Adsorption of amino acids by fullerenes and fullerene nanowhiskers

We have investigated the adsorption of some amino acids and an oligopeptide by fullerene (C₆₀) and fullerene nanowhiskers (FNWs). C₆₀ and FNWs hardly adsorbed amino acids. Most of the amino acids used have a hydrophobic side chain. Ala and Val, with an alkyl chain, were not adsorbed by the C₆₀ or FNWs. Trp, Phe and Pro, with a cyclic structure, were not adsorbed by them either. The aromatic group of C₆₀ did not interact with the side chain. The carboxyl or amino group, with the frame structure of an amino acid, has a positive or negative charge in solution. It is likely that the C₆₀ and FNWs would not prefer the charged carboxyl or amino group. Tri-Ala was adsorbed slightly by the C₆₀ and FNWs. The carboxyl or amino group is not close to the center of the methyl group of Tri-Ala. One of the methyl groups in Tri-Ala would interact with the aromatic structure of the C₆₀ and FNWs. We compared our results with the theoretical interaction of 20 bio-amino acids with C₆₀. The theoretical simulations showed the bonding distance between C₆₀ and an amino acid and the dissociation energy. The dissociation energy was shown to increase in the order, Val < Phe < Pro < Asp < Ala < Trp < Tyr < Arg < Leu. However, the simulation was not consistent with our experimental results. The adsorption of albumin (a protein) by C₆₀ showed the effect on the side chains of Try and Trp. The structure of albumin was changed a little by C₆₀. In our study Try and Tyr were hardly adsorbed by C₆₀ and FNWs. These amino acids did not show a different adsorption behavior compared with other amino acids. The adsorptive behavior of mono-amino acids might be different from that of polypeptides.     

Synthesis of fullerene nanowhiskers using the liquid–liquid interfacial precipitation method and their mechanical,electrical and superconducting properties

Fullerene nanowhiskers (FNWs) are thin crystalline fibers composed of fullerene molecules, including C₆₀, C₇₀, endohedral, or functionalized fullerenes. FNWs display n-type semiconducting behavior and are used in a diverse range of applications, including field-effect transistors, solar cells, chemical sensors, and photocatalysts. Alkali metal-doped C₆₀ (fullerene) nanowhiskers (C₆₀NWs) exhibit superconducting behavior. Potassium-doped C₆₀NWs have realized the highest superconducting volume fraction of the alkali metal-doped C₆₀ crystals and display a high critical current density (J_c) under a high magnetic field of 50 kOe. The growth control of FNWs is important for their success in practical applications. This paper reviews recent FNWs research focusing on their mechanical, electrical and superconducting properties and growth mechanisms in the liquid–liquid interfacial precipitation method.     

Synthesis of fullerene nanowhiskers using the liquid–liquid interfacial precipitation method and their mechanical,electrical and superconducting properties

Abstract

Fullerene nanowhiskers (FNWs) are thin crystalline fibers composed of fullerene molecules, including C₆₀, C₇₀, endohedral, or functionalized fullerenes. FNWs display n-type semiconducting behavior and are used in a diverse range of applications, including field-effect transistors, solar cells, chemical sensors, and photocatalysts. Alkali metal-doped C₆₀ (fullerene) nanowhiskers (C₆₀NWs) exhibit superconducting behavior. Potassium-doped C₆₀NWs have realized the highest superconducting volume fraction of the alkali metal-doped C₆₀ crystals and display a high critical current density (J_c) under a high magnetic field of 50 kOe. The growth control of FNWs is important for their success in practical applications. This paper reviews recent FNWs research focusing on their mechanical, electrical and superconducting properties and growth mechanisms in the liquid–liquid interfacial precipitation method.     

