Scanning Tunneling Microscopy Study of Lipoic Acid, Mannose, and cRGD@AuNPs Conjugates.

The functionalization of AuNPs with different biological elements was achieved to investigate their possibility in biomedical applications such as drug delivery, vaccine development, sensing, and imaging. Biofunctionalized AuNPs are pursued for applications such as drug delivery, vaccine development, sensing, and imaging. In this study, AuNPs with diameters of 20 nm were functionalized with lipoic acid, mannose, or the cRGD peptide. By using UV-vis spectroscopy, Fourier transform infrared spectroscopy, dynamic light scattering, transmission electron microscopy, and scanning tunneling microscopy techniques, we showed that AuNPs can be functionalized by these biomolecules in a reliable way to obtain conjugates to explore potential biomedical applications. In particular, we demonstrate that the STM technique can be employed to analyze biofunctionalized AuNPs, and the obtained information can be valuable in the design of biomedical applications.

Adsorption of lanthanide double-decker phthalocyanines on single-walled carbon nanotubes: structural changes and electronic properties as studied by density functional theory.

CONTEXT: Molecular modeling of carbon nanotubes and lanthanide double-decker phthalocyanines hybrids is challenging due to the presence of 4f-electrons. In this paper, we analyzed the trends in structural changes and electronic properties when a lanthanide (La, Gd, and Lu) bisphthalocyanine molecule is adsorbed on the surface of two single-walled carbon nanotubes (SWCNTs) models: armchair and zigzag. The density functional theory (DFT) computations showed that the height of bisphthalocyanines complexes (LnPc2) when adsorbed on a nanotube (LnPc2+SWCNT) is the structural feature which is most affected by the nanotube model. The formation energy of the LnPc2+SWCNT hybrid depends on the metal atom and the nanotube chirality. LaPc2 and LuPc2 bind stronger to the zigzag nanotube, while for GdPc2, bonding to the armchair nanotube is the stronger one. The HOMO-LUMO gap energy (Egap) shows a correlation between the nature of lanthanide and the nanotube chirality. In the case of adsorption on armchair nanotube, Egap tends to match the gap of isolated LnPc2, whereas for adsorption on the zigzag nanotube, it is closer to the value for the isolated nanotube model. The spin density is localized on the phthalocyanines ligands (plus on Gd in the case of GdPc2), when the bisphthalocyanine is adsorbed on the surface of the armchair nanotube. For bonding to zigzag nanotube (ZNT), it extends over both components, except for LaPc2+ZNT, where spin density is found on the nanotube only. METHOD: All DFT calculations were carried out using the DMol3 module of Material Studio 8.0 software package from Accelrys Inc. The computational technique chosen was the general gradient approximation functional PBE in combination with a long-range dispersion correction developed by Grimme (PBE-D2), the double numerical basis set DN, and the DFT semi-core pseudopotentials.

Strong Bending Distortion of a Supercoronene Graphene Model upon Adsorption of Lanthanide Atoms.

Numerous applications of graphene involve quasi-infinite sheets, as well as finite structures with edges, pores, graphene quantum dots, etc. In theoretical studies of adsorption of diverse chemical species, including single atoms, molecules, cations, and anions, graphene usually behaves as a very rigid planar structure. However, we found that when adsorbing lanthanide atoms, finite size structures, represented by the widely used supercoronene model, can undergo considerable distortion, and the degree of distortion depends on the number of unpaired electrons, reaching a maximum for Gd (eight unpaired electrons). Lanthanides closely approach the supercoronene surface and increase the interaction energy. Extrapolating to real-world systems, one can expect the existence and magnitude of lanthanide-induced distortion to depend on the size of graphene structures. Quasi-infinite or very large graphene sheets are too rigid to undergo such bending, but it becomes tangible for graphene quantum dots and for atom adsorption closer to graphene edges.

Adsorption of Lanthanide Atoms on Graphene: Similar, Yet Different.

Many theoretical studies address the interaction of different atoms with graphene; however, the relevant information on the adsorption of the lanthanide species remains limited and controversial, creating a gap in this important area of graphene chemistry and physics. By employing periodic density functional theory calculations, we provide the key theoretical information for the entire series from lanthanum to lutetium interacting with defect-free graphene, including the interaction strength and distances, charge and spin of the lanthanide atoms, and comparative features of the density of states. The central lanthanides Gd, Tb, and Dy exhibit the strongest bonding and shortest distances. The positive charge acquired by the lanthanide atoms varies insignificantly, with the exception of Yb and Lu with a filled 4f shell. The spin increases from La to Tb and then decreases sharply, achieving minimal values for Tm, Yb, and Lu. Interaction with graphene influences even the deeper 5s and 5p shells.

