KR20070017319A - Inorganic nanowires - Google Patents

Abstract

An inorganic nanowire having an organic scaffold substantially removed from the inorganic nanowire and consisting essentially of fused inorganic nanoparticles substantially free of an organic skeleton, and a method for preparing the same. For example, viral-based backbones for the synthesis of single crystal ZnS, CdS and free-standing L10 CoPt and FePt nanowires can be used with means for modifying substrate specificity through standard biological methods. Peptides can be selected via evolutionary screening methods that control composition, size, and phase during nanoparticle nucleation, which were expressed on highly ordered filamentous capsids of M13 bacteriophages. Mixing specific nucleation peptides into the general backbone of the M13 envelope structure can provide viral templates for direct synthesis of a variety of materials including semiconducting and magnetic materials. Removal of the viral template through annealing can promote oriented crystal growth (forming individual crystalline nanowires) based on aggregation. The unique ability to incorporate substrate specific peptides into the linear self-assembled filamentous structures of the M13 virus introduces material tunability not seen in conventional synthetic routes. Thus, the system provides a genetic toolkit for growing and organizing nanowires from a variety of materials, including semiconducting and magnetic materials.

Description

Inorganic Nanowires {INORGANIC NANOWIRES}

This application claims benefit under 35 USC 119 (e) for US Provisional Application No. 60 / 534,102 (filed Jan. 5, 2004, Belcher et al.), Which is incorporated herein by reference in its entirety. .

This study was conducted by NIRT from National Science Foundation (Grant No. _); From the Defense Research Office (grant number _); He was also supported by the Air Force Scientific Research Office (grant number _). The government may have rights to the invention.

introduction

The reliability of a wide variety of technologies in the development of scalable and cost-effective one-dimensional material fabrication methods, including nanowires and nanotubes, has sparked intense and rapid development in the field of material synthesis. For example, one-dimensional materials have been intensively studied for their application, for example, in the study of (1) electric transporters, (2) optical phenomena, and (3) functional units in nanocircuits. The performance of the "bottom up" method for the synthesis of semiconducting, metallic and magnetic nanowires yielded a variety of synthetic strategies, including (4) vapor liquid solids (VLS), (5) chemical, (6) Solvent thermal, vapor phase, and mold derivatization fabrication include, but are not limited to. Each method developed for the production of nanowires has achieved some basic success in achieving high quality materials, but has not produced monodisperse crystalline nanowires of essentially different compositions. Typically, conventional methods for nanowire fabrication are distracting, synthetically cumbersome, and not universal. See, for example, US Pat. No. 6,225,198 (Alivisatos et al.) And references cited therein for the manufacture of II-VI semiconductors in liquid media. Reference 4 to Lieber et al. States that it is difficult to find a universal approach. This describes a VLS process for producing nanowires with distal nanoparticles that require the use of lasers and high temperatures and which may be undesirable.

Recently, biological factors have been developed as synthetic derivatives for (7, 8) nanofibers, (9) virus based particle cages, (10, 11, 12) virus-particle assemblies, and (13) nonspecific peptide templates. . This is due to its high degree of organization, which makes it easy for chemical modification and naturally occurs self-assembled motifs in the system.

Belcher et al. Produced nanowires associated with and associated with genetically treated viral scaffolds (see, eg, US Patent Publication 2003/0068900 (Belcher et al.)). The skeleton acts as a template because nanoparticles or nanocrystals form on the skeleton. Although the technique offers attractive and significant advantages, there is a need to improve it. For example, it is desirable to generate improved properties such as improved fusion between nanocrystals and reduction of defects. It is also desirable to fuse the nanoparticles into one long single crystal rod or into large crystalline domains. In addition, in many applications, it is desirable to have a viral backbone that is bound to or associated with a viral backbone and is substantially removed. It is also desirable to control the size and statistical size distribution of the nanowires, including, for example, the production of monodisperse materials and materials with controlled lengths. If possible, the nanowires should be readily available without the need for size separation steps before use. There is also a need to be able to connect the nanowires with other components such as electrodes so that the nanowires are commercially useful. If possible, the connection should not be purely accidental, but strategically purposeful and controllable.

Numerical references cited herein are listed at the end of this specification, the entirety of which is incorporated herein by reference.

summary

Many embodiments of the invention are summarized herein in a non-limiting outline.

In one embodiment, the invention provides an inorganic nanowire having an organic backbone substantially removed from the inorganic nanowire, the inorganic nanowire consisting essentially of fused inorganic nanoparticles substantially free of organic backbone ("implementation Inorganic nanowires of Example 1)).

The present invention also provides a composition and device comprising a plurality of said inorganic nanowires. In another embodiment, the present invention provides a composition comprising a plurality of inorganic nanowires, wherein the inorganic nanowires comprise fused inorganic nanoparticles substantially free of organic backbone.

In another embodiment, the present invention provides a method of forming an inorganic nanowire, comprising the steps of: (1) providing a precursor material for one or more inorganic nanowires; (2) providing an elongated organic backbone; (3) reacting the one or more precursor materials in the presence of the backbone to form nanoparticles, wherein the nanoparticles are disposed along the length of the elongated organic backbone; And (4) heat treating the backbone and nanoparticles to form inorganic nanowires by fusion of nanoparticles. In some embodiments, the organic skeleton can be removed, for example, during heat treatment. The present invention also provides a nanowire produced by the above method.

Also provided is a method of forming an inorganic nanowire comprising the steps of: (1) providing a precursor material for one or more inorganic nanowires; (2) providing an organic skeleton; (3) reacting said at least one precursor material in the presence of said backbone under conditions in which inorganic nanowires are formed. In some embodiments, the organic backbone can be removed, for example, during the reaction. The present invention also provides a nanowire produced by the above method.

In addition, the present invention provides an inorganic nanowire precursor on the filamentous organic skeleton and the skeleton, and converting the inorganic nanowire precursor into inorganic nanowires while removing the filamentous organic skeleton, yielding inorganic nanowires. Provided is the use of a filamentous organic skeleton as a sacrificial organic skeleton in the manufacture of nanowires.

An additional use provided herein is the use of an extended organic backbone for controlling the length of inorganic nanowires disposed on the backbone, comprising controlling the length of the backbone by genetically treating the backbone.

Also an important embodiment is a device comprising an electrode in electrical contact with the inorganic nanowire of embodiment 1 or any other nanowire described herein. In another embodiment, the device may further comprise two or more electrodes, each in electrical contact with the inorganic nanowire of embodiment 1 or any other nanowire described herein. Examples of devices include field effect transistors or sensors. In another embodiment, the device comprises two or more nanowires according to embodiment 1, or any other nanowires described herein, wherein the nanowires are arranged in parallel or crosswise.

The present invention also provides fragmented nanowires comprising a plurality of linked fragments of the inorganic nanowires of embodiment 1 or any other nanowires described herein. In some embodiments, the backbone was used to form nanowires and / or to place nanowires before they were removed.

The present invention also provides a composition comprising a plurality of inorganic nanowires, wherein the inorganic nanowires comprise fused inorganic nanoparticles disposed on an organic backbone. In some embodiments, the framework (s) have been used to form nanowires and / or allow placement of nanowires, such as placement on a circuit board, before they are removed.

The present invention also provides a method of making a nanowire comprising the use of an extended organic backbone, comprising the following steps: (1) a binding site along the backbone length and a binding site at at least one terminal end of the backbone Providing an extended organic skeleton comprising a plurality of binding sites comprising a; (2) placing the nanowire precursor composition along the backbone length to form the backbone precursor composition; And (3) treating the skeletal precursor composition to form nanowires. In some embodiments, the backbone is substantially removed during, for example, the processing step. In one embodiment, the extended organic backbone has binding sites at both ends of the backbone. In another embodiment, the method further comprises binding to another structure using a binding site at the backbone end. For example, the other structure may be another extended organic backbone.

The present invention also provides a composition. For example, in one embodiment, a nanowire having a thermodynamically high energy phase, or a collection of nanowires according to the present embodiment, wherein the nanowire is of length, width, or length and width It provides a nanowire composition that is substantially monodisperse. In this embodiment, the nanowires may be inorganic nanowires such as, for example, nanowires of semiconducting material, metallic material, metal oxide material, magnetic material, or mixtures thereof.

The present invention also provides a composition comprising an inorganic nanowire comprising a fused inorganic nanoparticle, or a collection of inorganic nanowires according to the present embodiment. In this embodiment, the present invention also provides a collection of these nanowires as well as inorganic nanowires comprising fused inorganic nanoparticles comprising semiconducting material, metallic material, metal oxide material, or magnetic material.

The present invention also provides inorganic nanowires consisting essentially of fused inorganic nanoparticles disposed on an organic backbone.

A basic and novel feature for many embodiments of the present invention is that the organic backbone is substantially removed when used in the manufacture of nanowires. In many embodiments, it is desirable that the organic backbone is completely removed. In addition, a basic and novel advantage in many embodiments is that it is possible to directly fabricate nanowires with good monodispersity without using the step of separating some nanowires from other nanowires in size.

Numerous additional embodiments are provided. For example, the first embodiment (1) is an inorganic nanowire having an organic skeleton substantially removed from the inorganic nanowires and consisting essentially of fused inorganic nanoparticles substantially free of an organic skeleton.

2. The inorganic nanowire of 1, wherein the inorganic nanowire is crystalline.

3. The inorganic nanowire of 2 above, wherein the crystallographic axis of the nanoparticles is oriented with respect to the skeletal surface.

4. The inorganic nanowire of 1, wherein the inorganic nanowire is a single crystalline domain.

5. The inorganic nanowire of 1, wherein the inorganic nanowire has one or more crystalline domains.

6. The inorganic nanowire of 1, wherein the fused nanoparticles are single crystalline.

7. The inorganic nanowire of 1, wherein the inorganic nanowire is essentially composed of a semiconducting material, a metallic material, a metal oxide material, a magnetic material, or a mixture thereof.

8. The inorganic nanowire of 1 above, wherein the nanowires consist essentially of semiconducting materials.

9. The inorganic nanowire of 1 above, wherein the nanowires consist essentially of a metallic material.

10. The inorganic nanowire of 1 above, wherein the nanowires consist essentially of a metal oxide material.

11. The inorganic nanowire of 1 above, wherein the nanowires consist essentially of a magnetic material.

12. The inorganic nanowire of 1, wherein the nanowire has a length of about 250 nm to about 5 microns and a width of about 5 nm to about 50 nm.

13. The inorganic nanowire of 1 above, wherein the nanowires have a length of about 400 nm to about 1 micron and a width of about 10 nm to about 30 nm.

14. The inorganic nanowire of 1 above, wherein the nanowires consist essentially of semiconducting material and have a length of about 250 nm to about 5 microns and a width of about 5 nm to about 50 nm.

