Применение углеродных нанотрубок в биомедицине 2 / Polizu, S., Savadogo, O., Poulin, P., & Yahia, L. (2006). Applications of Carbon Nanotubes-Based Biomaterials in Biomedical Nanotechnology. Journal of Nanoscience and Nanotechnology, 6(7), 1883–1904. doi10.1166jnn.2006.197
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Applications of Carbon Nanotubes-Based Biomaterials in Biomedical Nanotechnology |
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5. BIOMEDICAL APPLICATIONS OF |
sheet dimension, with a minimum length corresponding to |
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CARBON NANOTUBES |
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0.5 V was observed. In fact, the mechanism for convert- |
5.1. CNTs Smart Materials |
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ing electrical energy into mechanical energy is based on |
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the double-layer charge injection and it involves the inter- |
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5.1.1. Artificial Muscles and Actuators |
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face nanotubes-solution.137 139 The actuation is due to a |
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geometrical expansion of the C–C covalent bonds caused |
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An artificial muscle analogous to a biological muscle is |
by charge injection and originates from quantum chemical |
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composed of an actuator material that must be able to |
and double layer electrostatic effect.140 Such response, |
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work in a specific way in order to successfully mimic |
devoid of an ionic contribution, eliminates the disadvan- |
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the natural one. The natural muscles are distinguished by |
tages related to the faradaic conducting polymer actuators, |
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some characteristics: anisotropic behaviour consisting in |
for which the life cycle, the discharge rate, and the energy |
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contraction-elongation along the fiber axis, high energy |
conversion efficiency are limiting parameters.141 This new |
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density, fast speed and response, as well as large stroke. |
mechanism is sustained by structural model of SWNT, its |
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With a maximum power output of 150–225 w/Kg, they can |
electrical conductivity along with mechanical and charge |
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withstand a stress up to 150–300 KPa. The work of mus- |
transfer properties.138 Since this assertion, the non-faradaic |
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cles is defined by three variables: the stress which they can |
actuation concept has been predicted by theoretical studies |
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exert, the strain by which they can be shortened and the |
and experimentally demonstrated using both individual and |
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contraction frequency.135 Actuation capacity consists in the |
ropes SWNTs as well as the MWNTs.140 The first isomet- |
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ability to efficiently convert electrical energy into mechan- |
ric measurements shows high values for elastic modulus, |
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ical movement and its requirements are defined in terms |
of 1–2 GPa, and maximum deformation of 0.2%, corre- |
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of stroke and force. Generally, an actuator is composed |
sponding to a stress equal to 0.75 MPa. In fact, individual |
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of at least three elements: two electrodes whose function |
nanotubes display much better mechanical and electronic |
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is to apply the potential, and an interposed element.136 |
properties, expressed by a stress of 1 000 GPa and 1% |
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The ideal actuating material would operate at low voltage |
actuation strain. It has been demonstrated that the struc- |
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and at match least performance of skeletal muscle:137 10% |
tural deformation as well as the conversion of electrical |
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strain, 0.3% MPa stress generated and 10% s−1 strain rate. |
energy into mechanical force, through radial and longitu- |
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Characteristics such as light, low-volume, long cycle-life, |
dinal expansion or contraction, are more due to the elec- |
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Delivered by Publishing Technology to: University of Waterloo |
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large displacement, and high forcesIP:are200required.59.59.16forOn:actuTue,- |
tronic structure than to the coulomb interactions. Since, |
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138 |
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Copyright: American Scientificseveral worksPublishweres performed attempting to explain the |
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ator design and some of them correspond to CNTs. |
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actuation performance of nanotubes and hence improve |
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The nanotube’s actuation behaviour is generated by its |
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good electronic and mechanical properties coupled with |
these characteristics.141 They principally focus on both the |
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a high surface area as well as a non-faradaic nature of |
fabrication and manipulation of CNTs in order to obtain |
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the electrochemical response. Owing to these properties, |
suspended nanotubes.140 By manipulating these nanotubes |
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the nanotube actuators perform high strain per movement |
with AFM tip, and examining the change in cantilever |
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and generate greater mechanical stress than any other |
deflection, the measurements of both the Young’s modulus, |
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materials,139 when a current of a few volts is applied. In |
and actuation force are easily performed.140 142–144 More- |
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this type of actuator, the nanotube acts as an active material |
over, Frayse and his collaborators144 studied nanotubes |
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and constitutes one of the electrodes which are immersed in |
obtained by CVD growth and deposited on trenched quartz |
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an electrolytic solution or solid polymer electrolyte.138 139 |
substrate with the NT’s ends fixed. They thus estimated |
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Theoretical predictions and experimental measurements |
the actuation capability under bias voltage in an electro- |
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have suggested that actuators using carbon nanotubes allow |
chemical cell by measuring the deformation of nanotubes |
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high performances consisting in higher work densities by |
with AFM cantilever.140 According to the hypothesis that a |
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cycle138 and have significant contribution in term of time |
limited macroscopic response arises from the building and |
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and speed as well as reproducibility of its response. |
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entanglement of individual nanotubes at mesoand macro- |
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scopic scale, the authors found the possibility of taking |
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5.1.2. CNTs Actuators for Artificial Muscles |
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measurements at individual nanotube level. In the same |
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prospect, Roth and Baughman experimented with individ- |
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In 1999138 Baughman has demonstrated, for the first time, |
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ual nanotubes as actuators and demonstrated that the nano- |
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that carbon nanotubes can act as an actuator thus proposing |
objects change their shape when electrically charged.145 |
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the first prototype for a bimorph actuator. The macroscopic |
Since the purification level of nanotube was identified |
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sheets, so called buckypapers, consisting of randomly |
as a concern for the efficiency of the actuation pro- |
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entangled SWNT bundles act like working electrodes, |
cess, cumulated efforts contributed to the development of |
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connected to a potentiostat in electrochemical cells. An |
highly purified, aligned CNT, with high surface area.112–114 |
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axial strain of up to 0.2% was provided by using buky- |
Moreover, significant improvement of actuation strain |
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paper while switching the electrochemical potential from |
rate was achieved by operating carbon nanotubes in an |
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0.5 V to −1 0 V A roughly parabolic dependence of |
organic electrolyte.146 147 For instance, the use of resistance |
1893
Applications of Carbon Nanotubes-Based Biomaterials in Biomedical Nanotechnology |
Polizu et al. |
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compensation resulted in a higher rate, of 0.6% s−1 |
addition reaction on nanotube external surfaces and its sol- |
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[148] with an increasing pulse amplitude and more nega- |
ubilisation in aqueous media. At the same time, an exhaus- |
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tive potential limit. Thus, a strain amplitude of 0.3% |
tive work on solubilization of SWNT has been directed |
