**5. CNTs-MIPs composites: innovative materials for analytical determinations**

Among the different applications of CNTs in nanotechnology, polymer composites, consisting of additives and polymer matrices, including thermoplastics, thermosets and elastomers, are considered to be an important group of relatively inexpensive materials for many engineering applications (Ma et al., 2010; Yang et al., 2007). The technology implications are significant to

Carbon Nanotubes – Imprinted Polymers: Hybrid Materials for Analytical Applications 193

The "grafting from" approach involves the polymerization of monomers from surfacederived initiators on CNTs. These initiators are covalently attached using the various functionalization reactions developed for small molecules, including acid-defect group chemistry and side-wall functionalization of CNTs. (See Figure 4). The advantage of "grafting from" approach is that the polymer growth is not limited by steric hindrance, allowing high molecular weight polymers to be efficiently grafted. In addition, nanotube– polymer composites with quite high grafting density can be prepared. However, this method requires strict control of the amounts of initiator and substrate as well as accurate control of conditions required for the polymerization reaction. Moreover, the continuous πelectronic properties of CNTs would be destructed by the acid oxidation, even worse, CNTs may be destroyed to several hundred nanometers in length. As a result, compared with the "grafting from", the "grafting to" has much less alteration of the structure of CNTs (Yan &

Fig. 4. Synthesis of CNTs-polymer composites by "Grafting from" approach as reported by

Many techniques including esterification (Gao C. et al., 2007; Sano et al., 2001; Kahn et al., 2002; Huang W. et al., 2003; Lin et al., 2003), "click" chemistry (Li H.M. et al., 2005), layer-bylayer self-assembly (Kong H. et al., 2005; He & Bayachou, 2005; Qin et al., 2005; Artyukhin et al., 2004), pyrene moiety adsorption (Bahun et al., 2006; Martin et al., 2004; Qu et al., 2002; Petrov et al., 2003; Gomez et al., 2003), radical coupling (Liu Y.Q. et al., 2005; Lou et al., 2004), anionic coupling (Huang H.M. et al.,2004), radical polymerization (Qin et al., 2004a; Shaffer & Koziol, 2002), supercritical CO2-solubilized polymerization or coating (Wang J.W. et al., 2006; Dai et al., 2004), *γ*-ray irradiation (Xu H.X. et al., 2006), cathodic electrochemical grafting (Petrov et al., 2004) polycondensation (Zeng H.L. et al., 2006a; Gao C. et al., 2005; Nogales et al., 2004), reversible addition fragmentation chain-transfer (RAFT) polymerization (Xu G.Y. et al., 2006; You et al., 2006; Cui H. et al., 2004; Hong et al., 2005, 2006), anionic polymerization (Chen S.M. et al. 2006; Liu I.C. et al., 2004), ring-opening polymerization (Zeng H.L. et al., 2006b; Qu et al., 2005; Buffa et al., 2005; Gao J.B. et al., 2005) and atom transfer radical polymerization (ATRP) (Kong H. et al., 2004; Qin et al., 2004b; Yao

CNTs exhibit a high aspect ratio and high conductivity, which makes CNTs excellent

The observation of an enhancement of electrical conductivity by several orders of magnitude of CNTs in polymer matrices without compromising other performance aspects of the polymers such as their low weight, optical clarity, low melt viscosities, etc., has

Yang, 2009; Mylvaganam & Zhang, 2004; Zhang M.N. et al., 2004).

et al., 2003) have been employed to functionalize CNTs with polymers.

candidates for conducting composites (Sahoo et al., 2010) (Figure 5).

Balasubramanian & Burghard, 2005.

many fields, from semiconductor device manufacturing to emerging areas of nanobiotechnology, nanofluidics, and chemistry where the ability to mold structures with molecular dimensions might open up new pathways to molecular recognition, drug discovery, catalysis, and molecule specific chemio-biosensing (Hua et al., 2004).

The main approaches for the fabrication of these materials can be divided into "grafting to" and "grafting from" approaches (Liu M. et al., 2009; Baskaran et al., 2004).

The "grafting to" approach involves pre-formed polymer chains reacting with the surface of either pristine or pre-functionalized carbon nanotubes. (See Figure 3). The main approaches exploited in this functionalization strategy are radical or carbanion additions as well as cycloaddition reactions to the CNT double bonds. Since the curvature of the carbon nanostructures imparts a significant strain upon the sp2 hybridized carbon atoms that make up their framework, the energy barrier required to convert these atoms to sp3 hybridization is lower than that of the flat graphene sheets, making them susceptible to various addition reactions. Therefore, to exploit this chemistry, it is only necessary to produce a polymer centered transient in the presence of CNT material. Alternatively, defect sites on the surface of oxidized CNTs, as openended nanostructures with terminal carboxylic acid groups, allow covalent linkages of oligomer or polymer chains. The "grafting to" method onto CNT defect sites means that the readymade polymers with reactive end groups can react with the functional groups on the nanotube surfaces. An advantage of the "grafting to" method is that preformed commercial polymers of controlled molecular weight and polydispersity can be used. The main limitation of the technique is that initial binding of polymer chains sterically hinders diffusion of additional macromolecules to the CNT surface, leading to a low grafting density. Also, only polymers containing reactive functional groups can be used.

