Fluorescence spectroscopy of single-walled carbon nanotubes in aqueous suspension

Optical studies of single-walled carbon nanotubes have advanced greatly through the recent discovery of near-infrared band gap photoluminescence from single-walled carbon nanotubes (SWNT) isolated in aqueous surfactant suspensions. This fluorescence emission has enabled the detection of many distinct optical transitions and their assignment to specific (n,m) semiconducting species of SWNT. The resulting set of precise transition energies presents a challenge to current theoretical models of nanotube electronic structure and a guide to nanotube researchers using resonance Raman spectroscopy. In the near future, structure-resolved fluorimetry should prove useful for revealing the quantitative (n,m) composition of mixed SWNT samples through sensitive, rapid, and nondestructive measurements. It will also permit detailed studies of many physical and chemical processes that vary with nanotube structure. PACS 71.35.Cc; 78.67.Ch; 78.67.-n     

Demetalization of single-walled carbon nanotube thin films with microwave irradiation

The microwave irradiation effects on purified HiPCO and CoMoCat single-walled carbon nanotube (SWNT) thin films are investigated. The surface conductivities of the SWNT films are extracted from the measured THz transmission coefficients to provide a direct indication of the metallic content in the films. The observed drastic conductivity decrease indicates a significant metallic content reduction after the microwave irradiation. Two different laser excitations are applied for Raman spectroscopy to reveal the response of different nanotube species. The Raman spectra of both HiPCO and CoMoCat thin films confirm the decrease of metallic carbon nanotubes. The observed microwave-induced effects may potentially lead to a convenient scheme for demetalization of single-walled carbon nanotube mixtures.     

Electrochemical functionalisation of SWNTs with poly(3,4‐ethylenedioxythiophene) evidenced by anti‐Stokes/Stokes Raman spectroscopy

The capability of anti‐Stokes/Stokes Raman spectroscopy to evaluate chemical interactions at the interface of a conducting polymer/carbon nanotubes is demonstrated. Electrochemical polymerisation of the monomer 3,4‐ethylenedioxythiophene (EDOT) on a Au support covered with a single‐walled carbon nanotube (SWNT) film immersed in a LiClO₄/CH₃CN solution was carried out. At the resonant optical excitation, which occurs when the energy of the exciting light coincides with the energy of an electronic transition, poly(3,4‐ethylenedioxythiophene) (PEDOT) deposited electrochemically as a thin film of nanometric thickness on a rough Au support presents an abnormally intense anti‐Stokes Raman spectrum. The additional increase in Raman intensity in the anti‐Stokes branch observed when PEDOT is deposited on SWNTs is interpreted as resulting from the excitation of plasmons in the metallic nanotubes. A covalent functionalisation of SWNTs with PEDOT both in un‐doped and doped states takes place when the electropolymerisation of EDOT, with stopping at +1.6 V versus Ag/Ag⁺, is performed on a SWNT film deposited on a Au plate. The presence of PEDOT covalently functionalised SWNTs is rationalised by (1) a downshift by a few wavenumbers of the polymer Raman line associated with the symmetric C C stretching mode and (2) an upshift of the radial breathing modes of SWNTs, both variations revealing an interaction between SWNTs and the conjugated polymer. Raman studies performed at different excitation wavelengths indicate that the resonant optical excitation is the key condition to observe the abnormal anti‐Stokes Raman effect. Copyright © 2010 John Wiley & Sons, Ltd.     

Biophysical and electrochemical properties of Self-assembled noncovalent SWNT/DNA hybrid and electroactive nanostructure