Gadolinium-containing carbon nanomaterials for magnetic resonance imaging: Trends and challenges.

Gadolinium-containing carbon nanomaterials are a new class of contrast agent for magnetic resonance imaging. They are characterized by a superior proton relaxivity to any current commercial gadolinium contrast agent and offer the possibility to design multifunctional contrasts. Intense efforts have been made to develop these nanomaterials because of their potential for better results than the available gadolinium contrast agents. The aim of the present work is to provide a review of the advances in research on gadolinium-containing carbon nanomaterials and their advantages over conventional gadolinium contrast agents. Due to their enhanced proton relaxivity, they can provide a reliable imaging contrast for cells, tissues or organs with much smaller doses than currently used in clinical practice, thus leading to reduced toxicity (as shown by cytotoxicity and biodistribution studies). Their active targeting capability allows for improved MRI of molecular or cellular targets, overcoming the limited labelling capability of available contrast agents (restricted to physiological irregularities during pathological conditions). Their potential of multifunctionality encompasses multimodal imaging and the combination of imaging and therapy.

A dispersion-corrected density functional theory study of the noncovalent interactions between nucleobases and carbon nanotube models containing stone-wales defects.

The noncovalent bonding between nucleobases (NBs) and Stone-Wales (SW) defect-containing closed-end single-walled carbon nanotubes (SWNTs) was theoretically studied in the framework of density function theory using a dispersion-corrected functional PBE-G06/DNP. The models employed in this study were armchair nanotube (ANT) (5,5) and zigzag nanotube (ZNT) (10,0), which incorporated SW defects in different orientations. In one of them, the (7,7) junction is tilted with respect to SWNT axis (ANT-t and ZNT-t), whereas in ANT-p and ZNT-p models the (7,7) junction is parallel and perpendicular to the axis, respectively. The binding energies for uracil, thymine, cytosine, 5-methylcytosine, adenine, and guanine interacting with the defect-containing nanotube models were compared to the values previously obtained with the same calculation technique for the case of defect-free SWNTs, both in the gas phase (vacuum) and in aqueous medium. For most models, the interaction strength tends to be higher for purine than for pyrimidine complexes, with a clear exception of the systems including ZNT-p, both in vacuum and in aqueous medium. As it could be expected, the binding strength in the latter case is lower as compared to that in vacuum, roughly by 2-4 kcal/mol, due to the implicit inclusion of a medium (i.e., water) via the conductor-like screening model model. The closest contacts between NBs and SWNT models, frontier orbital distribution, and highest-occupied molecular orbital-lowest-unoccupied molecular orbital gap energies are analyzed as well. © 2019 Wiley Periodicals, Inc.

Preparation and Characterization of a Novel Organic Semiconductor Indacenedithiophene Derivative and the Corresponding Langmuir-Blodgett Thin Films.

The synthesis of a novel indacenedithiophene derivative (IDT-DPA) is described, which exhibits semiconducting behavior. Its properties were measured by means of UV-visible and fluorescence spectroscopies using toluene as solvent. An extinction molar coefficient of 2.05×104 M-1 cm-1 and a Stokes shift of 50 nm were obtained. A theoretical study was performed using the density functional theory, from which HOMO-LUMO band gap of 1.711 eV was calculated. IDT-DPA was deposited on the water-air interface to form Langmuir monolayers. π-A curves and hysteresis were measured showing reversibility behavior. The monolayers were transferred to glass substrates as Langmuir-Blodgett thin films. Their morphological properties were characterized by using scanning electron and atomic force microscopy, which showed that the films tend to form clusters with a homogeneous distribution. Absorption and emission spectra of the films were measured, from which the optical band gap and Stocks shift were derived. Based on the electronic properties and light emission spectra of IDT-DPA, this compound can be proposed for the applications in organic lightemitting diodes and other organic semiconductor devices.

Carbon Nanotubes and Graphene Promote Pyrolysis of Free-Base Phthalocyanine.

