Carboxyl-functionalized Single-walled Carbon Nanotubes Research Articles

Carbon nanotubes conjugated with cisplatin activate different apoptosis signaling pathways in 2D and 3D-spheroid triple-negative breast cancer cell cultures: a comparative study.

The type of experimental model for the in vitro testing of drug formulations efficiency represents an important tool in cancer biology, with great attention being granted to three-dimensional (3D) cultures as these offer a closer approximation of the clinical sensitivity of drugs. In this study, the effects induced by carboxyl-functionalized single-walled carbon nanotubes complexed with cisplatin (SWCNT-COOH-CDDP) and free components (SWCNT-COOH and CDDP) were compared between conventional 2D- and 3D-spheroid cultures of human breast cancer cells. The 2D and 3D breast cancer cultures were exposed to various doses of SWCNT-COOH (0.25-2μg/mL), CDDP (0.158-1.26μg/mL) and the same doses of SWNCT-COOH-CDDP complex for 24 and 48h. The anti-tumor activity, including modulation of cell viability, oxidative stress, proliferation, apoptosis, and invasion potential, was explored by spectrophotometric and fluorometric methods, immunoblotting, optical and fluorescence microscopy. The SWCNT-COOH-CDDP complex proved to have high anti-cancer efficiency on 2D and 3D cultures by inhibiting cell proliferation and activating cell death. A dose of 0.632μg/mL complex triggered different pathways of apoptosis in 2D and 3D cultures, by intrinsic, extrinsic, and reticulum endoplasmic pathways. Overall, the 2D cultures showed higher susceptibility to the action of complex compared to 3D cultures and SWCNT-COOH-CDDP proved enhanced anti-tumoral activity compared to free CDDP.

Linear correlation between electronegativity and adsorption energy of hydrated metal ions by carboxyl-functionalized single-walled carbon nanotubes

Linear correlation between electronegativity and adsorption energy of hydrated metal ions by carboxyl-functionalized single-walled carbon nanotubes

Effect of Carboxyl-Functionalized Single Walled Carbon Nanotubes on the Interfacial Barrier Height of Malachite Green Dye Based Organic Device

In this study, we have estimated the interfacial barrier height (Φb) of Indium Tin Oxide (ITO) coated glass/Malachite Green (MG) dye/Aluminium (Al) based organic device and subsequently we have also observed the effect of carboxylfunctionalized SWCNT (COOH-SWCNT) on the Φb. Presence of COOH-SWCNT reduces the interfacial barrier height as SWCNT acts as filler and provides easy path for charge percolation. We have used ITO coated glass and aluminium as front electrode and back electrode respectively to form the organic device. This organic device has been prepared with and without COOH-SWCNT by using spin coating technique. We have measured the steady state current-Voltage (I-V) characteristics of the device to estimate the interfacial barrier height (Φb) of the device. Φb is reduced from 0.67 eV to 0.59 eV in the presence of COOH-SWCNT. We have also estimated the Φb by using Norde’s Method. This method also shows a reduction of interfacial barrier height from 0.72 eV to 0.64 eV due to incorporation of COOH-SWCNT. Both the methods show good consistency with each other. Reduction of the interfacial barrier height in presence of COOH-SWCNT indicates the enhancement of charge injection through the metal-organic dye interface. By suitable doping or addition of COOH-SWCNT within the MG dye it is possible to reduce the barrier height and enhance the current injection through metal-organic dye interface.

A regenerative and selective electrochemical aptasensor based on copper oxide nanoflowers-single walled carbon nanotubes nanocomposite for chlorpyrifos detection