15. The inorganic nanowire of 1 above, wherein the nanowires consist essentially of II-VI semiconducting material and have a length of about 250 nm to about 5 microns and a width of about 5 nm to about 50 nm.

16. The inorganic nanowire of 1, wherein the nanowire is substantially straight.

17. The inorganic nanowire of item 1, wherein the nanowire is essentially composed of a semiconducting material and is substantially straight.

18. The inorganic nanowire of 1, wherein the nanowires consist essentially of a thermodynamically high energy phase.

19. The inorganic nanowire of 1, wherein the inorganic nanowire is crystalline and consists essentially of a semiconducting material, a metallic material, a metal oxide material, a magnetic material, or a mixture thereof.

20. The inorganic nanowire of 19, wherein the inorganic nanowire is single crystalline.

21. The inorganic nanowire of 19, wherein the fused nanoparticles are single crystalline.

22. The inorganic nanowire of 19, wherein the nanowire is substantially straight.

23. The inorganic nanowire of 19, wherein the nanowire has a length of about 250 nm to about 5 microns and a width of about 5 nm to about 50 nm.

24. The inorganic nanowire of 19, wherein the nanowire has a length of about 400 nm to about 1 micron and a width of about 10 nm to about 30 nm.

25. The inorganic nanowire of 23 above, wherein the nanowires are substantially straight.

26. The inorganic nanowire of 24 above, wherein the nanowires are substantially straight.

27. A composition comprising a plurality of inorganic nanowires according to 1 above, wherein the nanowires are substantially monodisperse in average length.

28. A composition comprising a plurality of inorganic nanowires according to 1 above, wherein the nanowires are substantially monodisperse in average width.

29. A composition comprising a plurality of inorganic nanowires according to 1 above, wherein the nanowires are substantially monodisperse in average length and substantially monodisperse in average width.

30. The composition of 29 above, wherein the nanowires have a coefficient of variation for length less than 10% and a coefficient of variation for width less than 10%.

31. The composition of 29 above, wherein the nanowires have a coefficient of variation for length less than 5% and a coefficient of variation for width less than 5%.

32. A composition comprising a plurality of inorganic nanowires according to 19 above, wherein the nanowires are substantially monodisperse in average length.

33. A composition comprising a plurality of inorganic nanowires according to 19 above, wherein the nanowires are substantially monodisperse in average width.

34. A composition comprising a plurality of inorganic nanowires according to 19 above, wherein the nanowires are substantially monodisperse in average length and substantially monodisperse in average width.

A thirty-fifth (35) aspect is a composition, comprising a plurality of inorganic nanowires, wherein the inorganic nanowires comprise fused inorganic nanoparticles substantially free of an organic backbone.

36. The composition according to 35 above, wherein the inorganic nanowires are crystalline.

37. The composition of 36, wherein the crystallographic axis of the nanoparticles is oriented with respect to the surface of the skeleton.

38. The composition of 35, wherein the individual inorganic nanowires comprise a single crystalline domain.

39. The composition of 35, wherein the individual inorganic nanowires comprise one or more crystalline domains.

40. The composition of 35, wherein the fused nanoparticles are single crystalline.

41. The composition of 35, wherein the inorganic nanowires comprise a semiconducting material, metallic material, metal oxide material, magnetic material, or mixtures thereof.

42. The composition of 35, wherein the nanowires comprise a semiconducting material.

43. The composition of 35 above, wherein the nanowires comprise a metallic material.

44. The composition of 35, wherein the nanowires comprise a metal oxide material.

45. The composition of 35, wherein the nanowires comprise a magnetic material.

46. The composition of 35, wherein the nanowires have an average length of about 250 nm to about 5 microns and an average width of about 5 nm to about 50 nm.

47. The composition of 35, wherein the nanowires have an average length of about 400 nm to about 1 micron and an average width of about 10 nm to about 30 nm.

48. The composition of 35, wherein the nanowires comprise semiconducting material and have an average length of about 250 nm to about 5 microns and an average width of about 5 nm to about 50 nm.

49. The composition of 35, wherein the nanowires comprise II-VI semiconducting material and have an average length of about 250 nm to about 5 microns and an average width of about 5 nm to about 50 nm.

50. The composition according to 35 above, wherein the nanowires are substantially straight.

51. The composition of 35, wherein the nanowires are substantially monodisperse in width.

52. The composition of 35, wherein the nanowires are substantially monodisperse in length.

53. The composition of 35, wherein the nanowires are substantially monodisperse in width and length.

54. The composition of 53 above, wherein the nanowires have a coefficient of variation for length less than 10% and a coefficient of variation for width less than 10%.

55. The composition of 53 above, wherein the nanowires have a coefficient of variation for length less than 5% and a coefficient of variation for width less than 5%.

A fifty-eighth embodiment (56) provides a method of forming an inorganic nanowire, comprising the steps of: (1) providing a precursor material for one or more inorganic nanowires; (2) providing an extended organic backbone; (3) reacting the one or more precursor materials in the presence of the backbone to form nanoparticles, wherein the nanoparticles are disposed along the length of the elongated organic backbone; And (4) heat treating the backbone and nanoparticles to form inorganic nanowires by fusion of nanoparticles.

57. The method of 56, wherein the organic backbone is substantially removed from the nanowires.

58. The method of 57, wherein the backbone is removed during the heat treatment step.

59. The method of 56, wherein the nanoparticles are crystalline.

60. The method of 56, wherein the precursor material is a precursor to a semiconducting material, metallic material, metal oxide material, magnetic material.

61. The method of 56, wherein the precursor material is a precursor to a semiconducting material.

62. The method of 56, wherein the precursor material is a precursor to a metallic material.

63. The method of 56, wherein the precursor material is a precursor to a metal oxide material.

64. The method of 56, wherein the precursor material is a precursor to a magnetic material.

65. The method of 56, wherein the extended organic backbone is a viral backbone.

66. The method according to 56 above, wherein the extended organic backbone is a filamentous viral backbone.

67. The method of 56, wherein the extended organic backbone comprises a surface peptide that binds to the nanoparticles along the backbone length.

68. The method of 56, wherein the heat treating step is performed at about 100 ° C to about 1,000 ° C.

69. The process according to 56, wherein the heat treatment step is performed at about 300 ° C to about 500 ° C.

70. The method of 56, wherein the nanoparticles have an average diameter of about 2 nm to about 10 nm.

71. The method of 56, wherein the nanoparticles have an average diameter of about 3 nm to about 5 nm.

72. The method of 56, wherein the nanowires are crystalline.

73. The method of 56, wherein the nanowires are a single crystalline domain.

74. The method of 56, wherein the nanowires have one or more crystalline domains.

75. The method of 56, wherein the nanowires comprise a thermodynamically high energy phase.

76. The method of 56, wherein the heat treating step converts the nanowires from the polycrystalline state to the single crystalline state.

77. The method of 56, wherein the crystallographic axis of the nanoparticles is oriented with respect to the skeletal surface.

78. The method of 56, wherein the nanoparticles are not fused before the heat treatment step.

79. The method of 56, wherein the nanowires are substantially straight.

80. The method of 56, wherein the method is used to make a plurality of nanowires, wherein the nanowires are substantially monodisperse in length.

81. The method of 56, wherein the method is used to make a plurality of nanowires, wherein the nanowires are substantially monodisperse in width.

82. The method of 56, wherein the method is used to make a plurality of nanowires, wherein the nanowires are substantially monodisperse in width and length.

83. The method of 56, wherein the precursor material is a precursor to a semiconducting material, metallic material, metal oxide material, magnetic material, wherein the nanowires are crystalline and substantially straight.

84. The method of 83, wherein the method is used to make a plurality of nanowires, wherein the nanowires are substantially monodisperse in length.

85. The method of 83, wherein the method is used to make a plurality of nanowires, wherein the nanowires are substantially monodisperse in width.

86. The method of 83, wherein the method is used to make a plurality of nanowires, wherein the nanowires are substantially monodisperse in width and length.

87. The method of 86, wherein the nanowires have a coefficient of variation for length less than 10% and a coefficient of variation for width less than 10%.

88. The method of 86, wherein the nanowires have a coefficient of variation for length less than 5% and a coefficient of variation for width less than 5%.

89. A method of forming an inorganic nanowire comprising the steps of: (1) providing a precursor material for one or more inorganic nanowires; (2) providing an organic skeleton; (3) reacting said at least one precursor material in the presence of said skeleton under conditions for forming inorganic nanowires.

90. The method of 89 above, wherein the organic backbone is substantially removed from the nanowires.

91. The process according to 89 above, wherein the organic backbone is removed during the reaction step.

92. The method of 89, wherein the precursor material is nanoparticles or forms nanoparticles.

93. The method of 92, wherein the nanoparticles are crystalline.

94. The method of 92, wherein the crystallographic axis of the nanoparticles is oriented with respect to the skeletal surface.

95. The method of 89, wherein the precursor material is a precursor to a semiconducting material, metallic material, metal oxide material, magnetic material.

96. The method of 89 above, wherein the precursor material is a precursor to a semiconducting material.

97. The method of 89, wherein the precursor material is a precursor to a metallic material.

98. The method of 89, wherein the precursor material is a precursor to a metal oxide material.

99. The method of 89, wherein the precursor material is a precursor to a magnetic material.

100. The method according to 89 above, wherein the organic backbone is a viral backbone.

101. The method according to 89 above, wherein the organic backbone is a filamentous viral backbone.

102. The method of 89 above, wherein the extended organic backbone comprises surface peptides that bind the nanoparticles along the backbone length.

103. The method of 89, wherein the reaction step is performed using a temperature of about 100 ° C. to about 1,000 ° C. to form nanowires.

104. The method of 89, wherein the nanowires are crystalline.

105. The method of 89 above, wherein the nanowires are single crystalline domains.

106. The method of 89, wherein the nanowires have one or more crystalline domains.

107. The method of 89, wherein the nanowires are substantially straight.

108. The method of 89, wherein the method is used to make a plurality of nanowires, wherein the nanowires are substantially monodisperse in length.

109. The method of 89, wherein the method is used to make a plurality of nanowires, wherein the nanowires are substantially monodisperse in width.

110. The method of 89, wherein the method is used to make a plurality of nanowires, wherein the nanowires are substantially monodisperse in width and length.

111. The method of 110, wherein the nanowires have a coefficient of variation for length less than 10% and a coefficient of variation for width less than 10%.

112. The method of 110, wherein the nanowires have a coefficient of variation for length less than 5% and a coefficient of variation for width less than 5%.

113. The method of 89 above, wherein the precursor material is a precursor to a semiconducting material, metallic material, metal oxide material, magnetic material, wherein the nanowires are crystalline and substantially straight.

114. The method of 113, wherein the method is used to make a plurality of nanowires, wherein the nanowires are substantially monodisperse in length.