Ion–Ion Collisions Involving Fullerene Ions

Abstract

Fullerenes are a direct link between atoms with discrete electronic energy levels and solids with a band structure and a well defined surface. In collision experiments, both between energetic ions or electrons and neutral C₆₀ molecules [Walch, B.; Cocke, C.L.; Voelpel, R.; Salzborn, E. Electron capture from C₆₀ by slow multiply charged ions. Phys. Rev. Lett. 1994, 72, 1439–1442; Scheier, P.; Hathiramani, D.; Arnold, W.; Huber, K.; Salzborn, E. Multiple ionization and fragmentation of negatively charged fullerene ions by electron impact. Phys. Rev. Lett. 2000, 84, 55–58; Hathiramani, D.; Aichele, K.; Arnold, W.; Huber, K.; Salzborn, E.; Scheier, P. Electron‐impact induced fragmentation of fullerene ions. Phys. Rev. Lett. 2000, 85, 3604–3607], as well as between charged fullerene ions and neutral targets [Hvelplund, P.; Andersen, L.; Haugen, H.; Lindhard, L.; Lorents, D.C.; Malhotra, R.; Rouff, R. Dynamical fragmentation of C₆₀ ions. Phys. Rev. Lett. 1992, 69, 1915–1918; Hvelplund, P.; Andersen, L.; Brink, C.; Yu, D.; Lorents, D.C.; Rouff, R. Charge transfer in collisions involving multiply charged C₆₀ molecules. Z. Phys. D 1994, 30, 323; Rohmund, F.; Campbell, E.E.B. Resonant and non‐resonant charge transfer in C₆₀ ⁺ + C₆₀ and C₇₀ ⁺ and C₆₀ collisions. J. Phys. B: At. Mol. Opt. Phys. 1997, 30, 5293–5304; Shen, H.; Hvelplund, P.; Mathur, D.; Barany, A.; Cederquist, H.; Selberg, N.; Lorents, D.C. Fullerene–fullerene collisions: fragmentation and electron capture. Phys. Rev. A 1995, 52, 3847–3851], the fundamental processes of electron transfer, ionization, and fragmentation have been studied extensively. Here we report on our experiments on electron transfer in the collision systems C₆₀ ⁺ + ³He²⁺ → C₆₀ ²⁺ + ³He⁺ and C₆₀ ⁺ + C₆₀ ²⁺ → C₆₀ ²⁺ + C₆₀ ⁺. For the latter system we also report on an upper level for the fragmentation probability.     

Synthesis,Spectral Investigations,and Thermal Stability of [60]Fullerene Complexes with TMTSF: 2(C60) · 2(TMTSF) · (C6H6), C60 · TMTSF · 2(CS2), and 2(C60) · 2(TMTSF) · (C6H5Cl)

Abstract

Molecular complexes of [60]fullerene with tetramethyltetraselenafulvalene (TMTSF): C₆₀ · (TMTSF) · 2(CS₂) (1), 2(C₆₀) · (2(TMTSF) · (C₆H₆) (2), and 2(C₆₀) · (2(TMTSF) · (C₆H₅Cl) (3) have been synthesized and their thermal stability and IR spectra vs. light polarization and temperature have been performed.     

On Some Complexes of Allyl Derivatives of C60 Fullerene: Simulation of Molecular and Electron Structure by DFT

Abstract

The problem of existence of η³–π‐complexes of transition metal atoms with the allyl type derivatives C₆₀X₃ of C₆₀ fullerene is discussed. It is shown that complexes C₆₀X₃Co(CO)₃ (X = H, F, Cl, Br), C₆₀H₃NiC₅H₅, C₆₀H₃Fe(CO)C₅H₅, where three atoms X are bound to the C atoms of fullerene in the α‐positions relative to the same five‐membered ring in the C₆₀ fullerene, must be sufficiently stable. In these complexes the metal atoms are η³–π‐bound to the fullerene cage. In contrast to this, the metal atoms with the same allyl type C₆₀H₃ derivative of C₆₀ fullerene in the C₆₀H₃Li and C₆₀H₃FeC₅H₅ complexes are η⁵–π‐coordinated to the carbon cage. Calculations were carried out by the DFT with the exchange‐correlation potential by Perdew–Burke–Ernzerhow.     