Fig. 3. Synthesis of CNTs-polymer composites by "Grafting to" approach as reported by Venkatesan & Kim, 2010.

many fields, from semiconductor device manufacturing to emerging areas of nanobiotechnology, nanofluidics, and chemistry where the ability to mold structures with molecular dimensions might open up new pathways to molecular recognition, drug discovery,

The main approaches for the fabrication of these materials can be divided into "grafting to"

The "grafting to" approach involves pre-formed polymer chains reacting with the surface of either pristine or pre-functionalized carbon nanotubes. (See Figure 3). The main approaches exploited in this functionalization strategy are radical or carbanion additions as well as cycloaddition reactions to the CNT double bonds. Since the curvature of the carbon nanostructures imparts a significant strain upon the sp2 hybridized carbon atoms that make up their framework, the energy barrier required to convert these atoms to sp3 hybridization is lower than that of the flat graphene sheets, making them susceptible to various addition reactions. Therefore, to exploit this chemistry, it is only necessary to produce a polymer centered transient in the presence of CNT material. Alternatively, defect sites on the surface of oxidized CNTs, as openended nanostructures with terminal carboxylic acid groups, allow covalent linkages of oligomer or polymer chains. The "grafting to" method onto CNT defect sites means that the readymade polymers with reactive end groups can react with the functional groups on the nanotube surfaces. An advantage of the "grafting to" method is that preformed commercial polymers of controlled molecular weight and polydispersity can be used. The main limitation of the technique is that initial binding of polymer chains sterically hinders diffusion of additional macromolecules to the CNT surface, leading to a low grafting density. Also, only polymers containing reactive functional groups can be used.

Fig. 3. Synthesis of CNTs-polymer composites by "Grafting to" approach as reported by

Venkatesan & Kim, 2010.

catalysis, and molecule specific chemio-biosensing (Hua et al., 2004).

and "grafting from" approaches (Liu M. et al., 2009; Baskaran et al., 2004).

The "grafting from" approach involves the polymerization of monomers from surfacederived initiators on CNTs. These initiators are covalently attached using the various functionalization reactions developed for small molecules, including acid-defect group chemistry and side-wall functionalization of CNTs. (See Figure 4). The advantage of "grafting from" approach is that the polymer growth is not limited by steric hindrance, allowing high molecular weight polymers to be efficiently grafted. In addition, nanotube– polymer composites with quite high grafting density can be prepared. However, this method requires strict control of the amounts of initiator and substrate as well as accurate control of conditions required for the polymerization reaction. Moreover, the continuous πelectronic properties of CNTs would be destructed by the acid oxidation, even worse, CNTs may be destroyed to several hundred nanometers in length. As a result, compared with the "grafting from", the "grafting to" has much less alteration of the structure of CNTs (Yan & Yang, 2009; Mylvaganam & Zhang, 2004; Zhang M.N. et al., 2004).

Fig. 4. Synthesis of CNTs-polymer composites by "Grafting from" approach as reported by Balasubramanian & Burghard, 2005.

Many techniques including esterification (Gao C. et al., 2007; Sano et al., 2001; Kahn et al., 2002; Huang W. et al., 2003; Lin et al., 2003), "click" chemistry (Li H.M. et al., 2005), layer-bylayer self-assembly (Kong H. et al., 2005; He & Bayachou, 2005; Qin et al., 2005; Artyukhin et al., 2004), pyrene moiety adsorption (Bahun et al., 2006; Martin et al., 2004; Qu et al., 2002; Petrov et al., 2003; Gomez et al., 2003), radical coupling (Liu Y.Q. et al., 2005; Lou et al., 2004), anionic coupling (Huang H.M. et al.,2004), radical polymerization (Qin et al., 2004a; Shaffer & Koziol, 2002), supercritical CO2-solubilized polymerization or coating (Wang J.W. et al., 2006; Dai et al., 2004), *γ*-ray irradiation (Xu H.X. et al., 2006), cathodic electrochemical grafting (Petrov et al., 2004) polycondensation (Zeng H.L. et al., 2006a; Gao C. et al., 2005; Nogales et al., 2004), reversible addition fragmentation chain-transfer (RAFT) polymerization (Xu G.Y. et al., 2006; You et al., 2006; Cui H. et al., 2004; Hong et al., 2005, 2006), anionic polymerization (Chen S.M. et al. 2006; Liu I.C. et al., 2004), ring-opening polymerization (Zeng H.L. et al., 2006b; Qu et al., 2005; Buffa et al., 2005; Gao J.B. et al., 2005) and atom transfer radical polymerization (ATRP) (Kong H. et al., 2004; Qin et al., 2004b; Yao et al., 2003) have been employed to functionalize CNTs with polymers.

CNTs exhibit a high aspect ratio and high conductivity, which makes CNTs excellent candidates for conducting composites (Sahoo et al., 2010) (Figure 5).

