm²,为未修饰MPPM的1123倍。以大肠杆菌和金黄色葡萄球菌为代表,采用平板活菌计数法考察了修饰膜的抗菌性能和抗菌稳定性。研究结果表明,修饰膜具有良好的抗菌活性,对大肠杆菌的抗菌率可达98%,对金黄色葡萄球菌的抗菌率可达100%,且抗菌效果稳定,在水处理领域具有潜在的应用前景。     

季铵盐改性茶皂素的合成与性能研究

以茶皂素与3-二甲胺基丙胺反应生成叔胺茶皂素中间体,再与溴乙烷季铵化反应生成季铵盐改性茶皂素。叔胺茶皂素中间体制备较佳条件为:以三甘醇为溶剂,n(茶皂素)∶n(3-二甲胺基丙胺)=1∶2.5,在130℃条件下反应8 h,收率为85.7%。测定了季铵盐改性茶皂素的表面活性,其cmc为0.398 g/L,γ_(cmc)为40.82 m N/m;其发泡性能良好但稳泡性能差;测定了其抗氧化性能,在质量浓度为1.0 g/L时,其对羟自由基(·OH)和超氧阴离子自由基(·O_2~-)的清除率分别达到55.4%和66.3%;其对大肠杆菌、枯草芽孢杆菌和金黄色葡萄球菌的抑菌性能均优于茶皂素。     

Synthesis and photoinitiation properties of a novel quaternary ammonium tetraphenylborate salt

Quaternary ammonium salts are photobase generators. Recently, we prepared a novel quaternary ammonium tetraphenylborate salt bearing a 6‐methoxynaphthoylmethyl group. The structure of the products was confirmed by elemental analysis and ¹H‐NMR. Thermogravimetry showed its good thermostability. UV spectra and fluorescence emission spectra of the samples were studied. A mass spectrometry method for the analysis of the tertiary amine and other fragments produced by photolysis was established. Photolysis was found to produce both tertiary amine and free radicals. Therefore, the products of photolysis not only could cause thermal curing of epoxide but also could initiate the free‐radical polymerization of acrylate or methyl acrylate monomer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 399–405, 2006     

树枝状大分子季铵盐的制备及抑菌性能研究

以丙烯酸甲酯和乙二胺为原料合成了树枝状大分子聚酰胺-胺(PAMAM),采用1HNMR进行了结构表征。在此基础上用2,3-环氧丙基三甲基氯化铵(GTA)对其表面进行修饰,制备了树枝状大分子季铵盐。采用单因素法确立了制备树枝状季铵盐的最优反应条件:1.0G PAMAM与GTA摩尔比为1∶7,混合溶剂中水的质量分数为60%,反应温度60℃,反应时间8 h。制备的树枝状季铵盐用FTIR进行结构表征,并对其抑菌性能进行了研究。结果表明:树枝状大分子季铵盐对大肠杆菌、金黄色葡萄球菌和黑曲霉菌有抑菌作用,对黑曲霉菌的抑菌浓度最小,为8.5μg/m L,抑菌活性最大。     

季铵盐改性聚氨酯弹性纤维的结构与性能

为改善聚氨酯弹性纤维的酸性染料染色性能,采用物理混合的方法制备了季铵盐/聚氨酯脲纺丝原液,然后经干法纺丝制得了季铵盐改性聚氨酯弹性纤维;研究了改性聚氨酯弹性纤维的表面形貌、力学性能及酸性染料染色性能。结果表明:改性前后的聚氨酯弹性纤维表面形貌没有变化;改性聚氨酯弹性纤维伸长300%时的拉伸应力提高了16%,断裂强度提高了21%,断裂伸长率下降了6.4%,弹性回复率没有变化;改性聚氨酯弹性纤维的酸性染料上染率有了明显的提高,耐洗色牢度达到4级。     

超级电容器用双草酸硼酸螺环季铵盐的合成及性能

以溴代8-氧杂-螺[4,5]季铵盐(ASB)、二水草酸(OD)、硼酸(BA)为原料,通过离子交换法制备电解质双草酸硼酸螺环季铵盐(BSQA),通过核磁共振(¹³C NMR)和液相色谱-质谱联用(LC-MS)分析对其进行表征,验证了其结构。采用正交实验对合成工艺进行优化,优化工艺条件为n_ASB:n_BA 2.8:1,反应时间4 h,反应温度90℃,溴代螺环季铵盐的转化率为90.2%。将BSQA、市售四氟硼酸四乙基铵(ET₄NBF₄)分别与乙腈配制成电解液并模拟组装成超级电容器并测试电化学性能。结果表明,BSQA电解液工作电压达3.0 V,充放电效率达94.89%,能量密度达11.63 W·h·kg^-1,产品电化学性能优于常用的有机电解质ET₄NBF₄,适用于更高的工作电压。     

有机硅季铵盐的制备及其抗菌性能研究

利用三甲氧基硅烷(WD-930)与二甲基十八烷基烯丙基氯化铵(DAOAAC)进行反应,合成了阳离子抗菌剂[N,N-二甲基-N-十八烷基氨丙基三甲氧基硅烷氯化铵(DOATAC)]。以溴酚蓝为指示剂、二氯乙烷为分相溶剂,采用两相化学滴定法测定DOATAC的含量;用红外光谱(FT-IR)、元素分析和熔点测定仪等对DOATAC产物进行了理化分析;利用薄层色谱法,对所制备的阳离子抗菌剂的合成路线及其纯化过程进行跟踪;最后对产物的抗菌性能和耐洗性能进行测定。研究结果表明,当抗菌整理液中w(DOATAC)=0.06%时,经该整理液整理的棉布,对金黄色葡萄球菌和大肠杆菌的抑菌率均超过90%,并具有优良的抗菌耐洗性,洗涤50次后其抑菌率仍超过70%。