Effect of Quaternary Ammonium Salts on Carrier-Mediated Transport of Lanthanide Ions through Cellulose Triacetate Membranes

Abstract

Fluxes of all lanthanides, except promethium, across cellulose triacetate membranes were determined by using mixtures of o-nitrophenyl n-octyl ether and quaternary ammonium salts as plasticizers, and 4-benzoyl-3-methyl-1-phenyl-5-pyrazolone (BMPP) and 4-trifluoroacetyl-3-methyl-1-phenyl-5-pyrazolone (TMPP) as carriers. The quaternary ammonium salts used were didodecyldimethyl-, distearyldimethyl-, tetrahexyl-, tetraoctyl-, and tetradecylammonium bromides [referred to as (C₁₂)₂NBr, (C₁₈)₂NBr, (C₆)₄NBr, (C₈)₄NBr, and (C₁₀)₄NBr, respectively]. The effect of these ammonium bromides on the flux was demonstrated. For membranes containing 0.1 M (C₁₂)₂NBr and (C₁₈)₂NBr, BMPP exhibited considerably high fluxes. The fluxes of lanthanum and cerium using BMPP for (C₁₂)₂NBr were higher than those of the other lanthanides. For the membranes containing 0.5 M (C₁₂)₂NBr and 0.1 M (C₁₈)₂NBr, however, no difference in flux among the lanthanides was observed. The fluxes using TMPP for (C₁₂)₂NBr and (C₁₈)₂NBr were very small, with the exception of some lanthanides. Appreciably high fluxes were observed for membranes containing 0.1 M (C₆)₄NBr using BMPP. For (C₈)₄NBr and (C₁₀)₄NBr, BMPP exhibited low fluxes. For these membranes using TMPP, the lanthanides were scarcely transported.     

聚硅氧烷季铵盐的合成及应用研究进展

阐述了聚硅氧烷季铵盐的4种合成方法:氨基硅烷(油)与季铵化试剂的季铵化反应法、卤烃基硅烷与叔胺的取代反应法、含氢硅油(烷)与含活性基团的不饱和化合物的硅氢加成及季铵化反应法、甲基硅油与氨基硅烷、季铵盐的平衡反应法,介绍了其在织物整理、日化产品、农药、污水处理等方面的应用,并对其发展前景进行了展望。     

Synthesis, Surface Active and Thermodynamic Parameters of Novel Quaternary Ammonium Salts

Reactions of octanol, nonanol, decanol, and dodecanol with epichlorohydrin were carried out in the presence of sodium hydroxide as a catalyst. The synthesized non-ionic surfactants were modified with triethanolamine. Surface activity at the water-air interface and electrical conductivity of the resulting surfactants at 10, 20, 30 and 40?°C were determined and thermodynamic parameters of micellization and adsorption were calculated. It was established that the synthesized quaternary ammonium salts have the ability to localize thin crude oil films on the water surface formed due to spill.     

Novel Hydroxylated Cardanol Quaternary Ammonium Salts from Renewable Resource and its Synergistic Vesicles of Binary and Ternary Composite System in Detergent

A series of novel hydroxylated cardanol quaternary ammonium salts (HCQAS 3a–3g) with one or two hydroxyl groups, derived from renewable cardanol, a plant-based and low-cost material natural cashew nut shell liquid (CNSL), have been rationally designed and investigated as additive in detergent. CMC, γ_CMC, C₂₀, pC₂₀, and CMC/C₂₀ were employed to exhibit the surface properties of HCQAS, reflecting that the surfactivity were superior to general cationic surfactants. In addition, HCQAS revealed excellent water solubility and wettability by krafft point and contact angle tests. Moreover, emulsifiability and foamability conversions were monitored versus time and volume of foam, respectively. Also, TEM micrographs were taken to provide the aggregation morphologies of HCQAS 3a aqueous solution at different concentration. Furthermore, HCQAS 3a and BGF-10 binary composite system as well as HCQAS 3a, BGF-10, and SDBS ternary composite system were investigated by CMC, γ_CMC, emulsifiability, and foamability to determine the optimum molar ratio (HCQAS 3a: BGF-10: SDBS = 0.24:0.36:0.4), and then, analysis of morphology by TEM showed that the incorporation of HCQAS 3a, BGF-10, and SDBS in aqueous solution accelerated the formation of abundant vesicles with large volume and surface area. Finally, a green concentrated detergent was designed and prepared with the filtered ratio, where the presence of vesicles greatly enhanced detergency to promisingly replace the familiar use of petroleum-based TX-10 in detergent. This study on the structure and performance of HCQAS may shed some light on the development of novel environmentally friendly surfactant.     