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in 0.5 s was attained which is considerably better than |
towards the assembly of coated peptides.119 |
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0.5% in 1 s, previously reported. Despite a small dis- |
Nanotube-based supramolecular structures have been |
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placement of nanotubes, these results sustain the unde- |
prepared by controlling the factors that influence peptide- |
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niable actuation capacity of advanced carbon nanotube |
peptide interactions.159 Based on both molecular modeling |
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structure and forecast their promising potential149 for actu- |
and experimental data, an amphiphilic -helical peptide |
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ators with a performance similar, in some respects, to that |
model was developed with the aim to predict the self |
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of a biological muscle. This CNTs resource to emulate |
assembly function. This construction is the first step |
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artificial muscles opens the door for nanoscale devices150 |
towards a new architectural arranging of carbon nanotubes |
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with various applications. Other actuating designs, such |
for molecular sensing mechanisms. Thus, a recent identi- |
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implants for tissue stimulation151 152 or electrical stimula- |
fication of polypeptides with selectivity for nanotubes160 |
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tor capable of encouraging ostoeogenezis are envisaged.153 |
announces a new method for the manipulation and use of |
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In combination with biopolymers, such as collagen,154 or |
CNTs in the biological and medical area. These peptide |
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functionalized,155 carbon nanotubes are processed as mate- |
sequences, with specific affinity for nanotubes, naturally |
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rial for the creation of engineered tissue or as component |
bind to the surface of carbon nanotubes, in a selective man- |
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for other devises. Although our focus is not the presen- |
ner; this ability is owed to the flexibility and conformation |
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tation of carbon nanotubes as macroscopic material, we |
of their chains. It seems that peptidic chains act as symmet- |
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mention that, the advantages coming from this avenue are |
ric detergents, with hydrophobic sequence in the middle |
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very enriching for the design of biocompatible biomateri- |
and hydrophilic ones at the ends. Their inherent selectivity |
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als. Indeed it has been proven that the insertion of func- |
enables them to discriminate between different nanotube |
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tionalized CNTs in a collagen scaffold induce positive |
structures, according to their chirality and diameter, and |
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effects155 in terms of physiology, electrical conductivity, |
thus facilitates the CNTs manipulation for biosensors. |
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and mechanical behaviour. |
The multifunctionalization of CNTs finds application in |
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With regard to the macroscopic formulation of the |
the design of systems for delivery of antibiotics to different |
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CNTs, it is important to note that composite structure is |
type of cells. Using selective transport through the mem- |
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another alternative of material whichIP: 200could.59improve.59.16 On:actu-Tue,brane,20 Octa 2015new approach13:16:49is proposed for the modulation of
ator performance. In this context SWNT-Nafion composite |
the therapeutic actions. |
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Such strategy was experimented |
Copyright: Amer can Sci ntific Publishers |
161 |
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actuators were created and tested.156 The results qualify the |
in the last year and demonstrated, in vitro, the aptitude |
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system as promising potential for MEMS switches con- |
of oxidized MWNTs to conjugate with both fluorescin |
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struction. Moreover, combinatory actuator effect of both |
and amphotericin (AmB) molecules. Even though AmB is |
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carbon nanotubes and conductor polymer, such as polyani- |
known to be the most effective antibiotic for cronical fun- |
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line, are in exploration.157 Film composites were tested in |
gal infection, a high toxicity risk appears when in contact |
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order to evaluate the actuation synergism of two compo- |
with mammalian cells. Consequently, the advantage of this |
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nents in a new actuator material. The influence of elec- |
new conjugated system consists in its capacity to partially |
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trolyte has also been evaluated by using both salt and basic |
avoid the molecules aggregation resulting in more aque- |
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solutions. Thus, the contribution of redox process was evi- |
ous solubility for AmB and internationalization capacity |
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denced while demonstrating the increase in conductivity |
of CNTs, which finally improve antibiotic activity. |
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of composite by participation of CNTs, leading to more |
The influence of interfacing of carbon nanotubes with |
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electrochemical efficiency. It is more evident that mate- |
biomolecules is various162 and could be extended to certain |
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rial processing offers a diversification of smart materials |
reactions which they influence. Indeed, an investigation of |
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for actuators. Indeed, the experimental work on nanotube- |
effects generated by addition of SWNT to the polymerase |
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epoxy layered actuator is promising for the development of |
chain reaction163 illustrate an increase in efficiency of poly- |
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dry nanocomposites actuator material.158 In spite of man- |
merase mechanism, proving the capacity of nanotubes to |
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ufacturing challenge, it appears that these composites may |
act as catalysts in a variety of biochemical reactions as elec- |
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become a new smart material for structural application, |
tron/donor receptors. With regards to biologic cells, carbon |
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which could promote the development of dry actuator, as |
nanotubes showed excellent proliferation164 for cell culture. |
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component of active prostheses. |
These effects can be accommodating for exploitation of |
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carbon nanotubes as scaffold for regenerative medicine. |
5.2. Biomolecules and Carbon Nanotubes Assemblies
The first step towards the synthesis of peptides based carbon nanotubes started a few years ago with the achievement of derivatives of SWNTs and MWNTs with n-protected aminoacids.118 The method is based on the
5.3. CNT Neural Biomaterial
Neural prostheses provide the means to apply and monitor electrical signals in neural tissues. The development of systems able to restore the nerve function does not strictly
1894 |
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Polizu et al. |
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Applications of Carbon Nanotubes-Based Biomaterials in Biomedical Nanotechnology |
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lie in the realm of neuroscience, medicine and engineer- |
(ii) small particle size minimizes possible irritant reactions |
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ing; new possibilities arise at the interface of all three and |
at the injection site; |
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demand the use of advanced biomaterials. Carbon nano- |
(iii) miniaturised size allows the penetration of carriers in |
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tubes possess excellent electrical properties which have |
the membrane of the sicken cells, thus providing a way |
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been proven useful in the area of neural prostheses. The |
to selectively deliver the drug to cancerous tumours, while |
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pertinence of nanotube fibers as neural prosthetic biomate- |
avoiding the healthy cells. |
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rial has been demonstrated by McKenzie and his collabora- |
As presented in the section about functionalization, well |
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tors.165 Thanks to their capacity to minimize the astrocites |
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functionalized nanotubes and their derivatives are destined |
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function, the CNTs possessing high surface energy become |
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for biomedical and biotechnological applications. Indeed, |
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interesting |
biomaterials for a new |
generation of neural |
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the organic modification |
of nanotubes creates multiple |
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prosthesis. Haddon and his colleagues reported the appli- |
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attachment sites for bioactive molecules and hence facili- |
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cation of carbon nanotube in neural research and estab- |
