化学所仿生制备多通道微纳米管取得新进展

    由于微纳米管特殊的物理化学性质在很多领域都有广阔的应用前景,管状微纳米材料的制备与应用在近年来受到科研人员的广泛关注。自然界中的许多生物采用了多通道的超细管状结构，例如：许多植物的茎都是中空的多通道微米管，这使其在保证足够强度的前提下可以有效节约原料及输运水和养分；鸟类的羽毛也具有多通道管状结构，这可以极大地减轻重量以及保温；许多极地动物能够在严寒的环境中生存下来，也是因为其皮毛具有多通道或多空腔的微纳米管状结构赋予其卓越的隔热性能。
    化学所有机固体院重点实验室江雷研究员领导的课题组近几年一直致力于仿生纳米材料的研究工作。最近，在国家自然科学基金委、科技部、中国科学院的大力支持下，研究人员在仿生制备多通道微纳米管方面取得突破，成功得到了具有内部通道数目可控的多通道TiO2微纳米管。相关工作已经申请专利并发表在  J.  Am.  Chem.  Soc.(2007,  Vol.  129,  No.  4,  p.  764-765)上。
    他们提出了一种新颖的多流体复合电纺丝方法，通过简单的调控内流体的数目，就可以精确得到与内流体相应数目的2，3，4，5……通道微米管。该方法简单通用，易于大规模制备，广泛适用于无机和有机材料体系。这种多通道管具有很多独特的优势，比如：更大的比表面积，更节约原料以及更好的结构稳定性。这些特性使其在高效催化、超滤分离、微纳流体管路、超保暖织物以及多组分药物输运等领域具有广泛的应用前景。该工作已被选为American  Chemical  Society  News并被多家国内外网站报道。  

英文原文：

J. Am. Chem. Soc., 129 (4), 764 -765, 2007. 10.1021/ja068165gS0002-7863(06)08165-0
Web Release Date: January 5, 2007 Copyright © 2007 American Chemical Society

Bio-mimic Multichannel Microtubes by a Facile Method

Yong Zhao,Xinyu Cao, andLei Jiang*

Center of Molecular Sciences, Institute of Chemistry, The Chinese Academy of Sciences, Beijing 100080, P. R. China, Graduate School of Chinese Academy of Sciences, Beijing 100080, P. R. China

Received November 15, 2006

Abstract:

Bio-mimic multichannel microtubes were fabricated by a novel multifluidic compound-jet electrospinning technique. The channel number, diameter, and inner morphology of tubes are all controllable. This method is very simple and promising. The multichannel tubes should be of broad applications, such as for bio-mimic materials, macro/nanofluidic devices, high efficient catalysts, and multicomponent drug delivery.

Envied by many scientists, delicate multichannel (or multichamber) tubular structures have been adopted by a number of animals in long-term evolution. For example, feathers of many birds are of multichannel inner structure. It could reduce weight by increasing friction with air and serve as heat-shields from intense solar radiation.1 To survive in an extremely formidable polar environment, pelts of some polar homeothermic species (e.g., polar bear) show excellent thermoinsulation properties which also benefit from their hair with multichamber structures.2 These attractive features of nature are all results from the unique multichannel tubular inner structures.

Partially similar with nature, traditional nanotubes with a single inner channel have attracted considerable interest for their broad applications.3 Accordingly, various strategies have been proposed for building these materials.4 Recently, another promising coaxial electrospinning method has been developed for preparing ultralong nanotubes.5-8 Electrospinning is a versatile top-down method for manufacturing 1-D nanomaterials9 with various applications.10,11 Coaxial electrospinning is an evolution of electrospinning, which is based on a spinneret consisting of two coaxial capillaries with different diameters. By co-electrospinning two fluids with such special spinneret, nanotubes or core-shell nanofibers can be prepared.5-8 Although methods for production of single channel nanotubes have been well established, artificial mimic multichannel tubular structures of nature in micro- to nanometer scale are still a giant challenge. To meet the emerging needs of multifunctional, integrative, and miniature devices, micro/nanomaterials with more complex inner structures are urgently expected.