Synthesis of bipyramidal gold nanoparticle-[C60]fullerene nanowhisker composites and catalytic reduction of 4-nitrophenol

The seed solution was prepared by dissolving hydrogen tetrachloroaurate(III) trihydrate (HAuCl₄·3H₂O), trisodium citrate dihydrate (C₆H₅Na₃O₇·2H₂O), and sodium borohydride (NaBH₄) in distilled water. The resulting reddish-purple seed solution was stirred for 3 h at room temperature. The growth solution was prepared by mixing hydrogen tetrachloroaurate(III) trihydrate (HAuCl₄·3H₂O), cetyltrimethylammonium bromide (CTAB, (C₁₆H₃₃)N(CH₃)₃Br), silver nitrate (AgNO₃), hydrochloric acid (HCl), and ascorbic acid (C₆H₈O₆) in distilled water. Subsequently, 100 μL of this seed solution was transferred into 10 mL of the growth solution. The mixed solution was maintained at 30 °C for 3 h to obtain a solution of bipyramidal gold nanoparticles. The bipyramidal gold nanoparticle-[C₆₀] fullerene nanowhisker composites were synthesized by applying the liquid-liquid interfacial precipitation (LLIP) method to a saturated solution of C₆₀ in toluene, the solution of bipyramidal gold nanoparticles, and isopropyl alcohol. The prepared bipyramidal gold nanoparticle-[C₆₀] fullerene nanowhisker composites were characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, and transmission electron microscopy. The catalytic activity of these composites was confirmed in the reduction of 4-nitrophenol by UV-Vis spectroscopy.     

Noncovalent interactions of amino acids with fullerene C60: A dispersion-corrected DFT study

By using the general gradient approximation functional PBE with Grimme's empirical dispersion correction in conjunction with the double numerical basis set DNP, we studied the noncovalent interaction of twenty proteinogenic l-amino acids (AAs) with fullerene C₆₀. The calculations were performed both under vacuum conditions and in aqueous medium. We analyzed the calculated geometries and binding energies for AA+C₆₀ complexes, the shape of HOMO and LUMO orbitals and the corresponding gap energies. Generally, we found a poor correlation between binding energies calculated for AA+C₆₀ complexes in aqueous medium and hydrophobicity scales proposed by other other authors. Despite of C₆₀ cage can be envisioned as a typical hydrophobic surface, the AA adsorption apparently takes place according to a mechanism different from classical hydrophobic interactions, or due to a combination of several types of interactions with a limited contribution of hydrophobic mechanism.     

Fullerane,the Hydrogenated C60 Fullerene: Properties and Astrochemical Considerations

Abstract

Hydrogenated C₆₀ fullerene, C₆₀H₃₆ was prepared in different solvents using Zn/HCl as reducing agents. The structure of C₆₀H₃₆ was confirmed both by electronic and FT‐IR spectroscopy and the purity of the reaction product was checked by HPLC analysis. It has been confirmed that C₆₀H₃₆ is not stable in air, especially in presence of light which enhances the oxidation. The oxidation of C₆₀H₃₆ was studied by FT‐IR spectroscopy and by differential scanning calorimetry (DSC) in air; the formation of hydroxyl groups on the fullerene cage and ketonic groups (involving cage breakdown) have been detected. Furthermore, the action of O₃ on C₆₀H₃₆ was investigated and it has been found that O₃ exerts practically the same effect of air but causing an enhanced cage breakdown. The thermal stability of C₆₀H₃₆ was checked by a thermogravimetric analysis (TGA) coupled with a differential thermal analysis (DTA) under N₂ flow. The vaporization of C₆₀H₃₆ occurs at very high temperature: the DTA trace has shown an endothermic peak at 540°C (at a heating rate of 20°C/min). C₆₀H₃₆ shows an electronic absorption spectrum with a maximum at about 217 nm and it is able to match both in position and in half width the peak at 217.5 nm observed in the spectrum of the interstellar extinction of light which was attributed to hydrogenated, radiation processed and thermally annealed carbon dust. Similarly, the absorption spectrum of C₆₀H₃₆ is able to match several infrared emission bands (called UIBs) detected from certain astrophysical objects like the protoplanetary nebulae (PPNe). It is proposed that hydrogenated fullerenes can be used as model compounds in the laboratory simulation studies of interstellar carbon dust.     