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tates the assembly in complex nanodevices. A very recent |
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lished the |
function of nanotubes as |
a support for nerve |
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study demonstrated the capacity of nanotubes to serve as |
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cell growth as well as substrates for probes with neu- |
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vehicles for the administration of vaccines84 85 |
by devel- |
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ronal function at nanometer scale.166 Using nanotubes of |
oping new and |
effective |
delivery |
approaches |
of protec- |
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diameters similar to those of small nerve fibers, they devel- |
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tive antigens. They offer the possibility to effectively use |
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oped methods for growing embryonic rat-brain neurons |
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the antigens while enhancing and modulating the immune |
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on MWNT. The chemically modified MWNT coated with |
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response. The |
potential |
of CNTs |
to present |
a biologi- |
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4-hydroxynonenal bioactive molecules stimulated neurite |
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cally important |
epitope, |
with the |
appropriate |
conforma- |
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growth with extensive branching. A similarity between the |
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tion, in vitro and in vivo tests, enables them to be used in |
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diameter of nanotubes, ranging from 1 nm for SWNT and |
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vaccine delivery. The peptide-carbon nanotube conjugated |
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10–100 |
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nm for MWNT, and those |
of neurites, favours |
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system, integrating aminoderivatized nanotubes selectively |
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localized molecular interactions, necessary for the forma- |
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bonded to a peptide, provides the peptide bis-adducts.85. |
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tion of a neuronal circuit. Furthermore, the conductivity |
This conjugated system elicited strong anti-peptide anti- |
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of nanotubes renders them a valuable candidate for elec- |
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body response and retains the antigen conformation, which |
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trophysiological analysis of neuronal micro circuitry. It is |
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fulfills the main requirements for the induction of an anti- |
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known that neural development is based on a complex |
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tubes do not have any detectable immunogeneicity, the |
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neurites. |
167 |
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Copyright: American Scientific Publishers |
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The investigation of CNTs as neural biomate- |
system is very appropriate for the delivery of a vaccine |
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rials directly requires biocompatibility studies. Investigat- |
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antigen. More |
specifically, new structures are designed |
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ing the in vitro cytocompatibility of CNTs,168 the authors |
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using water soluble SWNT derivatives which are able to |
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demonstrated the beneficial effects of carbon nanofibers |
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cross the cell membrane;84 they can be accumulated in the |
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to limit |
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astrocyte functions, leading |
to a decreased glial |
cytoplasm or reach the nucleus without being toxic up to |
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scar tissue formation and further established a relationship |
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a quantity/concentration of 10 pm; their investigation as |
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between fiber characteristics and astrocyte interactions. |
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delivery systems in targeting therapy171 demonstrated that |
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These investigations promote the development of minia- |
the absence of immunogenicity of nanotubes increases the |
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turized devices in which the nanotubes play a role in the |
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efficacy of their function. |
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formation of a nerve cell network with an active func- |
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tion, possibly to contribute to the restoration of a damaged |
5.5. Miniaturized Devices and Nanorobotics |
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neuronal |
circuit. These encouraging results recommend |
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for Nanomedicine |
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CNTs as promising neural biomaterial for the innova- |
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tion of implant devices for the central nervous system. |
5.5.1. CNTs Electrodes and Biosensors |
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Today this area is limited by the use of silicon material |
CNT Electrode: Carbon nanotube is a better electrode |
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which shows the capacity to induce significant glial scar |
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tissue formation169 which is known as a common diffi- |
material than the classical carbon and its development |
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culty in the field of neural prosthetics. Indeed very recent |
becomes a relatively new topic in electrochemical stud- |
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results demonstrating the biocompatibility of native and |
ies. The useful electrochemical properties combined with |
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functionalized single-walled carbon nanotubes for neural |
its high surface area provide some advantage to the field. |
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applications170 promote the CNTs potential for regenera- |
Although the CNTs inertness is evident, it has been proven |
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tive medicine. |
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that the chemical environment to which the nanotubes are |
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exposed influences their conducting capacity and thus cre- |
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5.4. CNTs for Delivery Systems |
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ates an additional transduction mechanism. It |
has been |
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demonstrated that CNTs can enhance the electron transfer |
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Three characteristics of nanostructured materials recom- |
when used as an electrode in electrochemical reactions.9 11 |
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mend them for the design delivery system: |
An important advantage lies in the fact that these materials |
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(i) nanoscale size enables intravenous injection; |
are very sensitive to various molecules with the reactivity |
J. Nanosci. Nanotechnol. 6, 1883–1904, 2006
Applications of Carbon Nanotubes-Based Biomaterials in Biomedical Nanotechnology |
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Polizu et al. |
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controlled by the redox system. Moreover, due to its highly |
CNTs provide an excellent platform for biosensors and |
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specific capacitance, the CNTs can be used as electro- |
even for integrated systems, able to analyse the chemical |
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chemical devices. The well-aligned MWNTs based elec- |
and biological environment. Owing to their high surface |
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trodes have demonstrated their successful application for |
area and outstanding electrical properties, the nanotubes |
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the detection of uric acid in urine samples with excel- |
performance is superior when compared to conventional |
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lent sensitivity and selectivity.172 When employed as an |
materials. Experimental results clearly demonstrate that |
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electrode, the relationship between structure-topology and |
electrical conductivity changes as the carbon nanotubes |
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properties enables the use of the enzyme-immobilized |
are exposed to a minuscule amount of a certain gas |
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CNTs for biomolecular sensing or as a miniaturised sensor |
molecules.10 16 Thus, SWNT based chemical sensors183 |
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in gas environmental analysis. These chemically modified |
display a dramatic change in their electrical resistance |
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CNTs enhance the electrode sensitivity and selectivity.173 |
when exposed to gaseous molecules such as N, O2, and |
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Therefore, using layer-by-layer methodology, the nano- |
NH3.184–186 Recent achievements have confirmed the apti- |
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scale biosensors were constructed. These electrodes enable |
tude of individual SWNTs to detect the smallest concen- |
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to generate an electrochemical signal as function of sub- |