In this communication, we describe a multifluidic compound-jet electrospinning technique for the first time that could fabricate bio-mimic hierarchical multichannel microtubes in a facile and straightforward way. The experimental setup of the multifluidic compound-jet electrospinning is sketched in Figure 1a, where the three-channel tube (TCT) fabrication system is demonstrated as an example. Three metallic capillaries embedded in a plastic syringe were arranged at three vertexes of an equilateral triangle. These conductive metallic inner capillaries serve as inner fluid vessels and electrode at the same time. Two immiscible viscous liquids were fed separately to the three inner capillaries and an outer syringe in an appropriate flow rate. An ethanol solution of Ti(OiPr)4 and poly(vinyl pyrrolidone)6 served as outer liquid, while a commercially available innocuous paraffin oil was chosen for inner liquid. After a compound fluidic electrospinning process, a fibrous film was collected on the counter electrode. By removing the organics of as-prepared products through calcination, TiO2 TCT was obtained.

Figure 1 (a) Schematic illustration of the three-channel tube fabrication system. The immiscible inner and outer fluids (red for paraffin oil and blue for Ti(OiPr)4 solution) were issued out separately from individual capillaries. When an appropriate high electric potential was applied, a liquid thread jetted out from the vertex of the compound drop and then formed a fibrous film on the counter electrode. The inset shows the outlet section of the spinneret. (b) Side-view SEM image of sample after the organics have been removed. (c) Magnified SEM image of tubes in which the channels were divided into three independent flabellate parts by a Y-shape inner ridge. (d) TEM image of a three-channel tube; the individual channels of tube are straight and continuous.

Figure 1b is a side-view image of the sample taken by field emission scanning electron microscopy (SEM), which exposes the cross section of the TCT. It can be clearly seen that most of tubes are of hollow structures with three cavums. The diameter distribution of the tubes is relatively uniform with an average value of 2.3 m. More details of inner structures of TCT are revealed in Figure 1c. A three-pointed star shape trifurcate ridge embeds in the tube shell and partitions the tube into three flabellate parts. The inner channels of the tube correspond to the vacancy of the inner fluids after they were removed. Figure 1d shows the transmission electron microscopy (TEM) image of TCT. It is obvious that the middle wall of the Y-shape ridge in the vertical direction is straight and divides the tube into "two" parallel equal parts without discontinuity (the tube should be divided into three parts actually, but only one ridge can be clearly shown in the TEM image, and the other two ridges are difficult to be seen because of the trifurcate geometry).

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The rational design of spinneret is utmost important to the successful fabrication of TCT. To ensure outer fluid could surround three inner fluids effectively, each inner capillary is isolated from the other two capillaries and the outer nozzle. The gaps between each capillary and the capillary to the inner wall of the outer nozzle are equal. Such spinneret makes inner liquids flow out independently and do not mix with each other. In the multifluidic compound-jet electrospinning process, the outer Ti(OiPr)4 solution and inner paraffin oil were co-issued from respective nozzles, and the outer liquid flowed through the gaps between three capillaries and formed a liquid jacket envelope for the three inner fluids. When the high voltage was applied, the conductive outer solution (75.0 S·cm-1) was charged and the compound liquid was stretched and whipped to a thin liquid thread in order to release the static electric repulse by dispersing electric charge.9 However, this repulsive force could not act on the three inner fluids directly because of the insulation of paraffin oil (0.05 S·cm-1). This means that the paraffin oil cannot be electrospun on its own. As a result, the inner fluids were subjected to the pressure transferred from the outer fluid and were compressed to a thin liquid thread accompanied with an outer liquid. At the same time, with the evaporation of solvent and gelation of Ti(OiPr)4, the outer liquid shell solidified very quickly and suppressed the Reyleigh instability of the whipping jet.9 Consequently, solid tubes with three independent channels formed in which paraffin oil was enveloped.

