A Highly Sensitive and Selective Multiwall Carbon Nanotubes/Nafion/Au Microarrays Electrode for Dopamine Determination

This work presents the fabrication of Nafion (Nf) or Nafion/Multiwalled Carbon Nanotubes (Nf/MWCNTs) modified gold microarray (Au‐µA) and macro‐(Au‐M)electrode biosensors. The surface morphologies of the above electrodes were examined using SEM. The catalytic properties of the above electrodes towards dopamine were tested using square wave voltammetric technique. The Nf/MWCNT/Au‐µA electrode exhibited a wide range (0.1–1000 nM) of linearity among the other electrodes. The LOD of Nf/MWCNT/Au‐µA electrode was 50 pM for dopamine in the presence of 5000 µM ascorbic acid. Therefore, the Nf/MWCNT/Au‐µA biosensor was applied for the determination of dopamine in human serum.     

Fluorescence Polarization Based Nucleic Acid Testing for Rapid and Cost‐Effective Diagnosis of Infectious Disease

A new nucleic acid detection method was developed for a rapid and cost‐effective diagnosis of infectious disease. This approach relies on the three unique elements: 1) detection probes that regulate DNA polymerase activity in response to the complementary target DNA; 2) universal reporters conjugated with a single fluorophore; and 3) fluorescence polarization (FP) detection. As a proof‐of‐concept, the assay was used to detect and sub‐type Salmonella bacteria with sensitivities down to a single bacterium in less than three hours.     

Ultrasensitive Fluorescence Polarization Aptasensors Based on Exonuclease Signal Amplification and Polystyrene Nanoparticle Amplification

Here, we combine T7 exonuclease (T7 Exo) signal amplification and polystyrene nanoparticle (PS NP) amplification to develop novel fluorescence polarization (FP) aptasensors. The binding of a target/open aptamer hairpin complex or a target/single‐stranded aptamer complex to dye‐labeled DNA bound to PS NPs, or the self‐assembly of two aptamer subunits (one of them labeled with a dye) into a target/aptamer complex on PS NPs leads to the cyclic T7 Exo‐catalyzed digestion of the dye‐labeled DNA or the dye‐labeled aptamer subunit. This results in a substantial decrease in the FP value for the amplified sensing process. Our newly developed aptasensors exhibit a sensitivity five orders of magnitude higher than that of traditional homogeneous aptasensors and a high specificity for the target molecules. These distinct advantages of our proposed assay protocol make it a generic platform for the design of amplified aptasensors for ultrasensitive detection of various target molecules.     

Filling Carbon Nanotubes with Prussian Blue Nanoparticles of High Peroxidase‐Like Catalytic Activity for Colorimetric Chemo‐ and Biosensing

Facile filling of multiwalled carbon nanotubes (MWCNTs) with Prussian blue nanoparticles (PBNPs) of high peroxidase‐like catalytic activity was performed to develop novel colorimetric sensing protocols for assaying H₂O₂ and glucose. Fine control of PBNP growth was achieved by modulating the concentration ratio of K₃[Fe(CN)₆] and FeSO₄ precursors in an acidic solution containing ultrasonically dispersed MWCNTs, and thus size‐matched PBNPs could be robustly immobilized in the cavities of the MWCNTs (MWCNT‐PB_in). Unlike other reported methods involving complicated procedures and rigorous preparation/separation conditions, this mild one‐pot filling method has advantages of easy isolation of final products by centrifugation, good retention of the pristine outer surface of the MWCNT shell, and satisfactory filling yield of (24±2) %. In particular, encapsulation of PBNPs of poor dispersibility and limited functionality in dispersible and multifunctional MWCNT shells creates new and valuable opportunities for quasihomogeneous‐phase applications of PB in liquid solutions. The MWCNT‐PB_in nanocomposites were exploited as a peroxidase mimic for the colorimetric assay of H₂O₂ in solution by using 3,3′,5,5′‐tetramethylbenzidine (TMB) as reporter, and they gave a linear absorbance response from 1 μM to 1.5 mM with a limit of detection (LOD) of 100 nM . Moreover, glucose oxidase (GOx) was anchored on the outer surface of MWCNT‐PB_in to form GOx/MWCNT‐PB_in bionanocomposites. The cooperation of outer‐surface biocatalysis with peroxidase‐like catalysis of interior PB resulted in a novel cooperative colorimetric biosensing mode for glucose assay. The use of GOx/MWCNT‐PB_in for colorimetric biosensing of glucose gave a linear absorbance response from 1 μM to 1.0 mM and an LOD of 200 nM . The presented protocols may be extended to other multifunctional nanocomposite systems for broad applications in catalysis and biotechnology.     