Chlorpyrifos is a commonly used organophosphorus pesticide in agriculture. However, its neurotoxicity poses a huge threat to human health. To detect trace amounts of chlorpyrifos, we herein developed a regenerative electrochemical aptasensor for the sensitive detection of chlorpyrifos. The nanocomposite consisting of copper oxide nanoflowers (CuO NFs) and carboxyl-functionalized single walled carbon nanotubes (c-SWCNTs) was prepared to improve the sensing performance for chlorpyrifos detection. Various characterization methods such as scanning electron microscopy (SEM), fourier transform infrared spectroscopy (FT-IR) and cyclic voltammetry (CV) were used to demonstrate the successful fabrication of biosensor. Differential pulse voltammetry (DPV) was utilized to optimize test conditions and quantify chlorpyrifos. Under optimal conditions, the biosensor obtained a good linearity for chlorpyrifos ranging from 0.1 to 150ng/mL, with a lower detection limit of 70pg/mL. This aptasensor also exhibited high selectivity and outstanding repeatability, and was successfully applied to the determination of chlorpyrifos in spiked apple and celery cabbage with satisfactory recoveries. Furthermore, the sensor can be easily regenerated by urea for continuous application. With all the features, the proposed strategy provides an excellent platform for regenerative and selective detection of chlorpyrifos.

High performance flexible pH sensor based on carboxyl-functionalized and DEP aligned SWNTs

The detection and control of the pH is very important in many biomedical and chemical reaction processes. A miniaturized flexible pH sensor that is light weight, robust, and conformable is very important in many applications, such as multifunctional lab-on-a-chip systems or wearable biomedical devices. In this work, we demonstrate a flexible chemiresistive pH sensor based on dielectrophoresis (DEP) aligned carboxyl-functionalized single-walled carbon nanotubes (SWNTs). Decorated carboxyl groups can react with hydrogen (H+) and hydroxide (OH−) ions, enabling the sensor to be capable of sensing the pH. DEP is used to deposit well-organized and highly aligned SWNTs in desired locations, which improves the metal-nanotube interface and highly rapid detection of the pH, resulting in better overall device performance. When pH buffer solutions are dropped onto such SWNTs, the H+ and OH− ions caninteract with the carboxyl groups and affect the generation of holes and electrons in the SWNTs, leading to resistance variations in the SWNTs. The results shows that the relative resistance variations of the sensor increases linearly with increasing the pH values in the range from 5 to 9 and the response time ranges from 0.2s to 22.6s. The pH sensor also shows high performance in mechanical bendability, which benefited from the combination of flexible PET substrates and SWNTs. The SWNT-based flexible pH sensor demonstrates great potential in a wide range of areas due to its simple structure, excellent performance, low power consumption, and compatibility with integrated circuits.

An ultrasensitive electrochemical DNA biosensor based on a copper oxide nanowires/single-walled carbon nanotubes nanocomposite

Here, we developed a novel and sensitive electrochemical biosensor to detect specific-sequence target DNA. The biosensor was based on a hybrid nanocomposite consisting of copper oxide nanowires (CuO NWs) and carboxyl-functionalized single-walled carbon nanotubes (SWCNTs-COOH). The resulting CuO NWs/SWCNTs layers exhibited a good differential pulse voltammetry (DPV) current response for the target DNA sequences, which we attributed to the properties of CuO NWs and SWCNTs. CuO NWs and SWCNTs hybrid composites with highly conductive and biocompatible nanostructure were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and cyclic voltammetry (CV). Immobilization of the probe DNA on the electrode surface was largely improved due to the unique synergetic effect of CuO NWs and SWCNTs. DPV was applied to monitor the DNA hybridization event, using adriamycin as an electrochemical indicator. Under optimal conditions, the peak currents of adriamycin were linear with the logarithm of target DNA concentrations (ranging from 1.0×10−14 to 1.0×10−8M), with a detection limit of 3.5×10−15M (signal/noise ratio of 3). The biosensor also showed high selectivity to single-base mismatched target DNA. Compared with other electrochemical DNA biosensors, we showed that the proposed biosensor is simple to implement, with good stability and high sensitivity.