Keggin型磷钨钒杂多酸季铵盐的合成、表征及抑菌效果的研究

以不同钒原子数取代Keggin型磷钨杂多酸并与十六烷基三甲基溴化铵反应合成了3种杂多酸季铵盐.通过红外光谱(IR)、X-射线衍射(XRD)、紫外(UV)等表征手段确定了杂多酸以及杂多酸季铵盐的结构.结果表明,在红外光谱中,引入钒原子后阴离子负电荷增加,导致相应的特征峰出现红移现象;从X-射线衍射谱图中确定了杂多酸季铵盐的二级结构,最后通过热重分析(TG)得出杂多酸季铵盐所含结晶水的数目.通过杯碟法测试了目标产物对大肠杆菌、金黄色葡萄球菌、枯草芽孢杆菌、蜡样芽孢杆菌的抑菌性能,结果表明杂多酸季铵盐对枯草芽孢杆菌的抑菌能力最好,并且钒原子所占比例越高,抑菌效果越好.     

胺基接枝纤维的制备及其对铜离子吸附的应用研究

以漂白蔗渣浆纤维素为基体,二乙烯三胺为单体,硝酸铈铵为引发剂,制备胺基接枝纤维,得到高效重金属吸附剂。研究了单体用量、引发剂用量、温度、时间等反应因素对胺基接枝纤维制备的影响。采用红外光谱、X射线衍射和扫描电镜分析表征胺基接枝纤维的结构。从温度、时间、pH值、接枝纤维加入量和铜离子溶液初始浓度方面对胺基接枝纤维吸附二价铜离子进行研究,探究较好的吸附条件。结果表明,当绝干蔗渣纤维∶单体二乙烯三胺=1∶1（质量比）,硝酸铈铵的用量为25%,温度为70℃,时间为2h时,可以获得较高的吸附量,其吸附量可以达到12.8 mg·g-1。通过红外光谱和扫描电镜分析手段对接枝纤维的结构进行表征。胺基接枝纤维对铜离子溶液吸附的较优条件为：时间20min,温度为30℃,pH值为4.5,初始浓度为400mg·L-1。对吸附过程进行动力学研究,拟合得到Lagrange二级动力学方程y=0.0116x＋0.021。     

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.     

壳聚糖对废水中Cu(Ⅱ)吸附研究

用正交实验考察了pH、Cu(Ⅱ)初始浓度、温度等因素对壳聚糖吸附废水中Cu(Ⅱ)的影响.结果表明各因素对壳聚糖吸附Cu(Ⅱ)的影响关系为:pH＞Cu(Ⅱ)初始浓度＞温度,其最佳组合为pH为7,Cu(Ⅱ)初始浓度5mg·L-1,温度为15℃,Cu(Ⅱ)最高吸附率达98.85%;等温吸附曲线拟合表明,Langmuir模型、...     

Preparation,Surface-Active Properties and Antimicrobial Activities of Bis(Ester Quaternary Ammonium) Salts

New cationic surfactants, bis-quaternary ammonium salts, were prepared from N,N-dimethylaminoalkyl esters of saturated fatty acids and products of the reactions of epichlorohydrin with primary amines: pentyl-, hexyl- and octylamine. The bis (ester–ammonium) salts obtained were examined in respect to their surface-active properties: critical micelle concentration (CMC), effectiveness of surface tension reduction (γ_CMC), and adsorption efficiency (pC₂₀). All these surfactants showed good water solubility and low critical micelle concentrations of more than two orders of magnitude lower than these of corresponding mono-alkylammonium salts. They also showed good wetting capability, but worse foaming properties. All the surfactants tested were nontoxic to gram-negative bacteria, but some of them inhibited the growth of gram-positive bacteria and yeast.

Gemini季铵盐粘土稳定剂的合成及其防膨性能评价

采用环氧氯丙烷和三甲胺为原料合成了粘土稳定剂Gemini季铵盐,探讨了合成条件并测试了其防膨性能.确定Gemini季铵盐的最佳合成条件如下:反应温度为96℃,反应时间为8 h,n(三甲胺):n(三甲胺盐酸盐):n(环氧氯丙烷)为1.2:1:1,反应溶剂选用醇-水混合溶剂,溶剂占反应体系总质量的35%.此时所得产物收率为86.5%.该Gemini阳离子表面活性剂防止粘土膨胀性能良好,防膨率达到88.7%.     

