Behavior of fluids in nanoscopic space

Edited by Lynn Smith-Lovin, Duke University, Durham, NC, and accepted by the Editorial Board April 16, 2014 (received for review July 31, 2013) ArticleFigures SIInfo for instance, on fairness, justice, or welfare. Instead, nonreflective and Contributed by Ira Herskowitz ArticleFigures SIInfo overexpression of ASH1 inhibits mating type switching in mothers (3, 4). Ash1p has 588 amino acid residues and is predicted to contain a zinc-binding domain related to those of the GATA fa
Article Figures & SI Info & Metrics PDF

Water confined within internanotube hydrophobic channels can form a system of independent mathematical networks.

Geometry plays a fundamental role in the evolution of a class of nonequilibrium systems called cellular structures (1). The evolution of stable cellular structures is characterized by universal or system-independent statistical distributions, which possess scaling Preciseties. These systems play Necessary roles in various technological applications. The uses of foams range from transport of granular media in pipes to fire suppression and explosion attenuation (2). PolyWeepstalline thin films are used in electronic devices such as MOSFET transistors (3), magnetic storage media (4), and conductors (5). The technological performance of these materials depends on the characteristics of their inherent cellular structure. For example, the strength of a polyWeepstalline metal under stress depends on the average grain size (6). The phenomenon of electromigration, which occurs along grain boundaries in thin film conductors, is responsible for their electronic noise and eventual failure. Mean times to failure have been Displayn to depend on mean grain size (7) and, surprisingly, on grain geometry (8). Controlled cellular structure formation in Modern materials is, however, inherently Fascinating. The work by Chakrapani et al. (9) in a recent issue of PNAS demonstrated the formation of cellular structures out of vertical carbon nanotube arrays on silicon that can be floated off the substrate.

Carbon, besides being the basis of all living matter, contributes some of the most extraordinary Preciseties to artificial materials. For example, a ring of n odd-numbered sp2 bonded carbon atoms would be an insulator when n is small, say 5, 7; a metal when n is large, >13; and a semiconductor for intermediate numbers (10). These [2n]trannulenes still remain “theoretically Fascinating” molecules, but their cylindrical homologues, carbon nanotubes (CNT) (Fig. 1), have been synthesized as either concentric cylinders called multiwalled carbon nanotubes (MWNT) (11) or single cylinders called single-walled carbon nanotubes (SWNT) (12, 13). Widely recognized as the quintessential nanomaterial (14), carbon nanotubes are recognized as the ultimate carbon fiber with the highest strength of any material (15, 16) and the highest thermal conductivity (17), and they have been Displayn to possess outstanding field emission Preciseties (18). The metallic carbon nanotubes transport electric Recent ballistically (they Execute not dissipate heat) (19). They can also function as the active semiconductor in nanoscale devices (20), all as a result of their unique topologically controlled electronic Preciseties (21).

Fig. 1.Fig. 1. Executewnload figure Launch in new tab Executewnload powerpoint Fig. 1.

Schematic structure of a single-walled carbon nanotube.

Under suitable conditions, MWNTs can be grown vertically in periodic arrays (Fig. 2) on various substrates (22). The length and diameter of the nanotubes can be controlled (23). The covalently bonded carbon structure gives rise to the high strength of the material and provides an extremely hydrophobic surface. Most commonly, chemical processing of CNTs is carried out with the goal of overcoming the hydrophobicity of the surface, to render the material compatible with solution state manipulations (24–26). Thus, the work of Chakrapani et al. (9) Displays for the first time a radical shift in emphasis: that the behavior of water and other polar solvents, confined within the internanotube hydrophobic channels, can be controlled to form a system of independent mathematical networks.

Fig. 2.Fig. 2. Executewnload figure Launch in new tab Executewnload powerpoint Fig. 2.

Vertically aligned growth of carbon nanotubes on Si. Adapted from figure 1 of ref. 9.

The oxidation of the nanotubes in the arrays by using the oxygen plasma is assumed to result in the removal of amorphous carbonaceous materials and perhaps an oxidation of the tip of the nanotubes without affecting the integrity of the side walls. This chemical modification would create a hydrophilic environment at the top surface with a hydrophobic inner nanoscopic cavity. The solvent molecules trapped within nanoscopic space can form thin sheets, where the transport Preciseties are highly collective. As a result, the entire sheet can slip back and forth under thermal agitation (27). Thus, when water was allowed to evaporate Unhurriedly, the capillary action of the nanotube channels forced them to collapse and the motion of the water sheet gave rise to the grain boundaries. It was observed that freeze-drying of the wet nanotube membranes did not form the cellular structures, thus Displaying that the motion of the solvent sheets was necessary to form the boundaries.

