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1.  Enhancing performance of ZnO dye-sensitized solar cells by incorporation of multiwalled carbon nanotubes 
Nanoscale Research Letters  2012;7(1):166.
A low-temperature, direct blending procedure was used to prepare composite films consisting of zinc oxide [ZnO] nanoparticles and multiwalled carbon nanotubes [MWNTs]. The mesoporous ZnO/MWNT films were fabricated into the working electrodes of dye-sensitized solar cells [DSSCs]. The pristine MWNTs were modified by an air oxidation or a mixed acid oxidation treatment before use. The mixed acid treatment resulted in the disentanglement of MWNTs and facilitated the dispersion of MWNTs in the ZnO matrix. The effects of surface property and loading of MWNTs on DSSC performance were investigated. The performance of DSSCs was found to depend greatly on the type and the amount of MWNTs incorporated. At a loading of 0.01 wt%, the acid-treated MWNTs were able to increase the power conversion efficiency of fabricated cells from 2.11% (without MWNTs) to 2.70%.
doi:10.1186/1556-276X-7-166
PMCID: PMC3320520  PMID: 22390565
ZnO; nanoparticle; multiwalled carbon nanotube; composite film; dye-sensitized solar cells; conversion efficiency
2.  Delivery of small interfering RNAs in human cervical cancer cells by polyethylenimine-functionalized carbon nanotubes 
Nanoscale Research Letters  2013;8(1):267.
Carbon nanotubes are capable of penetrating the cell membrane and are widely considered as potential carriers for gene or drug delivery. Because the C-C and C=C bonds in carbon nanotubes are nonpolar, functionalization is required for carbon nanotubes to interact with genes or drugs as well as to improve their biocompatibility. In this study, polyethylenimine (PEI)-functionalized single-wall (PEI-NH-SWNTs) and multiwall carbon nanotubes (PEI-NH-MWNTs) were produced by direct amination method. PEI functionalization increased the positive charge on the surface of SWNTs and MWNTs, allowing carbon nanotubes to interact electrostatically with the negatively charged small interfering RNAs (siRNAs) and to serve as nonviral gene delivery reagents. PEI-NH-MWNTs and PEI-NH-SWNTs had a better solubility in water than pristine carbon nanotubes, and further removal of large aggregates by centrifugation produced a stable suspension of reduced particle size and improved homogeneity and dispersity. The amount of grafted PEI estimated by thermogravimetric analysis was 5.08% (w/w) and 5.28% (w/w) for PEI-NH-SWNTs and PEI-NH-MWNTs, respectively. For the assessment of cytotoxicity, various concentrations of PEI-NH-SWNTs and PEI-NH-MWNTs were incubated with human cervical cancer cells, HeLa-S3, for 48 h. PEI-NH-SWNTs and PEI-NH-MWNTs induced cell deaths in a dose-dependent manner but were less cytotoxic compared to pure PEI. As determined by electrophoretic mobility shift assay, siRNAs directed against glyceraldehyde-3-phosphate dehydrogenase (siGAPDH) were completely associated with PEI-NH-SWNTs or PEI-NH-MWNTs at a PEI-NH-SWNT/siGAPDH or PEI-NH-MWNT/siGAPDH mass ratio of 80:1 or 160:1, respectively. Furthermore, PEI-NH-SWNTs and PEI-NH-MWNTs successfully delivered siGAPDH into HeLa-S3 cells at PEI-NH-SWNT/siGAPDH and PEI-NH-MWNT/siGAPDH mass ratios of 1:1 to 20:1, resulting in suppression of the mRNA level of GAPDH to an extent similar to that of DharmaFECT, a common transfection reagent for siRNAs. Our results indicate that the PEI-NH-SWNTs and PEI-NH-MWNTs produced in this study are capable of delivering siRNAs into HeLa-S3 cells to suppress gene expression and may therefore be considered as novel nonviral gene delivery reagents.
doi:10.1186/1556-276X-8-267
PMCID: PMC3683344  PMID: 23742156
SWNTs; MWNTs; PEI; Small interfering RNA; Gene delivery
3.  Exploring the Chemical Sensitivity of a Carbon Nanotube/Green Tea Composite 
ACS nano  2010;4(11):6854-6862.
Single-walled carbon nanotubes (SWNTs) possess unique electronic and physical properties, which make them very attractive for a wide range of applications. In particular, SWNTs and their composites have shown a great potential for chemical and biological sensing. Green tea, or more specifically its main antioxidant component, epigallocatechin gallate (EGCG), has been found to disperse SWNTs in water. However, the chemical sensitivity of this SWNT/green tea (SWNT/EGCG) composite remained unexplored. With EGCG present, this SWNT composite should have strong antioxidant properties and thus respond to reactive oxygen species (ROS). Here we report on fabrication and characterization of SWNT/EGCG thin films and the measurement of their relative conductance as a function of H2O2 concentrations. We further investigated the sensing mechanism by Fourier-transform infrared (FTIR) spectroscopy and field-effect transistor measurements (FET). We propose here that the response to H2O2 arises from the oxidation of EGCG in the composite. These findings suggest that SWNT/green tea composite has a great potential for developing simple resistivity-based sensors.
doi:10.1021/nn100988t
PMCID: PMC3026703  PMID: 21043457
resistivity sensors; ROS; hydrogen peroxide; relative humidity
4.  Fabrication of a Microbial Biosensor Based on QD-MWNT Supports by a One-Step Radiation Reaction and Detection of Phenolic Compounds in Red Wines 
Sensors (Basel, Switzerland)  2011;11(2):2001-2012.