115. The method of 113 above, wherein the method is used to produce a plurality of nanowires, wherein the nanowires are substantially monodisperse in width.

116. The method of 113, wherein the method is used to make a plurality of nanowires, wherein the nanowires are substantially monodisperse in width and length.

117. The preparation of an inorganic nanowire comprising providing a filamentous viral backbone and an inorganic nanowire precursor on the backbone, and removing the filamentous viral backbone to yield an inorganic nanowire, wherein the filamentous organic backbone is filamentous Use of the virus.

118. Nanowires produced by the method according to 56 above.

119. Nanowires produced by the method according to 89 above.

Another embodiment 120 includes providing a filamentous organic backbone and inorganic nanowire precursors on the backbone, and converting the inorganic nanowire precursors to inorganic nanowires while removing the filamentous organic backbone to yield inorganic nanowires. It is a use of a filamentous organic skeleton as a sacrificial organic skeleton in manufacture of the inorganic nanowire which is mentioned.

Another aspect 121 is the use of an extended organic skeleton to control the length of inorganic nanowires disposed on the skeleton, comprising controlling the length of the skeleton by genetically treating the skeleton.

122. A device comprising an electrode in electrical contact with a nanowire according to 1 above.

123. The device of 122, wherein each device comprises at least two electrodes in electrical contact with the nanowire according to 1 above.

124. The apparatus of 122 above, which is a field effect transistor.

125. The apparatus of 122 above, which is a sensor.

126. A device comprising at least two nanowires according to 1, wherein the nanowires are arranged in parallel.

127. A device comprising at least two nanowires according to 1 above, wherein the nanowires are arranged crosswise.

128. Fragmented nanowires comprising a plurality of linked fragments of the nanowires according to 1 above.

Yet another embodiment 129 is a method of making nanowires using an extended organic backbone comprising the following steps:

Providing an extended organic backbone comprising a plurality of binding sites comprising a binding site along a backbone length and a binding site at at least one end of the backbone;

Placing the nanowire precursor composition along the backbone length to form a backbone precursor composition; And

Treating the skeletal precursor composition to form nanowires.

130. The method of 129 above, wherein the organic backbone is substantially removed from the nanowires.

131. The method of 129 above, wherein the organic backbone is removed during the treatment step.

132. The method of 129 above, wherein the extended organic backbone has binding sites at both termini of the backbone.

133. The method of 129, further comprising binding to another structure using a binding site at the distal end of the backbone.

134. The method of 133, wherein the other structure is another extended organic skeleton.

135. The method of 129 above, wherein the other structure is a circuit element or an electrode.

136. The method of 129 above, further comprising coupling the skeleton to the patterned structure prior to removing the skeleton.

137. Nanowire composition comprising nanowires having a thermodynamically high energy phase.

138. The collector of 137, wherein the nanowires are substantially monodisperse in length.

139. The collector of 137, wherein the nanowires are substantially monodisperse in width.

140. The collector of 137, wherein the nanowires are substantially monodisperse in length and width.

141. The collection of 140, wherein the nanowires have a coefficient of variation for length less than 10% and a coefficient of variation for width less than 10%.

142. The composition of 140 above, wherein the nanowires have a coefficient of variation for length less than 5% and a coefficient of variation for width less than 5%.

143. The nanowire composition of 137, wherein the nanowire is an inorganic nanowire.

144. The nanowire composition of 137, wherein the nanowire is a nanowire of a semiconducting material, a metallic material, a metal oxide material, a magnetic material, or a mixture thereof.

145. The nanowire composition of 137, wherein the nanowire is a nanowire of a semiconducting material.

146. The nanowire composition of 137, wherein the nanowire is a nanowire of a metallic material.

147. The nanowire composition of 137, wherein the nanowire is a nanowire of a metal oxide material.

148. The nanowire composition of 137, wherein the nanowire is a nanowire of a magnetic material.

149. Inorganic nanowires comprising fused inorganic nanoparticles.

150. A composition comprising a collection of inorganic nanowires according to 149 above.

151. An inorganic nanowire comprising fused inorganic nanoparticles comprising a semiconducting material.

152. A composition comprising a collection of inorganic nanowires according to 151 above.

153. An inorganic nanowire comprising fused inorganic nanoparticles comprising a metallic material.

154. A composition comprising a collection of inorganic nanowires according to 153 above.

155. An inorganic nanowire comprising fused inorganic nanoparticles comprising a metal oxide material.

156. A composition comprising a collection of inorganic nanowires according to 155 above.

157. An inorganic nanowire comprising fused inorganic nanoparticles comprising a magnetic material.

158. A composition comprising a collection of inorganic nanowires according to 157 above.

159. An inorganic nanowire comprising fused inorganic nanoparticles disposed on an organic skeleton.

160. The inorganic nanowire of 159, wherein the inorganic nanowire is crystalline.

161. The inorganic nanowire of 160 above, wherein the crystallographic axis of the nanoparticles is oriented with respect to the skeletal surface.

162. The inorganic nanowire of 159, wherein the inorganic nanowire is a single crystalline domain.

163. The inorganic nanowire of 159, wherein the inorganic nanowire has one or more crystalline domains.

164. The inorganic nanowire of 159, wherein the fused nanoparticles are single crystalline.

165. The inorganic nanowires of 159, wherein the inorganic nanowires consist essentially of a semiconducting material, a metallic material, a metal oxide material, a magnetic material, or a mixture thereof.

166. The inorganic nanowire of 159, wherein the nanowire has a length of about 250 nm to about 5 microns and a width of about 5 nm to about 50 nm.

167. The inorganic nanowire of 159, wherein the nanowire has a length of about 400 nm to about 1 micron and a width of about 10 nm to about 30 nm.

168. The inorganic nanowire of 159, wherein the nanowires consist essentially of semiconducting material and have a length of about 250 nm to about 5 microns and a width of about 5 nm to about 50 nm.

169. The inorganic nanowire of 159, wherein the nanowire comprises a II-VI semiconducting material and has a length of about 250 nm to about 5 microns and a width of about 5 nm to about 50 nm.

170. The inorganic nanowire of 159, wherein the nanowire is substantially straight.

171. The inorganic nanowire of 159, wherein the nanowire comprises a semiconductor material and is substantially straight.

172. The inorganic nanowire of 159, wherein the nanowire comprises a thermodynamically high energy phase.

173. The inorganic nanowire of 159, wherein the inorganic nanowire is crystalline and comprises a semiconducting material, a metallic material, a metal oxide material, a magnetic material, or a mixture thereof.

174. The inorganic nanowire of 173, wherein the inorganic nanowire is single crystalline.

175. The inorganic nanowire of 173, wherein the fused nanoparticles are single crystalline.

176. The inorganic nanowire of 173, wherein the nanowire is substantially straight.

177. The inorganic nanowire of 173, wherein the nanowire has a length of about 250 nm to about 5 microns and a width of about 5 nm to about 50 nm.

178. The inorganic nanowire of 173, wherein the nanowire has a length of about 400 nm to about 1 micron and a width of about 10 nm to about 30 nm.

179. The inorganic nanowire of 177, wherein the nanowires are substantially straight.

180. The inorganic nanowire of 178, wherein the nanowires are substantially straight.

181. A composition comprising a plurality of inorganic nanowires according to 159, wherein the nanowires are substantially monodisperse in average length.

182. A composition comprising a plurality of inorganic nanowires according to 159, wherein the nanowires are substantially monodisperse in average width.

183. A composition comprising a plurality of inorganic nanowires according to 159, wherein the nanowires are substantially monodisperse in average length and substantially monodisperse in average width.

184. The composition of 183, wherein the nanowires have a coefficient of variation for length less than 10% and a coefficient of variation for width less than 10%.

185. The composition of 183, wherein the nanowires have a coefficient of variation for length less than 5% and a coefficient of variation for width less than 5%.

186. A composition comprising a plurality of inorganic nanowires according to 173, wherein the nanowires are substantially monodisperse in average length.

187. A composition comprising a plurality of inorganic nanowires according to 173, wherein the nanowires are substantially monodisperse in average width.

188. A composition comprising a plurality of inorganic nanowires according to 173, wherein the nanowires are substantially monodisperse in average length and substantially monodisperse in average width.

189. A composition comprising a plurality of inorganic nanowires, wherein the inorganic nanowires comprise fused inorganic nanoparticles disposed on an organic backbone.

190. The composition of 189 wherein the inorganic nanowires are crystalline.

191. The composition of 190 above, wherein the crystallographic axis of the nanoparticles is oriented with respect to the skeletal surface.

192. The composition of 189, wherein the individual inorganic nanowires comprise a single crystalline domain.

193. The composition of 189, wherein the individual inorganic nanowires have one or more crystalline domains.

194. The composition of 189, wherein the fused nanoparticles are single crystalline.

195. The composition of 189, wherein the inorganic nanowires comprise semiconducting material, metallic material, metal oxide material, magnetic material, or mixtures thereof.

196. The composition of 189, wherein the nanowires have an average length of about 250 nm to about 5 microns and an average width of about 5 nm to about 50 nm.

197. The composition of 189, wherein the nanowires have an average length of about 400 nm to about 1 micron and an average width of about 10 nm to about 30 nm.

198. The composition of 189, wherein the nanowires comprise semiconducting material and have an average length of about 250 nm to about 5 microns and an average width of about 5 nm to about 50 nm.

199. The composition of 189, wherein the nanowires comprise II-VI semiconducting material and have an average length of about 250 nm to about 5 microns and an average width of about 5 nm to about 50 nm.

200. The composition of 189, wherein the nanowires are substantially straight.

201. The composition of 189, wherein the nanowires are substantially monodisperse in width.

202. The composition of 189, wherein the nanowires are substantially monodisperse in length.

203. The composition of 189, wherein the nanowires are substantially monodisperse in width and length.

204. The composition of 203, wherein the nanowires have a coefficient of variation for length less than 10% and a coefficient of variation for width less than 10%.

205. The composition of 203, wherein the nanowires have a coefficient of variation for length less than 5% and a coefficient of variation for width less than 5%.

A-D of FIG. 1 depicts a virus that can be used as a backbone.

A-F of FIG. 2 shows the characteristics of nanowires made of semiconducting materials.

A-F of Figure 3 shows the characteristics of the nanowires made of magnetic material.

I. Preface

The present invention provides, in one embodiment, an inorganic nanowire having an organic backbone substantially removed from the inorganic nanowires, the inorganic nanowire consisting essentially of fused inorganic nanoparticles substantially free of organic backbones. In addition, the present invention provides a composition comprising a plurality of the inorganic nanowires. The present invention also provides a composition comprising a plurality of inorganic nanowires, wherein the inorganic nanowires comprise fused inorganic nanoparticles substantially free of organic frameworks.