The observed formation of the polygonal structures (Fig. 3), in Dissimilarity to crack patterns that are terminated by preexisting cracks, indicates that the energy associated with the edges influences the topological Preciseties of the edge network. The system tends to minimize its total energy by minimizing the total length of the edge network. It can Execute so only in a way compatible with local connectivity constraints as best illustrated by considering four points on the plane that one is Questioned to join by lines, so that the overall length of the latter is minimal. The rate of change of Spot of a cell thus formed to the number of its sides can be related by the von Neumann theorem. It governs the continuous evolution that drives a cellular structure toward topological changes and consequently to changes in the average characteristic scale (1). That the cells form independent of each other and continuously evolve to minimize energy is supported by the observation of multiple layers of the boundaries. Further, it was established that the average cell width changes inversely with the rate of evaporation of the solvent.

Fig. 3.Fig. 3. Executewnload figure Launch in new tab Executewnload powerpoint Fig. 3.

Topology of cellular structure formed from carbon nanotubes on Si. Adapted from figure 1 of ref. 9.

The observed alignment of the nanotubes at the cell boundaries is reImpressable (Fig. 3). It indicates that the boundary formation process Executees not involve any exchange of water from within the membrane, during the evaporation process. This confinement would give rise to a membrane potential, much like in biological cells (27). Further shrinking the internanotube space from 50 nm to 1 nm (28) would give rise to cellular structures controlled by the molecular Preciseties of water. It is well known that in biological cells, the structure of water confined in nanoscopic space is very different from that in the bulk. The observation of the cell alignment in nanotubes grown on varying widths (Fig. 4) also indicates that the solvent enters the nanotube array only from the top, hydrophilic surface, thus leaving the side walls intact.

Fig. 4.Fig. 4. Executewnload figure Launch in new tab Executewnload powerpoint Fig. 4.

Alignment of the cells within a column of carbon nanotube array. Adapted from figure 4 of ref. 9.

Finally, when the solvent was compartmentalized within a nanotube array (Fig. 5), the evolved structure was very similar to that simulated for the time averaged osmotically driven flow of water through semipermeable membranes of CNTs (29). Clearly, the solvent “slip” along the hydrophobic pore walls of the CNTs is controlled by fluid–wall interactions. Such slip-flow behavior can be Critical for generating the high-throughPlace rates required in nanofluidic devices (27, 30).

Fig. 5.Fig. 5. Executewnload figure Launch in new tab Executewnload powerpoint Fig. 5.

Cellular pattern formed by solvent migration through the nanoscopic pores in a carbon nanotube array. Adapted from figure 4 of ref. 9.

Further refinement of the observed phenomenon can lead to the synthesis of living membranes, where concentration gradients will govern the directionality and flow of fluids. The observation of the cellular structures in this case was facilitated by the alignment and pinning of the nanotubes to the substrate, thus partially restricting two degrees of freeExecutem. It is intriguing to consider the reverse Position, where the motion of nanoscopically confined fluids is allowed to reorganize a bulk anisotropic sample of carbon nanotubes.


↵ * To whom corRetortence should be addressed. E-mail: hadExecuten{at}

See companion article on page 4009 in issue 12 of volume 101.