The observation of an enhancement of electrical conductivity by several orders of magnitude of CNTs in polymer matrices without compromising other performance aspects of the polymers such as their low weight, optical clarity, low melt viscosities, etc., has

Carbon Nanotubes – Imprinted Polymers: Hybrid Materials for Analytical Applications 195

ambient conditions (Shao et al., 2010). Authors found that the grafted PAAM and PDMA improved MWCNT adsorption capacity in the removal of Pb2+ from large volumes of aqueous solutions. Furthermore, MWCNTgPAAM had much higher adsorption capacity than MWCNT-g-PDMA, which was attributed to higher amide group content in acrylamide

A particular kind of CNTs-polymer composites is represented by CNTs-MIPs composites, in which the polymer part is a molecularly imprinted polymer (Chang et al., 2011; Walcarius et al., 2005). CNTs impart electrical conductivity to MIPs, while molecular imprinting on these one-dimensional nanostructures will endow the nanotubes with molecular recognition functions, further expanding their application fields (Guan et al., 2008). Several example of using these materials are reported in literature for biomedical, pharmaceutical and

In pharmaceutical fields, in Zhang Z. et al., 2010b, a novel sensitive and selective imprinted electrochemical sensor was constructed for the direct detection of L-histidine by combination of a molecular imprinting film and MWNTs. The sensor was fabricated onto an indium tin oxide electrode via stepwise modification of MWNTs and a thin film of MIPs via sol–gel technology. The introduced MWNTs exhibited noticeable enhancement on the sensitivity of the MIPs sensor, meanwhile, the molecularly imprinted film displayed high sensitivity and excellent selectivity for the target molecule. H. Y. Lee & Kim, 2009 reports of the synthesis of CNTs-MIP composite to be potentially applied to probe materials in

biosensor system for theophylline recognition based on CNT field effect. Hydroxyl-

Fig. 6. Schematic representation of CNTs-MIPs recognition process. Adapted from Z. Zhang

Extraction

CNT

MIP

Rebinding

functionalized CNT was modified by silanisation with 3-chloropropyl trimethoxysilane. The iniferter groups were then introduced by reacting the CNT-bound chloropropyl groups with sodium *N*,*N*-diethyldithiocarbamate. UV light-initiated copolymerization of ethylene glycol dimethacrylate (crosslinking agent) and methacrylic acid (functional monomer) resulted in grafting of MIP on CNT for theophylline as a model template. The theophylline-imprinted polymer on CNT showed higher binding capacity for theophylline than non-imprinted polymer on CNT and selectivity for theophylline over caffeine and theobromine (similar structure molecules). Another theophylline sensor

than that in N,N-dimethylacrylamide.

environmental applications (Figure 6).

CNT

et al., 2010d.

MIP

Fig. 5. Schematic representation of electrochemical detection by CNTs composite electrode. Adpted from Teles & Fonseca, 2008.

triggered an enormous activity worldwide in this scientific area (Spitalsky et al., 2010). Nanotube-filled polymers could potentially, among the others, be used for transparent conductive coatings, electrostatic dissipation, electrostatic painting and electromagnetic interference shielding applications (Bauhofer & Kovacs, 2009; Breuer & Sundararaj, 2004; Moniruzzaman & Winey, 2006; Winey et al., 2007). The electrical conductivity in CNTspolymer nanocomposites depends on dispersion (Sandler et al., 2003; Li J. et al., 2007b; Song & Youn, 2005), alignment (Choi et al., 2003; Fangming et al., 2003), aspect ratio (Bai & Allaoui, 2003; Bryning et al., 2005), degree of surface modification (Georgakilas et al., 2002) of CNTs, polymer types (Ramasubramaniam et al., 2003) and composite processing methods (Li J. et al., 2007b). Based on their characteristic, CNTs-polymer composites can behave as conductors, semiconductors or insulators (Maruccio et al., 2004).

CNTs-polymer composites were successfully synthesized and employed for different applications, both in biomedical and engineering fields. One of the most representative example is a study regarding an ammonia gas sensors based on single-walled carbon nanotubes functionalized with covalently attached poly(m-aminobenzenesulfonic acid). The sensor was operated as a chemiresistor, with the carbon nanotubes forming a random network between interdigitated electrodes, and improved response and recovery times were observed (on the order of 15 min) (Bekyarova et al., 2004). In another work, a carbon nanotube/poly(ethylene-co-vinyl acetate) composite electrode was developed for amperometric detection in Capillary Electrophoresis (Frost et al., 2010). The new electrode also generated improved S/N, decreased fouling, and resulted in better long-term stability (Chen Z. et al., 2009). Zhou D. et al., 2008 describes a novel sieving matrix composed of both a quasi-interpenetrating polymer network (IPN) and PDMA functionalized MWNTs. Atom transfer radical polymerization was used to graft PDMA on MWNTs. The functionalized MWNTs were compatible with the quasi-IPN network. The rigid structure of MWNTs increased the stability and sieving ability of the matrix. Results showed that this novel matrix was advantageous in terms of resolution, speed, and reproducibility. Carbon nanotubes have been used to improve the efficiency of Ru(bpy)3 2+ modified polyacrylamide electrode because of their high conductivity (Xing & Yin, 2009). Carbon nanotubes modified with polypyrrole-silica nanocomposites seem very promising for electrochemical DNA sensor design (Ramanacius et al., 2006). MWCNTs were also grafted with poly(acrylamide) (PAAM) and with poly(N,Ndimethylacrylamide) (PDMA) at same grafting percentage by using N2 plasma technique and used in the removal of Pb2+ from aqueous solution under

i

V

Analyte Detection

Fig. 5. Schematic representation of electrochemical detection by CNTs composite electrode.