The organic backbone is typically removed and preferably cannot be detected on nanowires. Substantial removal of this can be described in terms of remaining weight percentage.

For example, the remaining amount of the organic skeleton relative to the total amount of nanowires and the skeleton may be less than 1% by weight, more preferably less than 0.5% by weight, more preferably less than 0.1% by weight. A basic and novel feature of the present invention is that in the fabrication of high quality nanowires, the backbone is substantially removed.

In another patent application, the entirety of which is incorporated herein by reference [2003. US Patent No. 10 / 665,721 to Belcher et al., Entitled “Peptide Mediated Synthesis of Metallic and Magnetic Materials”, filed on September 22, filed with the combustion and removal of the viral skeleton from a material to which the skeleton can selectively bind. It is additionally described. In this application, annealing temperatures of 500-1,000 ° C. are described for combustion of the skeleton. In addition, Science 303: 213-217 (2004), Mao et al., On a virus-based toolkit for direct synthesis of magnetic and semiconducting nanowires, provide some teachings that may be useful for practicing the present invention. Which is incorporated herein by reference, including all figures and experimental sections. Fairley, Peter, (2003) Germs That Build Circuits, IEEE Spectrum 37-41, also includes teachings that may be useful in the practice of the present invention, such as the application of nanowires, which is applicable to all figures and nanowires. The entirety of which is incorporated herein by reference, including the use of electrodes connected by it. Priority Provisional Application No. 60 / 534.102 (filed Jan. 5, 2004, Belcher et al.) Is hereby incorporated by reference in its entirety.

The detailed description of the invention is organized into the following sections: (1) Preface, (2) Substantially eliminated backbone, (3) Nanowires, (4) Methods of making nanowires, (5) Application of nanowires And (6) working examples.

II. skeleton

Although the backbone may ultimately be substantially removed from the nanowires, the backbone is an important part of the present invention. In practicing the present invention, those skilled in the art can refer to the technical literature (including the documents cited herein and the documents listed at the conclusion of this specification) for guidance on how to design and synthesize the skeleton. For example, the present invention relates to an organic backbone and, in the broadest scope, will not only be limited to the viral backbone, but the viral backbone is a preferred embodiment. In particular, it may be used that the extended organic framework is a virus, and the term virus may include both complete viruses and subunits of viruses such as capsids. This document describes the preparation of viral backbones through genetic processing using recognized properties for pioneering material synthesis. This includes the use of viruses in preparing inorganic materials having technically useful properties and nanoscale dimensions. In the present invention, those skilled in the art can use the above documents in the practice of the present invention for producing a skeleton-shaped inorganic nanowire, in which the skeleton is subsequently removed substantially so that the inorganic nanowire is substantially free of skeleton. If the skeleton is to be removed, the skeleton may be referred to as a "sacrificing skeleton".

Those skilled in the art may, for example, refer to the following patent literature regarding selection of viruses, methods of genetic processing, and materials to be used with genetically treated viruses. Phage expression libraries, and experimental methods for using them in biopanning, are further described, for example, in the following US patent publications by Belcher et al., Each of which is incorporated herein by reference in its entirety: (1) "Biological Control of Nanoparticle Nucleation, Shape, and Crystal Phase"; 2003/0068900 (published April 10, 2003); (2) "Nanoscale Ordering of Hybrid Materials Using Genetically Engineered Mesoscale Virus"; 2003/0073104 (published April 17, 2003); (3) "Biological Control of Nanoparticles"; 2003/0113714 (published June 19, 2003); And (4) "Molecular Recognition of Materials"; 2003/0148380 (published 7 August 2003). Additional patent applications useful to those of skill in the art describe viral and peptide recognition studies with the use of genetically treated viruses for material synthesis and application, including, for example, the following each of which are referred to herein: It is included as: (1) US Series No. 10 / 654,623, filed Sep. 4, 2003, Belcher et al., "Compositions, Methods, and Use of Bi-Functional BioMaterials", (2) US Series No. 10 / 665,721, filed September 22, 2003, Belcher et al., "Peptide Mediated Synthesis of Metallic and Magnetic Materials", and (3) US Series No. 10 / 668,600, filed September 24, 2003, Belcher Et al., "Fabricated BioFilm Storage Device"), (4) US Provisional Application No. 60 / 510,862, filed Oct. 15, 2003, and US Utility Application No. 10 / 965,665, filed Oct. 15, 2004, Belcher et al., "Viral Fibers"), and (5) US Provisional Application No. 60 / 511,102 (October 15, 2003) Pending) and the United States _ the practical applications, such as Ho (filed October 15, 2004, Belcher, "Multifunctional Biomaterials ..."). These references describe modifications of various specific bindings that can be performed for binding to the conjugate structure, as well as forming the conjugate structure in the presence of a material modified for specific binding. Doing. In particular, polypeptide and amino acid oligomer sequences can be expressed on the surface of viral particles, and polypeptide and amino acid oligomer sequences can also be expressed at and along the length of extended viral particles, such as M13 bacteriophages (pIX, pVII, and pVI expression, and combinations thereof, as well as pIII and pVIII expression. By using these expression sites, the virus can be treated to express surface peptides along the length of the virus, at the distal end of the virus, or at any number of other sites and in combination. Single sites for modification may be modified in more than one unit for specific binding. For example, the pVIII site may be modified to have two distinctly different binding units. In addition, different sites for modification may be modified in the same or different units for binding. For example, the distal end of the viral particles can be specifically bound to the first material, while the body of the viral particles can be modified to bind the second material. Among other applications, multiple binding sites can be used to create multifunctional backbones that can be used to form nanowires with various compositions that have been specifically processed. The binding site may be designed to allow nanoparticles to nucleate at the binding site, or the binding site may be designed to bind preformed nanoparticles. The backbone may be functionalized with sufficient binding units to achieve the desired concentration necessary to form the nanowires.

In addition, the paper "Selection of Peptides with Semiconductor Binding Specificity for Directed Nanocrystal Assembly" (Whaley et al., Nature, Vol. 405, June 8, 2000, 665-668) uses a combinatorial library to select peptides with binding specificities. The method is described and the article is incorporated herein by reference. Specifically, the paper shows how to select peptides with binding specificities for semiconductor materials using a combinatorial library with about 10 ⁹ different peptides. The combinatorial library of random peptides, each comprising 12 amino acids, is fused to the pIII coat protein of M13 coliphages and exposed to crystalline semiconductor structures. Peptides bound to the semiconductor material are eluted and amplified and reexposed to the semiconductor material under more stringent conditions. After five selections, the semiconductor specific phage is isolated and sequenced to determine the binding peptide. In this way, peptides with high binding specificities depending on the crystallographic structure and composition of the semiconductor material were selected. Modifications of the present technology can result in peptides having binding specificities for both organic and inorganic materials as well as semiconductor materials.

In addition, those skilled in the art can, for example, see [C. E. Flynn et al., Acta Materialia, vol 13, 2413-2421 (2003), "Viruses as vehicles for growth, organization, and assembly of materials". The above references and all references cited therein are hereby incorporated by reference in their entirety. In addition, Reference 12 (Mao et al., PNAS), below, is incorporated herein by reference for all its teachings, including nucleation and structure shown in FIG. In particular, reference 17 (Flynn et al., J. Mater. Chem) is also incorporated herein by reference in its entirety, which is a nanocrystal that is directed into the crystal structure and oriented by the recognition site by using an aqueous salt composition. Contains a description of nucleation. In the present invention, these nucleated nanocrystals can be converted into single crystalline and polycrystalline nanowires in which the backbone is substantially removed.

For this framework, further description is provided, including the role of gene programming for preferred embodiments. While the viral backbone is a preferred embodiment, the present invention also encompasses other types of nonviral backbones. In addition, although the M13 virus is a preferred embodiment for the backbone, the present invention is not limited to this virus.

The backbone includes viral subunits comprising whole virus, virions, or capsids. Viral service units include proteins, peptides, nucleic acids, DNA, RNA, and the like, and combinations thereof. The backbone does not need to have both peptide and nucleic acid present. For example, viral mimics are used or processed whose size, shape or structure simulates that of a virus but may not contain nucleic acids and / or may not have the ability to infect a host for replication. Can be. Those skilled in the art can not only produce viral backbones from the bottom up based on pure synthetic methods, but also using more traditional methods in which the material is supplied unmodified by humans.

In a preferred embodiment, the framework, which is a virus or viral subunit, is designed and constructed by genetic processing and / or genetic programming for the production of one-dimensional materials such as nanowires. Genetic programming can be used to create frameworks for specific applications, the applications of which are described further below. References in section I describe the genetic programming further described in this section for use in the practice of the present invention. For development and application of viruses as vehicles and expressers of genetic material, including, for example, prokaryotic viruses, insect viruses, plant viruses, animal DNA viruses and animal RNA viruses, see, eg, Genetically Engineered. Viruses, Christopher Ring and ED Blair (Eds.), Bios Scientific, 2001. In the present invention, genetic programming can be performed to process the backbone using different expressing peptide properties of viruses such as filamentous bacteriophages such as rod-shaped M13 viruses. Genetic programming can be used to control the viral backbone comprising a backbone for material synthesis, one or more viral particle subunits, which may or may not include the nucleic acid subunits of a virus.

In addition to material specific addressability, the overall commercial advantage of the genetic programming approach to material processing is the potential for specifying viral length and geometry. For example, an extended organic backbone can be genetically treated to control the length of the backbone. Treatment of this length can, for example, allow nanowires of specific controlled length to be designed. Thus, various methods can be used to control the skeleton length and geometry.

For example, the length of a filamentous virus is typically related to the size of its packaged genetic information and the electrostatic balance between the DNA and the virion's pVIII-derived core. For example, [B. K. Kay, J. Winter, J. McCafferty, Phage Display of Peptides and Proteins: A Laboratory Manual, Academic Press, San Diego, 1996; Greenwood et al., Journal of Molecular Biology 217: 223-227 (1992). Phage observed by AFM can typically be approximately 860 nm or as small as 560 nm, depending on whether the complete M13 genome or smaller phagemid is used for sample preparation. For example, reference 12, [C. Mao, C. E. Flynn, A. Hayhurst, R. Sweeney, J. Qi, J. Williams, G. Georgiou, B. Iverson, A. M. Belcher, Proc. Natl. Acad. Sci. 2003, 100, 6946. In addition, converting single lysine on the inner end of pVIII to glutamine can produce particles that are approximately 35% longer than wild-type phage. For example, [J. Greenwood, G. J. Hunter, R. N. Perham, J. Mol. Biol. 1991, 217, 223.