Unsubstituted phthalocyanines (including free-base H2Pc and many of its metal complexes) are among the most stable organic compounds. They can sublime without decomposition under reduced pressure and temperatures of up to 550 °C. This property was previously employed to design a novel approach to noncovalent functionalization of pristine single-walled carbon nanotubes (SWNTs) with 3d metal(II) phthalocyanine complexes. However, when we attempted to use the same sublimation protocol to prepare a SWNTs-H2Pc hybrid, an unexpected side effect of partial H2Pc pyrolysis was detected, phthalonitrile being a main decomposition product, under the conditions when H2Pc is supposed to be totally stable. By using density functional theory calculations, we offer an explanation for the thermal behavior of H2Pc based on its covalent attachment to the pentagonal-ring topological defects, which are very common in all graphene-derived carbon nanomaterials and capable of reacting with amines via nucleophilic addition process.

One-step nondestructive functionalization of graphene oxide paper with amines.

Direct functionalization of prefabricated free-standing graphene oxide paper (GOP) is the only approach suitable for systematic tuning of its mechanical, thermal and electronic characteristics. However, the traditional liquid-phase functionalization can compromise physical integrity of the paper-like material up to its total disintegration. In the present paper, we attempted to apply an alternative, solvent-free strategy for facile and nondestructive functionalization of GOP with 1-octadecylamine (ODA) and 1,12-diaminododecane (DAD) as representatives of aliphatic amines, and with 1-aminopyrene (AP) and 1,5-diaminonaphthalene (DAN) as examples of aromatic amines. The functionalization can be carried out under moderate heating at 150-180 °C for 2 h in vacuum, and proceeds through both amidation and epoxy ring opening reactions. Comparative characterization of pristine and amine-modified GOP samples was carried out by means of Fourier-transform infrared, Raman, and X-ray photoelectron spectroscopy, thermogravimetric and differential thermal analysis, scanning electron and atomic force microscopy. In addition, we compared stability in water, wettability, electrical conductivity and elastic (Young's) modulus of GOP samples before and after functionalization. The highest content of amine species was obtained in the case of GOP-ODA, followed by GOP-DAD, GOP-AP and GOP-DAN. The functionalization increased mechanical and thermal stability, as well as the electrical conductivity of GOP. The magnitude of each effect depends on the structure of amine employed, which allows for tuning a given GOP characteristic. Morphological characterization showed that, compared to pristine graphene oxide paper, amine-modified mats become relatively ordered layered structures, in which individual GO sheets are organized in a near-parallel fashion.

Computer simulation and experimental self-assembly of irradiated glycine amino acid under magnetic fields: Its possible significance in prebiotic chemistry.

Ionizing radiation may have played a relevant role in chemical reactions for prebiotic biomolecule formation on ancient Earth. Environmental conditions such as the presence of water and magnetic fields were possibly relevant in the formation of organic compounds such as amino acids. ATR-FTIR, Raman, EPR and X-ray spectroscopies provide valuable information about molecular organization of different glycine polymorphs under static magnetic fields. γ-glycine polymorph formation increases in irradiated samples interacting with static magnetic fields. The increase in γ-glycine polymorph agrees with the computer simulations. The AM1 semi-empirical simulations show a change in the catalyst behavior and dipole moment values in α and γ-glycine interaction with the static magnetic field. The simulated crystal lattice energy in α-glycine is also affected by the free radicals under the magnetic field, which decreases its stability. Therefore, solid α and γ-glycine containing free radicals under static magnetic fields might have affected the prebiotic scenario on ancient Earth by causing the oligomerization of glycine in prebiotic reactions.

Solvent-Free Covalent Functionalization of Fullerene C60 and Pristine Multi-Walled Carbon Nanotubes with Crown Ethers.

The goal of the present work was to test the feasibility of simple, one-step and solvent-free covalent functionalization of pristine multi-walled carbon nanotubes (MWNTs) and fullerene C60 (as a model system) with amino-substituted crown ethers, namely, 4'-aminobenzo-15-crown-5 and 4'-aminobenzo-1 8-crown-6. The attachment technique proposed is based on thermal instead of chemical activation, and can be considered as ecologically friendly. The suggested covalent binding mechanism is the nucleophilic addition of amino functionalities of crown ethers to the 6,6 bonds of pyracylene units in the case of C60, and to pentagonal (and probably other) defects of similar nature in the case of pristine MWNTs. The hybrids of crown ethers with MWNTs were characterized by means of scanning and transmission electron microscopy, Fourier-transform infrared and Raman spectroscopy, as well as thermogravimetric analysis. The functionalized C60 samples were additionally studied by means of 13C cross-polarization magic angle spinning nuclear magnetic resonance spectroscopy and laser desorption/ionization time-of-flight mass spectrometry. The approach proposed allows for a facile preparation of crown ether-functionalized pristine MWNTs without contamination with other chemical reagents, detergents and solvents, which is especially important for a vast variety of nanotube applications ranging from nanoelectronics to nanomedicine.