Surface Activity,Thermodynamics of Micellization and Adsorption Properties of Quaternary Salts Based on Ethanolamines and Decyl Bromide

The surface-active properties of ionic-liquid type salts synthesized by the interaction of ethanolamines and decyl bromide have been studied. Surface tension as a function of concentration of the surfactant in aqueous solution was measured at 10, 20, 30 and 40 °C using a drop volume stalagmometer. From these measurements, the maximum surface excess concentration and the minimum area per molecule at the aqueous solution/air interface, the critical micelle concentration (CMC), the surface pressure at the CMC, and the standard thermodynamic parameters of adsorption and micellization were calculated. The structural effects on adsorption, micellization, and the effectiveness of surface tension reduction are discussed in terms of these parameters.     

含氟季铵盐的动态界面张力性能和润湿铺展性能

含氟季铵盐表面活性剂是一类具有高表面活性、高耐热稳定性、高化学稳定性和憎水、憎油等特殊性能的表面活性剂。该文通过测定不同时间、不同种类的油相、不同质量分数的表面活性剂以及不同无机盐添加比例对油水界面张力的影响以及不同浓度的含氟季铵盐表面活性剂水溶液在石蜡、金属铁等不同固体表面上的接触角,对其动态界面张力以及润湿铺展性能进行了研究。结果表明:界面张力值通常在10 min后基本达到平衡,且用渤61#油做油相时,界面张力值较低,效果比较好;随着表面活性剂质量分数的增加,界面张力先减小,达到一个最低值后渐渐趋于平缓;无机盐的加入使得界面张力先降后升,在Na Cl质量浓度为50~80 g/L内均降至低界面张力,最低值达到0.053 1 m N/m;同时,在典型的具有强疏水性的低能表面石蜡上的铺展性能优良。该研究为其在水溶性场合的应用提供了实验数据。     

纳米伊/蒙黏土吸附脱除水中Cu~(2+)和Cd~(2+)离子

探索经精细加工的纳米伊/蒙混层黏土吸附水中2种二价重金属离子(即Cu~(2+)和Cd~(2+))的吸附性能,并考察了该黏土在吸附过程中pH值、黏土用量、吸附时间、吸附温度和重金属离子浓度诸因素对水中Cu~(2+)和Cd~(2+)离子吸附性能的影响。结果表明:纳米伊/蒙黏土对水中重金属离子的吸附量随pH值的增加而增加,当pH4时,吸附量基本趋于稳定;在优化条件下,纳米伊/蒙黏土对水中Cu~(2+)和Cd~(2+)的最大吸附脱除率分别为95.15%和91.53%。用准一级和准二级动力学模型拟合纳米伊/蒙黏土吸附Cu2+和Cd2+的吸附动力学过程。结果表明,准二级动力学模型能够拟合纳米伊/蒙黏土对Cu~(2+)和Cd~(2+)的吸附过程。吸附热力学研究还表明,纳米伊/蒙黏土吸附Cu~(2+)和Cd~(2+)属于物理吸附过程。另外,利用Langmuir和Freundlich等温线模型分析纳米伊/蒙黏土分别吸附不同浓度Cu~(2+)和Cd~(2+)的吸附过程。Langmuir模型能有效地拟合纳米伊/蒙黏土吸附Cu~(2+)和Cd~(2+)的等温吸附过程,由其获得的单层纳米伊/蒙黏土对Cu~(2+)和Cd~(2+)饱和吸附量分别为7.99 mg/g和12.68 mg/g。     

Design,Synthesis, Antibacterial,Antifungal and Anticancer Evaluations of Novel β-Pinene Quaternary Ammonium Salts

β-pinene is a monoterpene isolated from turpentine oil and numerous other plants’ essential oils, which has a broad spectrum of biological activities. In the current work, six novel β-pinene quaternary ammonium (β-PQA) salts were synthesized and evaluated in vitro for their antifungal, antibacterial and anticancer activities. The in vitro assay results revealed that compounds 4a and 4b presented remarkable antimicrobial activity against the tested fungi and bacteria. In particular, compound 4a showed excellent activities against F. oxysporum f.sp. niveum, P. nicotianae var.nicotianae, R. solani, D. pinea and Fusicoccumaesculi, with EC₅₀ values of 4.50, 10.92, 9.45, 10.82 and 6.34 μg/mL, respectively. Moreover, compound 4a showed the best antibacterial action against E. coli, P. aeruginosa, S. aureus and B. subtilis, with MIC at 2.5, 0.625, 1.25 and 1.25 μg/mL, respectively. The anticancer activity results demonstrated that compounds 4a, 4b, 4c and 4f exhibited remarkable activity against HCT-116 and MCF-7 cell lines, with IC₅₀ values ranged from 1.10 to 25.54 μM. Notably, the compound 4c displayed the strongest cytotoxicity against HCT-116 and MCF-7 cell lines, with the IC₅₀ values of 1.10 and 2.46 μM, respectively. Furthermore, preliminary antimicrobial mechanistic studies revealed that compound 4a might cause mycelium abnormalities of microbial, cell membrane permeability changes and inhibition of the activity of ATP. Altogether, these findings open interesting perspectives to the application of β-PQA salts as a novel leading structure for the development of effective antimicrobial and anticancer agents.     

