Organic nanostructures DOI: 10.1002/smll.200500414 Surfactant-Templated Synthesis of 1D Single- Crystalline Polymer Nanostructures** Yan Yan, Haifeng Yang, Fuqiang Zhang, Bo Tu, and Dongyuan Zhao* In the past decade, there has been great interest in con- structing organic nanostructured materials. [1–3] Compared with inorganic materials, organic nanostructures are expect- ed to play an important role in advanced technology owing to their mechanical stability, rich variety of structures and components, convenient chemical modification, and efficient processability. [4–6] The traditional synthetic pathway for de- riving nanoscale organic materials is microemulsion poly- merization. [7,8] The method is useful for preparing nano- or microspherical polymer particles, however, one-dimensional (1D) polymer nanostructures are still rare. Recently, many methods, including amphiphilic self-assemblies, electrospray deposition, spin-casting, and a sonochemical process, have been widely developed for the preparation of organic nano- structures. [9, 10] However, they suffer from the limitations of needing specialized equipment and conditions or tedious procedures. Lately, a few methods for the preparation of inorganic nanostructures were introduced to organic nanomaterials. A successful example is the synthesis of anthracene (AN) nanowires and perylene (PY) nanorods by a solid-phase re- action. [11] The process includes the high-temperature reac- tion of the precursors with gas transportation and the collec- tion of products at the cool end of a tube furnace; this is similar to the syntheses of 1D metal oxide nanostructures by Wang and co-workers [12–13] and Yang and co-workers. [14] In another case, the hard-templating process of ordered mesoporous materials was employed in the preparation of polythiophene nanowire bundles, [15] which have shown po- tential application in photoelectrical devices. These results demonstrate the unlimited possibility of inorganic synthetic pathways in preparing organic nanostructures with various morphologies and sizes. Solvothermal synthesis is one of the most efficient methods for preparing inorganic nanomateri- als with different components. Recent studies verified that a solvothermal process under an organic-templating confine- ment shows extraordinary ability in controlling the morphol- ogy of the nanostructures. [11, 16–18] Therefore, exploring a gen- eral and simple solvothermal method to fabricate organic nanostructures is still challenging and may further demon- strate the concept of organic–organic interactions in the sol- ution phase. Poly(furfuryl alcohol) (PFA), a kind of furfuryl alcohol (FA) resin polymerized from FA by acidic catalysis or heat- ing, [19–22] is a material widely used for metal-casting molds, corrosion-resistant materials, or negative photoresists due to its ability to polymerize and its polyconjugated sequences. [23] Besides, it is also an important precursor in preparing vari- ous carbon materials with different nanostructures or meso- structures. [24–27] However, little attention has been devoted to the study of nanostructures of FA resins. Due to system- atic studies on the polycondensation process and the con- densation kinetics, [28–32] FA resin is an appropriate material for exploring novel pathways for synthesizing organic nano- structured materials. In this paper, a surfactant-templated polymerization method was engaged in fabricating PFA nanostrutures under solvothermal conditions. Single-crystalline PFA nano- structures with wirelike morphology were successfully syn- thesized for the first time under an organic–organic-assisted assembly. Both the size and shape of the PFA nanostruc- tures can be controlled by the organic template species and the reaction time. The organic–organic assembly by means of the solvothermal process is compatible with fabricating 1D polymeric nanostructures with different components. The PFA materials derived by the surfactant-templated solvothermal process were observed by transmission elec- tron microscopy (TEM). Figure 1a and b clearly demon- strates the wirelike morphology of the PFA nanostructures. All the samples show regular shapes and uniform sizes, and the yield of material with such a morphology is as high as up to 100%, calculated based on the FA monomer precur- sor. A typical nanowire has a width ranging from 15–20 nm, and a length up to 600–800 nm. The energy dispersive X-ray spectra (EDX, see Supporting Information, Figure S1) of observed areas detected little or no S signals, indicating that the surfactant, sodium dodecylbenzene sulfonate (SDBS), was removed by ethanol washing. The crystalline nature of the PFA was further confirmed with selected area electron diffraction (SAED) measurements. The inset of Figure 1a, taken from a large area, illustrates that those nanowires are highly crystalline, which is also proved by X-ray diffraction (XRD) characterization (see Supporting Information, Fig- ure S2). Meanwhile, the SAED pattern of a single nanowire (Figure 1 c) shows a typical single-crystal diffraction pattern. The high-resolution transmission electron microscopy (HRTEM) image shows the lattice fringes of an individual PFA nanowire (Figure 1d). The result further confirms the single-crystalline nature of the PFA nanowires with a lattice spacing of  0.32 nm, which is in good accordance with the [*] Y. Yan, H. Yang, F. Zhang, B. Tu, D. Zhao Department of Chemistry Laboratory of Molecular Catalysis and Innovative Materials Fudan University Shanghai 200433 (P.R. China) Fax: (+ 86)21-6564-1740 E-mail: dyzhao@fudan.edu.cn [**] We thank Ying Chen and Songhai Xie for TEM, Dr. Haojie Lu for mass spectra, and Juan Hu for DR-IR spectra measurements. The authors gratefully acknowledge support for this research from the NSFC (20373013, 204213031, 20521140450), the State Key Basic Research Program of PRC (2001CB610506, 001CB510202), the Shanghai Science and Technology Committee (03527001, 04 JC14087), the Shanghai Education Committee (02SG01), and the Program for New Century Excellent Talents in University. Supporting information for this article is available on the WWW under http://www.small-journal.com or from the author. small 2006, 2, No. 4, 517 – 521 # 2006 Wiley-VCH Verlag GmbH & Co. KGaA, D-69451 Weinheim 517