In addition, certain connections, bonds, and concatenations of viral particles can result in longer viral backbones, resulting in longer nanowires. Multiple additions can be controlled by treating binding motifs in one virus, which can then accurately recognize the binding site of another virus. For example, the pIII protein is at one end of the M13 virus and can be used to express a fusion of peptides and proteins. At other ends of the virus, the pIX and pVII proteins may also be modified. For example, Gao and co-workers used pIX and pVII fusions to express antibody heavy and light chain variable regions [eg, (C. Gao, S. Mao, G. Kaufmann, P. Wirsching, RA Lerner). , KD Janda, Proc. Natl. Acad. Sci. 2002,99, 12612). See also, eg, US Pat. No. 6,472,147 for genetic alteration of viruses. These terminal modifications can be used to directly link viral particles, or terminal modifications can specifically bind to the linker. The linker may be any suitable material. For example, the linker may be a nanoparticle, an amino acid oligomer, a nucleic acid oligomer, or a polymer. The present invention includes dual terminal viral phenotypes that produce bimodal heterostructures or that combine with pVIII to produce terminally functionalized nanowires.

In addition, the dual terminal designating linkages can generate other interesting and commercially available geometries such as cyclics, squares and other arrangements. Of course, binding one end of the virus directly to the other end of the virus without the use of a linkage can be used to form a cyclic, wire, or other viral system structure. By treating the recognition site and the corresponding conjugate portion with a single virus or multiple viruses, the entire system can be genetically programmed.

An important advantage of the present invention is that the organic backbone may be an active backbone, wherein the backbone not only serves as a template for inorganic nanowire synthesis, but also actively assists in coupling the inorganic nanowires to other structures. For example, inorganic nanowires can be coupled to the structure using an organic backbone designed for one end to bind to another structure. The backbone and nanowires can be coupled to one another to form, for example, similar or dissimilar material fragments. In this embodiment, the composition of nanowires will vary as a function of length.

Additional types are described of viral structures that can be devised by genetic programming for specific applications based on length control, geometry control, binding control, and the like. The viral backbone is not particularly limited and a combination of different types of viruses can be used. Typically, viruses that can be multifunctional can be used. Typically, viral particles having a long filamentous structure can be used. See, eg, Genetically Engineered Yiruses, Christopher Ring (Ed.), Bios Scientific, 2001, pp. 11-21. In addition, other viral geometries, such as 12-sided and 20-sided, can be multifunctionalized and used to produce composite materials. Viral particles can be used that can function as flexible bars and form liquid crystalline and otherwise ordered structures.

In particular, phage expression libraries, directed evolution, and biopanning are an important part of the genetic programming of the virus, and the virus design allows the virus particles to specifically recognize and bind to the material targeted for biopanning. Viruses applied to biopanning can be used. In addition, the material can be nucleated and synthesized in particulate form (including nanoparticulate forms) in the presence of specific recognition and binding sites. The use of filamentous viruses in the so-called directed evolution or biopanning is further described in patent literature including, for example, US Pat. Nos. 5,223,409 and 5,571,698 (Ladner et al., "Directed Evolution of Novel Binding Proteins"). have. Additional references to the recognition properties of viruses include US Pat. No. 5,403,484 (phage expression library, currently commercially available), and WO 03/078451.

Mixtures of two or more different viruses can be used. Mixtures of viral particles and nonviral materials can be used to form the material using the present invention.

Viruses and viral particles may comprise whole viruses and portions of viruses including at least viral capsids. The term virus can refer to both viruses and phages. The whole virus may comprise a nucleus genome, capsid, and optionally may include an envelope. The virus as described herein may further comprise natural and heterologous amino acid oligomers such as cell adhesion factors. The nucleic acid genome can be a native genome or a processed genome. The virus particle further comprises a portion of the virus comprising at least the capsid.

Typically, viral particles have a natural structure, wherein the peptide and nucleic acid portions of the virus are arranged in specific geometries that must be preserved in solid form, self-supporting forms such as films and fibers until incorporation.

Preferred are viruses that express peptides (including peptide oligomers and amino acid oligomers) as specific binding sites. Amino acid oligomers may comprise amino acids of any sequence, depending on whether they are natural or heterologous to the virus. Amino acid oligomers can be of any length and can include non-amino acid components. As specific binding sites oligomers having from about 5 to about 100, more particularly from about 5 to about 30 amino acid units can be used. Non-amino acid components include, but are not limited to, sugars, lipids, or inorganic molecules.

The size and dimensions of the viral particles can be such that the particles are anisotropic and elongated. Typically, the virus may be characterized by an appearance ratio (length to width, eg, 25: 1) of at least 25, at least 50, at least 75, at least 100, or even at least 250 or 500.

A wide variety of viruses can be used to practice the invention. The compositions and materials of the present invention may comprise a single type or a plurality of different types of viruses. Preferably, the viral particle comprising the present invention is a helical virus. Examples of helical viruses include, but are not limited to, tobacco mosaic virus (TMV), phage pf1, phage fd1, CTX phage, and phage M13. The virus is typically rod-shaped and may be rigid or flexible. One skilled in the art can select a virus, depending on its intended use and viral nature.

Preferably, the virus of the invention has been treated to express one or more peptide sequences (including amino acid oligomers) on the virus surface. Amino acid oligomers may be natural to viral or heterologous sequences from other organisms or may be processed to meet specific requirements.

A number of references teach viral treatment to express amino acid oligomers and can be used to assist in the practice of the present invention. For example, US Pat. No. 5,403,484 to Ladner et al. Discloses the selection and expression of heterologous binding domains on the virus surface. US Pat. No. 5,766,905 (Studier et al.) Discloses a cloning site for insertion of an expression vector comprising DNA encoding at least a portion of a capsid protein, followed by an external DNA sequence. The described compositions are useful for preparing viruses that express a protein or peptide of interest. US Pat. No. 5,885,808 to Spooner et al. Discloses a method for modifying adenoviruses using adenoviruses and modified cell-binding moieties. US Pat. No. 6,261,554 to Valerio et al. Discloses a processed gene transport vehicle comprising a viral capsid or envelope that carries members of the gene and specific binding pairs of interest. US Patent Application Publication No. 2001/0019820 (Li) discloses a virus that has been processed to express a ligand on its surface for the detection of molecules such as polypeptides, cells, receptors, and channel proteins.

Genetically treated viruses are described in Kay, B. K .; Winter, J .; McCafferty, J. Phage Display of Peptides and Proteins: A Laboratory Manual; Academic Press: San Diego, 1996], in particular, by the methods and vectors described in Chapter 3, "Vectors for Phage Display" and references cited therein. Genetically treated viruses are also prepared by methods as described in Phage Display, A Laboratory Manual, Barbas et al. (2001) (including Chapter 2, “Phage Display Vectors” and references cited therein). Can be. The type of vector is not particularly limited. Table 2.1 of Barbas provides exemplary vectors that can be used in various combinations to provide multifunctional viruses. For example, type 3, type 8 + 8, and phagemid type p7 / p9 can be combined. Alternatively, type 8 and type 3 can be combined with phagemid p7 / p9 as desired. One skilled in the art can develop other combinations based on the specific application. Methods can be developed to express peptides on some or substantially all copies of envelope proteins.

Although the M13 strain is a preferred example of the filamentous viral backbone, other types of filamentous viral backbones may also be used. Wild-type filamentous M13 virus is approximately 6.5 nm in diameter and 880 nm in length. The length of the cylinder reflects the length of the packaged single stranded DNA genome size. At one end of the M13 virus, there are approximately five molecules of each of protein VII (pVII) and protein IX (pIX). The other termini has about 5 molecules of protein III (pIII) and protein VI (pVI), all 10-16 nm in length. The wild type M13 virus envelope consists of approximately 2800 copies of the major envelope protein VIII (pVIII), stacked on five units in a spiral arrangement.

In summary, the development of substrate specific peptides via phage expression technology for nanometer-scale material nucleation has already been reported by Angela Belcher and co-workers' papers and patents (see above), and the viral framework of the present invention. Or in mold 16 provides a basis for material specificity. Inorganic strains including, for example, ZnS, CdS (12,17), FePt and CoPt strains (18) using commercially available bacteriophage libraries expressing disulfide constrained heptapeptides or linear dodecapeptides Consensus sequences CNNPMHQNC (called A7; ZnS), SLTPLTTSHLRS (called J140; CdS), HNKHLPSTQPLA (called FP12; FePt), by screening phage libraries for their ability to nucleate and assemble ACNAGDHANC (called CP7; CoPt) was calculated. The incorporation of peptides into the highly ordered and self-assembled capsids of the M13 bacteriophage virus provides a linear template that can simultaneously control the phase and composition of the particles, while at the same time through genetic tuning of the basic protein building blocks. Maintains ease of material compliance. Since the protein sequence responsible for material growth is a gene linked to and contained in the capsid of the virus, the exact genetic replica of the backbone is relatively easily reproduced by infecting a large suspension of bacterial hosts.

For the production of nanowires, anisotropic skeletons can be used that have the ability to collect nanoparticles formed around them and place them on the skeleton for fusion to the nanowires. In the present invention, an inorganic nanowire composition having a skeleton substantially removed from the inorganic nanowires can be formed. Non-viral backbones may also be used, including, for example, various other organic backbones, including, for example, backbones having peptide or protein recognition units as lateral groups on the organic backbone. For example, the organic backbone may be a synthetic polymer backbone that is well known in the art. For example, a polymer backbone can be used, which includes, for example, modified polystyrenes of uniform molecular weight distribution functionalized with peptide units. Another example is a branched polypeptide or nucleic acid that has been modified to have a recognition site. Another example is nanolithography printed peptide structures such as lines with nanoscale widths. Typically, recognition units can be used to modify DNA, proteins and polypeptides to act as an organic backbone. Suitable recognition units include, but are not limited to, amino acid oligomers, nucleic acid oligomers, polymers, organic molecules (eg, antibodies, antigens, cell adhesion factors, and nutritional factors), and inorganic materials.

In one embodiment, skeletal and viral particles that are not directly genetically processed can be used. Typically, however, desirable properties can be achieved when the virus is genetically processed or when genetic processing is used in framework design.

III. Nanowire

Using the methods described in the foregoing section, the virus can be genetically processed such that the virus functions as a backbone to bind to the conjugate portion of the overall process and ultimately produce the inorganic nanowires according to the present invention. For example, rod-shaped viruses can be made to synthesize nanoparticulate materials along rod length, and these nanoparticulate materials can be fused to nanowires.