CNT

triggered an enormous activity worldwide in this scientific area (Spitalsky et al., 2010). Nanotube-filled polymers could potentially, among the others, be used for transparent conductive coatings, electrostatic dissipation, electrostatic painting and electromagnetic interference shielding applications (Bauhofer & Kovacs, 2009; Breuer & Sundararaj, 2004; Moniruzzaman & Winey, 2006; Winey et al., 2007). The electrical conductivity in CNTspolymer nanocomposites depends on dispersion (Sandler et al., 2003; Li J. et al., 2007b; Song & Youn, 2005), alignment (Choi et al., 2003; Fangming et al., 2003), aspect ratio (Bai & Allaoui, 2003; Bryning et al., 2005), degree of surface modification (Georgakilas et al., 2002) of CNTs, polymer types (Ramasubramaniam et al., 2003) and composite processing methods (Li J. et al., 2007b). Based on their characteristic, CNTs-polymer composites can behave as

CNTs-polymer composites were successfully synthesized and employed for different applications, both in biomedical and engineering fields. One of the most representative example is a study regarding an ammonia gas sensors based on single-walled carbon nanotubes functionalized with covalently attached poly(m-aminobenzenesulfonic acid). The sensor was operated as a chemiresistor, with the carbon nanotubes forming a random network between interdigitated electrodes, and improved response and recovery times were observed (on the order of 15 min) (Bekyarova et al., 2004). In another work, a carbon nanotube/poly(ethylene-co-vinyl acetate) composite electrode was developed for amperometric detection in Capillary Electrophoresis (Frost et al., 2010). The new electrode also generated improved S/N, decreased fouling, and resulted in better long-term stability (Chen Z. et al., 2009). Zhou D. et al., 2008 describes a novel sieving matrix composed of both a quasi-interpenetrating polymer network (IPN) and PDMA functionalized MWNTs. Atom transfer radical polymerization was used to graft PDMA on MWNTs. The functionalized MWNTs were compatible with the quasi-IPN network. The rigid structure of MWNTs increased the stability and sieving ability of the matrix. Results showed that this novel matrix was advantageous in terms of resolution, speed, and reproducibility. Carbon nanotubes have been used to improve the efficiency of Ru(bpy)32+ modified polyacrylamide electrode because of their high conductivity (Xing & Yin, 2009). Carbon nanotubes modified with polypyrrole-silica nanocomposites seem very promising for electrochemical DNA sensor design (Ramanacius et al., 2006). MWCNTs were also grafted with poly(acrylamide) (PAAM) and with poly(N,Ndimethylacrylamide) (PDMA) at same grafting percentage by using N2 plasma technique and used in the removal of Pb2+ from aqueous solution under

conductors, semiconductors or insulators (Maruccio et al., 2004).

Adpted from Teles & Fonseca, 2008.

Electrode Polymer

ambient conditions (Shao et al., 2010). Authors found that the grafted PAAM and PDMA improved MWCNT adsorption capacity in the removal of Pb2+ from large volumes of aqueous solutions. Furthermore, MWCNTgPAAM had much higher adsorption capacity than MWCNT-g-PDMA, which was attributed to higher amide group content in acrylamide than that in N,N-dimethylacrylamide.

A particular kind of CNTs-polymer composites is represented by CNTs-MIPs composites, in which the polymer part is a molecularly imprinted polymer (Chang et al., 2011; Walcarius et al., 2005). CNTs impart electrical conductivity to MIPs, while molecular imprinting on these one-dimensional nanostructures will endow the nanotubes with molecular recognition functions, further expanding their application fields (Guan et al., 2008). Several example of using these materials are reported in literature for biomedical, pharmaceutical and environmental applications (Figure 6).

In pharmaceutical fields, in Zhang Z. et al., 2010b, a novel sensitive and selective imprinted electrochemical sensor was constructed for the direct detection of L-histidine by combination of a molecular imprinting film and MWNTs. The sensor was fabricated onto an indium tin oxide electrode via stepwise modification of MWNTs and a thin film of MIPs via sol–gel technology. The introduced MWNTs exhibited noticeable enhancement on the sensitivity of the MIPs sensor, meanwhile, the molecularly imprinted film displayed high sensitivity and excellent selectivity for the target molecule. H. Y. Lee & Kim, 2009 reports of the synthesis of CNTs-MIP composite to be potentially applied to probe materials in biosensor system for theophylline recognition based on CNT field effect. Hydroxyl-

Fig. 6. Schematic representation of CNTs-MIPs recognition process. Adapted from Z. Zhang et al., 2010d.

functionalized CNT was modified by silanisation with 3-chloropropyl trimethoxysilane. The iniferter groups were then introduced by reacting the CNT-bound chloropropyl groups with sodium *N*,*N*-diethyldithiocarbamate. UV light-initiated copolymerization of ethylene glycol dimethacrylate (crosslinking agent) and methacrylic acid (functional monomer) resulted in grafting of MIP on CNT for theophylline as a model template. The theophylline-imprinted polymer on CNT showed higher binding capacity for theophylline than non-imprinted polymer on CNT and selectivity for theophylline over caffeine and theobromine (similar structure molecules). Another theophylline sensor

Carbon Nanotubes – Imprinted Polymers: Hybrid Materials for Analytical Applications 197

of prepolymerization monomers. The resulting MWNTs-MIPs possessed a faster adsorption dynamics, higher selectivity for the template. The modified electrode fabricated by modifying the MWNTs-MIPs on the glassy carbon electrode can recognize