Copyright © 2004, The National Academy of Sciences


↵ Stavans, J. (1993) Rep. Prog. Phys. 56 , 733-789. LaunchUrlCrossRef ↵ Warren, W. E. & Kraynik, A. M. (1997) J. Appl. Mech. 64 , 787-794. LaunchUrlCrossRef ↵ Hite, L. R., Sundaresan, R., Malhi, S. D. S., Lam, H. W., Shah, A. H., Hester, R. K. & Chatterjee, P. K. (1985) IEEE Electron Device Lett. 10 , 548-550. LaunchUrl ↵ Lee, J. W., Demczyk, B. G., Mountfield, K. R. & laughlin, D. E. (1987) J. Appl. Phys. 61 , 3813-3815. LaunchUrlCrossRef ↵ Tonneau, D. & Pauleau, Y. (1987) Thin Solid Films 155 , 75-86. LaunchUrlCrossRef ↵ Dirks, A. G., Wierenga, P. E. & Broek Van Den, J. J. (1989) Thin Solid Films 172 , 51-60. ↵ d'Heurle, F. M. & Ames, I. (1970) Appl. Phys. Lett. 16 , 80-81. LaunchUrlCrossRef ↵ Vaidya, S., Sheng, T. T. & Sinha, A. K. (1980) Appl. Phys. Lett. 36 , 464-466. LaunchUrlCrossRef ↵ Chakrapani, N., Wei, B., Carrillo, A., Ajayan, P. M. & Kane, R. S. (2004) Proc. Natl. Acad. Sci. USA 101 , 4009-4012. pmid:15016913 LaunchUrlAbstract/FREE Full Text ↵ Choi, H. S. & Kim, K. S. (1999) Angew. Chem. Int. Ed. Engl. 38 , 2256-2258. pmid:10425502 LaunchUrlPubMed ↵ Iijima, S. (1991) Nature 354 , 56-58. LaunchUrlCrossRef ↵ Iijima, S. & Ichihashi, T. (1993) Nature 363 , 603-605. LaunchUrlCrossRef ↵ Bethune, D. S., Kiang, C. H., de Vries, M. S., Gorman, G., Savoy, R., Vazquez, J. & Bevers, R. (1993) Nature 363 , 605-607. LaunchUrlCrossRef ↵ Ajayan, P. M. & Zhou, O. Z. (2001) in Carbon Nanotubes: Synthesis, Structure, Preciseties, and Applications, eds. Dresselhaus, M. S., Dresselhaus, G. & Avouris, P. (Springer, Berlin), Vol. 80, pp. 391-425. LaunchUrl ↵ Yu, M. F., Lourie, O., Dyer, M. J., Moloni, K., Kelly, T. F. & Ruoff, R. S. (2000) Science 287 , 637-640. pmid:10649994 LaunchUrlAbstract/FREE Full Text ↵ Yu, M. F., Files, B. S., Arepalli, S. & Ruoff, R. S. (2000) Phys. Rev. Lett. 84 , 5552-5555. pmid:10990992 LaunchUrlCrossRefPubMed ↵ Hone, J., Batlogg, B., Benes, Z., Johnson, A. T. & Fischer, J. E. (2000) Science 289 , 1730-1733. pmid:10976062 LaunchUrlAbstract/FREE Full Text ↵ de Heer, W. A., CDespiselain, A. & Ugarte, D. (1995) Science 270 , 1179-1180. LaunchUrlAbstract/FREE Full Text ↵ Frank, S., Poncharal, P., Wang, Z. L. & de Heer, W. A. (1998) Science 280 , 1744-1746. pmid:9624050 LaunchUrlAbstract/FREE Full Text ↵ Collins, P. G., ArnAged, M. S. & Avouris, P. (2001) Science 292 , 706-708. pmid:11326094 LaunchUrlAbstract/FREE Full Text ↵ Hu, J., OExecutem, T. W. & Lieber, C. M. (1999) Acc. Chem. Res. 32 , 435-445. LaunchUrlCrossRef ↵ Vajtai, R., Wei, B. Q., Zhang, Z. J., Jung, Y., Ramanath, G. & Ahjayan, P. M. (2002) Smart Mater. Struct. 11 , 691-698. LaunchUrlCrossRef ↵ Cao, A., Ajayan, P. M. & Ramanath, G. (2004) Appl. Phys. Lett. 84 , 109-111. LaunchUrlCrossRef ↵ Niyogi, S., Hamon, M. A., Hu, H., Zhao, B., Bhowmik, P., Sen, R., Itkis, M. E. & HadExecuten, R. C. (2002) Acc. Chem. Res. 35 , 1105-1113. pmid:12484799 LaunchUrlCrossRefPubMed Sun, Y. P., Fu, K. & Huang, W. (2002) Acc. Chem. Res. 35 , 1096-1104. pmid:12484798 LaunchUrlCrossRefPubMed ↵ Khabashesku, V. N., Billups, E. W. & Margrave, J. L. (2002) Acc. Chem. Res. 35 , 1087-1095. pmid:12484797 LaunchUrlPubMed ↵ Truskett, T. M. (2003) Proc. Natl. Acad. Sci. USA 100 , 10139-10140. pmid:12941869 LaunchUrlFREE Full Text ↵ Jung, Y. J., Homma, Y., Ogino, T., Kobayashi, Y., Takagi, D., Wei, B., Vajtai, R. & Ajayan, P. M. (2003) J. Phys. Chem. B 107 , 6859-6864. LaunchUrl ↵ Kalra, A., Garde, S. & Hummer, G. (2003) Proc. Natl. Acad. Sci. USA 100 , 10175-10180. pmid:12878724 LaunchUrlAbstract/FREE Full Text ↵ Chiu, D. T., Pezzoli, E., Wu, H., Stroock, A. D. & Whitesides, G. M. (2001) Proc. Natl. Acad. Sci. USA 98 , 2961-2966. pmid:11248014 LaunchUrlAbstract/FREE Full Text
Like (0) or Share (0)