Improvement of the fracture toughness of hydroxyapatite (HAp) by incorporation of carboxyl functionalized single walled carbon nanotubes (CfSWCNTs) and nylon

The potential of improving the fracture toughness of synthetic hydroxyapatite (HAp) by incorporating carboxyl functionalized single walled carbon nanotubes (CfSWCNTs) and polymerized ε-caprolactam (nylon) was studied. A series of HAp samples with CfSWCNTs concentrations varying from 0 to 1.5wt.%, without, and with nylon addition was prepared. X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), and Transmission Electron Microscopy (TEM) were used to characterize the samples. The three point bending test was applied to measure the fracture toughness of the composites. A reproducible value of 3.6±0.3MPa.√m was found for samples containing 1wt.% CfSWCNTs and nylon. This value is in the range of the cortical bone fracture toughness. Increase of the CfSWCNTs content results to decrease of the fracture toughness, and formation of secondary phases.

Correction to Co-Exposure of Carboxyl-functionalized Single-walled Carbon Nanotubes and 17α-ethinylestradiol in Cultured Cells: Effects on Bioactivity and Cytotoxicity

Correction to Co-Exposure of Carboxyl-functionalized Single-walled Carbon Nanotubes and 17α-ethinylestradiol in Cultured Cells: Effects on Bioactivity and Cytotoxicity

Co-exposure of carboxyl-functionalized single-walled carbon nanotubes and 17α-ethinylestradiol in cultured cells: effects on bioactivity and cytotoxicity.

17α-Ethinylestradiol (EE2) is the representative of environmental estrogens. Although EE2 can interact with some engineered nanoparticles (NPs), little is known about the bioactivity of NP-associated EE2 in organisms. In this study, we investigated the combined effects of the co-exposed carboxyl-functionalized single-walled carbon nanotubes (cf-SWCNTs) and EE2 in the human breast adenocarcinoma cell line (MCF-7 cells), focusing on the cytotoxicity and bioactivity. There were no significant differences in mitochondrial activity, membrane damage, and cell apoptosis when exposed to cf-SWCNTs with and without adsorbed EE2. However, the bioactivity of adsorbed EE2 on cf-SWCNTs was significantly inhibited. The calculated effective concentration of EE2 in cultured cells showed that less than 0.2% of the total adsorbed EE2 was released, indicating that most EE2 was retained on the cf-SWCNTs during cellular exposure. Furthermore, there were no obvious changes in the bioactivity of adsorbed EE2 in the culture medium containing 5-20% fetal bovine serum (FBS), even up to 10 days of incubation, indicating that the adsorbed EE2 on cf-SWCNTs is highly stable in the cell culture medium. These results mark a promising possibility for EE2 to be adsorbed by cf-SWCNTs in environmentally relevant settings and thereby influenced its toxicity and biological fate. This is also tempting for future studies involving risk assessment ways for association between NPs and contaminants in the environment.

Use of whole genome expression analysis in the toxicity screening of nanoparticles

The use of nanoparticles (NPs) offers exciting new options in technical and medical applications provided they do not cause adverse cellular effects. Cellular effects of NPs depend on particle parameters and exposure conditions. In this study, whole genome expression arrays were employed to identify the influence of particle size, cytotoxicity, protein coating, and surface functionalization of polystyrene particles as model particles and for short carbon nanotubes (CNTs) as particles with potential interest in medical treatment. Another aim of the study was to find out whether screening by microarray would identify other or additional targets than commonly used cell-based assays for NP action. Whole genome expression analysis and assays for cell viability, interleukin secretion, oxidative stress, and apoptosis were employed. Similar to conventional assays, microarray data identified inflammation, oxidative stress, and apoptosis as affected by NP treatment. Application of lower particle doses and presence of protein decreased the total number of regulated genes but did not markedly influence the top regulated genes. Cellular effects of CNTs were small; only carboxyl-functionalized single-walled CNTs caused appreciable regulation of genes. It can be concluded that regulated functions correlated well with results in cell-based assays. Presence of protein mitigated cytotoxicity but did not cause a different pattern of regulated processes.

