Overcoming the insolubility of carbon nanotubes through high degrees of sidewall functionalization

The use of carbon nanotubes in materials applications has been slowed due to nanotube insolubility and their incompatibility with polymers. We recently developed two protocols to overcome the insoluble nature of carbon nanotubes by affixing large amounts of addends to the nanotube sidewalls. Both processes involve reactions with aryl diazonium species. First, solvent-free functionalization techniques remove the need for any solvent during the functionalization step. This delivers functionalized carbon nanotubes with increased solubility in organic solvents and processibility in polymeric blends. Additionally, the solvent-free functionalization process can be done on large scales, thereby paving the way for use in bulk applications such as in structural materials development. The second methodology involves the functionalization of carbon nanotubes that are first dispersed as individual tubes in surfactants within aqueous media. The functionalization then ensues to afford heavily functionalized nanotubes that do not re-rope. They remain as individuals in organic solvents giving enormous increases in solubility. This protocol yields the highest degree of functionalization we have obtained thus far-up to one in nine carbon atoms on the nanotube has an organic addend. The proper characterization and solubility determinations on nanotubes are critical; therefore, this topic is discussed in detail.     

Room-temperature icelike water in kanemite detected by 2H NMR T1 relaxation

2H NMR was used to study the nature of deuterated water in kanemite. Evidence is presented that shows that the water changes state from liquid to solid at room temperature during the hydration reaction that forms kanemite. The deuterium nuclei in the water experience rapid tetrahedral jumps in a hydrogen-bonded lattice like those observed in 2H2O ice.     

Covalent Functionalization of Single-Walled Carbon Nanotubes Through the Fluorination Stage for Integration into an Epoxy Composite

The upper limit of the elastic modulus has been estimated for a polymer–carbon nanotube–epoxy matrix nanocomposite. This limit can be achieved if the nanotubes are integrated into the matrix, i.e., they form a continuous reinforcing network inside the matrix, and if the nanotubes are single-walled or double-walled carbon nanotubes. A technique for carbon nanotube functionalization via fluorination and fluorine substitution and a technique for calculating the degree of nanotube functionalization based on reaction yield measurements are proposed. For fluorine substitution by epoxy-diane resin and diaminodiphenylmethane, the degree of functionalization is С–(FG)_x, x ~ 0.011–0.013 and the FG-molecular fragment containing the epoxy (amino) group corresponding to functionalization of ~5% of the surface С atoms of nanotubes. The control reaction showed that the epoxy groups preserve the chemical activity, while part of the amino groups are deactivated. The grafted epoxy(amino) groups ensure nanotube surface lyophilicity in epoxy composites and integrate the nanotubes into the epoxy matrix owing to the chemical bonds.     

Synthesis and characterization of deuterated poly(arylene ether sulfones)

Selectively deuterated poly(arylene ether sulfones) were prepared for neutron scattering studies and for deuterium NMR investigations. The availability of these model macromolecules permits molecular-level identification of the motions responsible for the low temperature relaxations that have been observed in the dynamic mechanical spectra of these engineering polymers. Three labeled sites on the appropriate monomers (bisphenol-A and 4,4′-dichlorodiphenylsulfone) were prepared from deuterated intermediates and characterized via chromatographic, spectroscopic, and thermal analysis. The deuterium exhcange between methyl and aromatic sites that occurred during synthesis was quantified. These labeled monomers were mixed with hydrogenous monomers to synthesize high molecular weight, selectively deuterated poly(arylene ether sulfones). A synthetic technique involving N-methyl-2-pyrrolidone/potassium carbonate was employed to afford high molecular weight polymers. The polymers were characterized by FT-IR, proton, carbon, and deuterium NMR, intrinsic viscosities, and thermal analysis. Molecular weights of the labeled polymers were similar to unlabeled systems.     

Visible luminescence of carbon nanotubes and dependence on functionalization

Strong luminescence emissions over a broad wavelength region were detected from well-dispersed carbon nanotubes in most functionalized samples, even with excitation wavelengths into the near-IR. Apparently, the better dispersion and functionalization of the nanotubes resulted in more intense luminescence emissions. These emissions may logically be attributed to the trapping of excitation energy by defect sites in the nanotube structure, which are passivated upon the appropriate functionalization of the nanotubes. Better functionalization improves not only the nanotube dispersion (thus diminishing the quenching due to intertube interactions) but also the surface passivation to make the energy trapping sites more emissive, leading to stronger luminescence emissions. Because of such high sensitivity, the visible luminescence emissions may prove valuable in the evaluation of dispersion in functionalized carbon nanotube samples and related nanocomposite materials.     