A sensor for the detection of Uric acid was proposed in (Yu J.C.C. & Lai, 2006) by polymerization of polymethacrylic acid on the surface of vinyl-functionalized CNTs in the presence of the template. The MIP adsorbs more Uric acid than NIP and the imprinting efficiency was found to be about 4.41. The MIP modified MWCNTs can be deposited on the MWCNTs electrode surface and used for the electrochemical detection for the template. The differences of adsorption amounts between MIP and NIP electrodes were determined by CVs with different adsorption times. The adsorption reached saturation after 5min of adsorption and the result was close to the rebinding experiments. The sensitivities of the MIP and NIP modified electrodes were about 11.03 and 5.39 mAM−1 cm−2, respectively, and the difference mainly came from the affinity cavities which were created by the imprinted

A novel protein molecularly imprinted membrane (PMIM) was synthesized in Zhang M. et al., 2010 on the surface of MWNTs through a surface molecular imprinting technique by using bovine serum albumin as the template molecule, acrylamide as the functional monomer, N,N′methylenebisacrylamide as the crosslinker. The selectivity adsorption experiments showed that the PMIM/MWNTs also had higher adsorption capacities for BSA than for such molecules, as HSA, HB, pepsin and HRP. The PMIM/MWNTs displayed a 2.6 fold increase in affinity to BSA compared to the nPMIM/MWNTs. The PMIM/MWNTs, on the other hand, did not exhibit any significant change in affinity to other molecules

An estrone sensor was developed in Gao R. et al., 2011 by using a semicovalent imprinting strategy, which employed a thermally reversible covalent bond at the surface of silica coated CNTs. The synthesis of the nanocomposites involves silica shell deposition on the surface of CNTs, MIPs functionalized onto the silica surface, and final extraction of estrone by thermal reaction and generation of the recognition site. Authors state that the core–shell CNTs@MIPs nanocomposites developed in this work can also be applied as a selective coating for electrochemical or quartz crystal microbalance sensors to monitor for estrone

MIP-CNTs nanocomposites are also proposed as innovative drug delivery devices (Yin et al., 2010). MIP nanotubes were fabricated by atom transfer radical polymerization (ATRP) and applied in enantioselective drug delivery and controlled release. Authors found that Spropranolol imprinted nanotubes provided differential release of enantiomers, whereby the release of the more therapeutically active S-propranolol (eutomer) is greatly promoted

In environmental field, a recent work (Zhang Z. et al., 2010c) a novel MIPs with core–shell structure is fabricated by using MWNTs as the core material. Prior to polymerization, the silicon–oxygen group was grafted onto the MWNTs surface, then silicon–oxygen groups grafted onto the MWNTs surface could copolymerize directly with functional monomers and crosslinkers in the presence of the template molecules by hydrolysis and condensation, which can lead to the formation of MIPs on the surface of MWNTs. The imprinted material,

whilst the release of the less active R-enantiomer (distomer) is retarded.

dopamine with a linear range from 5.0 10-7 to 2.0 10-4 mol/L.

template.

compared to the nPMIM/MWNTs.

residue in environmental water

based on CNTs-MIPs composites is shown in Lee E. et al., 2008. In this study acrylated Tween 20 was used as a linking molecule of MIPs to CNT. MIPs were formed for theophylline as a model template on the surface of CNT with methacrylic acid (functional monomer) and ethylene glycol dimethacrylate (crosslinking agent) using a photografting polymerization technique. The adsorbed layer of 2,2-dimethoxy-2-phenylacetophenone initiated a radical polymerization near the surface by UV-light irradiation. The theophylline-imprinted polymer on CNT showed higher binding capacity for theophylline than non-imprinted polymer (NIP) on CNTand selectivity for theophylline over caffeine (similar structure molecules).

In another work (Prasad et al., 2010a), MIP–carbon composite is prepared via in situ free radical polymerization of a synthetic monomer and subsequent crosslinkage with ethylene glycol dimethacrylate, in the presence of carbon powder and folic acid as template . The detection of folic acid with the MIP fiber sensor was found to be specific and quantitative in aqueous, blood serum and pharmaceutical samples, without any problem of nonspecific false positive contribution and crossreactivity.

An insulin imprinted polymer (Prasad et al., 2010b) was synthesized over the surface of vinyl group functionalized MWCNTs using phosphotidylcholine containing functional monomer and crosslinker. Phosphotidylcholine is a major component of all biological membrane; its incorporation in polymer backbone assures water compatibility, biocompatibility and specificity to molecularly imprinted nanomaterials, without any crossreactivity or interferences from biological sample matrices. An electrochemical sensor fabricated by modifying multiwalled carbon nanotubes molecularly imprinted polymer onto the pencil graphite electrode, was used for trace level detection of insulin in aqueous, blood serum, and pharmaceutical samples by differential pulse anodic stripping voltammetry.

