Conducting nanocomposites of poly(N-vinylcarbazole) with single-walled carbon nanotubes

The in situ solid-state polymerization of N-vinylcarbazole (NVC) at an elevated temperature in the presence of single-walled carbon nanotubes (SWCNTs) leads to the formation of new types of composite materials, the morphology and properties of which were characterized by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and electrical property measurements. FTIR spectroscopy and XPS studies confirmed the ability of SWCNTs to initiate the in situ polymerization of NVC monomers. FE-SEM and TEM results showed the coating of the outer surfaces of SWCNTs by the PNVC hompolymer with separation of individual SWCNTs from the bundles. Thermogravimetric analysis revealed a moderate improvement in the thermal stability of the nanocomposites at a higher temperature region relative to the base polymer. The electrical conductivity of neat polymer dramatically improved in the presence of SWCNTs. For example, dc electrical conductivity increased from 10(-16)-10(-12) S x cm(-1) for neat PNVC to approximately 10(-6) S x cm(-1) for nanocomposite containing 9 wt% SWCNTs.     

Optical properties of single-walled carbon nanotubes functionalized with copolymer poly(3,4-ethylenedioxythiophene-co-pyrene)

Optical properties are reported for composites based on single-walled carbon nanotubes (SWNTs) and copolymer poly(3,4-ethylenedioxythiophene-co-pyrene) (PEDOT-Py) prepared by chemical polymerization of two monomers in the presence of carbon nanotubes. A charge transfer between SWNTs and the PEDOT-Py copolymer was demonstrated by Raman scattering. The increase in the relative intensity of the Raman lines peaked at 440–577 cm⁻¹, which were assigned to the ethylenedioxy ring vibrational modes, indicated a significant hindrance steric in the case of the composites based on the PEDOT-Py copolymer and metallic SWNTs. The increase in the absorbance of IR band peaked at 984 cm⁻¹ occurred simultaneously with the disappearance of the IR band at 1639 cm⁻¹. This finding was a consequence of the formation of new covalent bonds between SWNTs and the thiophene and benzene rings of the repeating units of the PEDOT-Py copolymer. The photoluminescence (PL) quenching process of the PEDOT-Py copolymer was induced by semiconducting SWNTs. The PL quenching of PEDOT-Py copolymer in the presence of SWNTs was demonstrated based on the energy level diagrams of the two constituents of the PEDOT-Py/SWNTs composite material.     

Ozonolysis of functionalized single-walled carbon nanotubes

Room temperature ozonolysis of fluorinated SWNT and phenyl-sulfonated SWNT have been studied in perfluoropolyether (PFPE) solvents. Etching at the end caps (approximately 70 nm/hour for fluorinated SWNT/PFPE suspension with 1 g/l concentration) has been demonstrated to be the dominating effect during the ozonolysis of fluorinated SWNT. Base on characterization by AFM analysis, X-ray Photoelectron Spectroscopy (XPS) and Raman Spectroscopy, fluorination along the SWNT sidewalls protects F-SWNT from extensive functionalization by ozonolysis. An ozone reaction with fluorinated SWNT has been found to improve its solubility in 96% sulfuric acid. This allows oxidative cutting by ammonium peroxydisulfate without defluorination. In comparison to fluorinated SWNT, phenyl-sulfonated SWNT was found to be effectively and homogeneous cut by ozonolysis in a water suspension.     

Poly(ethylene-co-vinyl alcohol) functionalized single-walled carbon nanotubes and related nanocomposites

Single-walled carbon nanotubes (SWNTs) were functionalized by poly(ethylene-co-vinyl alcohol) (EVOH) copolymer under carbodiimide-activated esterification reaction conditions. Similar to the parent EVOH copolymer, the EVOH-functionalized carbon nanotubes are soluble in highly polar solvent systems such as DMSO and hot ethanol-water mixtures. The soluble EVOH-SWNT sample was characterized by various techniques, including optical absorption, Raman, NMR, electron microscopy, and thermogravimetric analysis. The common solubility of EVOH and EVOH-SWNT allowed their intimate mixing in solution, and thus the fabrication of nanocomposites in which the SWNTs are homogeneously dispersed in the polymer matrix.     