trations of toxic gas molecules, such as NO2 and NH3, as |
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strate concentration, resulting in very good detection |
documented by Dai and his group.187 In fact, this molec- |
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limit.174 |
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ular wire benefits from the full exposure of nanotube sur- |
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CNTs Biosensors: One of the most important and far |
face to chemical environment, thus conducting to a fast |
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reaching applications of nanotubes is in the biosensors |
response and sensitivity as high as 103. |
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field where their biorecognition function is combined with |
Moreover, the capacity of CNTs to detect ppm-level |
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signal transduction. Combining biological selectivity with |
compounds at room temperature allows the development |
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the electronic process, the biosensors provide direct infor- |
of nanotube sensor at physiological temperatures because, |
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mation about the chemical composition of their biological |
once fully immersed in water, the SWNT still maintains |
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environment. They constantly screen the presence, absence |
its intrinsic electronic properties. |
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Such ability |
propels nanotubes towards the design |
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or concentration of organic or inorganic substances with |
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of |
miniaturized |
implantable devices such |
as, |
biomedi- |
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a rapid time of response, thus allowing a continuous real |
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cal nanosensors with high impact on nanomedecine;187–189 |
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time monitoring of analysts. The biosensors not only have |
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these nanodevices will further promote innovation in early |
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175 176 |
detection diagnostic techniques. More specifically, the sen- |
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cal |
devices for the |
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detection of |
toxic substances |
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or therapeutic drug |
monitoring. |
177 178Copyright: American ScsitiveentificdetectionPublishersof nanotubes-based probes in conjunction |
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Several biological |
with the modulation of mechanical or electrical character- |
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events such as genotoxicity, immunotoxicity, biotoxin, and |
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istics favours the interactions with a biologic host, i.e., the |
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endocrine effects are measured using biosensors.179–182 |
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The sensing process is divided in two parts: recogni- |
deposited cellular materials on the surface.190–192 |
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Endowed with a high specificity, these devices are dedi- |
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tion, which results in selectivity and amplification which |
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cated to accurate control performance of environment193–195 |
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increases the power of weak signals to a level at which |
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and even for in vivo and in vitro evaluation.196–198 Thus, |
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it can be conveniently manipulated by electronic devices. |
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a drastically |
change |
in |
nanotube electrical properties, |
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The multiplicity in transduction mechanisms and amplifi- |
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in |
response |
to |
the |
surrounding |
environment, |
is con- |
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cation, processing variety along with its suppleness in ele- |
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verted in |
high |
specific, sensitive |
signal |
as |
predicted by |
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ments recognition create a wide range of biosensors. Five |
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theoretical |
studies199 |
and |
demonstrated |
by |
experimental |
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principal groups of biologically sensitive materials can be |
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measurements.200 201 |
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used for selective recognition: |
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In fact, |
the potential of nanotube as |
electrodes for in |
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(i) enzymes; |
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vitro and in vivo investigation was experimented, for the |
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(ii) |
antibodies; |
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first time, |
in |
1996 when |
the Ajayan’s |
group |
construc- |
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(iii) |
nucleic acid; |
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ted |
a nanotube-electrode |
for neurotransmitters |
involving |
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(iv) |
receptors; |
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dopamine, using bromophorm as binder.198 The voltamo- |
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(v) |
intact cells. |
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grame profile, corresponding to the oxidation of active molecules, such dopamine, has demonstrated the superiority of the CNT electrode, versus the untreated one. This new attainment of the electrode has been attributed to the carbon nanotubes size, as well as to their electronic structure combined with their topological parameters.
Moreover, in 1998, the foremost demonstration of the CNTs potential for protein immobilization202 has proven that small proteins are not only immobilised at the nanotube surface, but they can also be readily placed within the interior cavity of the opened nanotube. This assertion
J. Nanosci. Nanotechnol. 6, 1883–1904, 2006
Polizu et al. |
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Applications of Carbon Nanotubes-Based Biomaterials in Biomedical Nanotechnology |
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reveals the capability of SWNTs to act as a benign host |
involves the use of purely electrical transducers in pro- |
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for the selective encapsulation of proteins inside the tube, |
teomic applications with the aim to detect different pro- |
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which is a real potential for biosensors. At the same |
teins without labelling them. |
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time, Gao has researched the possibility of deposing DNA |
On the other hand, the nanotubes compound with a |
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molecules on robust nanotubes, thus proving the nanotubes |
polymer resulting in the production of composite material |
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capacity to recognize different biomolecules as a function |
for the construction of electrochemiluminescence-sensing |
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of their diameter and helicity.203 These progresses con- |
device.211 Adapted for immobilization of streptavidin, they |
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tributed to a better comprehension of the interactions bet- |
are attractive for the realization of a nanotube based quan- |
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ween nanotubes and molecular species, in addition to their |
titative biosensor, capable for wide range measurements |
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sensing mechanisms. Furthermore, a relationship between |
of biological analytes, with application in areas of med- |
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electronic properties and the absorption of gas molecules |
ical diagnoses, drug discovery, etc. Moreover, the con- |
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was formulated.204 |
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struction of a 3D electrode for a stable, very sensitive |
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Theoretical calculations indicate that the molecule abs- |
and high selective glucose sensor was realised by using |
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orption on the surface or inside the nanotube bundle is |
aligned CNT coated with conducting polymer favouring |
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stronger than that on an individual tube. In addition, the |
enzymes accessibility, thus increasing efficiency.172 The |
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impressive properties of nanotubes, such as nanometer |
use of CNTs facilitates the development of single enz- |
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size, large surface area, and chirality—dependent on elec- |
yme biosensors, with activity toward thiocoline, without |
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trical conductivity, have been exploited for building the |
the use of mediating redox species. A surface modifica- |
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nano-arrays, functioning as biosensors or double layer |
tion of MWNT electrode makes possible immobilization |
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capacitor, with higher resolution. Hence, the use MWNT |
of the enzyme213 in a simple construction which per- |
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arrays as an immobilization matrix for the development of |
forms with good precision and excellent limit of detec- |
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amperometric biosensor have been reported by Sotiropoulu |
tion whilst ensuring good stability and reproducibility. |
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and Chaniotakis.10 Using oxidation for opening and func- |