Protonation of carbon single-walled nanotubes studied using 13C and 1H-13C cross polarization nuclear magnetic resonance and Raman spectroscopies

The reversible protonation of carbon single-walled nanotubes (SWNTs) in sulfuric acid and Nafion was investigated using solid-state nuclear magnetic resonance (NMR) and Raman spectroscopies. Magic-angle spinning (MAS) was used to obtain high-resolution 13C and 1H-13C cross polarization (CP) NMR spectra. The 13C NMR chemical shifts are reported for bulk SWNTs, H2SO4-treated SWNTs, SWNT-Nafion polymer composites, SWNT-AQ55 polymer composites, and SWNTs in contact with water. Protonation occurs without irreversible oxidation of the nanotube substrate via a charge-transfer process. This is the first report of a chemically induced change in a SWNT 13C resonance brought about by a reversible interaction with an acidic proton, providing additional evidence that carbon nanotubes behave as weak bases. Cross polarization was found to be a powerful technique for providing an additional contrast mechanism for studying nanotubes in contact with other chemical species. The CP studies confirmed polarization transfer from nearby protons to nanotube carbon atoms. The CP technique was also applied to investigate water adsorbed on carbon nanotube surfaces. Finally, the degree of bundling of the SWNTs in Nafion films was probed with the 1H-13C CP-MAS technique.     

A study of the stability of aqueous suspensions of functionalized carbon nanotubes

The properties of aqueous suspensions of carbon nanotubes have been studied as depending on the conditions of their functionalization in a mixture of sulfuric and nitric acids. The elemental composition and contents of carboxyl, lactone, and hydroxyl groups in carbon nanotubes have been determined at different durations and temperatures of functionalization. The influence of functionalization conditions on the value of the electrokinetic potential of carbon nanotubes in aqueous suspensions and the nanotube solubility in water has been investigated. It has been found that the absolute value of the electrokinetic potential of nanotubes and their solubility in water increase with both the duration and temperature of functionalization due to a rise in the number of functional groups on their surface. The optimal regimes of functionalization of carbon nanotubes have been determined from the point of view of preserving their structure and stability in aqueous dispersions.     

Preparation of micelle-encapsulated single-wall and multi-wall carbon nanotubes with amphiphilic hyperbranched polymer

The hyperbranched polyester (Boltorn^TM H20) was modified by maleic anhydride and then polystyrene (H20-MAh-PSt) to form amphiphilic micelles in water. The single-wall and multi-wall carbon nanotubes (SWCNTs and MWCNTs, respectively) were encapsulated in the formed micelles through non-covalent interactions. The formed structures were confirmed by FTIR, NMR, GPC, and XPS analysis. The dispersion and aggregation behaviors were observed by TEM and UV-vis and Raman spectroscopic analysis. The results showed that the dispersion performance of the obtained micelle-encapsulated carbon nanotubes in water was greatly improved compared to the pure carbon nanotubes. From the TEM observation, the individual SWCNT structure and the uniform polymer coating around the surface of SWCNT were seen after crosslinking. The Raman spectroscopic measurements also demonstrated that for the crosslinked samples, no effect occurred associated with concentration-dependent carbon nanotube aggregation.     

Lipid bilayers covalently anchored to carbon nanotubes

The unique physical and electrical properties of carbon nanotubes make them an exciting material for applications in various fields such as bioelectronics and biosensing. Due to the poor water solubility of carbon nanotubes, functionalization for such applications has been a challenge. Of particular need are functionalization methods for integrating carbon nanotubes with biomolecules and constructing novel hybrid nanostructures for bionanoelectronic applications. We present a novel method for the fabrication of dispersible, biocompatible carbon nanotube-based materials. Multiwalled carbon nanotubes (MWCNTs) are covalently modified with primary amine-bearing phospholipids in a carbodiimide-activated reaction. These modified carbon nanotubes have good dispersibility in nonpolar solvents. Fourier transform infrared (FTIR) spectroscopy shows peaks attributable to the formation of amide bonds between lipids and the nanotube surface. Simple sonication of lipid-modified nanotubes with other lipid molecules leads to the formation of a uniform lipid bilayer coating the nanotubes. These bilayer-coated nanotubes are highly dispersible and stable in aqueous solution. Confocal fluorescence microscopy shows labeled lipids on the surface of bilayer-modified nanotubes. Transmission electron microscopy (TEM) shows the morphology of dispersed bilayer-coated MWCNTs. Fluorescence quenching of lipid-coated MWCNTs confirms the bilayer configuration of the lipids on the nanotube surface, and fluorescence anisotropy measurements show that the bilayer is fluid above the gel-to-liquid transition temperature. The membrane protein α-hemolysin spontaneously inserts into the MWCNT-supported bilayer, confirming the biomimetic membrane structure. These biomimetic nanostructures are a promising platform for the integration of carbon nanotube-based materials with biomolecules.     