Spectroscopic Characterization of Carbon Nanotube-Polypyrrole Composites

The purpose of this study is to investigate the chemical interaction between carboxyl-functionalized single-walled carbon nanotubes (SWNTs) and multi-walled carbon nanotubes (MWNTs) with in situ chemically polymerized polypyrrole (PPy) films (approximately 8 nm) by resonance Raman spectroscopy. The composites (SWNT/PPy and MWNT/PPy) were synthesized using nitric acid functionalized nanotubes as the starting material. The resulting composites were characterized by transmission electronic microscopy (TEM) and by resonance Raman spectroscopy (λexc. = 514.5, 632.8, and 785 nm). The TEM images of the nanocomposites revealed that PPy wrapped around the carbon nanotubes. The resonance Raman data showed evidence of charge transfer between composite moieties and a stronger interaction between the carbon material and the polymer in the SWNT/PPy compared to MWNT/PPy. Specifically, an intense charge-transfer process occurred between PPy and the SWNTs, significantly perturbing the electronic structures of both moieties. Analysis of the SWNTs in the SWNT/PPy spectra showed a softening of the C–C bond in both metallic and semiconducting SWNTs and an increase in the Breit–Wigner–Fano (BWF) contribution to the G-band shape of the metallic SWNTs, which resulted from an increase in the electronic density of the SWNT π band. Accordingly, the resonant Raman spectra of PPy in SWNT/PPy showed an increase in the bipolaron/polaron ratio compared to standard PPy, indicating an increase in the polymer’s doping level. Thus, the resonance Raman data were consistent with an increase in the electronic density of metallic and semiconducting nanotubes and a decrease in the electronic density of the polymer, indicating a PPy → SWNT charge transfer in the composite. Our data suggested the formation of a true composite material in the SWNTs with enhanced conductive properties because the interaction with the SWNTs resulted in the stability of the most doped and conductive form of PPy.

Toxicity of Functionalized Single-Walled Carbon Nanotubes on Soil Microbial Communities: Implications for Nutrient Cycling in Soil

Culture-dependent and -independent methods were employed to determine the impact of carboxyl-functionalized single-walled carbon nanotubes (SWNTs) on fungal and bacterial soil microbial communities. Soil samples were exposed to 0 (control), 250, and 500 μg of SWNTs per gram of soil. Aliquots of soil were sampled for up to 14 days for culture-dependent analyses, namely, plate count agar and bacterial community level physiological profiles, and culture-independent analyses, namely, quantitative real-time polymerase chain reaction (qPCR), mutliplex-terminal restriction fragment length polymorphism (M-TRFLP), and clone libraries. Results from culture-independent and -dependent methods show that the bacterial soil community is transiently affected by the presence of SWNTs. The major impact of SWNTs on bacterial community was observed after 3 days of exposure, but the bacterial community completely recovered after 14 days. However, no recovery of the fungal community was observed for the duration of the experiment. Physiological and DNA microbial community analyses suggest that fungi and bacteria involved in carbon and phosphorus biogeochemical cycles can be adversely affected by the presence of SWNTs. This study suggests that high concentrations of SWNTs can have widely varying effects on microbial communities and biogeochemical cycling of nutrients in soils.

Characteristics of third-generation glucose biosensors based on Corynascus thermophilus cellobiose dehydrogenase immobilized on commercially available screen-printed electrodes working under physiological conditions

In this article, we describe a third-generation amperometric glucose biosensor working under physiological conditions. This glucose biosensor consists of a recently discovered cellobiose dehydrogenase from the ascomycete Corynascus thermophilus (CtCDH) immobilized on different commercially available screen-printed electrodes made of carbon (SPCEs), carboxyl-functionalized single-walled carbon nanotubes (SPCE–SWCNTs), or multiwalled carbon nanotubes (SPCE–MWCNTs) by simple physical adsorption or a combination of adsorption followed by cross-linking using poly(ethyleneglycol) (400) diglycidyl ether (PEGDGE) or glutaraldehyde (GA). The CtCDH-based third-generation glucose biosensor has a linear range between 0.025 and 30mM and a detection limit of 10μM glucose. Biosensors based on SWCNTs showed a higher sensitivity and catalytic response than the ones functionalized with MWCNTs and the SPCEs. A drastic increase in response was observed for all three electrodes when the adsorbed enzyme was cross-linked with PEGDGE or GA. The operational stability of the biosensor was tested for 7h by repeated injections of 50mM glucose, and only a slight decrease in the electrochemical response was found. The selectivity of the CtCDH-based biosensor was tested on other potentially interfering carbohydrates such as mannose, galactose, sucrose, and fucose that might be present in blood. No significant analytical response from any of these compounds was observed.