There were two great progresses in the evolution of electrospinning: coaxial electrospinning5-8 and dual nozzle side-by-side electrospinning.12 A number of biphase core-shell or anisotropic Janus materials were obtained by these two methods. However, both of them were limited to two fluid systems and cannot be applied for producing multicomponent materials. The multifluidic compound-jet electrospinning technique breaks through the limit that could generate programmable multichannel or multicomponent 1-D micro/nanomaterials in a simple and promising way. As a matter of fact, tubes with two to five channels have been successfully fabricated. Figure 2a-d exhibits the cross section of these tubes. The insets describe the corresponding schematic diagram of spinneret. All of the multichannel tubes show good fidelity to the respective spinneret. It validates the effectiveness of this multifluidic compound-jet electrospinning technique. We do believe that tubes with six or even more inner channels could be fabricated by adjusting the parameters of the experiments. Besides channel number, the tube diameter, surface roughness, wall thickness, and inner ridge morphology are also easily controllable. For instance, the diameter of TCT could vary from several micron (Figure 1c) to micron (Figure 2b) to hundreds of nanometers by adjusting the experimental conditions (see Supporting Information).

Figure 2 SEM images of multichannel tubes with variable diameter and channel number. (a-d) Corresponding to tube with channel number from two to five. The inset in each figure shows the cross section illustration of spinneret that was used to fabricate the tube. The as-prepared tubes accord very well with the corresponding spinneret. Scale bars are 100 nm.   In summary, we developed a very simple and powerful multifluidic compound-jet electrospinning technique for fabricating bio-mimic multichannel microtubes that have been seldom obtained by other means. Compared with single channel, multichannel structures may possess considerable advantages such as independent addressable channels, better mechanic stability, and larger surface-to-volume area. Furthermore, by replacing inner fluids with other functional materials, multicore-shell nanofibers would be created and different components could be integrated in the nanodomain without interaction. Such compound nanofibers should be of novel and improved properties that do not exist in each component. It is a promising candidate for a wide range of applications, such as for bio-mimic super-lightweight thermoinsulated textiles, vessels for macro/nanofluidic devices, multicomponent drug delivery, and high efficient catalysts. Acknowledgment The authors thank the Special Research Foundation of the National Nature Science Foundation of China (G.90306011 and G.20571077) for continuing financial support. The Chinese Academy of Sciences is gratefully acknowledged. Supporting Information Available Detailed experimental procedures, characteristics of materials, and control of multichannel tube structures. This material is available free of charge via the Internet at http://pubs.acs.org. * In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed. Institute of Chemistry, The Chinese Academy of Sciences. Graduate School of Chinese Academy of Sciences. 