Properties of noncovalent tetraphenylporphine···C60 dyads as studied by different long-range and dispersion-corrected DFT functionals.

The noncovalent dyad of tetraphenylporphine and C60 fullerene (H2TPP···C60) and the tetraphenylporphine dimer (H2TPP···H2TPP) were studied by density functional theory (DFT), using functionals that incorporate empirical dispersion correction (DFT-D), functionals that use a long-range correction (LC) scheme, a hybrid functional (B3LYP) and a highly parametrized empirical exchange-correlation functional (M05-2X). The results were compared to X-ray structures and interaction energies reported in previous experimental and theoretical studies. It was found that B3LYP and CAM-B3LYP functionals fail to reproduce the X-ray structures and binding energies of the TPP···C60 system. DFT-D functionals overestimated the π···π energy interactions for both systems, however, the optimized structures agree well with those observed experimentally. The LC-BLYP functional predicts geometries similar to X-ray structures; nevertheless, due to the lack of correction in the dispersion energy, the predicted energies for both model systems are low. On the other hand, the M05-2X functional exhibited the best performance. Both the structures and binding energies calculated with M05-2X are consistent with experimental and theoretical evidence reported by other authors, as well as with our experimental results obtained by means of atomic force microscopy on H2TPP thin films grown on the HOPG/C60 substrate by physical vapor deposition.

Interaction of a Ni(II) tetraazaannulene complex with elongated fullerenes as simple models for carbon nanotubes.

Nickel(II) complex of 5,14-dihydro-6,8,15,17-tetramethyldibenzo[b,i][1,4,8,11] tetraazacyclotetradecine (NiTMTAA), which can be employed for noncovalent functionalization of carbon nanotubes (CNTs), represents a more complex and interesting case in terms of structure of the resulting nanohybrids, as compared to the related materials functionalized with porphyrins and phthalocyanines. Due to its saddle shape, the NiTMTAA molecule adsorbed can adopt different, energetically non-equivalent orientations with respect to CNT, depending on whether CH3 or C6H4 groups contact the latter. The main goal of the present work was to provide information on the interactions of NiTMTAA with simple single-walled CNT (SWNT) models accessible for dispersion-corrected DFT calculations. For reasons of comparison, we employed three such functionals: M06-2X and LC-BLYP as implemented in Gaussian 09 package, and PBE-G as implemented in Materials Studio 6.0. In order to roughly estimate the effect of nanotube chirality on the interaction strenght, we considered two short closed-end SWNT models (also referred to as 'elongated fullerenes'), one armchair and one zigzag, derived from C60 and C80 hemispheres. In addition, we calculated similar complexes with C60, as well as I h and D 5h isomers of C80. The results were analyzed in terms of optimized geometries, formation energies, HOMO-LUMO gap energies, and intermolecular separations. Graphical Abstract Interaction of Ni(II) tetraazaannulene complex with elongated fullerenes.

Green chemistry of carbon nanomaterials.

The global trend of looking for more ecologically friendly, "green" techniques manifested itself in the chemistry of carbon nanomaterials. The main principles of green chemistry emphasize how important it is to avoid the use, or at least to reduce the consumption, of organic solvents for a chemical process. And it is precisely this aspect that was systematically addressed and emphasized by our research group since the very beginning of our work on the chemistry of carbon nanomaterials in early 2000s. The present review focuses on the results obtained to date on solvent-free techniques for (mainly covalent) functionalization of fullerene C60, single-walled and multi-walled carbon nanotubes (SWNTs and MWNTs, respectively), as well as nanodiamonds (NDs). We designed a series of simple and fast functionalization protocols based on thermally activated reactions with chemical compounds stable and volatile at 150-200 degrees C under reduced pressure, when not only the reactions take place at a high rate, but also excess reagents are spontaneously removed from the functionalized material, thus making its purification unnecessary. The main two classes of reagents are organic amines and thiols, including bifunctional ones, which can be used in conjunction with different forms of nanocarbons. The resulting chemical processes comprise nucleophilic addition of amines and thiols to fullerene C60 and to defect sites of pristine MWNTs, as well as direct amidation of carboxylic groups of oxidized nanotubes (mainly SWNTs) and ND. In the case of bifunctional amines and thiols, reactions of the second functional group can give rise to cross-linking effects, or be employed for further derivatization steps.