In the present invention, the conjugate material may be an inorganic material for forming nanoparticles (including inorganic nanocrystals). From these inorganic nanoparticles, upon substantial removal of the backbone, inorganic nanowires consisting essentially of fused inorganic nanoparticles can be formed. Conjugate materials and inorganic nanowires include, for example, doped or undoped semiconducting materials; Metallic materials; Essentially made of technically useful materials such as metal oxide materials, and magnetic materials. Various oxide materials, including silica and alumina, fall into the scope of the present invention. Additional materials of interest in nanotechnology commercial applications are further described, for example, in: (a) Understanding Nanotechnology, Warner Books, 2002 [(“The Incredible Shrinking Circuit”, pp. 92-103, C. Lieber) Circuit materials such as nanowires and nanotubes), (b) Made to Measure, New Materials for the 21st Century, Philip Ball, Princeton University, (c) Introduction to Nanotechnology, CP Poole Jr., FJ Owens , Wiley, 2003. Preferably, for nanowires, the material produced on the backbone is electrically conducting as an electrical conductor, semiconducting (intrinsic or through doping), transmitting light, magnetic, Or some other technically useful property. Other properties include ferroelectricity, piezoelectricity, reverse-piezoelectricity and thermoelectricity.

Semiconductors are a particularly important type of inorganic nanowire material. The semiconductor material may be any of the standard types, for example, which may include group IV-IV (eg, Si, Ge, Si _(1-x) Ge _x ), group III-V duality (eg , GaN, GaP), group III-V ternary (eg Ga (As _{1 - x} P _x )), group II-VI binary (eg ZnS, ZnSe, CdS, CdSe, CdTe), IV Alloys including a Group VI binary (eg PbSe), transition metal oxide (eg BiTi0 ₃ ), and combinations thereof.

Magnetic materials can be those known in the art, including nanostructured magnetic materials. See, eg, Introduction to Nanotechnology, CP Poole Jr., FJ Owens, Wiley, 2003, Chapter 7, pages 165-193 ("Nanostructured Ferromagnetism) and references cited therein (see, eg, page 193). See also

Typically, the present invention is not limited by theory, but nanowires may be structures in which nanoparticles are formed of nanowires and collapse into a fused structure at the end of the process. The porosity of the nanowires is not particularly limited, but usually non-porous nanowire materials are particularly desirable for conductive applications where porosity can interfere with the desired conductivity. Alternatively, the nanowires can be porous.

Nanowires can be crystalline. The nanowires can be a single crystalline domain or can have one or more crystalline domains. In one embodiment, the fused nanoparticles are single crystalline. The crystalline phase may be a thermodynamically good crystalline state or a crystalline state that is not thermodynamically good but is trapped by the relative orientation of the crystalline nanoparticles prior to fusion. Nanoparticles can be oriented in any manner. For example, the crystallographic axis of the nanoparticles can be oriented relative to the skeletal surface. The heat treatment in the manufacturing method (see below) can be varied to achieve the desired crystalline structure or to convert the polycrystalline structure into a single crystalline structure. It is also possible to vary the heat treatment to remove the organic backbone. In some cases, fusion and organic backbone removal are achieved at the same temperature, in other cases fusion can occur prior to removal.

The length of the nanowires can be, for example, about 250 nm to about 5 microns, and more particularly about 400 nm to about 1 micron.

The width of the nanowires can be, for example, about 5 nm to about 50 nm, more particularly about 10 nm to about 30 nm.

In some embodiments, the length of the nanowires can be, for example, about 250 nm to about 5 microns, and the width can be, for example, about 5 nm to about 50 nm. In other embodiments, the length of the nanowires can be, for example, about 5 nm to about 50 nm, and the width can be, for example, about 10 nm to about 30 nm.

If there are a plurality of nanowires, their length and width can be expressed as average length and width, using statistical methods known in materials science. For example, the average length of the nanowires can be, for example, about 250 nm to about 5 microns, more particularly about 400 nm to about 1 micron. The average width of the nanowires can be, for example, about 5 nm to about 50 nm, more particularly about 10 nm to about 30 nm.

In addition, when a plurality of nanowires are present, the nanowires may be substantially monodisperse in length and / or width. Since the nanowires are assembled from the backbone, monodispersity can be a uniform length and width. Again, statistical methods known in materials science can be used to calculate polydispersities for length and width. For example, an image of nanowires can be obtained, for example 20-50 nanowires can be selected for statistical analysis. The coefficient of variation (CV) can be calculated, where the standard deviation is divided by the mean value. The CV may be, for example, less than about 20%, more preferably less than about 10%, more preferably less than about 5%, more preferably less than about 3%.

The nanowires can be substantially straight. For example, the linearity can be determined by (1) measuring the true length of the nanowire, (2) measuring the actual terminal to terminal length, and (3) calculating the ratio of true length to actual non-terminal length, Can be estimated. For perfectly straight nanowires, the ratio will be one. In the present invention, a ratio close to 1 can be achieved (including, for example, less than 1.5, less than 1.2, and less than 1.1).

In addition, the inorganic nanowires of the present invention may be formed in combination with other types of conjugate materials to form larger structures, for example using a multifunctional backbone. Thus, the conjugate material is not particularly limited to inorganic materials for larger structures, and combinations of materials may be used. Typically this will be chosen for a particular application. The viral particles may be selected to be biopanned relative to the conjugate material, wherein the conjugate material is selectively or specifically bound to the viral particles. For some applications, selective binding may be sufficient, while for other applications more robust specific binding may be desirable. Examples of conventional types of conjugate materials that can be used in larger structures include inorganic, organic, particulate, nanoparticulate, monocrystalline, polycrystalline, amorphous, metallic, magnetic, semiconductor, polymeric, electronically conductive, optically active , Conductive polymeric, light emitting, and fluorescent materials. Conjugate materials are further described, for example, in the patent publications and technical literature of Angela Belcher and its collaborators, which are cited throughout this specification.

In summary, the present invention relates to the common and universal synthesis of 1-D nanostructures (including nanowires), which in a preferred embodiment directs growth and assembly of crystalline nanoparticles in a 1-D arrangement, and subsequently, Based on a genetically modified viral backbone for annealing the virus-particle assembly with crystalline nanowires through oriented crystal growth 14, 15 based on aggregation (FIG. 2).

Synthesizing similar nanowire structures from fundamentally different materials, such as LI ₀ ferromagnetic alloys CoPt and FePt, and II-VI semiconductors ZnS and CdS, provides precise control of material properties through the generality and genetic modification of the viral backbone. To prove both the ability to do so. In contrast to other synthetic methods (6), this approach allows for the genetic control of crystalline semiconducting, metallic, oxide, and magnetic materials with universal skeletal templates.

IV. Method of Making Inorganic Nanowires

The present invention also provides a process for preparing inorganic nanowires, which is further illustrated in the following working examples. For example, the present invention provides a method of forming an inorganic nanowire, comprising the steps of: (1) providing a precursor material for one or more inorganic nanowires; (2) providing an extended organic backbone; (3) reacting the one or more precursor materials in the presence of the backbone to form nanoparticles, wherein the nanoparticles are disposed along the length of the elongated organic backbone; And (4) heat treating the backbone and nanoparticles to form inorganic nanowires by fusion of nanoparticles. In some embodiments, no heat treatment is carried out and the method comprises the steps listed in (1)-(3) above. The present nanowire forming method can also be used to form a plurality of nanowires.

In this method, inorganic nanowires are described in the aforementioned section, which includes size, monodispersity, and linearity, including crystallinity, material type, length, and width. In addition, in these methods, extended organic backbones are described above (including viral lines with potential for selective recognition). These methods include situations involving the selective removal of organic backbones.

The present invention is not particularly limited by the type of reaction and the precursor material used to form the nanowires. Typically, the reaction and precursor materials should be usable with the backbone. The reaction at temperatures below 100 ° C. may be used to form nanoparticles. In a preferred embodiment, the treating step comprises chemical reduction of the metal precursor salt. The precursor material may, for example, preform nanoparticles or materials forming the nanoparticles.

In a preferred embodiment, the nanoparticles may have an average diameter of about 2 nm to about 10 nm, more particularly about 3 nm to about 5 nm. Nanoparticles can be crystalline before and / or after heat treatment. Nanoparticles can be fused before and / or after heat treatment. For example, heat treatment can cause nanoparticles that have not been fused prior to heat treatment to fuse. The nanoparticles may or may not be oriented.

The temperature and time of the heat treatment step are not particularly limited, but may vary depending on the precursor material used and the material of the final nanowire. For example, the melting temperature and annealing behavior of the material can be taken into account in the temperature selection. Typically, temperatures of about 100 ° C. to about 1,000 ° C. may be used. Heat treatment can be used to fuse the nanoparticles into a single structure and also to remove the backbone, which can be tailored to specific applications using particular materials. In principle, the porosity of nanowires and the degree of fusion of nanoparticles can be affected by temperature. In a preferred embodiment, the heat treatment step can be carried out at about 300 ° C. or higher and about 500 ° C. or lower. Typically, if more porous nanowires require less fusion, lower temperatures may be used, such as from about 200 ° C. to about 300 ° C., depending on the material. The heat treatment step may be performed at a temperature below the melting point of the precursor material. The temperature may be selected to achieve the desired crystalline phase, which may be a low energy phase or a high energy phase. If desired, a temperature programming step can be used to tailor the fusion, target crystal phase, and backbone removal of the nanoparticles as desired. In order to ensure that the framework is completely removed and burned, higher temperatures may be used, for example between about 500 ° C and about 1,000 ° C. Lower temperatures, for example about 50 ° C. to about 300 ° C., may be used to avoid removing the backbone. However, the temperature and time can be chosen so that the nanowires are not excessively oxidized. The heat treatment time is not particularly limited, but may be, for example, 30 minutes to 12 hours. Preferably, the temperature and time for the heat treatment can be adjusted to reduce oxide formation and improve the stability of the crystal structure while achieving an optimal balance for nanoparticle fusion.

In one embodiment, the present invention provides a method for preparing nanowires using an extended organic backbone, comprising the following steps: (1) a binding site along the backbone length and a binding at at least one terminal end of the backbone Providing an elongated organic skeleton comprising a plurality of binding sites comprising sites; (2) placing the nanowire precursor composition along the backbone length to form the backbone precursor composition; And (3) treating the skeletal precursor composition to form nanowires. In another embodiment, the method further comprises binding to another structure using a binding site at the distal end of the backbone. Other structures can be, for example, other elongated organic backbones, electrodes, circuit elements, or biological molecules. The framework can be coupled to a patterned structure, such as a circuit board. The treatment step may be a heat treatment step as described in detail herein. The skeleton can be removed or left as is.