Attachment of functionalized single-walled carbon nanotubes (SWNTs) to silicon surfaces

Single-walled carbon nanotubes (SWNTs) were functionalized by direct fluorination and subsequent reaction with 6-aminohexanoic acid for water-soluble carboxylic acid functionalized SWNTs (AHA-SWNTs). Both of the compounds were used as precursors to attach SWNTs to APTES coated silicon surfaces. AHA-SWNTs in aqueous solution were reacted with APTES self-assembled monolayers (SAMs) with coupling reagents N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide (EDC) and N-hydroxysuccinimide (NHS). The surface coverage is a function of concentration of AHA-SWNTs, solvent and coupling method. While for the fluorinated SWNTs (F-SWNTs), direct addition of F-SWNTs to preformed APTES SAMs at 90 degrees C shows essentially no reaction, in contrast to the one-pot reaction of F-SWNTs with APTES molecules in the presence of SWNTs on a silicon substrate. This reaction route provides a convenient method to attach SWNTs to silicon surfaces.     

In situ raman measurements of suspended individual single-walled carbon nanotubes under strain

We present a technique for in situ Raman measurements of suspended individual single-walled carbon nanotubes (SWNTs) under strain. We observe a strong change in the radial breathing mode intensity with increasing strain as the nanotube moves out of (or into) resonance, and for strain greater than approximately 2%, there is a clear irreversible upshift in the G-mode frequencies accompanied by an increase in intensity of a broad peak at a position associated with the D mode. For lower strain, the G-mode peaks (A1, E1, and E2) do not change significantly in position but change in relative intensity.     

RF response of single-walled carbon nanotubes

We present for the first time an in-depth study of the RF response of a single-walled carbon nanotube (SWCNT) rope. Our novel electrode design, based on a tapered coplanar approach, allows for single tube measurements well into the GHz regime, minimizing substrate-related parasitics. From the analysis of the S-parameters, the ac transport mechanism in the range 30 kHz to 6 GHz is established. This work is an essential prerequisite for the fabrication of high-speed devices based on bundles of nanowires or low-dimensional structures.     

聚乙烯咔唑合成工艺的研究

为了简化合成聚乙烯咔唑的工艺,采用自制相转移剂,以咔唑和1,2-二氯乙烷为原料,通过相转移反应研究了合成工艺,并用UV-vis、FT-IR、XRD、TG分析了合成物的结构和性能.研究表明:在反应温度60℃,常压条件下,合成氯乙基咔唑,产物脱去氯化氢得到乙烯咔唑.在氮气保护下,乙烯咔唑以苯做溶剂,以AIBN为引发剂,70℃下聚合反应40h得到聚乙烯咔唑.首次采用氮气作为乙烯咔唑溶液聚合反应的保护气体,获得具有较好品质的聚乙烯咔唑,降低了合成条件.     

Biocompatibility of native and functionalized single-walled carbon nanotubes for neuronal interface

Single-walled carbon nanotubes (SWNTs) have unique mechanical, electrical, and optical properties and can be easily chemically modified; features that make them excellent candidate materials for applications as sensors and stimulators in neuronal tissue engineering. The purpose of this study was to demonstrate that SWNTs can support neuronal attachment and growth, that simple chemical modifications can be employed to control cell growth, that SWNTs do not interfere with ongoing neuronal function, and that neurons can be electrically coupled to SWNTs. Growth and attachment of the neuroblastoma*glioma NG108, a model neuronal cell, was assessed on unmodified SWNT substrates or substrates from SWNTs modified with 4-benzoic acid or 4-tert-butylphenyl functional groups using a simple functionalization method. SWNT films support cell growth, but at a reduced level compared to tissue culture-treated polystyrene. The order of viability and cell attachment was tissue culture treated polystyrene > SWNTs > 4-tert-butylphenyl-functionalized SWNTs > 4-benzoic acid-functionalized SWNTs. Decreased cell growth after culture on untreated (non adherent) polystyrene suggested that cell attachment was a critical determinant of proliferation and cell growth on SWNTs. Fluorescence and scanning electron microscopy revealed decreased neurite outgrowth in NG108 grown on SWNT substrates. We are also among the first groups to demonstrate electrical coupling of SWNTs and neurons by demonstrating that NG108 and rat primary peripheral neurons showed robust voltage-activated currents when electrically stimulated through transparent, conductive SWNT films. Our data suggest that SWNTs are flexible resource materials for tissue engineering application involving electrically excitable tissues such as muscles and nerves.     