Facile Synthesis and Enhanced Nonlinear Optical Properties of Porphyrin‐Functionalized Multi‐Walled Carbon Nanotubes

Two multi‐walled carbon nanotube (MWCNT)‐based nanohybrids, MWCNT–ZnTPP and MWCNT–TPP (TPP=5‐[4‐{2‐(4‐formylphenoxy)‐ ethyloxy}phenyl]‐10,15,20‐triphenylporphyrin, ZnTPP=5‐[4‐{(4‐formylphenyl)ethynyl}phenyl]‐10,15,20‐triphenylporphinatozinc(II)), were prepared directly from pristine MWCNTs through 1,3‐dipolar cycloaddition reactions. Covalent attachment of the porphyrins to the surfaces of the MWCNTs was confirmed by Fourier transform infrared spectroscopy, ultraviolet/visible absorption, fluorescence, Raman, and X‐ray photoelectron spectroscopy, elemental analysis, transmission electron microscopy, and thermogravimetric analysis. Attachment of the porphyrin moieties to the surface of the MWCNTs significantly improves the solubility and ease of processing of these MWCNT–porphyrin composite materials. Z‐scan studies reveal that these MWCNT–porphyrin nanohybrids exhibit enhanced nonlinear optical properties under both nanosecond and picosecond laser pulses at λ=532 nm in comparison with free MWCNTs and the free porphyrin chromophores, whereas superior optical limiting performance was displayed by MWCNT–porphyrin composite materials rather than MWCNTs/ZnTPP and MWCNTs/TPP blends, which is consistent with a remarkable accumulation effect as a result of the covalent linkage between the porphyrin and the MWCNTs.     

Core–shell functionalized MWCNT/poly(m‐aminophenol) nanocomposite with large dielectric permittivity and low dielectric loss

Core–shell carboxyl‐functionalized multiwall carbon nanotube (c‐MWCNT)/poly(m‐aminophenol) (PmAP) nanocomposite were prepared through in‐situ polymerization of m‐aminophenol (m‐AP) in the presence of MWCNTs, and explicated as a dielectric material for electronic applications. The formation of thin PmAP layer on individual c‐MWCNT with excellent molecular level interactions at interfaces was confirmed by morphological and spectroscopic analyses. Here we conducted a comparative study of the dielectric performances of PmAP based nanocomposite films with pristine MWCNTs and c‐MWCNTs as fillers. Compared to PmAP/MWCNT nanocomposites, the PmAP/c‐MWCNT nanocomposites exhibited higher dielectric permittivity and lower dielectric loss. The well dispersed c‐MWCNTs in PmAP/c‐MWCNT nanocomposite produce huge interfacial area together with numerous active polarized centers (crystallographic defects), which in turn intensified the Maxwell‐Wagner‐Sillars (MWS) effect based on excellent molecular level interactions and thus, produce large dielectric permittivity (8810 at 1 kHz). The percolation threshold of PmAP/c‐MWCNT nanocomposites is found lower than that of the PmAP/MWCNT nanocomposites, which could be attributed to homogeneous distribution of c‐MWCNTs and strong c‐MWCNT//PmAP interfacial interactions in the nanocomposites. Copyright © 2016 John Wiley & Sons, Ltd.     