DNA self-assembled hybrid nanostructures are widely used in recent research in nanobiotechnology. Combination of DNA with carbon based nanoparticles such as single-walled carbon nanotube (SWNT), multi-walled carbon nanotube (MWNT) and carbon quantum dot were applied in important biological applications. Many examples of biosensors, nanowires and nanoelectronic devices, nanomachine and drug delivery systems are fabricated by these hybrid nanostructures. In this study, a new hybrid nanostructure has been fabricated by noncovalent interactions between single or double stranded DNA and SWNT nanoparticles and biophysical properties of these structures were studied comparatively. Biophysical properties of hybrid nanostructures studied by circular dichroism, UV–vis and fluorescence spectroscopy techniques. Also, electrochemical properties studied by cyclic voltammetry, linear sweep voltammetry, square wave voltammetry, choronoamperometry and impedance spectroscopy (EIS). Results revealed that the biophysical and electrochemical properties of SWNT/DNA hybrid nanostructures were different compare to ss-DNA, ds-DNA and SWNT singly. Circular dichroism results showed that ss-DNA wrapped around the nanotubes through π-π stacking interactions. The results indicated that after adding SWNT to ss-DNA and ds-DNA intensity of CD and UV–vis spectrum peaks were decreased. Electrochemical experiments indicated that the modification of single-walled carbon nanotubes by ss-DNA improves the electron transfer rate of hybrid nanostructures. It was demonstrated SWNT/DNA hybrid nanostructures should be a good electroactive nanostructure that can be used for electrochemical detection or sensing.     

碳纳米管掺杂对聚合物聚(2-甲氧基-5-辛氧基)对苯乙炔-PbSe量子点复合材料性能的影响

基于碳纳米管的良好导电性、激子传输性能和量子点聚合物复合材料高的光电转换性能, 采用原位缩合法制备了聚合物聚(2-甲氧基-5-辛氧基)-对苯乙炔(MOPPV)功能化碳纳米管(SWNT)-PbSe量子点复合材料, 通过对复合材料的X射线衍射、透射电子显微镜和紫外可见吸收光谱研究, 发现MOPPV, SWNT与PbSe量子点可以有效地复合, 且SWNT与MOPPV形成网状结构; PbSe量子点尺寸为5.75 nm, 其可均匀地分散在MOPPV-SWNT基体中形成包覆或镶嵌结构, 并发生了光诱导电荷转移.通过对复合材料的光电性能研究发现, 当MOPPV, SWNT, PbSe三者的质量比为1: 0.3 : 1 时其光电性能最好, 开路电压为0.556 V, 短路电流为2.133 mA, 填充因子为34.48%, 转换效率为0.452%, 与聚合物MOPPV-PbSe量子点复合材料材料相比, 光电性能提高了2–3倍. 关键词： 量子点 碳纳米管 复合材料 转换效率     

Resonant Raman spectroscopy and spectroelectrochemistry characterization of carbon nanotubes/polyaniline thin film obtained through interfacial polymerization

Thin, transparent, and self‐assembled films of neat polyaniline and polyaniline/carbon nanotube nanocomposites were deposited over glass substrates by interfacial polymerization. The effect of the carbon nanotubes on the structure and conformation of the polyaniline, and the type of interaction between the polymer and the nanotubes, have been studied by resonant Raman spectroscopy and UV–Vis and Raman spectroelectrochemistry. The results indicate clearly that the carbon nanotubes induce important changes in the electronic structure of the polymer, resulting in a more polaronic organization. Additionally, an effective interaction between the polymer and the nanotube, based on a polyaniline‐to‐nanotube charge transfer, is proposed in this work. Copyright © 2012 John Wiley & Sons, Ltd.     

Computational analysis of effect of modification on the interfacial characteristics of a carbon nanotube-polyethylene composite system

In this study, the non-covalent association of single-walled nanotube (SWNT) with polyethylene (PE) molecule and the influence of sidewall modification on the interfacial bonding between the SWNTs and polymer were investigated using molecular mechanics (MM) and molecular dynamics (MD) simulations. The model of interaction between the initially separated PE and SWNT fragments, which can be either wrapping or filling, was computed. The possible extension of polymers wrapping or filling SWNTs can be used to structurally bridge the SWNTs and polymers to significantly improve the load transfer between them when SWNTs are used to produce nanocomposites. The interfacial bonding characteristics between the single-walled nanotubes, on which -COOH, -CONH₂, -C₆H₁₁, or -C₆H₅ groups have been chemically attached, and the polymer matrix were also investigated by performing pullout simulations. The results show that appropriate functionalization of nanotubes at low densities of functionalized carbon atoms drastically increase their interfacial bonding and shear stress between the nanotubes and the polymer matrix, where chemisorption with -C₆H₅ groups to as little as 5.0% of the nanotube carbon atoms increases the shear stress by about 1700%. Furthermore, this suggests the possibility to use functionalized nanotubes to effectively reinforce other kinds of polymer-based materials as well.     