Noncovalent functionalization of graphene with a Ni(II) tetraaza[14]annulene complex.

The few-layer graphene, produced by exfoliation of graphite in 4-methylanisole, was noncovalently functionalized with the Ni(ii) complex of 5,7,12,14-tetramethyldibenzo-1,4,8,11-tetraazacyclotetradeca-3,5,7,10,12,14-hexaene (Ni(ii)-tetramethyldibenzotetraaza[14]annulene, or NiTMTAA), which is a simple model of more complex porphyrins and phthalocyanines. The resulting hybrid materials with different content of NiTMTAA were characterized by means of thermogravimetric analysis, scanning and transmission electron microscopy (SEM and TEM, respectively), atomic force microscopy (AFM), energy dispersive X-ray, Fourier-transform infrared (FTIR), Raman and UV-visible spectroscopy, as well as fluorescence and conductivity measurements. Additional information on the mechanisms of NiTMTAA interaction with graphene was obtained from density functional theory (DFT) and molecular mechanics (MM) calculations. Both experimental and theoretical results suggest that NiTMTAA forms a full double-sided adsorption layer on the graphene surface. The presence of NiTMTAA molecules in the hybrid materials obtained manifests itself in the appearance of characteristic bands in all types of electromagnetic spectra recorded; in FTIR, they are relatively weak as compared to graphene absorption bands, but dominate in Raman spectra. The morphology of the nanohybrids observed by SEM, TEM and AFM, as well as their electrical conductivity, depends on the NiTMTAA content. According to the results of DFT calculations of NiTMTAA adsorption on different graphene models, flat orientation of the complex with respect to graphene is energetically preferable, with a little difference depending on whether benzo or methyl groups contact the sheet.

Nanostructured diamine-fullerene derivatives: computational density functional theory study and experimental evidence for their formation via gas-phase functionalization.

Nanostructure derivatives of fullerene C(60) are used in emerging applications of composite matrices, including protective and decorative coating, superadsorbent material, thin films, and lightweight high-strength fiber-reinforced materials, etc. In this study, quantum chemical calculations and experimental studies were performed to analyze the derivatives of diamine-fullerene prepared by the gas-phase solvent-free functionalization technique. In particular, the aliphatic 1,8-diamino-octane and the aromatic 1,5-diaminonaphthalene, which are diamines volatile in vacuum, were studied. We addressed two alternative mechanisms of the amination reaction via polyaddition and cross-linking of C(60) with diamines, using the pure GGA BLYP, PW91, and PBE functionals; further validation calculations were performed using the semiempirical dispersion GGA B97-D functional which contains parameters that have been specially adjusted by a more realistic view on dispersion contributions. In addition, we looked for experimental evidence for the covalent functionalization by using laser desorption/ionization time-of-flight mass spectrometry, thermogravimetric analysis, and atomic force microscopy.

Self-assemblies of meso-tetraphenylporphine ligand on surfaces of highly oriented pyrolytic graphite and single-walled carbon nanotubes: insights from scanning tunneling microscopy and molecular modeling.

The self-assembly of porphyrins into highly organized functional arrays supported on appropriate solid substrates is an area of research with multiple potential applications in the "bottom-up" approach to manufacturing. In order to analyze the self-assembly of meso-tetraphenylporphine (H2TPP) on the surfaces of highly oriented pyrolytic graphite (HOPG) and single-walled carbon nanotubes (SWNTs), we performed molecular mechanics modeling (by MM+ force field) and scanning tunneling microscopy (STM) imaging. Molecular modeling predicted an energetic preference of the H2TPP molecules to adsorb in monolayers on the surfaces of graphite and SWNT sidewall, rather than their stacking or separation. On graphite, the most favorable arrays were predicted to be ribbons composed of interacting parallel chains of H2TPP molecules. On the SWNT sidewall, the energetic preference pointed toward the formation of parallel and interacting long-period helixes, resulting in an almost full coverage of the SWNT surface. These preferable arrays on both carbon materials assure the interaction of every porphyrin unit with as many neighbors as possible, thus lowering the potential energy of the adsorption complexes. STM imaging results are in good agreement with molecular modeling predictions. The formation of self-assembled ribbons was a frequently observed phenomenon on the HOPG surface, while on the SWNT surface a full coverage of the exposed portion of the sidewalls was observed, suggesting the formation of interacting long-period helixes. A preferential adsorption of H2TPP molecules near graphite topographic defects was also observed.