Therefore, significant advancements are attempted in clin- |
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tionalizing of the nanotube array leads to an efficient |
ical medicine, enabling direct electrical detection of bio- |
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immobilization of glucose oxidaze enzyme. In this system, |
logical and chemical agents. In fact the preparation of |
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a platinum substrate acts as direct transduction platform |
polymeric nanocomposite from nanotubes and PVA214 and |
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for signal monitoring, whereas the nanotubes play a dual |
CNTs/nickel hexacyanoferrate nanocomposite215 resulted |
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Delivered by Publishing Technology to: University of Waterloo |
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role, as an immobilization matrice as well as a mediator. |
in significantly improved electrical conductivity and elec- |
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IP: 200.59.59.16 On: Tue, 20 Oct 2015 13:16:49 |
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The reported results are very promisingCopyright:for the thirdAmericangener- |
tro catalytic activity resulting in good electrochemical per- |
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Scientific Publishers |
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ation of biosensors. The SWNT capability to act as a build- |
formance for glucose detection when used as an electrode. |
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ing block for nanobiosensors, dedicated to the sub-cellular |
Moreover, using the bio-composite principle, a CNT epoxy |
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kinetic studies, has been investigated by Guisepi-Elie and |
composite biosensor was built which offers an excellent |
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collaborators.205 It seems that the nanotubes can perform |
sensitivity and stable electrochemical properties combined |
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as a benign host enables to trap and support biological |
with a reliable calibration profile.216 |
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molecules while the acidic sites present at the surface |
5.5.2. CNTs Flow Sensors |
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enhance molecule binding. This resulting proximity facili- |
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tates the redox process of proteins and enzymes from a |
The excellent sensing capacity of nanotubes was extended |
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kinetic and energetic point |
of view. Thus, coupling the |
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to the flow conditions resulting in systems for flow envi- |
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SWNTs with redox active enzymes favours nanobiosen- |
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ronment. Gosh and his collaborators reported the experi- |
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sors development, i.e., the |
evolution |
of |
glucose biosen- |
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mental observation of the voltage generated by the flow of |
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sors.206–210 |
This functional |
enrichment, |
resulting from |
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a polar liquid over SWNT bundles. The magnitude of volt- |
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nanoscale |
surface modification |
of implantable |
devices, |
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age induced along the nanotube significantly depends on |
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triggers many surface interactions with biological host tis- |
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the ionic strength and polar nature of the liquid.217 A high |
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sue, in order to either evade the host’s immune system or |
sensitivity along with a fast response time was detected at |
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to successfully engage it in a mutual reaction.211 |
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low velocities, following the direction of the current ver- |
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Noncovalent functionalization |
of SWNTs212 |
has also |
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sus the fluid flow. These results demonstrate the ability of |
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been considered for the development |
of |
highly |
specific |
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nanotubes to act as flow sensors for small volumes, in a |
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electronic |
biomolecule detectors, |
with |
a |
selective recog- |
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flowing liquid environment, which is ideal for biomedical |
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nition, enable to target proteins |
by the |
conjugation of |
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applications. |
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their specific receptors.195 These biosensors easily work in |
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the clinical detection of biomolecules, such as antibodies, |
5.5.3. CNTs Nanosensors and Probes |
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associated with human autoimmune diseases. Two princi- |
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pal applications have been found for this array system: the |
Carbon nanotubes are considered the primarily building |
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first brings into play the selective detection of proteins in |
materials for nanosensors because they function both as |
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solution and considers the detecting serum protein after a |
sensor elements and as electrical contacts.173 An innovative, |
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vaccination or a therapeutic intervention. The second one |
alternative method for the fabrication of nanowire sensor |
J. Nanosci. Nanotechnol. 6, 1883–1904, 2006
Applications of Carbon Nanotubes-Based Biomaterials in Biomedical Nanotechnology |
Polizu et al. |
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|
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arrays was developed using an electrodeposition technique. |
Topics regarding structural and mechanical character- |
||||
The main advantages are related to the effectiveness of this |
istics, fabrication methods along with tip characteristics, |
||||
process to produce individually or addressable nanowire |
resolution as well as functional imaging, are featured. The |
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sensor arrays with multi-chemical sensing capabilities, |
tips obtained by different methods,227 provide images of |
||||
thus stimulating the evolution of carbon nanotube based |
biomolecules or bio-assemblies, with a very high lateral |
||||
nanosensors.218 Such versed sensors are capable of fitting |
resolution owing to nanotubes robustness.222 New triple- |
||||
inside single cells thus capturing information related to the |
probe atomic force microscope, consisting in an AFM sys- |
||||
concentration of proteins in living cells during the body’s |
tem coupled to carbon nanotube nanotweezers, was tested |
||||
normal operation; they play a major role in the development |
for the first time with the aim to measure the electric |
||||
of miniaturized, implantable devices for full-time detec- |
properties of a tri-terminal single DNA molecule device.228 |
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tion of medical problems. Hence, the construction of nan- |
Hence, the operation of a single DNA molecule as a |
||||
otube based probes offers new possibilities for the sensitive |
three-terminal device has been demonstrated, leading to |
||||
detection of single particles and single molecules.219 The |
new opportunities for DNA electronics. Moreover, cur- |
||||
SWNTs are very hopeful for conducting probe techniques |
rently works demonstrated that changes in electronic char- |
||||
as AFM or STM, endowed with high lateral resolution, |
acteristics of carbon nanotube FET can be correlated with |
||||
high aspect ratio and good resistance. Through function- |
DNA detection, demonstrating that DNA adosorption and |
||||
alization, the nanotube becomes an ideal tip for biologi- |
hybridization were selective for nanotubes.229 This design, |
||||
cal molecule probes220 221 and opens up the possibility of |
with certain modifications, could serve as nanosensor for |
||||
inserting a nanoscale electrode into the small pore struc- |
discrimination of DNA in a milliliter of blood. |
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ture. These devices have the capacity to measure the length |
5.5.4. CNTs-FET Devices |
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dependence of electrical transport. |
222 |
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Interfacing nanotechnology with biology enables the |
Field Effect Transistors (FETs) have been fabricated by |
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integration of carbon into highly aligned and water stable |
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using semi conducting single wall nanotubes. Their exten- |
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process resulting in electrically-conductive probes.223 With |
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sive study confirmed that they are extremely sensitive to |
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several hundreds microns in length, the CNT probes have |
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the chemical or biological environment (oxygen) surround- |
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the ability to easily penetrate the cell membrane of epithe- |
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ing them.174 The capacity of proteins to crystallise in a |
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Deliv |
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ed by Publishing Te hnology to: University of Waterloo |
favours the |
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lial cells. Such local probes operate in a manner which |
helical configuration on the nanotube surface104 |
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IP: 200.59.59.16 On: Tue, 20 Oct 2015 13:16:49 |