Protein-assisted solubilization of single-walled carbon nanotubes

We report a simple method that uses proteins to solubilize single-walled carbon nanotubes (SWNTs) in water. Characterization by a variety of complementary techniques including UV-Vis spectroscopy, Raman spectroscopy, and atomic force microscopy confirmed the dispersion at the individual nanotube level. A variety of proteins differing in size and structure were used to generate individual nanotube solutions by this noncovalent functionalization procedure. Protein-mediated solubilization of nanotubes in water may be important for biomedical applications. This method of solubilization may also find use in approaches for controlling the assembly of nanostructures, and the wide variety of functional groups present on the adsorbed proteins may be used as orthogonal reactive handles for the functionalization of carbon nanotubes.     

Carbon nanotube sidewall functionalization with carbonyl compounds--modified Birch conditions vs the organometallic reduction approach

Covalent addition reactions turned out to be one of the most important functionalization techniques for a structural alteration of single walled carbon nanotube (SWCNT) scaffolds. During the last years, several reaction sequences based on an electrophilic interception of intermediately generated SWCNT(n-) carbanions, obtained via Birch reduction or by a nucleophilic addition of organometallic species, have been developed. Nevertheless, the scope and the variety of potential electrophiles is limited due to the harsh reaction conditions requested for a covalent attachment of the functional entities onto the SWCNT framework. Herein, we present a significant modification of the reductive alkylation/arylation sequence, the so-called Billups reaction, which extends the portfolio of electrophiles for covalent sidewall functionalization to carbonyl compounds--ketones, esters, and even carboxylic acid chlorides. Moreover, these carbonyl-based electrophiles can also be used as secondary functionalization reagents for anionic SWCNT intermediates, derived from a primary nucleophilic addition step. This directly leads to the generation of mixed functional SWCNT architectures, equipped with hydroxyl or carbonyl anchor groups, suitable for ongoing derivatization reactions. A correlated absorption and emission spectroscopic study elucidates the influence of the covalent sidewall functionalization degree onto the excitonic transition features of carbon nanotubes. The characterization of the different SWCNT adducts has been carried out by means of Raman, UV-vis/nIR, and fluorescence spectroscopy as well as by thermogravimetric analysis combined with mass spectrometry and X-ray photoelectron spectroscopy analysis.     

Characterization of a tamoxifen-tethered single-walled carbon nanotube conjugate by using NMR spectroscopy

We report the synthesis and characterization of a tamoxifen-tethered single-walled carbon nanotube (SWCNT) conjugate, in which tamoxifen is covalently attached to the single-walled carbon nanotube via oxidation and esterification reactions for the first time. The functionalized SWCNT derivative was characterized by using spectroscopic techniques: IR, UV-vis, Raman, and (1)H NMR Spectroscopy. The attachment of the drug tamoxifen to SWCNTs is analogous to the gold conjugate, which provided an endocrine treatment for breast cancer.     

聚丙烯酸功能化多壁碳纳米管

Covalent functionalization of multiwalled carbon nanotubes （MWNT） with poly（acrylic acid） has been successfully achieved via grafting of poly（acryloyl chloride） on nanotube surface by esterification reaction of acyl chloride-bound polymer with hydroxyl functional groups present on acid-oxidized MWNT and hydrolysis of polymer attached to nanotubes. Polymer-functionalized MWNT could possess remarkably high solubility in water, and their aqueous solution was very stable without any observable black deposit for a long time. Characterizations of such functionalized MWNT samples using Fourier transform infrared spectrometer, transmission electron microscopy and nuclear magnetic resonance techniques indicated that poly（acrylic acid） was covalently attached to the surface of MWNT.     

NMR detection of single-walled carbon nanotubes in solution

The detection of nanotube carbons in solution by (13)C NMR is reported. The highly soluble sample was from the functionalization of (13)C-enriched single-walled carbon nanotubes (SWNTs) with diamine-terminated oligomeric poly(ethylene glycol) (PEG(1500N)). The ferromagnetic impurities due to the residual metal catalysts were removed from the sample via repeated magnetic separation. The nanotube carbon signals are broad but partially resolved into two overlapping peaks, which are tentatively assigned to nanotube carbons on semiconducting (upfield) and metallic (downfield) SWNTs. The solid-state NMR signals of the same sample are similarly resolved. Mechanistic and practical implications of the results are discussed.     