An Acaligense sp.-immobilized biosensor was fabricated based on QD-MWNT composites as an electron transfer mediator and a microbe immobilization support by a one-step radiation reaction and used for sensing phenolic compounds in commercial red wines. First, a quantum dot-modified multi-wall carbon nanotube (QD-MWNT) composite was prepared in the presence of MWNT by a one-step radiation reaction in an aqueous solution at room temperature. The successful preparation of the QD-MWNT composite was confirmed by XPS, TEM, and elemental analysis. Second, the microbial biosensor was fabricated by immobilization of Acaligense sp. on the surface of the composite thin film of a glassy carbon (GC) electrode, which was prepared by a hand casting method with a mixture of the previously obtained composite and Nafion solution. The sensing ranges of the microbial biosensor based on CdS-MWNT and Cu2S-MWNT supports were 0.5–5.0 mM and 0.7–10 mM for phenol in a phosphate buffer solution, respectively. Total concentration of phenolic compounds contained in commercial red wines was also determined using the prepared microbial immobilized biosensor.
doi:10.3390/s110202001
PMCID: PMC3274030  PMID: 22319395
microbial biosensor; quantum dots; one-step radiation reaction; electron transfer supports; phenolic compounds; red wines
5.  Ecological Uptake and Depuration of Carbon Nanotubes by Lumbriculus variegatus 
Environmental Health Perspectives  2008;116(4):496-500.
Background
Carbon nanotubes represent a class of nanomaterials having broad application potentials and documented cellular uptake and ecotoxicological effects that raise the possibility that they may bioaccumulate in living organisms.
Objectives
Radioactively labeled nanotubes were synthesized using a novel methane chemical vapor deposition procedure. Single-walled carbon nanotubes (SWNTs), multiwalled carbon nanotubes (MWNTs), and pyrene were spiked to sediment samples, and the respective uptake and depuration of these nanotubes and pyrene were assessed by the oligochaete, Lumbriculus variegatus.
Results
14C-labeled carbon nanotubes were developed for these experiments to overcome significant previous limitations for quantifying nanotube materials in environmental and biological media. Biota-sediment accumulation factors for SWNTs and MWNTs were observed to be almost an order of magnitude lower than those for pyrene, a four-ringed polycyclic aromatic hydrocarbon (PAH). The depuration behaviors of the oligochaete suggested that the nanotubes detected in these organisms were associated with sediments remaining in the organism guts and not absorbed into cellular tissues as was the pyrene. The results suggest that, unlike PAHs, purified carbon nanotubes do not readily absorb into organism tissues.
doi:10.1289/ehp.10883
PMCID: PMC2290976  PMID: 18414633
bioaccumulation; carbon nanotubes; ecotoxicology; environmental risks; fullerenes; Lumbriculus variegatus; MWNT; nanomaterials; nanotechnology; SWNT
6.  In situ Polymerization of Multi-Walled Carbon Nanotube/Nylon-6 Nanocomposites and Their Electrospun Nanofibers 
Nanoscale Research Letters  2008;4(1):39-46.
Multiwalled carbon nanotube/nylon-6 nanocomposites (MWNT/nylon-6) were prepared by in situ polymerization, whereby functionalized MWNTs (F-MWNTs) and pristine MWNTs (P-MWNTs) were used as reinforcing materials. The F-MWNTs were functionalized by Friedel-Crafts acylation, which introduced aromatic amine (COC6H4-NH2) groups onto the side wall. Scanning electron microscopy (SEM) images obtained from the fractured surfaces of the nanocomposites showed that the F-MWNTs in the nylon-6 matrix were well dispersed as compared to those of the P-MWNTs. Both nanocomposites could be electrospun into nanofibers in which the MWNTs were embedded and oriented along the nanofiber axis, as confirmed by transmission electron microscopy. The specific strength and modulus of the MWNTs-reinforced nanofibers increased as compared to those of the neat nylon-6 nanofibers. The crystal structure of the nylon-6 in the MWNT/nylon-6 nanofibers was mostly γ-phase, although that of the MWNT/nylon-6 films, which were prepared by hot-pressing the pellets between two aluminum plates and then quenching them in icy water, was mostly α-phase, indicating that the shear force during electrospinning might favor the γ-phase, similarly to the conventional fiber spinning.
doi:10.1007/s11671-008-9199-0
PMCID: PMC2893824  PMID: 20596470
In situ polymerization; Nylon-6; Nanofibers; Carbon nanotube; Nanocomposite
7.  In situ Polymerization of Multi-Walled Carbon Nanotube/Nylon-6 Nanocomposites and Their Electrospun Nanofibers 
Nanoscale Research Letters  2008;4(1):39-46.