V. Application

The nanowires of the present invention can be used in very different commercial applications, some of which are well known above (including the cited patent applications cited above and cited references at the end of the specification). Nanowires can be used, for example, in applications requiring nanoscale electrical conductivity or semiconductivity. The large surface area to volume ratio of the nanowires is advantageous for applications such as fuel cells, thin film batteries, and supercapacitors. In some applications, a single nanowire may be used. In other applications, a plurality of nanowires may be used in parallel or crosswise. Typically, an organized arrangement of nanowires is advantageous. In some applications, the nanowires may be surface modified, doped, or otherwise modified to a material structure for that application. Modifications include both chemical and biological modifications. Microcircuits, nanocircuits, macroelectronics, photovoltaics, solar cells, chemical and biological sensors, optical components, field emission tips and devices, nanocomputing, nanoswitches, molecular wire crossbars, batteries, fuel cells, catalysts, highly Large flat panel displays, small radio frequency identification devices, smart cards, phased array RF antennas, disposable computer and storage electronics, nanoscale barcodes, crossbar nanostructures, biosensor arrays, high density data storage, field effect transistors, etc. Example of nanowire application. Particularly important semiconducting elements include, for example, p-n diodes, p-i-n diodes, LEDs, and dipole transistors. Nanowires can be included in many devices, such as electronic devices, optoelectronic devices, electrochemical devices, and electromechanical devices. A single nanowire can connect the devices in the device, or a series of connected fragments of nanowires can connect the devices. For example, the field effect transistor device can include nanowires in parallel and in cross arrangement.

Application of nanowires is described, for example, in US Patent Application Publication No. 2003/0089899 (filed May 15, 2003, Lieber et al.), Which includes, for example, field effect transistors, sensors, and logic. A gate is included. This publication is incorporated herein by reference in its entirety, and the publication also includes a description of a device made of nanowires. Other applications of nanowires are described, for example, in US Patent Application Publication No. 2003/0200521 (published October 23, 2003, Lieber et al.), Which includes nanoscale crosspoints and The publication is incorporated herein by reference in its entirety. Other applications of nanowires are described, for example, in US Patent Application Publication No. 2002/0130353 (published Sep. 19, 2002, Lieber et al.), Which includes devices with chemical patterning and bistable devices. Other applications of nanowires are described, for example, in US Patent Application Publication No. 2002/0117659 (published Aug. 29, 2002, Lieber et al.), Which includes nanosensors for chemical and biological detection. In addition, applications for related nanorods are described, for example, in US Pat. No. 6,190,634; 6,159,742; 6,159,742; 6,036,774; 6,036,774; 5,997,832; 5,997,832; And 5,897,945 (all, Lieber et al.). Numerous literature references teach the application of nanowires and related technologies, see, eg, Choi et al., J. Power Sources 124: 420 (2003); Cui et al., Science 293: 1289-1292 (2001); De Heer et al., Science 270: 1179-1180 (1995); And Dominko et al., Advanced Materials 14 (21): 1531-1534 (2002), all of which are incorporated herein by reference in their entirety.

A particularly important point of the present invention is that the skeleton can be used to direct the nanowires to other structures, so that the skeleton is an active skeleton rather than a passive skeleton. For example, viruses can be conjugated with one-dimensional nanowires / nanotubes, two-dimensional nano electrodes, and microscale bulk devices. One-dimensional materials, such as nanotubes or nanowires, when they are conjugated with the pIII terminus of the M13 virus, can form phase separated lamellar structures with inorganic nanotube or nanowire layers and phage building block layers. Two-dimensional nano-thickness flat electrode can be organized. Virus-semiconductor composite nanowires may be attached across metal electrodes (including precious metal electrodes such as gold electrodes) via binding sites at the distal end of the virus. Nanowires can act as bridges between feeds and emissions. The nanowire precursor may be disposed on or adjacent to the electrode, and then the backbone may be removed so that the nanowire is in close electrical contact with the electrode in its final state. As long as the nanowires ultimately function as bridges, thermal annealing can be performed prior to crosslinking the electrode with the nanowire or after crosslinking the nanowire to the electrode. These structures can function as nano-FET devices with improved performance due to gate regions of about 5 nm diameter. Unlike other proposed nanoscale devices, where wire placement must be done probabilistically, this approach allows a single wire to point at the correct electrode position. Alternating cathode and anode structures may be useful for nanoscale biofuel cells. When combining certain binding M13 viruses with microsized objects, periodic organization of these microdimensional objects is also possible. The role of the M13 virus will be specific adhesion units for different self-assembled multiple objects of periodic pattern. The processing capacity of the M13 viral protein may be a key factor in the development of viral-inorganic hybrid system arrangements. In addition, fibrous networks of fibers or viruses can be constructed with specifically designed mechanical properties based on secondary and tertiary structures induced by virus-virus binding. In addition, these materials may have special properties by further functionalizing the virus to bind regent or signaling elements.

In addition, a multifunctional virus based arrangement, in which one portion of the arrangement can selectively bind to the tissue type and the other portion can nucleate bone or other structural bio-materials, can be used for tissue repair. In addition, catalytic nanostructures can be developed by controlling the geometric arrangement and element identification of molecular catalytic moieties.

The development of self-assembling motifs used by M13 bacteriophages to generate biological backbones provides a way to generate templates for general synthesis of single crystal nanowires, complex, highly ordered and economical. By introducing programmable genetic control into the composition, phase, and assembly of nanoparticles, it is possible to realize common templates for universal synthesis of various materials. Further developments in nanoscale materials and device fabrication can be achieved through the incorporation of device-assembly directors by modifying four remaining proteins in the virus. Based on its shape anisotropy, the virus's ability to form liquid crystals, and other ordered and ordered strains, is another promising route for assembling virus-based nanowires into well ordered arrangements on multiple length scales. . In turn, modification of the biological lineage by the introduction of substrate specific peptides provides a way to achieve well-ordered nanomaterials in a cost-effective and performance-free manner.

In particular, when amino acid oligomers are expressed on the surface, expression of amino acid oligomers may provide a number of commercially available functions, including cell adhesion factors, flexural factors, or binding sites for organic or inorganic molecules. It is not limited to this. Expression of amino acid oligomers allows the virus to be treated with a particular application. For example, films and fibers comprising treated fibers may contain amino acid oligomers that initiate or enhance cell growth for use in tissue treatment applications. In another example, amino acid oligomers having specificity for specific inorganic molecules can be expressed to bind inorganic molecules, thereby increasing chemical reaction efficiency. In another example, expressed amino acid oligomers can bind organic molecules, such as bioprotectants. Such films or fibers can be incorporated into the first reactant as part of a personal military uniform or sensor system.

There are only a few examples of the usefulness of films and fibers made of treated viruses, and other applications are easy and apparent to those skilled in the art.

The invention is further characterized by the following non-limiting working examples, including FIGS. 2 and 3 and the description and discussion thereof. Those skilled in the art can use FIGS. 1-3 to provide an introduction to working embodiments as a guide in the practice of the present invention.

1

1A depicts nucleation, ordering and annealing of nanowire synthesis schemes or virus-particle assemblies. 1B shows virus symmetry. The symmetry allows the nucleated particles to be ordered along the x, y, and z directions that meet the requirements for aggregation based annealing. 1C shows M13 bacteriophage of highly ordered properties. The highly ordered, self-assembled M13 bacteriophage promotes the desired orientation seen in the nucleated particles through the stiffness and packing of the expressed peptide, which shows 20% incorporation. 1D shows the structure of the M13 bacteriophage virus. The construct has genetically modifiable capsids and termini, specifically gPVIII, gPIII, and gPIX, which are encoded in phageimide DNA encapsulated within the viral capsid.

2

2A-F are electron micrographs of pre and post annealed ZnS and CdS viral nanowires. FIG. 2A shows a dark field diffraction contrast image of a ZnS strain preannealed using (100) reflection, which shows crystallographic ordering of nucleated nanocrystals, where contrast is the (100) Bragg ( Bragg) originates from satisfying diffraction conditions. The implantation of FIG. 2A shows the ED pattern of the polycrystalline pre-annealed wire showing a single crystalline [001] region axis pattern and a wurtzite crystal structure, which is the preferred strong [001] of nanocrystals on viral templates. ] Region axis orientation. Although the sample region consists of many nanocrystals, the electron diffraction (ED) pattern (embedded in FIG. 2A) shows single crystalline behavior. The behavior suggests that the nanocrystals on the virus prefer to be oriented in their c-axis perpendicular to the viral surface. 2B is a brightfield TEM image of individual ZnS single crystal nanowires formed after annealing. The upper left inset of FIG. 2B shows the ED pattern along the [001] region axis, which shows the single crystal urgite structure of the annealed ZnS nanowires. The lower right inset of FIG. 2B is a low magnification TEM image, showing isolated single crystal nanowires that are monodisperse. 2C shows a typical HRTEM of ZnS single crystal nanowires, showing a lattice image that continuously extends wire length, confirming the single crystal properties of the annealed nanowires. The measured lattice space of 0.33 nm corresponds to the (010) plane of the Urgite ZnS crystal. The 30 ^o orientation of the (010) lattice plane with respect to the nanowire axis coincides with the (100) growth direction measured by ED. 2D shows a HAADF-STEM image of single crystal ZnS nanowires, which are annealed on silicon wafers. 2E shows a HAADF-STEM image of CdS single crystal nanowires. 2F is an HRTEM lattice image of individual CdS nanowires. The lattice stripe space of the experiment, 0.24 nm, is consistent with the distinctive 0.24519 nm separation between the two 102 planes in the bulk urzite CdS crystal.

3

3A shows CoPt wire synthesized by a modified virus template that is soluble in water. Reduction of the Co and Pt salts in the absence of virus immediately produced large precipitates from the solution. 3B shows a TEM image of an annealed CoPt strain. Insertion of FIG. 3B shows STEM images of unannealed CoPt wire. The scale bar shown there is 100 nm. 3C shows low resolution TEM images of crystalline L10 CoPt wires (about 650 nm X about 20 nm). The tendency for CoPt and FePt wires to not be straight may result from magnetic interactions between nanoparticles and / or wires that do not exist in the II-VI strain. The inset of FIG. 3C is ED showing the crystallinity of characteristic (110) and (001), L10 lines, and lineage. 3D is an HRTEM of a CoPt wire with a (111) plane perpendicular to the c-axis of the wire. The inserted ED shows a specific superlattice structure for L10. 3E is a TEM image of an annealed FePt wire. 3F shows the TEM of annealed FePt wire. The embedded ED pattern confirms the L10 properties of the FePt wire, which shows the crystalline properties of the material.

M13 Bacteriophage  process

M13 bacteriophages used in working examples include five genetically modifiable proteins (19, 20, 21); High product rate virus (200 mg / L) consisting of gene products (gP) -3, 6, 7, 8 and 9, wherein ˜2700 copies of gP8 protein form the capsid of wild type virus. The gP8 protein is genetically modified and expressed using the phagemid lineage, which results in the fusion of substrate specific peptides to the N-terminus of the gP8 protein (12). During assembly, gP8 unit cells accumulate, causing 5-fold symmetry below the virus length (c-axis), which is the origin of fusion peptide ordering in three-dimensional structures (FIG. 1B). Computational analysis of peptide expression on the capsid of the virus revealed that the nearest neighboring peptide separation was stabilized at around 3 nm at incorporation of at least 20% (FIG. 1C). In conclusion, high incorporation of substrate specific fusion peptides is not required for complete mineralization of the virus. Trifunctional templates can be realized through additional genetic modifications to the virus's near and distant tips (specifically gP3 and gP9 proteins, 22), which allows current systems to have higher appearance ratios. It may also be used to assemble functional heterostructured materials by introducing materials including materials such as, for example, precious metals, semiconductors, and oxides.