Raman‐induced Kerr effect spectroscopy of single‐wall carbon nanotubes aqueous suspensions in the range 0.1–10 and 100–250 cm−1

Here, we study a low (less than 0.1 µg/ml) concentration aqueous suspension of single‐wall carbon nanotubes (SWNTs) by Raman‐induced Kerr effect spectroscopy (RIKES) in the spectral bands 0.1–10 and 100–250 cm⁻¹. This method is capable of carrying out direct investigation of SWNT hydration layers. A comparison of RIKES spectra of SWNT aqueous suspension and that of milli‐Q water shows a considerable growth in the intensity of low wavenumber Raman modes. These modes in the 0.1–10 cm⁻¹ range are attributed to the rotational transitions of H₂O₂ and H₂O molecules. We explain the observed intensity increase as due to the production of hydrogen peroxide and the formation of a low‐density depletion layer on the water–nanotube interface. A few SWNT radial breathing modes (RBM)are observed (ω_RBM = 118.5, 164.7 and 233.5 cm⁻¹) in aqueous suspension, which allows us to estimate the SWNT diameters (∼2.0, 1.5, and 1 nm, respectively). Copyright © 2011 John Wiley & Sons, Ltd.     

X-ray irradiation effect of double walled carbon nanotube

We have studied double-walled carbon nanotube (DWNT) irradiated by soft X-ray by Raman scattering spectroscopy and the spectral characteristics are compared to single-walled carbon nanotube (SWNT) irradiated under the same condition. We proved that DWNT is more stable for the X-ray induced defect formation than SWNT. Moreover, we found that the outer tube of DWNT was more sensitive on X-ray irradiation than the inner tube. The defect was recovered by annealing in Ar at lower temperature than that of SWNT. Based on these results, we inferred that X-ray irradiation leads to formation of interstitial-vacancy pairs, Frenkel defects, in carbon nanotube. The interstitial-vacancy separation on the inner tube of DWNT is conceivably shorter than that of the outer tube.     

Transport properties of poly(GACT)-poly(CTGA) deoxyribonucleic acid: A ladder model approach

In this paper, based on the tight-binding Hamiltonian model and within the framework of a generalized Green’s function technique, the electronic conduction through the poly(GACT)-poly(CTGA) DNA molecule in SWNT/DNA/SWNT structure has been numerically investigated. In a ladder model, we consider DNA as a planar molecule containing M cells and four further sites (two base pair sites and two backbone sites) in each cell, sandwiched between two semi-infinite single-walled carbon nanotubes (SWNT) as the electrodes. Having relied on Landauer formalism, we focussed on studying the current-voltage characteristics of DNA, the effect of the coupling strength of SWNT/DNA interface and the role of tube radius of nanotube contacts on the electronic transmission through the foregoing structure. Finally, a characteristic time was calculated for the electron transmission, which measures the delay caused by the tunnelling through the SWNT/DNA interface. The results clearly show that the calculated characteristic time and also the conductance of the system are sensitive to the coupling strength between DNA molecule and nanotube contacts.     

Magnetoadsorptive Particles Enabling the Centrifugation‐Free,Preparative‐Scale Separation,and Sorting of Single‐Walled Carbon Nanotubes