Nanohybrid Materials Consisting of Poly[(3‐aminobenzoic acid)‐co‐(3‐aminobenzenesulfonic acid)‐co‐aniline] and Multiwalled Carbon Nanotubes for Immobilization of Redox Active Cytochrome c

The development of a new surface architecture for the efficient direct electron transfer of positively charged redox proteins is presented. For this reason different kinds of polyaniline terpolymers consisting of aminobenzoic acid (AB), aminobenzenesulfonic acid (ABS) and aniline (A) with different monomer ratios were synthesized. The P(AB‐ABS‐A) were grafted to the surface of multiwalled carbon nanotubes (MWCNTs). FTIR measurements prove the covalent binding to the carboxylic groups of the MWCNTs while conductivity tests show an increase in the conductivity of the nanohybrid in comparison to the polymers. The [MWCNT‐P(AB‐ABS‐A)] nanohybrids were used for the immobilization of redox active cytochrome c (cyt.c). The positively charged protein can electrostatically interact with the negatively charged nanohybrid. Cyclic voltammetry (CV) shows an increase in the protein loading on [MWCNT‐P(AB‐ABS‐A)] coupled to cysteamine modified gold electrodes in comparison to non‐grafted MWCNTs. A further increase in the sulfonation degree of P(AB‐ABS‐A) leads to an enhanced current output of the modified electrodes. The redox activity of the polymer decreases after the immobilization of the cyt.c on the nanohybrid. For the first time polymers covalently grafted to the surface of MWCNTs are used in a biosensor.     

The improvement in interfacial shear strength of wood fiber/epoxy composite by sizing with epoxy sizing agent containing MWCNTs

This paper discloses a feasible and high efficient strategy for wood fiber treatment to introducing multi‐wall carbon nanotubes (MWCNTs) to the surface of wood fibers for the aim of improving the interfacial shear strength of wood fiber/epoxy composite. Briefly, a layer of MWCNT was deposited on wood fibers through sizing wood fibers with epoxy sizing agent containing amine‐treated MWCNTs (MWCNT‐PEI). The surface functional groups, morphology, wettability, and interphase properties of MWCNTs on the surface of wood fiber were studied. The remarkable enhancements were achieved in interfacial shear strength of reinforced composites by dipping wood fiber in MWCNTCOOH suspension and wood fiber sizing containing MWCNT‐PEI.     

Influence of modification of MWCNTs on the structure and performance of MWCNT‐Poly(MMA‐AM) hybrid membranes

Hybrid membranes containing multi‐walled carbon nanotubes (MWCNTs) were initially prepared to separate benzene/cyclohexane mixtures. Subsequently, MWCNT surfaces were chemically modified using two methods to change the surface polarity of the MWCNTs and improve the distribution thereof in Poly(methylmethacrylate) (PMMA). This change consequently enhanced the separation performance of hybrid membranes with MWCNTs. Raman spectroscopy was used to characterize the structure of the pristine MWCNTs and the modified MWCNTs. The morphology and distribution of the MWCNTs in PMMA were investigated by transmission electron microscopy. The results showed that the addition of MWCNTs clearly improved the separation performance of the hybrid membranes. Surface modification introduced polar groups onto the MWCNT surface, which significantly improved the distribution of MWCNTs in the PMMA membranes and the performance of hybrid membranes. MWCNTs with higher surface polarity also increased the amount of MWCNTs distributed homogeneously in PMMA. Aminated MWCNTs (MWCNT‐NH₂) showed the highest surface polarity. Thus, the content of MWCNT‐NH₂ well distributed in PMMA was the highest among the three types of MWCNTs. The highest separation factor for the hybrid membranes with 1.0 wt% MWCNT‐NH₂ was about seven times that of membranes containing pristine MWCNTs. Copyright © 2013 John Wiley & Sons, Ltd.     

Turn‐On Fluorescence Sensor Based on Single‐Walled‐Carbon‐Nanohorn–Peptide Complex for the Detection of Thrombin

Proteases play a central role in several widespread diseases. Thus, there is a great need for the fast and sensitive detection of various proteolytic enzymes. Herein, we have developed a carbon nanotube (CNT)‐based protease biosensing platform that uses peptides as a fluorescence probe for the first time. Single‐walled carbon nanohorns (SWCNHs) and thrombin were used to demonstrate this detection strategy. SWCNHs can adsorb a fluorescein‐based dye (FAM)‐labeled peptide (FAM‐pep) and quench the fluorescence of FAM. In contrast, thrombin can cleave FAM‐pep on SWCNHs and recover the fluorescence of FAM, which allows the sensitive detection of thrombin. This biosensor has a high sensitivity and selectivity toward thrombin, with a detection limit of 100 pM .     