Multiwalled carbon nanotube/nylon-6 nanocomposites (MWNT/nylon-6) were prepared by in situ polymerization, whereby functionalized MWNTs (F-MWNTs) and pristine MWNTs (P-MWNTs) were used as reinforcing materials. The F-MWNTs were functionalized by Friedel-Crafts acylation, which introduced aromatic amine (COC6H4-NH2) groups onto the side wall. Scanning electron microscopy (SEM) images obtained from the fractured surfaces of the nanocomposites showed that the F-MWNTs in the nylon-6 matrix were well dispersed as compared to those of the P-MWNTs. Both nanocomposites could be electrospun into nanofibers in which the MWNTs were embedded and oriented along the nanofiber axis, as confirmed by transmission electron microscopy. The specific strength and modulus of the MWNTs-reinforced nanofibers increased as compared to those of the neat nylon-6 nanofibers. The crystal structure of the nylon-6 in the MWNT/nylon-6 nanofibers was mostly γ-phase, although that of the MWNT/nylon-6 films, which were prepared by hot-pressing the pellets between two aluminum plates and then quenching them in icy water, was mostly α-phase, indicating that the shear force during electrospinning might favor the γ-phase, similarly to the conventional fiber spinning.
doi:10.1007/s11671-008-9199-0
PMCID: PMC2893824  PMID: 20596470
In situ polymerization; Nylon-6; Nanofibers; Carbon nanotube; Nanocomposite
8.  Reagentless biosensor based on layer-by-layer assembly of functional multiwall carbon nanotubes and enzyme-mediator biocomposite*  
A simple and controllable layer-by-layer (LBL) assembly method was proposed for the construction of reagentless biosensors based on electrostatic interaction between functional multiwall carbon nanotubes (MWNTs) and enzyme-mediator biocomposites. The carboxylated MWNTs were wrapped with polycations poly(allylamine hydrochloride) (PAH) and the resulting PAH-MWNTs were well dispersed and positively charged. As a water-soluble dye methylene blue (MB) could mix well with horseradish peroxidase (HRP) to form a biocompatible and negatively-charged HRP-MB biocomposite. A (PAH-MWNTs/HRP-MB)n bionanomultilayer was then prepared by electrostatic LBL assembly of PAH-MWNTs and HRP-MB on a polyelectrolyte precursor film-modified Au electrode. Due to the excellent biocompatibility of HRP-MB biocomposite and the uniform LBL assembly, the immobilized HRP could retain its natural bioactivity and MB could efficiently shuttle electrons between HRP and the electrode. The incorporation of MWNTs in the bionanomultilayer enhanced the surface coverage concentration of the electroactive enzyme and increased the catalytic current response of the electrode. The proposed biosensor displayed a fast response (2 s) to hydrogen peroxide with a low detection limit of 2.0×10−7 mol/L (S/N=3). This work provided a versatile platform in the further development of reagentless biosensors.
doi:10.1631/jzus.B1000280
PMCID: PMC3109149  PMID: 21634040
Reagentless biosensor; Layer-by-layer assembly; Horseradish peroxidase-methylene blue (HRP-MB) biocomposite; Functional multiwall carbon nanotubes; Hydrogen peroxide
9.  Decoration of multi-walled carbon nanotubes by polymer wrapping and its application in MWCNT/polyethylene composites 
Nanoscale Research Letters  2012;7(1):240.
We dispersed the non-covalent functionalization of multi-walled carbon nanotubes (CNTs) with a polymer dispersant and obtained a powder of polymer-wrapped CNTs. The UV–vis absorption spectrum was used to investigate the optimal weight ratio of the CNTs and polymer dispersant. The powder of polymer-wrapped CNTs had improved the drawbacks of CNTs of being lightweight and difficult to process, and it can re-disperse in a solvent. Then, we blended the polymer-wrapped CNTs and polyethylene (PE) by melt-mixing and produced a conductive masterbatch and CNT/PE composites. The polymer-wrapped CNTs showed lower surface resistivity in composites than the raw CNTs. The scanning electron microscopy images also showed that the polymer-wrapped CNTs can disperse well in composites than the raw CNTs.
doi:10.1186/1556-276X-7-240
PMCID: PMC3432610  PMID: 22559082
CNTs; Polymer wrapping; Composites
10.  Cytotoxicity Screening of Single-Walled Carbon Nanotubes: Detection and Removal of Cytotoxic Contaminants from Carboxylated Carbon Nanotubes 
Molecular pharmaceutics  2011;8(4):1351-1361.