A novel magnetic composition of the high surface area particles with amide chemical functionality, Sephacryl S‐200, is reported enabling the preparative‐scale (1 L, ≈5–10 mg) separation of metallic and semiconducting single‐walled carbon nanotubes (SWNT) from completely unpurified and uncentrifuged nanotube stocks. Sephacryl S‐200 has previously been utilized in separating semiconducting SWNT (s‐SWNT) on the laboratory scale. Significantly, use of these magnetic derivative particles in absorptive separation of SWNT allows the unprecedented and industrially scalable purification of both metallic SWNT (m‐SWNT) as well as s‐SWNT directly from uncentrifuged, ultrasonicated surfactant‐based SWNT solutions by simple and scalable magnetic separation. These particles also allowed for the systematic study on the effect of SWNT–polymer interaction time on the resulting SWNT “payloads.” Ultimately, high ‐purity m‐SWNT and s‐SWNT products are independently achieved by controlling the SWNT–polymer interaction time and relative concentrations, as well as SWNT sonication conditions. Furthermore, by controlling these factors, single‐chirality (6,5) s‐SWNT can be isolated with 92% purity directly from unpurified stocks. Thermogravimetric analysis indicates a total process SWNT yield of 1.2% and 1.7% for m‐SWNT and s‐SWNT, respectively. These results demonstrate the potential for a preparative method for separating carbon nanotubes based on electronic properties.     

Optical transition energies for carbon nanotubes from resonant Raman spectroscopy: environment and temperature effects

This Letter reports the laser energy dependence of the Stokes and anti-Stokes Raman spectra of carbon nanotubes dispersed in aqueous solution and within solid bundles, in the energy range 1.52-2.71 eV. The electronic transition energies (E(ii)) and the radial breathing mode frequencies (omega(RBM)) are obtained for 46 different (18 metallic and 28 semiconducting) nanotubes, and the (n,m) assignment is discussed based on the observation of geometrical patterns for E(ii) versus omega(RBM) graphs. Only the low energy component of the E(M)(11) value is observed from each metallic nanotube. For a given nanotube, the resonant window is broadened and down-shifted for single wall carbon nanotube (SWNT) bundles compared to SWNTs in solution, while by increasing the temperature, the E(S)(22) energies are redshifted for S1 [(2n+m) mod 3=1] nanotubes and blueshifted for S2 [(2n+m) mod 3=2] nanotubes.     

Effect of PVA functionalization on hydrophilicity of Y-junction single wall carbon nanotubes

Hydrophilic surface of carbon nanotubes (CNTs) are of great interest for various applications including chemical and biological sensing. Surface functionalization of single wall carbon nanotubes (SWNTs) mats with a biocompatible polymer polyvinyl alcohol (PVA) was studied. PVA modification induced a drastic change in water wettability of the SWNT surface transforming it from hydrophobic to highly hydrophilic. These PVA modified SWNTs mats have also demonstrated increasing impedance variation in relative humidity compared to the pristine nanotubes. An appreciable change in conductivity of Y-junction SWNT mats as a function of relative humidity indicates its potential application as humidity sensor. This higher sensitivity for humidity variation shown in Y-junction SWNT mats could be attributed to the greater portion of semiconducting nanotubes in these mats revealed by Raman analysis. A possible conductance changing mechanism of surface modified SWNTs mats is discussed.     

利用径向呼吸模及其倍频模的共振特性精确测定单壁碳纳米管的电子跃迁能量

提出一个根据拉曼基频模及其倍频模的斯托克斯和反斯托克斯拉曼成分的不同共振行为来探测样品与激光共振的系统能级的方法.此方法被应用到不均匀单壁碳纳米管束样品中某一径向呼吸模频率为219波数的金属型碳纳米管.通过分析呼吸模及其倍频模和切向模的共振行为,获得了该碳纳米管的电子跃迁能量,并获得纳米管C-C最近邻重叠积分因子为2.80 eV.此数值可以很好的解释单壁碳纳米管径向呼吸模的共振行为. 关键词： 单壁碳纳米管 呼吸模 共振拉曼散射 电子跃迁能     

Visible fluorescence induced by the metal semiconductor transition in composites of carbon nanotubes with noble metal nanoparticles

We show that single-walled carbon nanotube (SWNT) bundles emit visible fluorescence in the presence of noble metal nanoparticles and nanorods in the solid state. Conductivity measurements with metallic nanotubes, isolated from pristine SWNTs, show that they become semiconducting in the presence of the metal nanoparticles. Nanoparticle binding increases the defects in the nanotube structures which is evident in the Raman spectra. The metal-semiconductor transition removes the nonradiative decay channels of the excited states enabling visible fluorescence. Nanotube structures are imaged using this emission with resolution below the classical limits.     