Adsorption of Endocrine Disruptors and Related Compounds Using Natural Polymer Composite Fibers Formed by Polyion Complexes

Endocrine disruptors are known as chemical compounds that affect living systems. The three investigated polyion complex (PIC) fibers are formed by the interaction of two kinds of oppositely charged polyelectrolytes in aqueous solution and examined for their adsorptive ability as endocrine disruptor adsorbents. Among nine compounds, seven endocrine disruptors and related compounds are adsorbed onto the PIC fibers. Particularly, benzo[a]pyrene is adsorbed in high amounts. The relationships between the structures of endocrine disruptors and the adsorption‐release behavior are investigated. Biphenyl exhibits mostly a repetitive adsorption‐release behavior.     

Effects of Nanometer Ni,Cu, Al and NiCu Powders on the Thermal Decomposition of Ammonium Perchlorate

A study of the decomposition behaviour for Ammonium Perchlorate(AP) was carried out by differential thermal analysis and the two decomposition peaks were observed. The high temperature peak was found to shift to lower temperatures, but the corresponding shift in the low temperature peak was smaller due to the effect of nanometer metal powders. Results shows that Cu and NiCu nanopowders decreased both the high and low decomposition temperature, while Ni and Al nanopowders just decreased the high decomposition temperature and increased the low decomposition temperature. Metal micron‐sized powders show catalytic effects on the thermal decomposition of AP, but their effects are less than that of nanometer metal powders. With the increase in content, nanometer metal powders enhanced their catalytic effect on the high temperature decomposition of AP, however their effect was weakened on the low temperature decomposition.     

季铵盐对蒙脱土插层效果及表面活化的研究

采用不同碳链的季铵盐阳离子作为插层剂，与钠基蒙脱土层间的无机阳离子Na^＋和Ca^2＋进行离子交换，制备了系列有机蒙脱土。利用红外光谱、x射线衍射对蒙脱土和有机化蒙脱土的结构进行了表征。结果表明：插层剂已进入蒙脱土的层问，蒙脱土的层间距由1．53nm增加到1．99—3．48nm。同时对有机蒙脱土在二甲苯中的流变学性质进行了研究，结果证明有机蒙脱土能在二甲苯中溶胀而形成凝胶，在相同剪切力时，凝胶的黏度与季铵盐阳离子烷基链的结构有关。     

Synthesis,Characterization and Inhibition Performance of Vanillin‐Modified Chitosan Quaternary Ammonium Salts for Q235 Steel Corrosion in HCl Solution

In order to enhance the solubility of chitosan in water and its corrosion inhibition performance on Q235 steel in 1 M HCl solution, N‐vanillyl‐O‐2′‐hydroxypropyltrimethylammonium chloride chitosan (VHTC) was synthesized. The structure of VHTC was characterized by FT‐IR and ¹H‐NMR spectroscopy. The corrosion inhibition performance of VHTC on Q235 steel in 1 M HCl solution was studied by weight loss, polarization, electrochemical impedance spectroscopy (EIS) and stereo microscope analysis. Experimental results indicate that VHTC shows better inhibition efficiency compared to chitosan. When the concentration of VHTC increases to 200 mg L^?1, the inhibition efficiency reaches 90 %, which is almost equal to the conventional corrosion inhibitors (e.g., imidazoline). The polarization study demonstrates that VHTC is a mixed‐type inhibitor caused by a geometrical blanketing effect. The charge transfer resistance is proportional to the inhibitor concentration as revealed by the EIS results, indicating that the protective film on the Q235 steel surface is formed by adsorption of the inhibitor molecules. The inhibition efficiency of VHTC achieves the maximum value within 24 h when the concentration of VHTC is 200 mg L^?1. The morphology observation of the corroded steel surface indicates that the corrosion of Q235 steel in 1 M HCl solution is significantly inhibited after introducing VHTC into the acidic solution.