1. Dyck, J. Zool. Scr. 1985, 14, 137-154. [CrossRef]  2. Grojean, R. E.; Sousa, J. A.; Henry, M. C. Appl. Opt. 1980, 19, 339-346. 3. (a) Hu, J. T.; Odom, T. W.; Lieber, C. M. Acc. Chem. Res. 1999, 32, 435-445.[Full text - ACS] [ChemPort]  (b) Law, M.; Goldberger, J.; Yang, P. D. Annu. Rev. Mater. Sci. 2004, 34, 83-122. [ChemPort] [CrossRef]  4. (a) Steinhart, M.; Wendorff, J. H.; Greiner, A.; Wehrspohn, R. B.; Nielsch, K.; Schilling, J.; Choi, J.; Gösele, U. Science 2002, 296, 1997-1997. [ChemPort] [Medline] [CrossRef]  (b) Schmidt, O. G.; Eberl, K. Nature 2001, 410, 168-168. [ChemPort] [Medline] [CrossRef]  5. (a) Loscertales, I. G.; Barrero, A.; Guerrero, I.; Cortijo, R.; Marquez, M.; Gañn-Calvo, A. M. Science 2002, 295, 1695-1698. [ChemPort] [Medline] [CrossRef]  (b) Larsen, G.; Velarde-Ortiz, R.; Minchow, K.; Barrero, A.; Loscertales, I. G. J. Am. Chem. Soc. 2003, 125, 1154-1155.[Full text - ACS] [ChemPort] [Medline]  (c) Loscertales, I. G.; Barrero, A.; Mrquez, M.; Spretz, R.; Velarde-Ortiz, R.; Larsen, G. J. Am. Chem. Soc. 2004, 126, 5376-5377.[Full text - ACS] [ChemPort] [Medline]  6. (a) Li, D.; Xia, Y. N. Nano Lett. 2004, 4, 933-938.[Full text - ACS] [ChemPort]  (b) Li, D.; McCann, J. T.; Xia, Y. N. Small 2005, 1, 83-86. [ChemPort] [Medline] [CrossRef]  (c) McCann, J. T.; Li, D.; Xia, Y. N. J. Mater. Chem. 2005, 15, 735-738. [ChemPort] [CrossRef]  7. Sun, Z. C.; Zussman, E.; Yarin, A. L.; Wendorff, J. H.; Greiner, A. Adv. Mater. 2003, 15, 1929-1932. [ChemPort] [CrossRef]  8. (a) Yu, J. H.; Fridrikh, S. V.; Rutledge, G. C. Adv. Mater. 2004, 16, 1562-1566. [ChemPort] [CrossRef]  (b) Wang, M.; Yu, J. H.; Kaplan, D. L.; Rutledge, G. C. Macromolecules 2006, 39, 1102-1107.[Full text - ACS] [ChemPort]  9. (a) Reneker, D. H.; Chun, I. Nanotechnology 1996, 7, 216-223. [ChemPort] [CrossRef]  (b) Reneker, D. H.; Yarin, A. L.; Fong, H.; Koombhongse, S. J. Appl. Phys. 2000, 87, 4531-4547. [ChemPort] [CrossRef] (c) Li, D.; Xia, Y. N. Adv. Mater. 2004, 16, 1151-1170. [CrossRef]  (d) Huang, Z. M.; Zhang, Y. Z.; Kotaki, M.; Ramakrishna, S. Compos. Sci. Technol. 2003, 63, 2223-2253. [ChemPort] [CrossRef]  10. (a) Patel, A. C.; Li, S. X.; Yuan, J. M.; Wei, Y. Nano Lett. 2006, 6, 1042-1046.[Full text - ACS] [ChemPort] [Medline]  (b) Matthews, J. A.; Wnek, G. E.; Simpson, D. G.; Bowlin, G. L. Biomacromolecules 2002, 3, 232-238.[Full text - ACS] [ChemPort] [Medline]  (c) Caruso, R. A.; Schattka, J. H.; Greiner, A. Adv. Mater. 2000, 13, 1577-1579. 11. (a) Jiang, L.; Zhao, Y.; Zhai, J. Angew. Chem., Int. Ed. 2004, 43, 4338-4341. [ChemPort] [CrossRef]  (b) Zhu, Y.; Zhang, J. C.; Zheng, Y. M.; Huang, Z. B.; Feng, L.; Jiang, L. Adv. Funct. Mater. 2006, 16, 568-574. [ChemPort] [CrossRef]  (c) Zhu, Y.; Zhang, J. C.; Zhai, J.; Zheng, Y. M.; Feng, L.; Jiang, L. Chem. Phys. Chem. 2006, 7, 336-341. [ChemPort]  (d) Zhao, Y.; Zhai, J.; Tan, S. X.; Wang, L. F.; Jiang, L.; Zhu, D. B. Nanotechnology 2006, 17, 2090-2097. [ChemPort] [CrossRef]  12. (a) Madhugiri, S.; Dalton, A.; Gutierrez, J.; Ferraris, J. P.; Balkus, K. J., Jr. J. Am. Chem. Soc. 2003, 125, 14531-14538.[Full text - ACS] [ChemPort] [Medline]  (b) Roh, K. H.; Martin, D. C.; Lahann, J. Nat. Mater. 2005, 4, 759-763. [ChemPort] [Medline] [CrossRef]