Surface modification of MWCNTs with glucose and their utilization for the production of environmentally friendly nanocomposites using biodegradable poly(amide‐imide) based on N‐trimellitylimido‐S‐valine matrix

In the present investigation, the preparation, characterization, and surface morphology of poly(amide‐imide) (PAI)/multi‐walled carbon nanotubes (MWCNTs) bionanocomposites (BNCs) were the main goals of the study. At first, an optically active PAI based on S‐valine as a biodegradable segment was synthesized. Then, carboxyl‐modified MWCNTs were functionalized with glucose (f‐MWCNT) as a biological active molecule in a green method to achieve a fine dispersion of f‐MWCNT bundles in the PAI matrix. The existence of S‐valine in the PAI matrix and functionalized MWCNT with glucose resulted in a series of potentially biodegradable nanocomposites. The obtained BNCs were characterized by various techniques. Field emission scanning and transmission electron microscopy micrographs of the composites showed a fine dispersion of f‐MWCNTs in the polymer matrix because of hydrogen bonding and π–π stacking interaction between f‐MWCNTs and polymer functional groups and aromatic moieties. Adding f‐MWCNTs into polymer matrix significantly improved the thermal stability of BNCs because of the increased interfacial interaction between the PAI matrix and f‐MWCNTs and also good dispersion of f‐MWCNT in the polymer matrix. Copyright © 2015 John Wiley & Sons, Ltd.     

Strengthening of liquid crystalline polymer by functionalized carbon nanotubes through interfacial interaction and homogeneous dispersion

Multiwalled carbon nanotubes (MWCNTs) were functionalized with two types of chemical moieties (i.e. carboxylic, ? COOH and hydroxyl benzoic acid groups, ‐HBA) on their sidewalls in order to improve their interaction with a liquid crystalline polymer (LCP) and dispersion in LCP. We have investigated the rheological, mechanical, dynamic mechanical, and thermal properties in detail with variation of HBA‐functionalized MWCNTs in the LCP matrix. Effect of the dispersion state of the functionalized MWCNTs in the LCP matrix on the rheological behavior was also studied. The composites containing HBA‐functionalized MWCNTs showed higher complex viscosity, storage, and loss modulus than the composites with the same loading of raw MWCNTs and MWCNT‐COOH. It was suggested that the HBA‐functionalized MWCNTs exhibited a better dispersion in the polymer matrix and formed stronger CNT‐polymer interaction in the composites than the raw MWCNTs and MWCNT‐COOH, which was also confirmed by FESEM and FTIR studies. As a result, the overall mechanical performance of the HBA‐MWCNT‐LCP composites could be improved significantly. For example, the addition of 4 wt% HBA‐MWCNT to LCP resulted in the considerable improvements in the tensile strength and modulus of LCP (by 66 and 90%, respectively). Copyright © 2010 John Wiley & Sons, Ltd.     

Heterogeneous Electron Transfer and Oxygen Reduction Reaction at Nanostructured Iron(II) Phthalocyanine and Its MWCNTs Nanocomposites

Electron transfer and oxygen reduction dynamics at nanostructured iron(II) phthalocyanine/multi‐walled carbon nanotubes composite supported on an edge plane pyrolytic graphite electrode (EPPGE‐MWCNT‐nanoFePc) platform have been reported. All the electrodes showed the category 3 diffusional behaviour according to the Davies–Compton theoretical framework. Both MWCNTs and MWCNT‐nanoFePc showed huge current responses compared to the other electrodes, suggesting the redox processes of trapped redox species within the porous layers of MWCNTs. Electron transfer process is much easier at the EPPGE‐MWCNT and EPPGE‐MWCNT‐nanoFePc compared to the other electrodes. The best response for oxygen reduction reaction was at the EPPGE‐MWCNT‐nanoFePc, yielding a 4‐electron process.     