Skeletal Mineralization

Mineralization of ZnS and CdS systems has been described previously (11, 12, 17) and involves incubating viral templates with metal salt precursors at low temperatures to promote uniform orientation of nanocrystals during nucleation (23 ), Which leads to the desired crystallographic orientation of the nucleated nanocrystals relative to the long axis of the virus. Prior to annealing, the urethane ZnS and CdS nanocrystals (3-5 nm) grown on the viral surface are in close contact and prefer to be oriented in the (100) plane and [001] direction perpendicular to the wire length direction This is supported by electron diffraction (ED), high resolution transmission electron microscopy (HRTEM), elevation circular dark field scanning transmission electron microscopy (HAADF-STEM), and dark field diffraction contrast imaging (FIG. 2) (24). Particles attached to the virus cannot be fused under initial synthetic conditions, perhaps due to, for example, the blocking effect of neighboring peptides, so the removal of the template was intended to form single crystal nanowires. Thermal analysis of the virus-particle system showed complete removal of the organic material at 350 ° C. (25), which was observed for fusion of adjacent particles by TEM, while annealing was carried out in situ using a thermal step. Corresponds to the minimum temperature (26).

Nanowire  formation

Annealing of mineralized viruses at temperatures below the ZnS and CdS particle melting points (400-500 ° C.) allows the polycrystalline assembly to form single crystal nanowires through minimization of interfacial energy and removal of organic templates (ZnS nanowires). For the length distribution was about 600-650 nm; for the CdS nanowires the length distribution was about 475-500 nm; the diameters of the ZnS and CdS nanowires were about 20 nm) (27) (FIG. 2B, E ). ED and HRTEM showed the single crystal properties of individual nanowires that inherited the desired orientation seen in precursor polycrystalline wires through the removal of grain boundaries (28, 29) (FIGS. 2C and 2D). Although there is a thermodynamically high energy plane, the observed [100] and (001) plane orientations of the ZnS nanowires coincide with the common extension direction for the II-VI nanowires (FIGS. 2B and 2C; 14, 30). , 31). The HRTEM of the single crystal CdS nanowires showed a lattice spacing of 2.4 kV, which coincided with the unique 2.4519 mm 3 separation between the two (102) planes in the bulk urzite CdS crystal (JCPDS # 41-1049). . The 43.1 ° orientation of the (102) lattice plane with respect to the nanowire axis indicates that the nanowires extended along the [001] direction, which again confirmed the urzite structure (FIG. 2F).

Ferromagnetic Nanowire  formation

Ferromagnetic L1 ₀ extended synthesis of viral-directional approach to the CoPt and FePt systems, was conducted to carry out all the current controversy about the technical development of two-dimensional magnetic materials and variety of available materials. Platinum alloy magnetic material on the L1 ₀ ordered chemically, has been a recent interest due to (important for high-density recording medium), its high coercive force, resistance to oxidation, and inherent magnetic anisotropy (32). Although synthetic pathways such as VLS produce sophisticated 1-D semiconducting structures and non-specific template reaction schemes are available for the material, both have difficulty in producing high quality crystalline metallic and magnetic nanowires in a free upright form ( 33).

Genetically processed skeleton

M13 bacteriophage was modified by fusing CP7 CoPt specific or FP12 FePt specific peptides into the viral capsid. Nucleation of CoPt and FePt particles was achieved through chemical reduction of metal precursor salts in the presence of gP8 modified virus (18, 34). Assembly annealing at 350 ° C. promoted the growth of crystalline CoPt and FePt nanowires on a uniform diameter (10 nm +/− 5%) L1 ₀ . The crystalline properties of the wires were seen in the selected area ED pattern, which also shows characteristic (001) and (110) L1 ₀ peaks by high resolution TEM grating imaging (FIG. 3C, D). The (111) plane perpendicular to the long axis of the CoPt wire with a lattice spacing of 2.177 Å was consistent with the reported 2.176 Å value, again confirming the highly crystalline properties of the material (FIG. 3D, JCPDS # 43-1358). Ll _o on the persistence (receiving the dynamic impact in more than 550 ℃ easiness 15) is caused in the tendency of the particles to maintain their alignment during the annealing based on the aggregation.

Nanowire  Design simulation

The invention, including working embodiments, can be further understood using simulation methods. For example, Monte Carlo simulations of the A7 constrained sequence resulted in a 21% reduction in the standard deviation of the backbone dihedron when transferring the peptide from the isolate to the capsid environment, demonstrating that the fusion peptide was given stiffness ( 35). With regard to the preferred crystallographic orientation along the virus length, the ordering of the nucleated particles is believed to be the result of the stability of peptide fusion and the symmetry of the viral envelope. Nanocrystal ordering facilitated the single crystal properties of annealed nanowires by meeting the orientation requirements of the crystal growth mechanism based on aggregation (14). Particles exhibiting orientation are anticipated that many of them will not be consistent, but few nanocrystals must rotate to adopt the desired crystallographic orientation and merge with multiple portions to minimize both interface and grain boundary energy. .

Details of additional experiments can be found below.

While making and using various embodiments of the invention have been discussed herein, it will be appreciated that the invention provides many available inventive concepts that can be implemented in a wide variety of specific contexts. The specific embodiments discussed herein are merely exemplary specific ways to make and use the invention, and do not limit the scope of the invention.

The following references are not to be regarded as prior art, but may be used by one of ordinary skill in the art to guide the practice of the present invention, which is also incorporated herein by reference in its entirety.

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Claims (32)

Inorganic nanowires having an organic scaffold substantially removed from the inorganic nanowires and consisting essentially of fused inorganic nanoparticles substantially free of organic skeletons. The inorganic nanowire of claim 1, wherein the inorganic nanowire has one or more crystalline domains. The inorganic nanowire of claim 1, wherein the inorganic nanowires consist essentially of a semiconductor material, a metallic material, a metal oxide material, a magnetic material, or a mixture thereof. The inorganic nanowire of claim 1, wherein the nanowires are from about 250 nm to about 5 microns in length and from about 5 nm to about 50 nm in width. The inorganic nanowire of claim 1, wherein the inorganic nanowires are crystalline and the inorganic nanowires consist essentially of a semiconductor material, a metallic material, a metal oxide material, a magnetic material, or a mixture thereof. The inorganic nanowire of claim 1, wherein the nanoparticles are oriented. A composition comprising a plurality of inorganic nanowires according to claim 1, wherein the nanowires are substantially monodisperse in average length. A composition comprising a plurality of inorganic nanowires according to claim 1, wherein the nanowires are substantially monodisperse in average width. A composition comprising a plurality of inorganic nanowires according to claim 1, wherein the nanowires are substantially monodisperse in average length and substantially monodisperse in average width. A composition comprising a plurality of inorganic nanowires according to claim 5, wherein the nanowires are substantially monodisperse in average length. A composition comprising a plurality of inorganic nanowires according to claim 5, wherein the nanowires are substantially monodisperse in average width. A composition comprising a plurality of inorganic nanowires according to claim 5, wherein the nanowires are substantially monodisperse in average length and substantially monodisperse in average width. A plurality of inorganic nanowires, wherein the inorganic nanowires comprise fused inorganic nanoparticles substantially free of organic backbone. A method of forming an inorganic nanowire, comprising the following steps: (1) providing one or more precursor materials for inorganic nanowires; (2) providing an elongated organic backbone; (3) reacting the one or more precursor materials in the presence of the backbone to form nanoparticles, wherein the nanoparticles are disposed along the length of the elongated organic backbone; And (4) heat treating the backbone and nanoparticles to form inorganic nanowires by fusion of nanoparticles. The method of claim 14, wherein the organic backbone is substantially removed from the nanowires. The method of claim 14, wherein the extended organic backbone comprises surface peptides along the backbone length that bind to the nanoparticles. The method of claim 14, wherein the heat treatment step is performed at about 100 ° C. to about 1,000 ° C. 16. A method of forming an inorganic nanowire, comprising the following steps: (1) providing one or more precursor materials for inorganic nanowires; (2) providing an organic skeleton; And (3) reacting the at least one precursor material in the presence of the skeleton under conditions for forming an inorganic nanowire and substantially removing the skeleton from the nanowire. Use of a filamentous virus as a sacrificial organic backbone in the manufacture of an inorganic nanowire comprising providing a filamentous viral backbone and an inorganic nanowire precursor on said backbone, and removing the filamentous viral backbone to produce inorganic nanowires. Providing a filamentous organic skeleton and an inorganic nanowire precursor on the skeleton, and converting the inorganic nanowire precursor into an inorganic nanowire while removing the filamentous organic skeleton to produce an inorganic nanowire. Use of a filamentous organic skeleton as a sacrificial organic skeleton in Use of an extended organic backbone to control the length of inorganic nanowires disposed on the backbone, comprising genetically treating the backbone to control the length of the backbone. An apparatus comprising an electrode in electrical contact with the nanowire of claim 1. 23. The device of claim 22, wherein the device is a field effect transistor. The device of claim 22, wherein the device is a sensor. Fragmented nanowires comprising a plurality of linked fragments of the nanowires according to claim 1. A plurality of linked fragments of nanowires, the nanowires comprising fused inorganic nanoparticles on an extended organic backbone, wherein the extended organic backbone is an amount of backbone used to bind to another extended organic backbone. Fragmented nanowires, which will have a binding site at the terminal. A method of making nanowires using an extended organic backbone, comprising the following steps: Providing an extended organic backbone comprising a plurality of binding sites comprising a binding site along a backbone length and a binding site at at least one end of the backbone; Placing the nanowire precursor composition along the backbone length to form a backbone precursor composition; And Treating said skeletal precursor composition to remove backbone and form nanowires. The method of claim 27, wherein the extended organic backbone has binding sites at both termini of the backbone. The method of claim 27, further comprising binding to another structure using a binding site at the backbone end. The method of claim 27, wherein the other structure is another extended organic skeleton. The method of claim 14, wherein the extended organic backbone comprises surface peptides along coat lengths on coat protein copies that bind nanoparticles, wherein the peptides are expressed on some copies of the coat proteins along the backbone length. How to be. The method of claim 14, wherein the extended organic backbone comprises surface peptides along the scaffold length that bind to the nanoparticles, wherein the peptides are expressed on substantially all copies of the coat protein along the backbone length. Way.

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