Lanthanide Atoms Induce Strong Graphene Sheet Distortion When Adsorbed on Stone-Wales Defects.

Local curvature in graphene can enhance its reactivity and catalytic activity and can be induced by the adsorption of certain chemical species. By employing periodic density functional theory (DFT) calculations, we demonstrate that significant local curvature can be systematically observed when lanthanide atoms (the full series from La to Lu) are adsorbed on the Stone-Wales (SW) defect in graphene, contrary to that in defect-free graphene. Despite the typical high coordination numbers of lanthanide species, their hapticity is always η (and not η, η, or η), where Ln atoms are adsorbed on the (7,7) junction, forming relatively short Ln···C separations.

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).

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.

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.

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

Unsubstituted phthalocyanines (including free-base HPc 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.

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.

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.

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.

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.

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.

Ecotoxicological effects of carbon nanomaterials on algae, fungi and plants.

The ecotoxicological effects of carbon nanomateriales (CNMs), namely fullerenes and carbon nanotubes, on algae, fungi and plants are analyzed. In different toxicity tests, both direct and indirect effects were found. The direct effects are determined by nanomaterial chemical composition and surface reactivity, which might catalyze redox reactions in contact with organic molecules and affect respiratory processes.

Fullerene thin films functionalized by 1,5-diaminonaphthalene: preparation and properties.

The gas-phase treatment with 1,5-diaminonaphthalene (DAN) is proposed as an efficient way of chemical functionalization of fullerene C60 thin films in order to modify their electronic properties; a temperature of 190 degrees C and reaction time of 4 h were found to be optimal reaction conditions. Two amino groups of DAN add on two neighboring C60 cages, thus producing cross-links in the fullerene phase. The resulting oligomeric and/or polymeric products exhibit a lower solubility in toluene as compared to pristine C60 films.

"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.

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.

Microwave irradiation of pristine multi-walled carbon nanotubes in vacuum.

The goal of the present paper was to study the behavior of commercially available pristine multi-walled carbon nanotubes (MWNTs) under microwave irradiation (exposures up to 200 s) in vacuum, by means of several experimental techniques. An intense glow and heating of the nanotube samples were observed. Raman spectra, scanning electron microscopy (SEM) and scanning tunneling microscopy (STM) images of the processed nanotubes did not show considerable changes as compared to those for pristine MWNTs.

Genotoxic properties of nylon-6/MWNTs nanohybrid.

We performed the micronucleus test to determine the level of biocompatibility of pristine multi-walled carbon nanotubes (MWNTs) and MWNTs functionalized with nylon-6, (referred to as the nylon-6/ MWNTs nanohybrid), when they interact with human lymphocytes in a cell culture medium. A comparative genotoxic analysis demonstrated a better degree of biocompatibility of nylon-6/MWNT with human lymphocytes, as compared to pristine MWNTs, for the concentration range of 10-60 microg/ml. An evidence was found that pristine MWNTs act as clastogenic agents and possibly as aneuploidogenic agents, increasing the frequency of genotoxic bioindicators.

Nanohybrids of nylon 6 with multi-walled carbon nanotubes: solvent-free polymerization of epsilon-caprolactam under variable experimental conditions.

The solvent-free polymerization of epsilon-caprolactam on 1,8-diaminooctane-functionalized multi-walled carbon nanotubes (DA-MWNTs) is proposed as a simple and ecologically friendly approach to the preparation of carbon nanotubes/nylon 6 hybrid materials. The main goal of the present study was to find a minimum temperature resulting in an efficient epsilon-caprolactam polymerization, along with the optimization of the weight ratio of DA-MWNTs to epsilon-caprolactam and reaction time. The effect of temperature was studied in the range of 170 degrees C to 210 degrees C.

Fullerene C60 films cross-linked with octane-1,8-dithiol: preparation, characterization and the use as template for chemical deposition of gold nanoparticles.

We report on the preparation of fullerene C60 thin films chemically cross-linked with octane-1,8-dithiol, which are capable of binding gold nanoparticles. The formation of a polymer was directly proved by means of laser desorption/ionization time-of-flight mass spectra, in which we observed the cleavage of fullerene-dithiol polymer at different bonds. Fourier-transform infrared, Raman and UV-visible spectra of the functionalized films exhibited notorious changes due to the formation of new covalent bonds between C60 molecules and bifunctional thiol.

Regioselectivity in azahydro[60]fullerene derivatives: application of general-purpose reactivity indicators.

To attempt theoretical predictions of the regioselectivity pattern in molecules with multiple reactive sites, the energies of formation of all possible isomers are usually considered. This means that the computing becomes highly demanding if high theoretical levels are used. The study objective was to predict the regioselectivity in the reaction of hydrogen addition onto azahydro[60]fullerene C 59H n+1 N ( n = 0-4) systems using a new reactivity indicator termed general-purpose reactivity indicator, Xi Delta N View Article and Find Full Text PDF

Effects of covalent functionalization on the biocompatibility characteristics of multi-walled carbon nanotubes.

We report the effect of chemical modification of multi-walled carbon nanotubes (MWNTs) on their activation of the human serum complement system, as well as the adsorption of human plasma proteins on MWNTs. Four different types of chemically-modified MWNTs were tested for complement activation via the classical and alternative pathways using haemolytic assays. Human plasma protein binding was also tested using an affinity chromatography technique based on carbon nanotube-Sepharose matrix.

Noncovalent functionalization of carbon nanotubes with porphyrins: meso-tetraphenylporphine and its transition metal complexes.

Noncovalent functionalization of carbon nanotubes with meso-tetraphenylporphine (H2TPP) and its metal(II) complexes NiTPP and CoTPP was studied by means of different experimental techniques and theoretical calculations. As follows from the experimental adsorption curves, free H2TPP ligand exhibits the strongest adsorption of three porphyrins tested, followed by CoTPP and NiTPP. At the highest porphyrin concentrations studied, the adsorption at multi-walled carbon nanotubes was about 2% (by weight) for H2TPP, 1% for CoTPP, and 0.

Deposition of gold nanoparticles onto thiol-functionalized multiwalled carbon nanotubes.

Gold nanoparticles were deposited on the surface of multiwalled carbon nanotubes (MWNTs) functionalized with aliphatic bifunctional thiols (1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, and 2-aminoethanethiol) through a direct solvent-free procedure. Small gold particles, with a narrow particle size distribution around 1.7 nm, were obtained on 1,6-hexanedithiol-functionalized MWNTs.

Solvent-free derivatization of pristine multi-walled carbon nanotubes with amines.

We performed direct solvent-free amination of multi-walled carbon nanotubes (MWCNTs) with nonylamine, dodecylamine, octadecylamine, 4-phenylbutylamine and 1,8-ocanediamine at a temperature of 150-170 degrees C and reduced pressure. Thermogravimetric analysis and temperature-programmed desorption-mass spectrometry revealed that a major amine fraction decomposes in a temperature interval of 250-500 degrees C, thus existing on multi-walled carbon nanotubes as chemically bonded species; a minor amine fraction was found in physisorbed form. The new derivatization technique combines simplicity in implementation and attractive features of "green" chemistry.