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preserves cells viability; this is a new promising technique |
topological compatibility between nanotubes and confor- |
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|
Copyright: American Scientific Publishers |
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||
for nanoassembly of nano-devices and nano-tools. More- |
mation of organic products, such as proteins. On the other |
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over, new instruments for performing cell-level surgical |
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hand, the carboxylic open ends of nanotubes, possessing |
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operation has been performed by using AFM and fabri- |
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an important hydrophilic behaviour, are not attractive for |
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cated probes shaped as ultrathin needles.224 This technique |
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hydrophobic proteins; they thus permit a specific reaction |
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enables the extended of AFM principle to analyses and |
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with analyte, leading to its identification.219 |
|
||||
surgery of living cells. In fact the needle enables to pen- |
A new technique for the electronic detection of proteins |
||||
etrate the cell membrane and could be easily insert into |
|||||
was recently experimented using CNTs as a conducting |
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a nucleus with highly accurate positioning. Furthermore, |
|||||
channel. Taking advantage of the capacity of biotin-strep- |
|||||
recent theoretical studies demonstrated the possibility to |
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tavidin to bind to CNTs, the authors produced a specific |
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obtain the arrangements as DNA-CNT arrays which could |
architecture that uses the nanotube field effect transducer |
||||
perform as functioning device.225 This complex system can |
and polymer functionalization to obtain a supramolecular |
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be used as an electronic switch or as device for DNA |
assembly.45 The application of a conducting polymer coat- |
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sequencing. |
|
|
ing leads to the conversion of nanotube from p- to n-type |
||
Announcing a promising function for CNT as neuron- |
conductor, thus preventing non-specific attachment of pro- |
||||
probes, the recent results reveal the CNTs capacity to offer |
teins. However, the coating with a hydrophilic polymer |
||||
a high spatial resolution required for probing neurons.15 |
results in a reduction of the affinity of nanotube for pro- |
||||
Endowed with high electrical conductance, the small and |
teins. Such modifications enhance the activity of a minia- |
||||
flexible nanotube enables the |
detection of the electri- |
turized device, acting as a rapid sensor within individually |
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cal signal from neuron to neuron. Since the concept of |
detect proteins or virus. |
|
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nanotube bio-nanoprobe has been proven, several studies |
The recent works reported a selective reaction path- |
||||
have been performed in order to evaluate the detection |
way of SWNTs, in which chemical functionalization is |
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and discrimination capacities of CNT probes towards pat- |
controlled by the difference in the nanotube’s electronic |
||||
terned samples, using molecular interactions and forces |
structure.220 The authors anticipate the extension of this |
||||
in bimolecular interactions.222 Thus, the use of nanotubes |
concept to cell-based electronic sensing devices for the |
||||
as probes has gained great interest in the recent years. A |
measurement of electronic responses to living systems, |
||||
review paper covering the most important aspects related |
with in vivo applications. For instance, the construction of |
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to this application has been presented.226 |
a complex architecture coupling SWNT to peptide nucleic |
1898 |
J. Nanosci. Nanotechnol. 6, 1883–1904, 2006 |
Polizu et al. |
Applications of Carbon Nanotubes-Based Biomaterials in Biomedical Nanotechnology |
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acid (PNA) was performed.221 This structure intermedi- |
of exposure. Functionalized nanotubes are tested for new |
||
ates the attachment to DNA, by hybridization at room |
applications in cell immobilization and transport meas- |
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temperature. Moreover, the incorporation of SWNTs into |
urement232 able to ensure biological recognition. |
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larger devices by interfacing nanotube ends with PAN |
5.5.7. CNTs Nanopipettes |
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enables the creation of highly selective nanotube sensors, |
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offering a new approach for complex devices, with selec- |
The nanopipettes, as new shaping of nanotubes, are based |
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tive recognition of target proteins in conjugation with their |
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on a new morphological manifestation of carbon nano- |
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specific receptors. |
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structure, characterised by a hollow conical structure. |
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5.5.5. CNTs-Cathode for Imaging X-ray Radiation |
This 1–3 nm hollowness remains constant throughout |
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the length of the structure,234 while the shape grow up, |
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The high performance CNT-based field emission cathode |
thanks to the simultaneous growth of nanotubes during |
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for the design of X-ray tubes has been reported230 by using |
the chemical vapour deposition process, with the atypi- |
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CNT film with optimized morphology. This device read- |
cal composition for gas phase. These whiskers with some |
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ily produces both continuous and pulsed X-rays in a pro- |
minor faceting on the surface have a pointed tip in the |
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grammable wave form and with a finite repetition rate. |
shape of pipette and the base at submicron size. These |
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The tubes are constructed using purified SWNT bundles |
new carbon nanotube pipettes could be ideal candidates |
||
created by laser ablation; they produce focused electron |
for simultaneous drug delivery and in vivo detection of |
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beams with small energy spread which is potentially used |
neurotransmitters.234 |
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as X-ray energy tubes, for high resolution imaging with |
|
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ultrafine focal spots. This CNT cathode X-ray technology |
5.5.8. CNTs Components for Medical Nanorobots |
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can potentially lead to portable miniature X-ray sources |
Nanorobotics is concerned with the interaction between |
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for specific medical |
applications. Recent works,231 pre- |
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sented the development of a dynamic radiography system |
atomicand molecular-sized objects and mainly deals with |
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their controlled manipulation.235 Nanorobots are nanodevi- |
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with CNT based microfocus X-ray tube that can generate |
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ces which, in a futuristic vision, will be used for maintain- |
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pulsed X-ray radiation with a temporal resolution as short |
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ing the human body and protecting it against pathogenic |
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as 50 ns, significantly better than thermionic X-ray tubes. |
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agents. Having a diameter of about 0.5 to 3 microns, |
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Delivered by Publishing Technology to: Uni ersity of Wa erloo |
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In spite of some limitations which could be overcome, this |
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IP: 200.59.59.16 On: Tue, nanorobots20 Oct 2015could13:16:49be constructed out of parts with dimen- |
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compact and versatile system is promising for non-invasive |
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Copyright: American Sc e tific Publishers |
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imaging devices for biomedical research, as proven by the |
sions in the range of 1 to 100 nanometers. They will allow |
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doctors to perform direct in vivo surgery on individual |
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first results.231 |
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human cells;235 the powering of nanorobots can be sup- |
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5.5.6. CNTs Nanotweezers for Biological Applications |
plied by metabolising local glucose and oxygen for energy, |
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or external energy. In spite of the complexity requirements |
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The nanotweezers, a powerful tool for manipulation and |
for the design and development of nanorobots, theoretical |
||
performing electric measurements at nanoscale level, fully |
and simulation studies are on going. This first step aims |
||
exploit the actuation effect of single nanotubes. Their con- |
to explain the role of nanorobot behaviour and to further |
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struction is based on individually connected, free-standing |
propose new approaches and strategies236 for future devel- |
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carbon nanotubes sitting on two metal terminals separated |
