Chemistry of inorganic compounds – Oxygen or compound thereof – Metal containing
Reexamination Certificate
2000-07-24
2003-01-07
Bos, Steven (Department: 1754)
Chemistry of inorganic compounds
Oxygen or compound thereof
Metal containing
C423S605000
Reexamination Certificate
active
06503476
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention relates to manganese oxide compositions. In particular, this invention relates to mixed-valence manganese oxide compositions capable of self-assembly into helices, rings, strands, and films.
The pursuit of new conducting thin films and wires has long been a goal of molecular engineering. Various materials of different morphologies have been pursued to fill the needs for various end-uses such as sensors, new conducting materials to enhance computing speed and storage density, and as effective membrane materials for separations.
Helical structures have been shown to occur at the nanomolecular, macromolecular, and molecular levels and are widely found throughout nature (see Rowan, A. E.; Nolte, R. J. M.
Angew. Chem. Int. Ed.,
1998, 37, 63-68). However, purely inorganic helices have only recently been reported (see Soghomonian, V.; Chen, Q.; Haushalter, R. C.; Zubieta, J.; O'Connor, C. J.; Lee, Y. S.,
Science,
1993, 259, 1596-1599). Transition metal arsenate and germanate zeolite-like UCSB-7 systems have been shown to have helical 3-D pores (see Gier, T. E.; Bu, X.; Feng, P.; Stucky, G. D.,
Nature,
1998, 395, 154-57). Chemical vapor deposition methods have been used to coat carbon and form inorganic ceramic spiral materials such as Si
3
N
4
(see Motojima, S.; Ueno, S.; Hattori, T.; Goto, K.
Appl. Phys. Lett.,
1989, 54, 1001-1003). Coil diameters of 10-15 microns have been observed. The formation of helices of MCM-41 type materials has been suggested for silicate systems and a true liquid crystal templating effect has been proposed (see Raimondi, M. E.; Maschmeyer, T.; Templer, R. H.; Seddon, J. M.
J. Chem. Soc. Chem. Comm.,
1997, 1843-1844). Redox active nanotubes of mixed valent vanadium oxide having diameters on the order of 0.5 to 4 nm have recently been reported (see Spahr, M. E.; Bitterli, P.; Nesper, R.; Muller, M.; Krumeich, F.; Nissen, H. U.
Angew. Chem. Int. Ed.,
1998, 37, 1263-1265). Large pore semicrystalline mesoporous transition metal oxides of manganese and other transition metals have been reported (see Tian, Z. R.; Tong, W.; Wang, J. Y.; Duan, N.; Krishnan, V. V.; Suib, S. L.
Science,
1997, 276, 926-930; and Yang, P.; Zhao, D.; Margolese, D. I.; Chmika, B. F.; Stucky, G. D.
Nature,
1998, 396, 152-155). Recently, disk-shaped crown ether phthalocyanine and polysiloxane coiled-coil aggregates, of 50 nm diameter and a few microns in length, have been grown in organic gels (see Engelkamp, H.; Middelbeek, Nolte, R. J. M.
Science,
1999, 284, 785-788). Filaments of single crystalline Ga a few cm in length and on the order of 2-100 microns diameter have recently been reported to grow via de-intercalation of Cr
2
GaN (see Barsoum, M. W.; Farber, L.
Science,
1999, 284, 937-939).
Metallic self-assembled rings of 0.9 micron diameter for potential use in electron transfer and in optical devices where the annulus widths and surface ring coverages can be controlled, have more recently been reported (see Ohara, P. C.; Heath, J. R.; Gelbart, W. M.