This study compares the cytotoxicity to cultured mammalian cells of nine different single-walled carbon nanotube (SWNT) products synthesized by a variety of methods and obtained from a cross section of vendors. A standard procedure involving sonication and centrifugation in buffered bovine serum albumin was developed to disperse all the SWNTs in a biocompatible solution to facilitate comparisons. The effect of the SWNTs on the proliferative ability of a standard cell line was then assessed. Of the nine different SWNT materials tested, only two were significantly toxic, and both were functionalized by carboxylation from different vendors. This was unexpected because carboxylation makes SWNTs more water soluble, which would presumably correlate with better biocompatibility. However, additional purification work demonstrated that the toxic material in the carboxylated SWNT preparations could be separated from the SWNTs by filtration. The filtrate that contained the toxic activity also contained abundant small carbon fragments that had Raman signatures characteristic of amorphous carbon species, suggesting a correlation between toxicity and oxidized carbon fragments. The removal of a toxic contaminant associated with carboxylated SWNTs is important in the development of carboxylated SWNTs for pharmacological applications.
doi:10.1021/mp2001439
PMCID: PMC3148312  PMID: 21688794
carbon nanotubes; nanotoxicology; cytotoxicity; amorphous carbon; carboxylation
11.  Characterization of Multiwalled Carbon Nanotube-Reinforced Hydroxyapatite Composites Consolidated by Spark Plasma Sintering 
BioMed Research International  2014;2014:768254.
Pure HA and 1, 3, 5, and 10 vol% multiwalled carbon nanotube- (MWNT-) reinforced hydroxyapatite (HA) were consolidated using a spark plasma sintering (SPS) technique. The relative density of pure HA increased with increasing sintering temperature, but that of the MWNT/HA composite reached almost full density at 900°C, and then decreased with further increases in sintering temperature. The relative density of the MWNT/HA composites increased with increasing MWNT content due to the excellent thermal conductivity of MWNTs. The grain size of MWNT/HA composites decreased with increasing MWNT content and increased with increasing sintering temperature. Pull-out toughening of the MWNTs of the MWNT/HA composites was observed in the fractured surface, which can be used to predict the improvement of the mechanical properties. On the other hand, the existence of undispersed or agglomerate MWNTs in the MWNT/HA composites accompanied large pores. The formation of large pores increased with increasing sintering temperature and MWNT content. The addition of MWNT in HA increased the hardness and fracture toughness by approximately 3~4 times, despite the presence of large pores produced by un-dispersed MWNTs. This provides strong evidence as to why the MWNTs are good candidates as reinforcements for strengthening the ceramic matrix. The MWNT/HA composites did not decompose during SPS sintering. The MWNT-reinforced HA composites were non-toxic and showed a good cell affinity and morphology in vitro for 1 day.
doi:10.1155/2014/768254
PMCID: PMC3960548  PMID: 24724100
12.  A Novel Electrochemical Sensor for Probing Doxepin Created on a Glassy Carbon Electrode Modified with Poly(4-Amino- benzoic Acid)/Multi-Walled Carbon Nanotubes Composite Film 
Sensors (Basel, Switzerland)  2010;10(9):8398-8410.
A novel electrochemical sensor for sensitive detection of doxepin was prepared, which was based on a glassy carbon electrode modified with poly(4-aminobenzoic acid)/multi-walled carbon nanotubes composite film [poly(4-ABA)/MWNTs/GCE]. The sensor was characterized by scanning electron microscopy and electrochemical methods. It was observed that poly(4-ABA)/MWNTs/GCE showed excellent preconcentration function and electrocatalytic activities towards doxepin. Under the selected conditions, the anodic peak current was linear to the logarithm of doxepin concentration in the range from 1.0 × 10−9 to 1.0 × 10−6 M, and the detection limit obtained was 1.0 × 10−10 M. The poly(4-ABA)/MWNTs/GCE was successfully applied in the measurement of doxepin in commercial pharmaceutical formulations, and the analytical accuracy was confirmed by comparison with a conventional ultraviolet spectrophotometry assay.
doi:10.3390/s100908398
PMCID: PMC3231211  PMID: 22163661
poly(4-aminobenzoic acid); multi-walled carbon nanotubes; nanocomposite; doxepin; detection
13.  Selective Deposition and Alignment of Single-Walled Carbon Nanotubes Assisted by Dielectrophoresis: From Thin Films to Individual Nanotubes 
Nanoscale Research Letters  2010;5(6):1072-1078.