Computer Simulation of Molecular and Electron Structure of C60 Fullerene Complexes with Twelve Half‐Sandwich Groups MC5H5 (M = Fe,Ru, Os)

Abstract

The C₆₀(MCp)₁₂ complexes of I _h ‐C₆₀ fullerene in which each of 12 MCp groups (M = Fe, Ru, Os; Cp = C₅H₅) is coordinated to one of the five‐membered cycles of C₆₀ via formation of η⁵–π‐bond are considered. Geometry and electron structure of these complexes are simulated by using of the PBE–DFT approach. Stability of complexes considered is evaluated. It is shown that energies of the M–C₆₀ bonds are increased in the sequence C₆₀(FeCp)₁₂, C₆₀(RuCp)₁₂, C₆₀(OsCp)₁₂.     

Adsorption Properties of Multi‐wall Carbon Nanotubes

Abstract

Preparation of multi‐wall carbon nanotubes by means of arc‐discharge in He atmosphere was worked out and optimized. Electron micrographs show that electrode deposit consists of crossed multi‐wall carbon nanotubes. For study of adsorption properties of multi‐wall carbon nanotubes, the thermodynamic characteristics of adsorption of different classes organic compounds at small coverage were determined by gas chromatography and compared with those for graphitized carbon black and molecular crystals of fullerene C₆₀ (fullerite). The comparison of adsorption data for organic compounds with different functional groups on multi‐wall carbon nanotubes, on graphitized carbon black and fullerene C₆₀ shows the similarity of adsorption properties of multi‐wall carbon nanotubes and graphitized carbon black and the differences in molecular interaction of adsorbed molecules with crystal C₆₀.     

Spatially Confined Growth of Fullerene to Super‐Long Crystalline Fibers in Supramolecular Gels for High‐Performance Photodetector

As a superstar organic semiconductor, fullerene (C₆₀) is versatile in nature for its multiple photoelectric applications. However, owing to its natural 0D structure, a challenge still remains unbeaten as to growth of 1D fullerene crystals with tunable sizes. Herein, reported is an efficient approach to grow C₆₀ as super‐long crystalline fibers with tunable lengths and diameters in supramolecular gel by synergic changes of anti‐solvent, gel length, crystallization time or fullerene concentration. As a result, the crystalline C₆₀ fibers can be modulated to as long as 70 mm and 70 000 in their length‐to‐width ratio. In this case, the gel 3D network provides spatial confinements for the growth of 1D crystal along the directional dispersion of anti‐solvent. The fabricated fullerene device exhibits high responsivity (2595.6 mA W^‐1) and high specific detectivity (2.7 × 10¹² Jones) at 10 V bias upon irradiation of 400 nm incident light. The on/off ratio and its quantum efficiency are near to 540 and about 800%, respectively, and importantly, its photoelectric property remains very stable after storage in air for six months. Therefore, spatially confined growth of fullerene in supramolecular gels will be another crucial strategy to synthesize 1D semiconductor crystals for photoelectrical device applications in near future.     

Two Alternative Ways for Formation of Mono‐atomic Carbon Layer on Ni(1 1 1): Organic‐Gas Cracking and Thermal Decomposition of Fullerenes in Thin Film

Abstract

Formation of graphite mono‐atomic layers (monolayer of graphite, MG) on Ni(1 1 1) single‐crystal surface by cracking of propylene C₃H₆ as well as by decomposition of fullerene molecules C₆₀ was investigated. Comparative analysis of carbon films was made in both cases by means of auger electron spectroscopy (AES), low energy electron diffraction (LEED), and scanning tunneling microscopy (STM) techniques. It was shown with the LEED measurements, that quality of graphite mono‐atomic layer obtained in the two different ways is similar and high enough. For the system prepared by fullerene fragmentation some fullerene‐similar topography features were found in STM images. These observations are explained as a result of arrangement of single C₆₀ molecules underneath the MG on Ni(1 1 1).     