Single-Walled Carbon Nanotubes Exhibit Limited Transport in Soil Columns

The increased production and commercial use of nanomaterials combined with a lack of regulation to govern their disposal may result in their introduction to soils and ultimately into groundwater systems. In this study, we investigated the transport behavior of carboxyl-functionalized single-walled carbon nanotubes (SWNTs) in columns packed with a natural soil. In general, SWNT deposition (filtration) rate increased with increasing solution ionic strength, with divalent cations (Ca(2+)) being more effective in increasing SWNT retention than monovalent cations (K(+)). However, SWNT deposition rate over a very wide range of monovalent and divalent cation concentrations (0.03 to 100 mM) was relatively high and changed only slightly above 0.3 mM KCl or 0.1 mM CaCl(2). In contrast, filtration of another type of engineered carbon-based nanomaterial, namely aqueous fullerene (C(60)) nanoparticles (radius of 51 nm), was more sensitive to solution ionic strength, displaying lower deposition rate and more effective transport in soil than SWNTs. These observations indicate that physical straining governs SWNT filtration and transport under all the solution chemistries investigated in the present study. It is proposed that SWNT shape and structure, particularly the very large aspect ratio and its highly bundled (aggregated) state in aqueous solutions, as well as the heterogeneity in soil particle size, porosity, and permeability, collectively contribute to straining in flow through soil media. Our results suggest that SWNTs of comparable properties to those used in the present study will not exhibit substantial transport and infiltration in soils because of effective retention by the soil matrix.

First Principles Calculations of Alanine Radicals Adsorbed on Pristine and Functionalized Carbon Nanotubes

The structural and electronic properties of alanine radicals adsorbed on pristine and carboxyl-functionalized (5,5) single-walled carbon nanotubes (SWCN) are investigated through ab initio calculations based on density functional theory. We find that the bonds between the alanine radicals and pristine SWCNs are stronger when the interaction occurs via the amine group. In particular, the strongest bond occurs for a structure where all C atoms belonging to the SWCN keep sp2-like hybridization. Interestingly, this is the only case where the system remains metallic. In all other cases, the systems result in a semiconductor or semiconductor with a half-filled level in the gap, depending on how the alanine radical is adsorbed. On the other hand, for carboxyl-functionalized SWCNs the properties of the systems do not significantly depend on how the alanine radical is absorbed.

Biocatalysts for fuel cells: efficient hydrogenase orientation for H2 oxidation at electrodes modified with carbon nanotubes

We report the modification of gold and graphite electrodes with commercially available carbon nanotubes for immobilization of Desulfovibrio fructosovorans [NiFe] hydrogenase, for hydrogen evolution or consumption. Multiwalled carbon nanotubes, single-walled carbon nanotubes (SWCNs), and amine-modified and carboxyl-functionalized SWCNs were used and compared throughout. Two separate methods were performed: covalent attachment of oriented hydrogenase by controlled architecture of carbon nanotubes at gold electrodes, and adsorption of hydrogenase at carbon-nanotube-coated pyrolytic graphite electrodes. In the case of self-assembled carbon nanotubes at gold electrodes, hydrogenase orientation based on electrostatic interaction with the electrode surface was found to control the electrocatalytic process for H(2) oxidation. In the case of carbon nanotube coatings on pyrolytic graphite electrodes, catalysis was controlled more by the geometry of the nanotubes than by the orientation of the enzyme. Noticeably, shortened SWCNs were demonstrated to allow direct electron transfer and generate high and quite stable current densities for H(2) oxidation via adsorbed hydrogenase, despite having many carboxylic surface functions that could yield unfavorable hydrogenase orientation for direct electron transfer. This result is attributable to the high degree of oxygenated surface functions in addition to the length of shortened SWCNs that yields highly divided materials.