Dielectrophoresis has been used in the controlled deposition of single-walled carbon nanotubes (SWNTs) with the focus on the alignment of nanotube thin films and their applications in the last decade. In this paper, we extend the research from the selective deposition of SWNT thin films to the alignment of small nanotube bundles and individual nanotubes. Electrodes with “teeth”-like patterns are fabricated to study the influence of the electrode width on the deposition and alignment of SWNTs. The entire fabrication process is compatible with optical lithography-based techniques. Therefore, the fabrication cost is low, and the resulting devices are inexpensive. A series of SWNT solutions is prepared with concentrations ranging from 0.0125 to 0.2 mg/ml. The alignment of SWNT thin films, small bundles, and individual nanotubes is achieved under the optimized experimental conditions. The electrical properties of these samples are characterized; the linear current–voltage plots prove that the aligned SWNTs are mainly metallic nanotubes. The microscopy inspection of the samples demonstrates that the alignment of small nanotube bundles and individual nanotubes can only be achieved using narrow electrodes and low-concentration solutions. Our investigation shows that it is possible to deposit a controlled amount of SWNTs in desirable locations using dielectrophoresis.
doi:10.1007/s11671-010-9604-3
PMCID: PMC2894206  PMID: 20672073
Single-walled carbon nanotubes (SWNT); Dielectrophoresis (DEP); Thin film; Nanotube bundle; Individual nanotube; Deposition
14.  Selective Deposition and Alignment of Single-Walled Carbon Nanotubes Assisted by Dielectrophoresis: From Thin Films to Individual Nanotubes 
Nanoscale Research Letters  2010;5(6):1072-1078.
Dielectrophoresis has been used in the controlled deposition of single-walled carbon nanotubes (SWNTs) with the focus on the alignment of nanotube thin films and their applications in the last decade. In this paper, we extend the research from the selective deposition of SWNT thin films to the alignment of small nanotube bundles and individual nanotubes. Electrodes with “teeth”-like patterns are fabricated to study the influence of the electrode width on the deposition and alignment of SWNTs. The entire fabrication process is compatible with optical lithography-based techniques. Therefore, the fabrication cost is low, and the resulting devices are inexpensive. A series of SWNT solutions is prepared with concentrations ranging from 0.0125 to 0.2 mg/ml. The alignment of SWNT thin films, small bundles, and individual nanotubes is achieved under the optimized experimental conditions. The electrical properties of these samples are characterized; the linear current–voltage plots prove that the aligned SWNTs are mainly metallic nanotubes. The microscopy inspection of the samples demonstrates that the alignment of small nanotube bundles and individual nanotubes can only be achieved using narrow electrodes and low-concentration solutions. Our investigation shows that it is possible to deposit a controlled amount of SWNTs in desirable locations using dielectrophoresis.
doi:10.1007/s11671-010-9604-3
PMCID: PMC2894206  PMID: 20672073
Single-walled carbon nanotubes (SWNT); Dielectrophoresis (DEP); Thin film; Nanotube bundle; Individual nanotube; Deposition
15.  Pt-TiO2/MWCNTs Hybrid Composites for Monitoring Low Hydrogen Concentrations in Air 
Sensors (Basel, Switzerland)  2012;12(9):12361-12373.
Hydrogen is a valuable fuel for the next energy scenario. Unfortunately, hydrogen is highly flammable at concentrations higher than 4% in air. This aspect makes the monitoring of H2 leaks an essential issue for safety reasons, especially in the transportation field. In this paper, nanocomposites based on Pt-doped TiO2/multiwalled carbon nanotubes (MWCNTs) have been introduced as sensitive materials for H2 at low temperatures. Pt-TiO2/MWNTs nanocomposites with different composition have been prepared by a simple wet chemical procedure and their morphological, microstructural and electrical properties were investigated. Resistive thick-film devices have been fabricated printing the hybrid nanocomposites on alumina substrates provided with Pt interdigitated electrodes. Electrical tests in air have shown that embedding MWCNTs in the TiO2 matrix modify markedly the electrical conductivity, providing a means to decrease the resistance of the sensing layer. Pt acts as a catalytic additive. Pt-TiO2/MWNTs-based sensors were found to be sensitive to hydrogen at concentrations between 0.5 and 3% in air, satisfying the requisites for practical applications in hydrogen leak detection devices.
doi:10.3390/s120912361
PMCID: PMC3478844  PMID: 23112717
hydrogen sensor; TiO2; MWCNTs; hybrid nanocomposites
16.  Supercapacitance from Cellulose and Carbon Nanotube Nanocomposite Fibers 
ACS Applied Materials & Interfaces  2013;5(20):9983-9990.
Multiwalled carbon nanotube (MWNT)/cellulose composite nanofibers have been prepared by electrospinning a MWNT/cellulose acetate blend solution followed by deacetylation. These composite nanofibers were then used as precursors for carbon nanofibers (CNFs). The effect of nanotubes on the stabilization of the precursor and microstructure of the resultant CNFs were investigated using thermogravimetric analysis, transmission electron microscopy and Raman spectroscopy. It is demonstrated that the incorporated MWNTs reduce the activation energy of the oxidative stabilization of cellulose nanofibers from ∼230 to ∼180 kJ mol–1. They also increase the crystallite size, structural order, and electrical conductivity of the activated CNFs (ACNFs). The surface area of the ACNFs increased upon addition of nanotubes which protrude from the fiber leading to a rougher surface. The ACNFs were used as the electrodes of a supercapacitor. The electrochemical capacitance of the ACNF derived from pure cellulose nanofibers is demonstrated to be 105 F g–1 at a current density of 10 A g–1, which increases to 145 F g–1 upon the addition of 6% of MWNTs.
doi:10.1021/am403622v
PMCID: PMC3807724  PMID: 24070254
cellulose; supercapacitor; nanocomposites
17.  Enhancements of thermal conductivities with Cu, CuO, and carbon nanotube nanofluids and application of MWNT/water nanofluid on a water chiller system 
Nanoscale Research Letters  2011;6(1):297.