Dielectric response of aligned semiconducting single-wall nanotubes

We report measurements of the full intrinsic optical anisotropy of isolated single-wall carbon nanotubes (SWNTs). By combining absorption spectroscopy with transmission ellipsometry and polarization-dependent resonant Raman scattering, we obtain the real and imaginary parts of the SWNT permittivity from aligned semiconducting SWNTs dispersed in stretched polymer films. Our results are in agreement with theoretical predictions, highlighting the limited polarizability of excitons in a quasi-1D system.     

Production and characterization of polymer nanocomposite with aligned single wall carbon nanotubes

We reported a simple method to fabricate polymer nanocomposites with single-walled carbon nanotubes (SWNTs) having exceptional alignment and improved mechanical properties. The composite films were fabricated by casting a suspension of single walled carbon nanotubes in a solution of thermoplastic polyurethane and tetrahydrofuran. The orientation as well as dispersion of nanotubes was determined by scanning electron microscopy, transmission electron microscopy and polarized Raman spectroscopy. The macroscopic alignment probably results from solvent-polymer interaction induced orientation of soft segment chain during swelling and moisture curing. The tensile behavior of the aligned nanotube composite film was also studied. At a 0.5 wt.% nanotube loading, a 1.9-fold increase in Young's modulus was achieved.     

An efficient route towards the covalent functionalization of single walled carbon nanotubes

A simple and efficient method of chemical functionalization of both single and multiwalled carbon nanotubes has been discussed to give enhanced water solubility by rapidly and efficiently generating an appreciable amount of hydrophilic functional groups using microwave radiation. Surface functionalization containing more than 30 wt% of oxygen has been achieved, resulting into solubility of 2–5 mg/mL. Further covalent functionalization of such soluble SWNTs provides a remarkable degree of aniline functionalization through amidation, where the formation of polyaniline has been avoided. Functionalization of SWNTs is confirmed by techniques like electron microscopy, Fourier transform infrared spectroscopy, thermogravimetry, Raman spectroscopy, cyclic voltammetry and impedance spectroscopy. Electrochemical analysis suggests an enhanced double layer capacitance (110 F/g) of nanotubes after microwave treatment. Aniline functionalization of SWNTs shows possible variations on the nanotube topography with concomitant formation of a dynamic polymer layer on the nanotube surface.     

Raman and SERS studies of carbon nanotube systems

In this paper, we report on Raman studies carried out on different carbon nanotube systems, namely single-walled and multi-walled carbon nanotubes and polymer/nanotube composites. We focus on different types of interactions which can take place in these materials. In single-walled nanotubes, the introduction of van der Waals interactions between tubes when arranged in bundles leads to an upshift of the radial breathing mode (RBM) ranging from 11 to 16 cm⁻¹ depending on the size of the bundle. In multi-walled carbon nanotubes, similar interactions between concentric tubes permit to interpret the low frequency Raman modes. In composites, PMMA/nanotubes, an upshift of the RBM is also observed, explained by the dynamical strain applied by the polymer on the bundles, in response to the breathing vibration. In addition, surface enhanced Raman scattering experiments have demonstrated the occurrence of interfacial reactions between the nanotubes and the metallic support. This is put in evidence by the degradation of tubes, especially metallic ones, and reconstruction of C₆₀-like molecules are in some cases observed.     

Detection of invisible phonon modes in individual defect-free carbon nanotubes by gradient-field Raman scattering

We provide an effective method to investigate the field gradient effect in nanoconfined plasmon-matter interaction.Aligned ultralong SWNTs without defects were grown on marked substrates, followed by assembling gold nanoparticle clusters around individual nanotubes. The Raman scattering behavior of a nanotube placed in an atomic scale nanogap between adjacent nanoparticles was studied. In addition to the expected plasmon-induced Raman enhancement up to 103,the defect-free D-mode of an individual SWNT induced by gradient field is found for the first time. When the light is confined at atomic scale, gradient field Raman scattering becomes significant and dipole-forbidden phonon modes can be activated by quadrupole Raman tensor variation, indicating breakdown of the Raman selection rules.