opments. In the light of properties and functions presented |
||
by a 50 nm gap.232 The application of a voltage to two |
herein, it becomes visible that carbon nanotubes are a very |
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electrodes causes an electrostatic attraction of the nano- |
promising support for some nanorobots components.237 |
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tubes, thus closing the two ends. Such nanoscale elec- |
Generally, the objectives of nanomanipulation refer to |
||
tromechanical system was realised, for the first time in |
the 3D manoeuvring of chemical compounds for molecule |
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1999 by Kim and Lieber;233 the electrically conducing and |
building which will be further assembled into larger |
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mechanically robust nanotubes were attached to indepen- |
devices. Thus, in living bodies, nanomanipulation involves |
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dent electrodes made of pulled glass micropipettes. The |
nano-scale biological entities such as DNA and proteins |
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free ends of nanotubes alternatively open and close, while |
for the clinical and scientific analysis. This requires mate- |
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applying a voltage to the electrode. These nanotweez- |
rials for the fabrication of nano-devices or components for |
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ers enable the manipulation of individual nanostructures, |
integrated systems, with very specific properties. Indeed, |
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and their electrical properties can be harnessed in sev- |
by manipulating carbon nanotubes at both the atomic and |
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eral manners.233 One of them finds application in the bio- |
molecular scale, the biological assemblies integrating car- |
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logical field, for manipulations/modifications within a cell. |
bon nanotubes are more accessible.235 |
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The construction of dual mechanical/chemical nanotweez- |
On the other side, nanorobots could assist the immune |
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ers is based on the self assembly principle, through bio- |
system by finding and disabling unwanted bacteria or |
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recognition on the molecular level.232 The resulting tubes |
viruses. When an invader is identified it can be punc- |
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have 50 nm in diameter and quite uniform length, with |
tured, letting its content spill out and thus ending its |
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the possibility of being quantitative control by the time |
efficiency.238 By following a predetermined search pattern, |
1899
Applications of Carbon Nanotubes-Based Biomaterials in Biomedical Nanotechnology |
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Polizu et al. |
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the nanorobots can ingest and destroy harmful bacteria |
imaging and in perspective, a constitutive element for |
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they encounter by using mechanical and chemical phago- |
nanorobots.221 |
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cytosis. Such devices enable to distinguish every cell type |
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by checking their surface antigen by |
chemotactic |
sen- |
6. TRENDS FOR THE FUTURE: |
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sors |
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keyed to specific antigens |
target |
cells. Nanorobots |
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CHALLENGES AND OPORTUNITIES |
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would even work in the bloodstream where they could nib- |
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ble away at arterisclerotic deposits, widening the diseased |
The |
CNTs |
contribution to biomaterials |
appears to |
be |
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blood vessels.239 240 |
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fascinating |
and they are of a |
major significance |
for |
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Carbon nanotubes and their nanocomposites offer sup- |
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the medicine and biomedical applications. However, the |
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port |
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for |
nanoelectromechanical |
systems |
(NEMS) |
and |
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scientists’ preoccupation concerning the potential risk of |
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microand nano-robots; endowed with high strength and |
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nanostructures to human health raises an uncertainty. Inter- |
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chemical inertness they can thus avoid an attack by the |
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pretation of information regarding the toxicological effects |
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host’s immune system. Recently, new methods have been |
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generated by |
inhalation and handling of |
carbon nano- |
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developed in order to construct, at the nanometer scale, |
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tubes suggest that a policy of industrial hygiene measures |
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building blocks |
of carbon nanotubes with |
these desired |
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must be elaborated. Additional confusions relating to the |
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features. These |
3D assemblies, |
built |
with great accu- |
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effects of their surface area and geometric parameters are |
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racy, could be functionalized using biological specimens. |
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pulling alarm trigger about the potential risks and there- |
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Indeed, based on controlled nanostructure interactions and |
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fore, necessitate precise requirements for the use of nano- |
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complexity, nanoassemblies can posses |
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a |
higher density |
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tubes into the body. Therefore, a sensible research able to |
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and |
thus |
become better electrical conductors, |
faster |
cir- |
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answer the growing concern regarding unintended negative |
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cuits as with more complex functions and with reduced |
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impacts would be of a great value for the enormous inter- |
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power consummation.241 Such sophisticated architectures |
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est generated by the use of carbon nanotubes in engineered |
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are in reality quite similar to biological entities with nano- |
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nano-biomaterials with advanced functions for biomedical |
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scale |
organization. This resemblance facilitates the |
sys- |
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applications. |
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tem’s integration to the living body, resulting in the estab- |
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From |
molecular-scale components of |
nanoelectronic |
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lishment of much more natural interactions, thus offering |
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devices to nanoactuators and nanorobots, the nanotubes |
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a greater |
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control and highDeliveredresolutionbymonitoringPublishingofTechnologythe |
to: University of Waterloo |
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235 240 |
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will be the support of a revolutionizing class of devices |
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phenomena, without secondary |
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effects. |
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Moreover, |
with diagnostic and therapeutic aims. Moreover, the in- |
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building a high level programming system for their manip- |
progress nanoscale |
research enhances nanotechnology’s |
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ulation is a big challenge since it involves the integration |
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contribution to medicine and thus new prototype devices |
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of various components.241 |
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will be able to overcome most of the limits of modern |
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In fact, the design of CNTs based SPM is currently in |
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medicine. Theoretical models and experimental research |
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progress and will play an important role in the advance- |
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demonstrated |
there |
bewildering |
potential. The chemical |
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ment |
of |
nanorobotics.242 Some |
representative develop- |
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inertness of |
CNTs |
along with |
their nanoscale dimen- |
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ment’s elements are: |
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sions renders them perfect candidates |
for |
biological |
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(i) substrate that serves as nanofixture; |
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and |