In this study, enhancements of thermal conductivities of ethylene glycol, water, and synthetic engine oil in the presence of copper (Cu), copper oxide (CuO), and multi-walled carbon nanotube (MWNT) are investigated using both physical mixing method (two-step method) and chemical reduction method (one-step method). The chemical reduction method is, however, used only for nanofluid containing Cu nanoparticle in water. The thermal conductivities of the nanofluids are measured by a modified transient hot wire method. Experimental results show that nanofluids with low concentration of Cu, CuO, or carbon nanotube (CNT) have considerably higher thermal conductivity than identical base liquids. For CuO-ethylene glycol suspensions at 5 vol.%, MWNT-ethylene glycol at 1 vol.%, MWNT-water at 1.5 vol.%, and MWNT-synthetic engine oil at 2 vol.%, thermal conductivity is enhanced by 22.4, 12.4, 17, and 30%, respectively. For Cu-water at 0.1 vol.%, thermal conductivity is increased by 23.8%. The thermal conductivity improvement for CuO and CNT nanofluids is approximately linear with the volume fraction. On the other hand, a strong dependence of thermal conductivity on the measured time is observed for Cu-water nanofluid. The system performance of a 10-RT water chiller (air conditioner) subject to MWNT/water nanofluid is experimentally investigated. The system is tested at the standard water chiller rating condition in the range of the flow rate from 60 to 140 L/min. In spite of the static measurement of thermal conductivity of nanofluid shows only 1.3% increase at room temperature relative to the base fluid at volume fraction of 0.001 (0.1 vol.%), it is observed that a 4.2% increase of cooling capacity and a small decrease of power consumption about 0.8% occur for the nanofluid system at a flow rate of 100 L/min. This result clearly indicates that the enhancement of cooling capacity is not just related to thermal conductivity alone. Dynamic effect, such as nanoparticle dispersion may effectively augment the system performance. It is also found that the dynamic dispersion is comparatively effective at lower flow rate regime, e.g., transition or laminar flow and becomes less effective at higher flow rate regime. Test results show that the coefficient of performance of the water chiller is increased by 5.15% relative to that without nanofluid.
doi:10.1186/1556-276X-6-297
PMCID: PMC3211363  PMID: 21711787
18.  Developing the dielectric mechanisms of polyetherimide/multiwalled carbon nanotube/(Ba0.8Sr0.2)(Ti0.9Zr0.1)O3 composites 
Nanoscale Research Letters  2012;7(1):132.
Various amounts of multiwalled carbon nanotubes [MWNTs] were embedded into polyetherimide [PEI] to form PEI/MWNT composites, and their dielectric properties were measured at 1 MHz. The Lichtenecker mixing rule was used to find a reasonable dielectric constant for the MWNTs used in this study. The dielectric constants of the developed composites were significantly increased, and the loss tangents were significantly decreased as 2.0 wt.% (Ba0.8Sr0.2)(Ti0.9Zr0.1)O3 ceramic powder [BSTZ] was added to the PEI/MWNTs to form PEI/MWNT/BSTZ composites. The Lichtenecker and Yamada mixing rules were used to predict the dielectric constants of the PEI/MWNT and PEI/MWNT/BSTZ composites. Equivalent electrical conduction models of both composites were established using the two mixing rules. In addition, the theoretical bases of the two mixing rules were used to explain the measured results for the PEI/MWNT and PEI/BSTZ/MWNT composites.
doi:10.1186/1556-276X-7-132
PMCID: PMC3305553  PMID: 22340201
composites; mixing rule; dielectric properties; electrical conduction mechanism
19.  Conductive cable fibers with insulating surface prepared by co-axial electrospinning of multi-walled nanotubes and cellulose 
Biomacromolecules  2010;11(9):2440-2445.