Luminescent Blooming of Dendronic Carbon Nanotubes through Ion‐Pairing Interactions with an EuIII Complex

A multiwalled carbon nanotube (MWCNT) scaffold was covalently functionalized with a second‐generation polyamidoamine (PAMAM) dendron, presenting four terminal amino groups per grafted aryl moiety. These reactive functions were alkylated to obtain a positively charged polycationic dendron/carbon nanotube system ( d‐MWCNTs?Cl ), which eventually underwent anion exchange reaction with a negatively charged and highly luminescent Eu^III complex ( [EuL₄]?NEt₄ , in which L =(2‐naphtoyltrifluoroacetonate)). This process afforded the target material d‐MWCNTs?[EuL₄] , in which MWCNTs are combined with red‐emitting Eu^III centers through electrostatic interactions with the dendronic branches. Characterization of the novel MWCNT materials was accomplished by means of TGA and TEM, whereas d‐MWCNTs?Cl and d‐MWCNTs? [EuL₄] further underwent XPS, SEM and Raman analyses. These studies demonstrate the integrity of the luminescent [EuL₄]^? center in the luminescent hybrid, the massive load of the cationic binding sites, and the virtually complete anion‐exchange into the final hybrid material. The occurrence of the ion‐pairing interaction with MWCNTs was unambiguously demonstrated through DOSY NMR diffusion studies. Photophysical investigations show that MWCNTs?[EuL₄] is a highly soluble and brightly luminescent red hybrid material in which MWCNTs act as photochemically inert scaffolds with negligible UV/Vis absorption, compared with the grafted Eu complex, and with no quenching activity. The high dispersibility of MWCNTs?[EuL₄] in a polymer matrix makes it a promising luminophore for applications in material science.     

Matrix‐polymer‐functionalized multiwalled carbon nanotubes as a highly efficient toughening agent for matrix polymers

Matrix‐polymer‐functionalized multiwalled carbon nanotubes (MWCNTs) are demonstrated as a highly efficient toughening agent for matrix polymers. With poly(vinylidene fluoride) (PVDF) as the matrix polymer, the PVDF/MWCNT‐PVDF nanocomposite films show high toughness. With a small load amount of MWCNT‐PVDF (0.07 wt %), the nanocomposite film shows a yield point and a constant‐stress extension region in stress–strain tests, compared with the typical low‐extensibility feature of neat PVDF film. The PVDF/MWCNT‐PVDF‐0.7 film exhibits a 180‐fold increase of toughness and about 38‐fold increase in strain at break compared with neat PVDF film. This toughening effect is attributed to (a) homogeneous dispersion of MWCNT‐PVDF in PVDF, (b) the high efficiency of load‐transfer across MWCNT/PVDF interface, and (c) the long length of the MWCNTs. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Effect of scale and surface chemistry on the mechanical properties of carbon nanotubes‐based composites

In this article, Multi‐Walled Carbon Nanotubes (MWCNTs) of varying diameters, both untreated and polycarboxylated, were dispersed at constant weight percentage in an epoxy matrix, and resulting fracture toughnesses (K_Ic) were measured in each case. We show that changing the MWCNT diameter has two effects on the composite fracture toughness: (i) a small MWCNT diameter enables larger interfacial surface for adhesion maximization, which increases toughness; (ii) at the same time, it limits the available pull‐out energy and reduces the MWCNT ability to homogeneously disperse in the matrix due to this same large active surface: this decreases toughness. Most commercially available MWCNTs have a length range of several μm, thus an optimal diameter exists which depends on MWCNT wall thickness and surface treatment. Such optimal diameter maximizes pull‐out energy and thus composite fracture toughness. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Improved Catalytic Performance of Pt Supported on Multi‐Wall Carbon Nanotubes as Cathode for Direct Methanol Fuel Cell Applications Prepared by Dual‐Stepped Surface Thiolation Processes

This study develops a simple surface modification process for modifying the MWCNT surface by thiolation reaction after the conventional nitric acid treatment for strong interface attachment of Pt NPs and improved dispersion onto MWCNTs. The thiolated MWCNTs (Pt/MWCNTs) showed significant improvement of methanol electro‐oxidation activity compared with that treated only by nitric acid solution. The prepared electrode with thiolated MWCNTs was used as the cathode for assembling MEA for DMFC single‐cell applications. Testing results indicate that the thiolated MWCNT cathode can improve the power density of MEA by more than 300% (from 4.6 to 20.6 mW cm^?2) compared with that treated only by conventional nitric acid reactions. The dual‐step modification process for MWCNT surface treatment showed significant improvement over the convention nitric acid treatment and can be successfully used in DMFC applications.     