Aggregation of human serum albumin on graphite and single-walled carbon nanotubes as studied by scanning probe microscopies.

Human serum albumin (HSA) is the most abundant protein in blood plasma showing a remarkable ability to bind a broad range of hydrophobic substrates. We employed scanning tunneling microscopy and atomic force microscopy to characterize the morphology of HSA aggregates on highly-ordered pyrolytic graphite (HOPG) and single-walled carbon nanotubes (SWNTs). The morphologies found for albumin aggregates on HOPG are quite different from the ones observed on SWNTs. On HOPG, HSA forms aggregates of roughly 10-20 molecules; single protein molecules were observed as well. In the case of SWNTs, nanotubes were partially or totally covered with HSA, exhibiting four general types of aggregation: (i) SWNT sidewalls contain single molecules of albumin which are away from each other at distances longer than the HSA molecular size; (ii) SWNTs are completely covered with HSA, which forms a thin and relatively homogeneous layer; (iii) SWNTs have a complete layer of HSA with additional accumulation of protein at separate sites; and (iv) several SWNTs totally covered with albumin assemble into a bundle-like structure common for bare nanotubes. These observations are interpreted in terms of stronger interactions of HSA with nanotube sidewalls than with flat graphite surface.

Noncovalent interaction of meso-tetraphenylporphine with C60 fullerene as studied by several DFT methods.

We performed density functional theory (DFT) calculations of noncovalently bonded 1:1 complex of meso-tetraphenylporphine H2TPP with fullerene C60. The functionals used were PW91, PBE and BLYP of general gradient approximation (GGA), as well as PWC and VWN of local density approximation (LDA) as implemented in the DMol3 module of Materials Studio package from Accelrys. The computed geometries were compared to the experimental X-ray diffraction data obtained elsewhere for rhombohedral and monoclinic H2TPP + C60 crystalline complexes. If the correlation coefficient between the calculated and experimental data is applied, the covalent bond lengths and angles within H2TPP unit are best reproduced by BLYP functional, whereas PWC and VWN are least precise. On the other hand, PWC and VWN are the best functionals in reproducing the separations between H2TPP and C60 found from X-ray diffraction analysis: the LDA-calculated N(H2TPP) ... C(C60) distances are of about 2.9-3.0 angstroms, whereas the corresponding experimental values are of ca. 3.0-3.1 angstroms. Next are PW91 and PBE functionals, giving N(H2TPP) ... C(C60) distances of ca. 3.5-3.6 angstroms. BLYP produced the separations of around 4.0-4.1 angstroms, which are inconsistent with both X-ray data and the results produced other functionals. We also analyzed functional-dependent variations in formation energies, electrostatic potential, HOMO, LUMO and charge transfer. We concluded that of DFT functionals incorporated into DMol3 module and tested in this study, PWC and VWN are the most adequate ones, and BLYP is the least recommended one for the studies of noncovalent interactions of porphyrins with carbon nanoclusters.

"Green" functionalization of pristine multi-walled carbon nanotubes with long-chain aliphatic amines.

Short pristine multi-walled carbon nanotubes (MWNTs) were functionalized with a series of long-chain (including polymeric) aliphatic amines, namely octadecylamine (ODA), 1,8-diaminooctane (DO), polyethylene glycol diamine (PEGDA) and polyethylenimine (PEI), via two "green" approaches: (1) gas-phase functionalization (for volatile ODA and DO) and (2) direct heating in the melt (for polymeric PEGDA and PEI). Both of them consist in one-step reaction between MWNTs and amine without the use of organic solvents. The nanostructures obtained were characterized by using infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, atomic force microscopy, and transmission electron microscopy. It was observed that both solvent-free methods were efficient in the nanotube functionalization, and the nanostructures of variable solubility and morphology were obtained depending on the amines attached. ODA, PEGDA and PEI-functionalized MWNTs were found to be soluble in propanol, meanwhile the MWNTs-PEGDA and MWNTs-PEI were soluble in water as well. The attachment of 1,8-diaminooctane onto MWNTs resulted in cross-linked stable nanostructure.