A core-sheath of multi-walled carbon nanotube (MWNT)-cellulose fibers of diameters from several hundreds nm to several µm were prepared by co-axial electrospinning from a non-valatile, non-flammable ionic liquid (IL) solvent, 1-methyl-3-methylimidazolium acetate ([EMIM][Ac]). MWNTs were dispersed in IL to form a gel solution. This gel core solution was electrospun surrounded by a sheath solution of cellulose disolved in the same IL. Electrospun fibers were collected in a coagulation bath containing ethanol-water to completely remove the IL and dried to form a core-sheath MWNT-cellulose fibers having a cable structure with a conductive core and insulating sheath. Enzymatic treatment of a portion of a mat of these fibers with cellulase selectively removed the cellulose sheath exposing the MWNT core for connection to an electrode. These MWNT-cellulose fiber mats demonstrated excellent conductivity due to a conductive pathway of bundleled MWNTs. Fiber mat conductivity increased with increasing ratio of MWNT in the fibers with a maximum conductivity of 10.7 S/m obtained at 45 wt% MWNT loading.
doi:10.1021/bm1006129
PMCID: PMC2939169  PMID: 20690644
20.  Effects of the electrical conductivity and orientation of silicon substrate on the synthesis of multi-walled carbon nanotubes by thermal chemical vapor deposition 
Nanoscale Research Letters  2013;8(1):110.
We studied the effects of the electrical conductivity and orientation of silicon substrate on both catalytic Fe thin film and the structure and morphology of multi-walled carbon nanotube (MWNT) grown by low-pressure chemical vapor deposition. Both p-type Si(100) and Si(111) substrates with three different doping concentrations (high, low, undoped) were used to evaluate the formation of catalytic nanoparticles and the growth of MWNTs. The morphology of catalytic nanoparticles such as size and density was characterized by field-emission scanning electron microscopy, Cs-corrected energy-filtered transmission electron microscopy, and X-ray photoelectron spectroscopy. Structural characteristics of MWNTs grown on different combinations of silicon substrate orientation and electrical conductivities (σ) were also systematically analyzed. Based on the experimental results, growth modes of MWNTs could be controlled by choosing an appropriate combination of σ and orientation of Si substrates.
doi:10.1186/1556-276X-8-110
PMCID: PMC3626923  PMID: 23445774
Multi-walled carbon nanotube; Catalytic nanoparticle; Substrate effect
21.  Transparent Conductors from Carbon Nanotubes LBL-Assembled with Polymer Dopant with π-π Electron Transfer 
Single-walled carbon nanotube (SWNT) and other carbon-based coatings are being considered as replacements for indium tin oxide (ITO). The problems of transparent conductors (TCs) coatings from SWNT and similar materials include poor mechanical properties, high roughness, low temperature resilience, and fast loss of conductivity. The simultaneous realization of these desirable characteristics can be achieved using high structural control of layer-by-layer (LBL) deposition, which is demonstrated by the assembly of hydroethyl cellulose (HOCS) and sulfonated polyetheretherketone (SPEEK)-SWNTs. A new type of SWNT doping based on electron transfer from valence bands of nanotubes to unoccupied levels of SPEEK through π-π interactions was identified for this system. It leads to a conductivity of 1.1×105 S/m at 66wt% loadings of SWNT. This is better than other polymer/SWNT composites and translates into surface conductivity of 920 ohms/sq and transmittance of 86.7% at 550nm. The prepared LBL films also revealed unusually high temperature resilience up to 500°C, and low roughness of 3.5 nm (ITO glass - 2.4 nm). Tensile modulus, ultimate strength, and toughness of such coatings are 13±2 GPa, 366±35 MPa and 8±3 kJ/m3, respectively, and exceed corresponding parameters of all similar TCs. The cumulative figure of merit, ΠTC, which included the critical failure strain relevant for flexible electronics, was ΠTC = 0.022 and should be compared to ΠTC = 0.006 for commercial ITO. Further optimization is possible using stratified nanoscale coatings and improved doping from the macromolecular LBL components.
doi:10.1021/ja111687t
PMCID: PMC3136082  PMID: 21524068
carbon nanotube; sulfonated polyetherether ketone; hydroxyethyl cellulose; transparent conductors; layer-by-layer; nanocomposites; conductivity; mechanical strength; helical wrapping; doping
22.  Controlling exfoliation in order to minimize damage during dispersion of long SWCNTs for advanced composites 
Scientific Reports  2014;4:3907.
We propose an approach to disperse long single-wall carbon nanotubes (SWCNTs) in a manner that is most suitable for the fabrication of high-performance composites. We compare three general classes of dispersion mechanisms, which encompass 11 different dispersion methods, and we have dispersed long SWCNTs, short multi-wall carbon nanotubes, and short SWCNTs in order to understand the most appropriate dispersion methods for the different types of CNTs. From this study, we have found that the turbulent flow methods, as represented by the Nanomizer and high-pressure jet mill methods, produced unique and superior dispersibility of long SWCNTs, which was advantageous for the fabrication of highly conductive composites. The results were interpreted to imply that the biaxial shearing force caused an exfoliation effect to disperse the long SWCNTs homogeneously while suppressing damage. A conceptual model was developed to explain this dispersion mechanism, which is important for future work on advanced CNT composites.
doi:10.1038/srep03907
PMCID: PMC3904143  PMID: 24469607
23.  Simple, Rapid, Sensitive, and Versatile SWNT-Paper Sensor for Environmental Toxin Detection Competitive with ELISA 
Nano letters  2009;9(12):4147-4152.
