Hollow nano-material is one of the hot researches in recent years because of special optical, electrical, magnetic and catalytic properties. Polymer nanotube (PNT) is a polymer nano-material with tubular structure. Template method is an effective preparation method for tubular polymer nano-materials. In this study, we have developed a simple technique for the fabrication of polymer nanotubes by using self-assembled metal organic nanotube (MONT) as a template and multiple amine and acid as precursor molecules. An amphiphilic molecule (N-tetradecanoic glycylglycine, 1) was firstly synthesized by the coupling reaction of N-tetradecanoic acid and glycylglycine ethyl ester under the function of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC•HCl), followed by a hydration process. The amphiphilic molecule 1 was successfully obtained in high yields. MONT was then prepared by the self-assembly of 1 with copper(II) nitrate in methanol. A solution of copper(II) nitrate in water was slowly added into a solution of 1 in methanol. The mixed solution was stirred for 24 h at room temperature and MONT was obtained by filtration, washing with water and freeze-dry. And finally, template reactions were carried out as follows: a certain amount of MONT was dispersed in tetrahydrofuran (THF), and then the multiple amine was added to complex with copper ions on the surface of MONT. The mixed solution was stirred for 3 h at room temperature and a coated layer formed on the surface of MONT. The coated layer on the nanotube surface was further cross-linked by an activated ester of citric acid. Finally, the self-assembled template was removed by hot filtration and the PNTs with good dispersibility in water were obtained. The surface topography, composition and structure of PNTs were characterized by scanning electron microscope (SEM), scanning transmission electron microscopy (STEM), differential scanning calorimetry (DSC), X-ray diffraction (XRD) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The results showed that up to 80% cross-linked products form PNTs when the amount of multiple amines is 0.4 molar equivalent of MONT. The lengths of PNTs are about 500 nm~3 μm, inner diameters are 60~100 nm and outer diameters are 80~120 nm.

中文翻译：

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以自组装金属有机纳米管为模板制备聚合物纳米管

中空纳米材料由于具有特殊的光、电、磁和催化等特性，是近年来研究的热点之一。聚合物纳米管（PNT）是一种具有管状结构的聚合物纳米材料。模板法是制备管状聚合物纳米材料的有效方法。在这项研究中，我们开发了一种通过使用自组装金属有机纳米管 (MONT) 作为模板和多种胺和酸作为前体分子来制造聚合物纳米管的简单技术。在1-乙基-3-(3-二甲氨基丙基)碳二亚胺盐酸盐(EDC•HCl)作用下，通过N-十四烷酸与甘氨酰甘氨酸乙酯的偶联反应，首次合成了一种两亲分子(N-十四烷酸甘氨酰甘氨酸，1)，然后是水化过程。以高产率成功获得了两亲分子1。然后通过 1 与硝酸铜 (II) 在甲醇中的自组装来制备 MONT。将硝酸铜 (II) 的水溶液缓慢加入 1 的甲醇溶液中。混合溶液在室温下搅拌24小时，过滤、水洗、冷冻干燥得到MONT。最后进行模板反应：将一定量的MONT分散在四氢呋喃(THF)中，然后加入多元胺与MONT表面的铜离子络合。混合溶液在室温下搅拌3小时，在MONT表面形成涂层。纳米管表面的涂层被活化的柠檬酸酯进一步交联。最后，通过热过滤去除自组装模板，得到在水中具有良好分散性的PNTs。通过扫描电子显微镜 (SEM)、扫描透射电子显微镜 (STEM)、差示扫描量热法 (DSC)、X 射线衍射 (XRD) 和漫反射红外傅立叶变换光谱 (DRIFTS) 对 PNT 的表面形貌、组成和结构进行表征。 ）。结果表明，当多胺的量为 0.4 摩尔当量 MONT 时，高达 80% 的交联产物形成 PNT。PNTs的长度约为500 nm~3 μm，内径为60~100 nm，外径为80~120 nm。通过扫描电子显微镜（SEM）、扫描透射电子显微镜（STEM）、差示扫描量热法（DSC）、X射线衍射（XRD）和漫反射红外傅里叶变换光谱（DRIFTS）对PNTs的组成和结构进行了表征。结果表明，当多胺的量为 0.4 摩尔当量 MONT 时，高达 80% 的交联产物形成 PNT。PNTs的长度约为500 nm~3 μm，内径为60~100 nm，外径为80~120 nm。通过扫描电子显微镜（SEM）、扫描透射电子显微镜（STEM）、差示扫描量热法（DSC）、X射线衍射（XRD）和漫反射红外傅里叶变换光谱（DRIFTS）对PNTs的组成和结构进行了表征。结果表明，当多胺的量为 0.4 摩尔当量 MONT 时，高达 80% 的交联产物形成 PNT。PNTs的长度约为500 nm~3 μm，内径为60~100 nm，外径为80~120 nm。