Chemically functionalized water soluble single-walled carbon nanotubes modulate neurite outgrowth

We report the use of chemically-functionalized water soluble single-walled carbon nanotube (SWNT) graft copolymers for modulation of outgrowth of neuronal processes. The graft copolymers were prepared by the functionalization of SWNTs with poly-m-aminobenzene sulphonic acid and polyethylene glycol. When added to the culturing medium, these functionalized water soluble SWNTs were able to increase the length of various neuronal processes.     

Near-infrared optical sensors based on single-walled carbon nanotubes

Molecular detection using near-infrared light between 0.9 and 1.3 eV has important biomedical applications because of greater tissue penetration and reduced auto-fluorescent background in thick tissue or whole-blood media. Carbon nanotubes have a tunable near-infrared emission that responds to changes in the local dielectric function but remains stable to permanent photobleaching. In this work, we report the synthesis and successful testing of solution-phase, near-infrared sensors, with beta-D-glucose sensing as a model system, using single-walled carbon nanotubes that modulate their emission in response to the adsorption of specific biomolecules. New types of non-covalent functionalization using electron-withdrawing molecules are shown to provide sites for transferring electrons in and out of the nanotube. We also show two distinct mechanisms of signal transduction-fluorescence quenching and charge transfer. The results demonstrate new opportunities for nanoparticle optical sensors that operate in strongly absorbing media of relevance to medicine or biology.     

Synthesis and characterization of multi-walled carbon nanotubes functionalized with hyperbranched poly(urea-urethane)

Two types of hyperbranched poly(urea-urethane)-functionalized multi-walled carbon nanotubes (GHPU) have been synthesized in the presence of bis- and tris-hydroxy terminated carbon nanotubes (MWNT-OH). For comparison of the grafting efficiency on carbon nanotubes, pure hyper-branched poly(urea-urethane)s (HPUs) were also synthesized to prepare pristine carbon nanotubes-reinforced nanocomposites (HPNTs). Better MWNT dispersion in the polymer matrix was obtained for GHPU than for HPNT, and the effect was superior in the case of highly branched GHPU from tris-hydroxy-functionalized MWNTs, compared to GHPU from bis-hydroxy-functionalized MWNTs. TEM measurements for GHPUs clearly showed hyperbranched polymer-wrapped MWNT structures. Crystallization of hyperbranched polymers in GHPU was more developed than that of the HPNT nanocomposites, although MWNT-induced crystallization was observed for both the GHPU and HPNT samples. The hyperbranched polymer-grafting effect on MWNTs resulted in greater enhancement of the mechanical properties of GHPU at the same nanotube loading, compared to the case of HPNT nanocomposites. However, a too highly branched structure was found to lower the crystallization and mechanical properties of both the GHPUs and HPNTs.     

Preparation and optical properties of a poly(N-vinylcarbazole) material

We report on the photorefractive properties of a stable polymeric material based on the host polymer, poly(N-vinylcarbazole). Two-beam coupling and four-wave mixing experiments were used to measure the performance of devices constructed by sandwiching the material, composed of host, plasticizer, photo-sensitizer, and non-linear optical chromophore, between transparent electrodes. A steady-state diffraction efficiency of 60% and a two-beam coupling gain of 22 cm^–1 in excess of the absorption of 4 cm^–1 were observed at the laser's operating wavelength of 670 nm. The devices are easily prepared and have lifetimes in excess of one year with no indication of degradation when stored at ambient temperatures.     

Chemically functionalized water-soluble single-walled carbon nanotubes modulate morpho-functional characteristics of astrocytes

We report the use of chemically functionalized water-soluble single-walled carbon nanotubes (ws-SWCNTs) for the modulation of morpho-functional characteristics of astrocytes. When added to the culturing medium, ws-SWCNTs were able to make astrocytes larger and stellate/mature, changes associated with the increase in glial fibrillary acidic protein immunoreactivity. Thus, ws-SWCNTs could have more beneficial effects at the injury site than previously thought; by affecting astrocytes, they could provide for a more comprehensive re-establishment of the brain computational power.     

Nanoscale optical imaging of excitons in single-walled carbon nanotubes

We present simultaneous near-field photoluminescence (PL) and Raman imaging of single-walled carbon nanotubes (SWNTs) with a spatial resolution better than 15 nm. Highly localized excitation is used to visualize the spatial extent of the contributing excited states. For SWNTs on glass, we typically observe highly confined PL from short segments of about 20 nm in length. The PL from micelle-encapsulated SWNTs on mica is extended along the tube up to several hundreds of nanometers. We find that near-field enhancement is much stronger for photoluminescence than for Raman scattering, an observation that is explained by the low intrinsic quantum yield of SWNTs.     