Safety of water was for a long time and still is one of the most pressing needs for many countries and different communities. Despite the fact that there are potentially many methods to evaluate water safety, finding a simple, rapid, versatile, and inexpensive method for detection of toxins in everyday items is still a great challenge. In this study, we extend the concept of composites obtained impregnation of porous fibrous materials, such as fabrics and papers, by single walled carbon-nanotubes (SWNTs) toward very simple but high-performance biosensors. They utilize the strong dependence of electrical conductivity through nanotubes percolation network on the width of nanotubes-nanotube tunneling gap and can potentially satisfy all the requirements outlined above for the routine toxin monitoring. An antibody to the microcystin-LR (MC-LR), one of the common culprits in mass poisonings, was dispersed together with SWNTs. This dispersion was used to dip-coat the paper rendering it conductive. The change in conductivity of the paper was used to sense the MC-LR in the water rapidly and accurately. The method has the linear detection range up to 10 nmol/L and non-linear detection up to 40 nmol/L. The limit of detection was found to be 0.6 nmol/L (0.6 ng/mL), which satisfies the strictest World Health Organization standard for MC-LR content in drinking water (1 ng/mL), and is comparable to the detection limit of traditional ELISA method of MC-LR detection, while drastically reducing the time of analysis by more than an order of magnitude, which is one of the major hurdles in practical applications. Similar technology of sensor preparation can also be used for a variety of other rapid environmental sensors.
doi:10.1021/nl902368r
PMCID: PMC2793542  PMID: 19928776
sensor; SWNT; nanotubes; environmental monitoring; liver cancer; microcystin; ELISA; water
24.  Effect of Purity and Substrate on Field Emission Properties of Multi-walled Carbon Nanotubes 
Nanoscale Research Letters  2007;2(7):331-336.
Multi-walled carbon nanotubes (MWNT) have been synthesized by chemical vapour decomposition (CVD) of acetylene over Rare Earth (RE) based AB2(DyNi2) alloy hydride catalyst. The as-grown carbon nanotubes were purified by acid and heat treatments and characterized using powder X-ray diffraction, Scanning Electron Microscopy, Transmission Electron Microscopy, Thermo Gravimetric Analysis and Raman Spectroscopy. Fully carbon based field emitters have been fabricated by spin coating a solutions of both as-grown and purified MWNT and dichloro ethane (DCE) over carbon paper with and without graphitized layer. The use of graphitized carbon paper as substrate opens several new possibilities for carbon nanotube (CNT) field emitters, as the presence of the graphitic layer provides strong adhesion between the nanotubes and carbon paper and reduces contact resistance. The field emission characteristics have been studied using an indigenously fabricated set up and the results are discussed. CNT field emitter prepared by spin coating of the purified MWNT–DCE solution over graphitized carbon paper shows excellent emission properties with a fairly stable emission current over a period of 4 h. Analysis of the field emission characteristics based on the Fowler–Nordheim (FN) theory reveals current saturation effects at high applied fields for all the samples.
doi:10.1007/s11671-007-9067-3
PMCID: PMC3246377  PMID: 21798103
Multi-walled carbon nanotubes; DyNi2alloy hydride; Spin coating; Dichloro ethane; Graphitized carbon paper; CNT field emitter; Fowler–Nordheim theory
25.  Functionalized Carbon Nanotubes in the Brain: Cellular Internalization and Neuroinflammatory Responses 
PLoS ONE  2013;8(11):e80964.
The potential use of functionalized carbon nanotubes (f-CNTs) for drug and gene delivery to the central nervous system (CNS) and as neural substrates makes the understanding of their in vivo interactions with the neural tissue essential. The aim of this study was to investigate the interactions between chemically functionalized multi-walled carbon nanotubes (f-MWNTs) and the neural tissue following cortical stereotactic administration. Two different f-MWNT constructs were used in these studies: shortened (by oxidation) amino-functionalized MWNT (oxMWNT-NH3+) and amino-functionalized MWNT (MWNT-NH3+). Parenchymal distribution of the stereotactically injected f-MWNTs was assessed by histological examination. Both f-MWNT were uptaken by different types of neural tissue cells (microglia, astrocytes and neurons), however different patterns of cellular internalization were observed between the nanotubes. Furthermore, immunohistochemical staining for specific markers of glial cell activation (GFAP and CD11b) was performed and secretion of inflammatory cytokines was investigated using real-time PCR (qRT-PCR). Injections of both f-MWNT constructs led to a local and transient induction of inflammatory cytokines at early time points. Oxidation of nanotubes seemed to induce significant levels of GFAP and CD11b over-expression in areas peripheral to the f-MWNT injection site. These results highlight the importance of nanotube functionalization on their interaction with brain tissue that is deemed critical for the development nanotube-based vector systems for CNS applications.
doi:10.1371/journal.pone.0080964
PMCID: PMC3832421  PMID: 24260521

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