A sensitive molecularly imprinted electrochemical sensor has been developed in Huang J. et al., 2011a for the selective detection of tyramine by combination of MWCNTs-gold nanoparticle composites and chitosan. Chitosan acts as a bridge for the imprinted layer and the nanocomposites. The molecularly imprinted polymer (MIP) was synthesized using tyramine as the template molecule, silicic acid tetracthyl ester and triethoxyphenylsilane as the functional monomers. The molecularly imprinted film displayed excellent selectivity towards tyramine. A thymidine sensor (Zhang Z.H. et al., 2010) was developed by casting thin film of molecularly imprinted sol–gel polymers with specific binding sites for thymidine on carbon electrode by electrochemical deposition. The excellent performance of the imprinted sol–gel/MWCNTs electrode towards thymidine can be ascribed to the MWCNTs functional layer with electrochemical catalytic activities and the porous imprinted film with plentiful selective binding sites. Under the optimized analytical conditions, the peak current was linear to thymidine concentration from 2 to 22 µmol-1 with the detection limit of 1.6 10-9 mol L-1.

A different MWNTs-MIPs composites was prepared by using dopamine as a template molecule by the selective copolymerization of methacrylic acid and trimethylolpropane trimethacrylate in the presence of the template and vinyl group functionalized MWNT surface (Kan et al., 2008b). In this work, for grafting MIPs on MWNTs, the vinyl group was first introduced on the surface of MWNTs, which directed the selective polymerization of functional monomers and cross linkers in the presence of DA on the MWNTs surface. The thickness of the MIPs can be adjusted by changing the concentration

based on CNTs-MIPs composites is shown in Lee E. et al., 2008. In this study acrylated Tween 20 was used as a linking molecule of MIPs to CNT. MIPs were formed for theophylline as a model template on the surface of CNT with methacrylic acid (functional monomer) and ethylene glycol dimethacrylate (crosslinking agent) using a photografting polymerization technique. The adsorbed layer of 2,2-dimethoxy-2-phenylacetophenone initiated a radical polymerization near the surface by UV-light irradiation. The theophylline-imprinted polymer on CNT showed higher binding capacity for theophylline than non-imprinted polymer (NIP) on CNTand selectivity for theophylline

In another work (Prasad et al., 2010a), MIP–carbon composite is prepared via in situ free radical polymerization of a synthetic monomer and subsequent crosslinkage with ethylene glycol dimethacrylate, in the presence of carbon powder and folic acid as template . The detection of folic acid with the MIP fiber sensor was found to be specific and quantitative in aqueous, blood serum and pharmaceutical samples, without any problem of nonspecific

An insulin imprinted polymer (Prasad et al., 2010b) was synthesized over the surface of vinyl group functionalized MWCNTs using phosphotidylcholine containing functional monomer and crosslinker. Phosphotidylcholine is a major component of all biological membrane; its incorporation in polymer backbone assures water compatibility, biocompatibility and specificity to molecularly imprinted nanomaterials, without any crossreactivity or interferences from biological sample matrices. An electrochemical sensor fabricated by modifying multiwalled carbon nanotubes molecularly imprinted polymer onto the pencil graphite electrode, was used for trace level detection of insulin in aqueous, blood serum, and pharmaceutical samples by differential pulse anodic stripping voltammetry.

A sensitive molecularly imprinted electrochemical sensor has been developed in Huang J. et al., 2011a for the selective detection of tyramine by combination of MWCNTs-gold nanoparticle composites and chitosan. Chitosan acts as a bridge for the imprinted layer and the nanocomposites. The molecularly imprinted polymer (MIP) was synthesized using tyramine as the template molecule, silicic acid tetracthyl ester and triethoxyphenylsilane as the functional monomers. The molecularly imprinted film displayed excellent selectivity towards tyramine. A thymidine sensor (Zhang Z.H. et al., 2010) was developed by casting thin film of molecularly imprinted sol–gel polymers with specific binding sites for thymidine on carbon electrode by electrochemical deposition. The excellent performance of the imprinted sol–gel/MWCNTs electrode towards thymidine can be ascribed to the MWCNTs functional layer with electrochemical catalytic activities and the porous imprinted film with plentiful selective binding sites. Under the optimized analytical conditions, the peak current was linear to thymidine concentration from 2 to 22 µmol-1 with the detection

A different MWNTs-MIPs composites was prepared by using dopamine as a template molecule by the selective copolymerization of methacrylic acid and trimethylolpropane trimethacrylate in the presence of the template and vinyl group functionalized MWNT surface (Kan et al., 2008b). In this work, for grafting MIPs on MWNTs, the vinyl group was first introduced on the surface of MWNTs, which directed the selective polymerization of functional monomers and cross linkers in the presence of DA on the MWNTs surface. The thickness of the MIPs can be adjusted by changing the concentration

over caffeine (similar structure molecules).

false positive contribution and crossreactivity.

limit of 1.6 10-9 mol L-1.

of prepolymerization monomers. The resulting MWNTs-MIPs possessed a faster adsorption dynamics, higher selectivity for the template. The modified electrode fabricated by modifying the MWNTs-MIPs on the glassy carbon electrode can recognize dopamine with a linear range from 5.0 10-7 to 2.0 10-4 mol/L.

A sensor for the detection of Uric acid was proposed in (Yu J.C.C. & Lai, 2006) by polymerization of polymethacrylic acid on the surface of vinyl-functionalized CNTs in the presence of the template. The MIP adsorbs more Uric acid than NIP and the imprinting efficiency was found to be about 4.41. The MIP modified MWCNTs can be deposited on the MWCNTs electrode surface and used for the electrochemical detection for the template. The differences of adsorption amounts between MIP and NIP electrodes were determined by CVs with different adsorption times. The adsorption reached saturation after 5min of adsorption and the result was close to the rebinding experiments. The sensitivities of the MIP and NIP modified electrodes were about 11.03 and 5.39 mAM−1 cm−2, respectively, and the difference mainly came from the affinity cavities which were created by the imprinted template.