Experimental and Computational Investigations of the Properties of Fluorinated Single‐Walled Carbon Nanotubes

Fluorination of single‐walled carbon nanotubes by reaction with elemental fluorine at elevated temperatures provides fluorinated single‐walled carbon nanotubes (F‐SWNT), which have the highest degree of functionalization (up to F/C=1/2) of any derivatized carbon‐nanotube material reported to date. Also, F‐SWNTs have received more scrutiny than any other functionalized carbon nanotubes. This Minireview covers experimental and computational investigations of F‐SWNTs with a focus on the nature and the strength of the C–F linkage.     

Polymer-masking for controlled functionalization of carbon nanotubes

An effective and versatile method for tube-length-specific functionalization of carbon nanotubes through a controllable embedment of vertically-aligned carbon nanotubes into polymer matrices is reported, which allows not only asymmetric functionalization of nanotube sidewalls, but also facile introduction of new properties (e.g. magnetic) onto the region-selectively functionalized carbon nanotubes.     

Selective metallic tube reactivity in the solution-phase osmylation of single-walled carbon nanotubes

Single-walled carbon nanotubes have been reacted with osmium tetroxide (OsO(4)) in solution in the presence of O(2) and UV irradiation at 254 nm. We observe one main structural motif, namely thickly coated nanotube structures, densely covered with OsO(2), consisting of multiple bundles of derivatized tubes. In a few instances, bridging uncoated tubes, connecting these thickly coated structures, incorporate a number of smaller nanotube bundles, projecting out from the larger functionalized aggregates of tubes. It is believed that OsO(2) (a) initially forms on the nanotubes by the preferential covalent sidewall functionalization of metallic nanotubes and (b) subsequently self-aggregates. The formation of an intermediate charge-transfer complex is likely the basis for the observed selectivity and reactivity of metallic tubes. Extensive characterization of these osmylated adducts has been performed using a variety of electron microscopy and optical spectroscopy techniques.     

Synthesis and characterization of styrene grafted carbon nanotube and its polystyrene nanocomposite

Effective side wall functionalization of single-walled carbon nanotube (SWCNT) with 4-vinylaniline was carried out through solvent free functionalization. The functionalized SWCNT was characterized through FT-IR and NMR. Typical peaks to identify the functionalization were observed. Thermal analysis shows around 48% weight loss in functionalized SWCNT in comparison to the pure SWCNT. The ratio of disordered to order transition (I_D/I_G) in FT-Raman, indicated the generation of some surface defects due to functionalization. Near infrared spectrum of functionalized SWCNT also confirmed the functionalization of SWCNT. The polystyrene nanocomposite materials were prepared with functionalized SWCNT as fillers by solution casting from tetrahydrofuran. The functionalized SWCNT nanocomposite showed significant improvement in mechanical properties and electrical properties. The dispersibility of the carbon nanotube in the composite was investigated by using scanning electron microscopy.     

An investigation of the mechanisms of electronic sensing of protein adsorption on carbon nanotube devices

It has been reported that protein adsorption on single-walled carbon nanotube field effect transistors (FETs) leads to appreciable changes in the electrical conductance of the devices, a phenomenon that can be exploited for label-free detection of biomolecules with a high potential for miniaturization. This work presents an elucidation of the electronic biosensing mechanisms with a newly developed microarray of nanotube "micromat" sensors. Chemical functionalization schemes are devised to block selected components of the devices from protein adsorption, self-assembled monolayers (SAMs) of methoxy(poly(ethylene glycol))thiol (mPEG-SH) on the metal electrodes (Au, Pd) and PEG-containing surfactants on the nanotubes. Extensive characterization reveals that electronic effects occurring at the metal-nanotube contacts due to protein adsorption constitute a more significant contribution to the electronic biosensing signal than adsorption solely along the exposed lengths of the nanotubes.     

十八醇亲核取代反应修饰溴代多壁碳纳米管

Octadecanol modified multiple-walled carbon nanotubes, with octadecanol covalently bound to the nanotube surface, have been synthesized by bromination of the carbon nanotubes followed by nucleophilic substitution using octadecanol and sodium hydride. Scanning electron microscopy and transmission electron microscopy images show that the morphologies of the nanotubes are largely intact after functionalization. The brominated carbon nanotubes and octadecanol modified carbon nanotubes were characterized using energy-dispersive X-ray spectroscopy, Raman spectroscopy and Fourier transform infrared spectroscopy. The mechanism of nucleophilic substitution was discussed, and it is believed that the reaction occurs with an SN1 mechanism.