Angew. Chem. Int. Ed.,
1997, 36, 1078-1080). Ring stains and deposits have been observed, and mechanisms for their formation have recently been related to capillary flow effects (see Deegan, R. D.; Bakajin, O.; Dupont, T. F.; Huber, G.; Nagel, S. R.; Witten, T. A.,
Nature,
1997, 389, 827-829). Control of 20 to 300 nmn widths of silver nanocrystalline wires on carbon coated copper grids was achieved via Langmuir-Schaeffer horizontal liftoff methods (see Chaung, S. W.; Markovich, G.; Heath, J. R.
J. Phys. Chem.,
1998, 102, 6685-6687). Rings of manganese oxide nanocrystals of 40 nm diameters have been photodeposited on mica (see Yamamoto, S.; Matsuoka, O.; Sugiyama,
S. Chem. Lett.,
1998, 809-810). Wires of manganese and manganese oxide are not known due to inherent problems with brittleness.
Helices have been reported to form as irreproducible curiosities under strongly imposed concentration gradients, and stochastic processes dominate in gradient-free precipitating systems. (see Muller, S. C.; Kai, S.; Ross,
J. Science,
1982, 216, 635-637). Structure formation in precipitating colloidal systems has been observed since more than a century ago, for example, in systems where a salt is allowed to diffuse in a gel containing another salt. Rings, Saturn-rings and even helices have been observed in such gradient and so-called Liesegan g systems (see Liesegang, R. E.;
Naturwiss Wochenschr.
1896, II, 353; Lloyd, F. E.; Moravek, V.
J. Phys. Chem.,
1931, 35, 1512-1564; Muller, S. C.; Kai, S.; Ross,
J. Science,
1982, 216, 635-637; Polezhaer, A. A.; Muller, S. C.
Chaos,
1994, 4, 631-636). However, no isolation of these structures, and furthermore, no functionality has ever been reported. Reproducible formation of helices in gradient-free rather than Liesegang (gradient) systems by self-organization along the hole volume of the system has not been reported.
SUMMARY OF THE INVENTION
Self-assembled helices, rings, and strands, as well as films, are formed by a method comprising:
preparing a solution comprising (a) a mixed-valence manganese oxide anion having an average manganese oxidation state of about 3 to about 4, (b) a quaternary arnmonium cation, and (c) a solvent;
contacting the solution with a surface comprising hydroxyl groups; and
evaporating the solvent to form a mixed-valence manganese oxide material.
The invention also relates to compositions formed by the method, as well as to the helixes, rings, strands, and films formed by the method.
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Barsoum, M. W., et al, “Room-Temperature Deintercalation and Self-Extrusion of Ga from Cr2 GaN”, Science, 1999, vol. 284, pp. 937-939, May.
Chung, S. W., et al, “Fabrication and Alignment of Wires in Two Dimensions”, J. Phys. Chem., 1998, vol. 102, pp. 6685-6687, Aug.
Deegan, R. D., et al, Capillary Flow as the Cause of Ring Stains from Dried Liquid Drops, Nature, 1997, vol. 389, 827-829, Oct.
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Gier, T. E., et al, “Synthesis and Organization of Zeolite-Like Materials With Three-Dimensional Helical Pores”, Nature, 1998, vol. 395, 154-57, Sep.
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Rowan, Alan E., et al, “Helical Molecular Programming”, Angew. Chem. Int. Ed., 1998, vol. 37, pp. 63-68, No month.
Soghomonian, V., et al, “An Inorganic Double Helix: Hydrothermal Synthesis Structure, and Magnetism of Chiral [(CH3)2NH2K4V10O10(H2O)2(OH)4(PO4)7] 4H20”, Science, 1993, vol. 259, pp. 1596-1599, Mar.
Spahr, M. E., et al, “Redox-Active Nanotubes of Vanadium Oxide”, Angew. Chem. Int. Ed., 1998, vol. 37, pp. 1263-1265, May.
Strobel, P., et al, “Thermal and Physical Properties of Ho
Brock Stephanie
Giraldo Oscar
Marquez Manuel
Suib Steven L.
Bos Steven
Cantor & Colburn LLP
The University of Connecticut
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