A novel protein molecularly imprinted membrane (PMIM) was synthesized in Zhang M. et al., 2010 on the surface of MWNTs through a surface molecular imprinting technique by using bovine serum albumin as the template molecule, acrylamide as the functional monomer, N,N′methylenebisacrylamide as the crosslinker. The selectivity adsorption experiments showed that the PMIM/MWNTs also had higher adsorption capacities for BSA than for such molecules, as HSA, HB, pepsin and HRP. The PMIM/MWNTs displayed a 2.6 fold increase in affinity to BSA compared to the nPMIM/MWNTs. The PMIM/MWNTs, on the other hand, did not exhibit any significant change in affinity to other molecules compared to the nPMIM/MWNTs.

An estrone sensor was developed in Gao R. et al., 2011 by using a semicovalent imprinting strategy, which employed a thermally reversible covalent bond at the surface of silica coated CNTs. The synthesis of the nanocomposites involves silica shell deposition on the surface of CNTs, MIPs functionalized onto the silica surface, and final extraction of estrone by thermal reaction and generation of the recognition site. Authors state that the core–shell CNTs@MIPs nanocomposites developed in this work can also be applied as a selective coating for electrochemical or quartz crystal microbalance sensors to monitor for estrone residue in environmental water

MIP-CNTs nanocomposites are also proposed as innovative drug delivery devices (Yin et al., 2010). MIP nanotubes were fabricated by atom transfer radical polymerization (ATRP) and applied in enantioselective drug delivery and controlled release. Authors found that Spropranolol imprinted nanotubes provided differential release of enantiomers, whereby the release of the more therapeutically active S-propranolol (eutomer) is greatly promoted whilst the release of the less active R-enantiomer (distomer) is retarded.

In environmental field, a recent work (Zhang Z. et al., 2010c) a novel MIPs with core–shell structure is fabricated by using MWNTs as the core material. Prior to polymerization, the silicon–oxygen group was grafted onto the MWNTs surface, then silicon–oxygen groups grafted onto the MWNTs surface could copolymerize directly with functional monomers and crosslinkers in the presence of the template molecules by hydrolysis and condensation, which can lead to the formation of MIPs on the surface of MWNTs. The imprinted material,

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CNTs were used successfully to enhance the binding capacity of a molecularly imprinted polypyrrole modified stainless steel frit for determination of ochratoxin A in red wines (Yu J.C.C. & Lai, 2007; Wei et al., 2007). In a different work (Li Y. et al., 2010), a molecularly imprinted polymer–graphene oxide hybrid material was synthesized by reversible addition and fragmentation chain transfer (RAFT) polymerization for the selective detection of 2,4 dichlorophenol in aqueous solution with an appreciable selectivity over structurally related compounds.

Diaz-Diaz et al., 2011 describes an electrochemical sensors based on a catalytic 2,4,6 trichlorophenol molecularly imprinted microgel that mimics the dehalogenative function of the natural enzyme chloroperoxidase for p-halophenols. Two strategies were explored: a carbon paste modified with the polymer and the drop-coating of screen-printed electrodes with powder suspensions of the polymer and carbon nanotubes. With this last design, 2,4,6 trichlorophenol concentrations above 25 mM could be detected.

In similar studies, an electrochemical imprinted sensor for sensitive and convenient determination of Bisphenol A (Huang J. et al., 2011b) and clindamycin (Zhang Z. et al., 2010a) were developed. In both the cases, MWCNTs and gold nanoparticles were introduced for the enhancement of electronic transmission and sensitivity, while thin film of molecularly imprinted sol-gel polymers with specific binding sites for the templates were cast on gold electrode by electrochemical deposition. The resulting composites displayed excellent selectivity towards.

A simple method was developed (Gao R. et al., 2010) to synthesize core–shell molecularly imprinted polymers for the extraction of triclosan with fast kinetics, high capacity and favorable selectivity by combining a surface molecular imprinting technique with a sol–gel process based on carbon nanotubes coated with silica.

By a surface imprinting technique, in Zhang H. et al., 2011, a composite imprinted material, on the basis of a MWCNTs-incorporated layer using melamine as a template, methacrylic acid as a functional monomer, and ethylene glycol dimethacrylate as a cross-linker, was synthesized. In this work, the poly(acrylic-acid)-functionalized CNTs were synthesized to increase the diameter of CNTs. Then, the vinyl group was introduced to the surface of poly(acrylic-acid)-functionalized CNTs by an amidation. Using Melamine as a template molecule, imprinted CNT composite material was fabricated by a thermal polymerization. Applied as a sorbent, the imprinted materials were used for the determination of Melamine in the spiked sample by online SPE combined with HPLC.

By the same approach, Ga(III)imprinted-CNTs sorbent was prepared in Zhang Z. et al., 2010d by using Ga(III) ion-8hydroxyquinoline complex as a template molecule. The imprinted sorbent was applied successfully for extraction of Ga(III) ion from fly ash lixivium followed by FAAS detection. Authors state that compared with the others literature methods for Ga determination, their method is sufficiently accurate and precise to be used for Ga(III) ion analysis in fly ash samples, and performed better characteristics such as selectivity and cleanliness of the extracts.

