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首页> 外文期刊>Advanced Functional Materials >Selective ion transport and complexation in layer-by-layer assemblies of p-sulfonato-calix[n]arenes and cationic polyelectrolytes
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Selective ion transport and complexation in layer-by-layer assemblies of p-sulfonato-calix[n]arenes and cationic polyelectrolytes

机译：对-磺基杯[n]芳烃和阳离子聚电解质的层状组装中的选择性离子迁移和络合

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摘要

ne first study of ion transport across self-assembled multilayered films of p-sulfonato-calix[n]arenes and poly(vinyl amine) (PVA) is presented. The films,are prepared by the alternate electrostatic layer-by-layer assembly of the anionic calixarenes and cationic PVA on porous polyacrylonitrile (PAN) supports. We use tetra-p-sulfonato-calix[4]arene (calix4), hexa-p-sulfonato-calix[6]arene (calix6), and octa-p-sulfonato-calix[8]arene (calix8) as the calixarenes. Ultraviolet (UV) studies indicate that dipping solutions of pH 6.8, without a supporting electrolyte, are most suited for film preparation. Calix8 is adsorbed in higher concentrations per layer than calix6 or calix4, probably because desorption is less pronounced. The permeation rates, P(R)s, of monovalent alkali-metal chlorides (Li, Na, K, Cs), magnesium chloride, divalent transition-metal chlorides (Ni, Cu, Zn), trivalent lanthanide chlorides (La, Ce, Pr, Sm), and sodium sulfate across the calix4/PVA, calix6/PVA, and calix8/PVA membranes are studied and compared with the corresponding P-R values across a poly(styrene sulfonate) (PSS)/PVA multilayer membrane prepared under the same conditions. The P-R values of the alkali-metal salts are between 4 and 17 X 10(-6) cm s(-1), those of magnesium chloride and the transition-metal salts are 0.2-1.3 x 10(-6) cm s(-1), and those of the lanthanide salts are about 0.1 X 10(-6) cm s(-1). Possible origins for the large differences are discussed. Ion transport is first of all controlled by electrostatic effects such as Donnan rejection of di- and trivalent ions in the membrane, but metal-ion complexation with the calixarene derivatives also plays a role. Complexation occurs especially between Li+ or Na+ and calix4, Mg2+, or Cu2+ and calix6, Cu2+, Zn2+, or the lanthanide ions and calix8. Divalent sulfate ions are found to replace the calixarene polyanions in the membrane. UV studies of the permeate solutions indicate that calix4especially is displaced during sulfate permeation.
机译：首次提出了跨自对磺基杯[n]芳烃和聚（乙烯基胺）（PVA）的自组装多层膜离子迁移的研究。膜是通过在多孔聚丙烯腈（PAN）载体上交替放置阴离子杯芳烃和阳离子PVA的静电逐层静电组装而成的。我们使用四-对-磺基-杯[4]芳烃（calix4），六-对-磺基-杯[6]芳烃（calix6）和八-对-磺基-杯[8]芳烃（calix8）作为杯芳烃。紫外线（UV）研究表明，没有支持电解质的pH值为6.8的浸渍溶液最适合薄膜制备。 Calix8每层的吸附浓度比calix6或calix4高，这可能是因为解吸不太明显。一价碱金属氯化物（Li，Na，K，Cs），氯化镁，二价过渡金属氯化物（Ni，Cu，Zn），三价镧系元素氯化物（La，Ce，研究了calix4 / PVA，calix6 / PVA和calix8 / PVA膜上的Pr，Sm）和硫酸钠，并将其与在相同条件下制备的聚（苯乙烯磺酸盐）（PSS）/ PVA多层膜上的相应PR值进行了比较条件。碱金属盐的PR值在4到17 X 10（-6）cm s（-1）之间，氯化镁和过渡金属盐的PR值在0.2-1.3 x 10（-6）cm s（-1）之间。 -1），镧系元素盐的那些约为0.1 X 10（-6）cm s（-1）。讨论了差异较大的可能原因。离子传输首先受静电作用控制，例如膜中二价和三价离子的Donnan排斥，但金属离子与杯芳烃衍生物的络合也起作用。络合尤其发生在Li +或Na +与杯4，Mg2 +或Cu2 +与杯6，Cu2 +，Zn2 +或镧系离子和杯8之间。发现二价硫酸根离子替代了膜中的杯芳烃聚阴离子。渗透溶液的UV研究表明，杯状硫酸盐在硫酸盐渗透过程中尤其被置换。

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