Uncross‐linked polypropylene (PP)/ethylene‐propylene‐diene (EPDM)/multi walled carbon nanotube (MWCNT) and dynamically vulcanized PP/EPDM/MWCNT nanocomposites

In this study, relatively large amounts of polypropylene (PP), ethylene‐propylene‐diene (EPDM), and multi‐walled carbon nanotube (MWCNT) were melt‐mixed with and without DCP. Dynamically vulcanized PP/EPDM (TPV)/MWCNT nanocomposites were prepared by two methods: the MWCNTs were added either before or after the dynamic vulcanization of the blends. The effects of composition, rotor speed, and dynamic vulcanization on their surface resistivity were investigated. The surface resistivity of uncross‐linked PP/EPDM/MWCNT nanocomposites increases with increasing the content of EPDM. At PP/EPDM (70/30 wt%) nanocomposite with 1.5 phr MWCNT, slightly lower surface resistivity is obtained by increasing the rotor speed during mixing. However, for PP/EPDM (50/50 wt%) and PP/EPDM (30/70 wt%) nanocomposites, surface resistivity decreases with increasing the rotor speed from 30 to 60 rpm. But further increase in rotor speed (90 rpm) leads to an increase of surface resistivity. When the MWCNTs were added after the dynamic vulcanization of the blends, the surface resistivity of TPV70/MWCNTnanocomposite is lower than that of uncross‐linked PP/EPDM/MWCNT nanocomposite. However, when the MWCNTs were added before the dynamic vulcanization of the blends, the surface resistivity of TPV70/MWCNT nanocomposite is >10¹² Ω/square. Copyright © 2010 John Wiley & Sons, Ltd.     

A fluorescence turn-on method for real-time monitoring of protease activity based on the electron transfer between a fluorophore labeled oligonucleotide and cytochrome c

A new continuous fluorescence turn-on assay for protease activity and inhibitor screening has been developed. A fluorophore labeled single stranded DNA (FAM-DNA) and cytochrome c (cyt c) were employed. The fluorescence of the FAM-DNA was efficiently quenched when binding to cyt c, through the electron transfer between the FAM fluorophore and the heme cofactor of cyt c. In the presence of a protease, such as trypsin, cyt c was digested into small peptide fragments. The FAM-DNA was released, which resulted in the recovery of the FAM fluorescence. The rate of the cyt c digestion could be reduced via the addition of an inhibitor. As a result, reduced degree of the fluorescence recovery was obtained. The limit of detection of our assay is 1 nM trypsin and the IC₅₀ values are 3.23 μg mL⁻¹ and 0.303 μg mL⁻¹ for the inhibitor from egg white and the inhibitor from soybean, respectively. Our method could be used for the sensing of protease activity for various biochemical applications, and for the screening of protease inhibitors as drugs for the treatment of various related diseases.     

Kinetic,Equilibrium and Isotherm Studies of Cadmium Removal from Aqueous Solutions by Oxidized Multi‐Walled Carbon Nanotubes and the Functionalized Ones with Thiosemicarbazide and Their Toxicity Investigations: A Comparison

The multi‐walled carbon nanotubes (MWCNTs) were first oxidized by nitric acid to form a MWCNT‐COOH. Then, it was modified with thiosemicarbazide to produce MWCNT‐semi. Thus, these carbon materials, MWCNTs, MWCNT‐COOH and MWCNT‐semi, have been used as efficient adsorbents for the removal of cadmium from aqueous solutions. The influence of variables including pH, concentration of the cadmium, amount of adsorbents and contact time was investigated by the batch method. The kinetic studies carried out using different kinetic models such as pseudo‐first‐order, pseudo‐second‐order, and intraparticle diffusion models. The sorption process with each adsorbent was well described by pseudo‐second‐order kinetics which it was agreed well with the experimental data. The values of regression coefficient of various adsorption isotherms like Langmuir, Freundlich and Tempkin to obtain the characteristic parameters of each model have been carried out. The results showed which the Langmuir isotherm for all adsorbents and Tempkin model for MWCNT‐COOH and MWCNT‐semi was found to best represent the measured sorption data. Toxicity of these samples was evaluated in human embryonic kidney HEK293 and human breast cancer SKBR3 cell lines after culturing cells for 24 h. Cellular investigations showed that the modified MWCNTs in particular MWCNT‐semi have considerably significant toxic impact on SKBR3 as compared to HEK293 at concentration 3 µg/mL.