### **6. Acknowledgements**

Authors are solely responsible for this work. Financial support of Regional Operative Program (ROP) Calabria ESF 2007/2013 – IV Axis Human Capital – Operative Objective M2 - Action D.5 is gratefully acknowledged.

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CNTs were used successfully to enhance the binding capacity of a molecularly imprinted polypyrrole modified stainless steel frit for determination of ochratoxin A in red wines (Yu J.C.C. & Lai, 2007; Wei et al., 2007). In a different work (Li Y. et al., 2010), a molecularly imprinted polymer–graphene oxide hybrid material was synthesized by reversible addition and fragmentation chain transfer (RAFT) polymerization for the selective detection of 2,4 dichlorophenol in aqueous solution with an appreciable selectivity over structurally related

Diaz-Diaz et al., 2011 describes an electrochemical sensors based on a catalytic 2,4,6 trichlorophenol molecularly imprinted microgel that mimics the dehalogenative function of the natural enzyme chloroperoxidase for p-halophenols. Two strategies were explored: a carbon paste modified with the polymer and the drop-coating of screen-printed electrodes with powder suspensions of the polymer and carbon nanotubes. With this last design, 2,4,6-

In similar studies, an electrochemical imprinted sensor for sensitive and convenient determination of Bisphenol A (Huang J. et al., 2011b) and clindamycin (Zhang Z. et al., 2010a) were developed. In both the cases, MWCNTs and gold nanoparticles were introduced for the enhancement of electronic transmission and sensitivity, while thin film of molecularly imprinted sol-gel polymers with specific binding sites for the templates were cast on gold electrode by electrochemical deposition. The resulting composites displayed

A simple method was developed (Gao R. et al., 2010) to synthesize core–shell molecularly imprinted polymers for the extraction of triclosan with fast kinetics, high capacity and favorable selectivity by combining a surface molecular imprinting technique with a sol–gel

By a surface imprinting technique, in Zhang H. et al., 2011, a composite imprinted material, on the basis of a MWCNTs-incorporated layer using melamine as a template, methacrylic acid as a functional monomer, and ethylene glycol dimethacrylate as a cross-linker, was synthesized. In this work, the poly(acrylic-acid)-functionalized CNTs were synthesized to increase the diameter of CNTs. Then, the vinyl group was introduced to the surface of poly(acrylic-acid)-functionalized CNTs by an amidation. Using Melamine as a template molecule, imprinted CNT composite material was fabricated by a thermal polymerization. Applied as a sorbent, the imprinted materials were used for the determination of Melamine

By the same approach, Ga(III)imprinted-CNTs sorbent was prepared in Zhang Z. et al., 2010d by using Ga(III) ion-8hydroxyquinoline complex as a template molecule. The imprinted sorbent was applied successfully for extraction of Ga(III) ion from fly ash lixivium followed by FAAS detection. Authors state that compared with the others literature methods for Ga determination, their method is sufficiently accurate and precise to be used for Ga(III) ion analysis in fly ash samples, and performed better characteristics such as

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**9** 

*China* 

**Mechanism of Nano-Machining and Mechanical** 

As the development of observing technology (such as the atomic force microscopy, AFM) and the increasing need of micro mechanical system in modern manufacturing industry, Nano-machining with machine tools and position-control techniques aim to produce high quality surfaces in terms to form accuracy, surface finish, surface integrity for optical mechanical and electronic components, has been a fundamental researching subject in ultraprecision machining area. Lots of researchers have shown extreme interest on the properties of nanoscale materials and the forming mechanism of nano-machining. Nowadays, although the AFM developed by Binnig et al [1] has been an effective instrument which is able to obtain directly the three-dimentional surface topography and can also been used to carry out the nanoindentation [2, 3] and nanocutting experiments[4, 5] in order to research on the mechanical properties and plastic deformation of materials. The details of plastic deformation, evolvement of defects and other important phenomenon in nano-machining processing are difficult to be observed clearly just by AFM. However, the molecular dynamics (MD) methods provides us a practical and effective way to research from the atomic perspective the removal mechanism, states of the stress and strain, the subsurface damaged layer, dislocation nucleation and propagation, surface friction and tool wear and so on [6-9]. In this chapter, we will introduce the method of applying MD simulation on the observing and analyzing of the nano-machining process to the readers in detail based on our

Meanwhile, as the basic components of micro mechanical system, nanostructures loaded show different mechanical response compared with macrostructures. Due to size effects, surface effects, and interface effects of nanostructures, properties of nanomaterials are enhanced, and nanoscale research has been an area of active research over the past decades. Many researchers use MD numerical simulation to investigate the physical mechanism of nanostructures by atomic motion in detail and have a rapid progress in recent years [10-21]. Most of those studies mainly concentrated on materials with free defects or artificial defects, however, as a matter of fact, a variety of defects can be generated in nano components during nanomachining process. Therefore, it is greatly important to have a suitable description of the material properties of nano-machined components. In this chapter, in order to find a better way to predict the material properties of microstructures, we established the model of real nanostructure with defect, and conduct the integrated MD

researching results which have been published previously.

**1. Introduction** 

**Behavior of Nanostructure** 

Jiaxuan Chen1, Na Gong1 and Yulan Tang2

*1Harbin Institute of Technology, 2Shenyang Jianzhu University* 

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