Ordered carbon nanotubes for optical power limiting devices

The electrospinning (ES) process was used to fabricate composite nanofibers (NFs) of poly(methyl methacrylate), PMMA, with embedded multiwalled carbon nanotubes (MWNTs) from a solution of PMMA in N,N-dimethylformamide (DMF) with homogenously dispersed MWNTs. Using both the sinklike and the elongation flows in the electrospinning process, we aligned the carbon nanotubes (CNTs) along the fiber axis. The NFs were subsequently deposited in an aligned manner on a glass surface using the electrostatic lens created by the edge of a rotating wheel collector. Semitransparent optical power limiter (OPL) films (~50% transmittance) were fabricated using an optically compatible polymeric resin infiltrated into the collected NFs. These comprised oriented NFs with different carbon nanotube loadings and film thicknesses. The OPLs exhibited high limiting abilities, with a limiting threshold of 1.5 J/cm(2) at about 50% linear transmittance. Some degree of polarization was also achieved, but significantly lower than expected because of the NF orientation.     

Mechano-optical modulation and optical limiting by multiwall carbon nanotubes

An optical limiting effect in multiwall carbon nanotubes was modulated by using a two-wave mixing experiment assisted with a mechanical actuator. We employed a 532 nm wavelength and 1 ns pulse duration for exciting the nonlinear optical absorption. The nanotubes were prepared by an aerosol pyrolysis method. The resulting samples were deposited on a pure silica substrate as an inhomogeneous thin film. The mechano-optical modulation was obtained by the orthogonal rotation of the sample with respect to the probe beam. In addition, low-irradiance patterns provided by a Michelson optical interferometer allowed us to comparatively corroborate the mechano-optical effect induced by the rotation of the film.     

An efficient nanocomposite based on carbon nanotubes functionalized with a fluorescent ink for ultrafast optical limiting

Functionalization of CNTs with different kinds of molecules is known to alter the optical properties of CNTs, leading to the development of new nanocomposites of interest to optoelctronics. This paper presents the design of a new and efficient optical limiting material based on carbon nanotubes (CNTs) functionalized with a commercial fluorescent ink. High resolution transmission electron microscopy (HRTEM) and optical spectroscopy indicate that the ink molecules get noncovalently attached to the surface of the CNTs. The mechanism of optical nonlinearity of the CNTs gets modified after functionalization. Z-scan studies on functionalized CNTs performed using mode-locked Ti:Sapphire femtosecond pulses at 780 nm reveal the predominance of two photon absorption (TPA). Efficient and low threshold ultrafast optical limiting is demonstrated in the new nanocomposite.     

Effects of single-walled carbon nanotubes on the optical and photo-conductive properties of their composite films with regio-regular poly(3-hexylthiophene)

The effect of a small admixture of single-walled carbon nanotubes (SWNTs) HiPCO (high pressure carbon monoxide) (from 0.5 to 2 wt%) on the supramolecular structure in regio-regular poly(3-hexylthiophene) (RR-P3HT) thin films is studied and their optical and photoconductivity properties are investigated. It is demonstrated that the presence of such small amounts of nanotubes improves the structural organization in the films as evidenced by X-ray diffraction (XRD) studies. This is confirmed by UV–visible optical absorption investigations which clearly show a better conjugation of P3HT in the presence of nanotubes. In Raman spectra of composites, changes in intensities and frequencies of the radial breathing modes are observed upon addition of nanotubes. This can be rationalized by a modification of the resonance conditions caused by a selective dispersion and wrapping of SWNTs via π-interaction (π-stacking). As a consequence of these interactions, a dramatic photoluminescence (PL) quenching is observed which becomes more and more pronounced with increasing the nanotube content. This implies a fast photo-induced electron transfer favoured by a large area of the SWNTs/P3HT interface and strong interactions between these two components. An increase in the composite photocurrent by at least one-order of magnitude, as compared to the case of pure P3HT film, is the most pronounced effect of this electron transfer. These two effects are of crucial importance for the application of the investigated composites in bulk hetero-junction photovoltaic cells (BHJPCs) and organic photo-detectors (OPDs).