biotechnological applications.84 85 171 |
Their intrin- |
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(ii) |
tips, probes, and molecules that serve as grippers or |
sic properties enable their bioconjugation for biosensing |
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end-effectors; |
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applications.16 187 188 |
Moreover, the remarkable combina- |
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(iii) |
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chemical and physical nanoassembly processes; |
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tion |
of |
electronic and mechanical |
properties |
of CNTs |
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(iv) |
primal nanoasssembly operation for insertion; |
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makes |
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a potential building |
block |
of |
revolution- |
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(v) |
methods exploiting selfassembly thus eliminating spa- |
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ary |
electronic |
devices and nano-electromechanical sys- |
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tial uncertainty; |
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tems with applications in the biological and biomedical |
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adequate hardware for building nanostructure; |
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fields.137 144 232 234 240 |
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(vii) |
algorithms and software for sensory interpretation; |
As biocompatible support for biological assemblies or |
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motion planning; |
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nanomechanical part in integrated |
systems, |
these new |
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(ix) |
SPM driving. |
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materials become components for implants, artificial org- |
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In response, CNTs obviously exert a multiplicity of |
ans and other prosthetic devices.153 156 157 They contribute |
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functions243 in nanoelectronics, and other nanodevices. |
to the advancement of medical applications and promote |
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Even though the fabrication of a complete circuit at |
a new approach to nanomedecine, with safer, more effi- |
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the molecular level remains a challenge, the realisation |
cient and ultimately, more powerful tools. Biosensors offer |
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of CNT based nano electronic devices is presently in |
a wide range of new biotechnological enhancements; they |
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progress and hence, paves the way to nanorobot produc- |
are the key to a number of major projects in medical |
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tion. As presented in a previous section, a complex sys- |
technology such as the development of artificial organs |
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tem has been manufactured using CNT probe tip.189 This |
that mimic the function of real organs more accurately. |
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system is |
the precursor of tips |
for molecular |
resolution |
Biosensoring technology, based on carbon nanotubes will |
1900 |
J. Nanosci. Nanotechnol. 6, 1883–1904, 2006 |
Polizu et al. Applications of Carbon Nanotubes-Based Biomaterials in Biomedical Nanotechnology
be unique due to its high sensitivity, selectivity, stability, |
18. |
M. S. Dresslhaus, G. Dresselhaus, and R. Saito, Physics of Carbon |
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size, and mobility.175 176 178 211 212 221 |
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19. |
Nanotubes. Imperial College Press, London (1998). |
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Device miniaturization and |
the |
creation of robots for |
P. M. Ajayan, T. W. Ebbessen, T. Ichihashi, S. Iijima, K. Tanigaki, |
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and H. Hiura, Nature 362, 522 (1993). |
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nanomedecine will be promoted by new designs and sophi- |
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20. |
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sticated models239 incorporating carbon nanotubes. Func- |
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P. M. Ajayan, |
Chem. Rev. 99, 1787 (1999). |
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tionalized CNTs allow the construction of new devices for |
22. |
H. W. Zhu, C. |
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L. Xu, D. H. Wu, B. Q. Wei, R. Vajtai, and P. M. |
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the identification of specific binding sites and chemically |
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distinct domains |
of |
proteins.54 71 These nanotube based |
T. W. Odom, J.-L. Huang, P. Kim, and C. Lieber, J. Phys. Chem. |
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devices offer new opportunities for the detection of biolog- |
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24. |
P. L. McEuen, Phys. World 31 (2000). |
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ical species clinically, as well as important sensing inter- |
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25. |
H. Dai, Opportunities and challenges, Surface Science 500, 218 |
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actions with a well defined transfer function.188 228 Many |
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new effects allow the creation of materials and machines |
26. |
S. Iijima and T. Ichihashi, Nature 363, 603 (1993). |
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27. |
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A. Casse, S. Fan, |
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with unique nanoscale properties without the macroscopic |
H. Dai, J. Kong, C. Zhou, N. Franklin, T. Tombler, |
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counterparts.9 Another fascinating application is molecular |
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28. |
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M. A. Hamon, H. Hu, P. Bhowmik, S. Niyogi, B. Zhao, M. E. Itkis, |
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recognition involving both classes of biomolecules, anti- |
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and R. C. Haddon, Chem. Phys. Lett. 347, 8 (2001). |
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bodies, and nucleotides.203 221 171 |
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29. |
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(1997). |
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R. S. Smalley, Reviews of Modern Physics 69, 723 |
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We conclude on the marvellous role that carbon nano- |
30. |
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A. Hirsch, Angew. Chem. Int. Ed. 41, 1853 (2002). |
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31. |
T. W. Odom, |
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tubes could |
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play |
in |
the development |
of biomaterials in |
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J.-L. Huang, P. Kim, and C. M. Limbers, Nature 391, |
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62 (1999). |
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the |
future, |
while |
emphasizing |
on |
the |
challenges related |
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32. |
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J. W. G. Wildöer, L. C. Venema, A. C. Rinzler, R. E. Smalley, and |
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to their fabrication and biocompatibility. Based on ongo- |
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C. Dekker, Nature 391, 59 (1998). |
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ing progresses, more concretizations are expected in their |
33. |
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C. T. White, Phys. Rev. Lett. 68, |
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J. W. Mintmire, B. I. Dunlap, and |
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formulation at macroscopic level, in sheets, fibers or com- |
34. |
631 (1992). |
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posite forms. Solving this problem will enable to extend |
M. Ouyang, |
J. L. Huang, and C. Lieber, Acc. Chem. Res. 35, 1018 |
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(2002). |
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the exploration of the unique properties of nanotubes, con- |
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35. |
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Eletskii, Physics-Uspekhi 40, 899 (1997). |
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A. V |
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firmed at the individual level, and will instigate original |
36. |
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V |
N. Popov, |
Materials Science and Engeering: |
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R: Reports R43, |
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initiatives in the promotion of new biomaterials. |
37. |
61 (2004). |
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P. M. Ajayan and O. Z. Zhou, in Carbon Nanotubes, Topics Appl. |
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Delivered by Publishing Technology to: University of Waterloo |
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Phys., Springer-Verlag, Berlin Heidelberg (2001), Vol. 80, p. 391. |
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References and Notes |
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IP: 200.59.59.16 On: Tue, 20 Oct 2015 13:16:49 |
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Copyright: American Scientific Publishers |
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38. |
R. M. D. Stevens, N. A. Frederick, B. L. Smith, D. E. Morse, G. D. |
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1. |
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K. Bogunia-Kubik and M. Sugisaka, BioSystems 65, 123 (2002). |
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Stucky, and P. K. Hansma, Nanotechnology 11, 1 (2001). |
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39. |
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