TEMPERATURE-DEPENDENT AGGREGATION STRUCTURES OF FULLERENE-BASED IONOMERS IN ELECTROLYTE SOLUTIONS

We have synthesized fullerene derivatives, C₆₀[CO(CH₂)₅O(CH₂)₄SO₃Na]₆ (FC₁₀S), which consists of a C₆₀ cage covalently bonded with six sulfonated arms for a high water solubility. We study the aggregation structures of the novel C60-derivatives in 0.1 M NaCl aqueous solutions by small angle X-ray scattering (SAXS). In the concentration range studied, 0.5 wt% to 2 wt %, the rod-like structure of FC₁₀S aggregates has a radius of 20 Å and a rod-length about 150 Å at 25°C, and the aggregation structure is insensitive to the concentration change. The aggregates, however, grow in length as the temperature increases, while the radius increases slightly with increasing temperature.     

Equilibrium Phase Diagram of Polymerized C60 and Kinetics of Decomposition of the Polymerized Phases

Abstract

Equilibrium phase diagram (T=0–1000 K; p=0–8 GPa) of pressure‐temperature polymerized C₆₀ has been constructed. It included rhombohedral; orthorhombic and tetragonal polymerized phases of C₆₀ along with fcc monomeric phases of C₆₀. The isothermal kinetics of depolymerization (T=373–513 K) of the O‐, R‐, T‐ and D‐phases was studied by means of the IR‐spectroscopy. The isothermal rate of decomposition goes up along the series: (T‐)<(O‐)<(R‐)<(D‐).     

Catalytic activity of hybrid platinum nanoparticle-[C60]fullerene nanowhisker composites for 4-nitrophenol reduction

Abstract

Composites comprising platinum nanoparticles loaded on [C₆₀]fullerene nanowhiskers were prepared by a liquid-liquid interfacial precipitation method. The synthesized platinum nanoparticle-[C₆₀]fullerene nanowhisker composites were characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, and transmission electron microscopy. The catalytic activity of the platinum nanoparticle-[C₆₀]fullerene nanowhisker composites was confirmed for the reduction of 4-nitrophenol by UV–vis spectroscopy. The reduction of 4-nitrophenol catalyzed by the platinum nanoparticle-[C₆₀]fullerene nanowhisker composites followed the pseudo-first-order reaction rate law.     

Structural and Superfluid Properties of the 4He Monolayer on a C28 Molecule

We have performed path-integral Monte Carlo calculations to study the adsorption of N ⁴He atoms on a single C₂₈ fullerene molecule. Radial density distributions show a layer-by-layer growth of ⁴He with the first adlayer being located at a distance of 5.3 Å from the center of C₂₈. The monolayer is found to show a commensurate structure at N=16 with each of the 16 adsorption sites on the molecular surface being occupied by one ⁴He atom. As more helium atoms are adsorbed beyond N=16, the adlayer is in a mixed state consisting of 4 localized atoms at the hexagonal faces and the other atoms delocalized over the pentagonal faces. Another structurally-ordered state is observed at N=32, where the helium layer shows the same crystalline structure with an icosahedral symmetry as observed for 32 ⁴He atoms on a C₆₀ molecule. It is found that more ⁴He atoms can be squeezed into the first layer to disrupt this icosahedral structure when enough ⁴He atoms are added in the second layer. Finally we observe the reentrant superfluid response of the monolayer with superfluidity being quenched completely at the ordered states of N=16 and 32.     

Radical-scavenging Ability of Hydrophilic Carbon Nanoparticles: From Fullerene to Its Soot

We have recently developed a facile synthetic method for highly water-soluble fullerene, so-called fullerenol, for the treatment of fullerene with hydrogen peroxide. This method was applied to fullerene soot to yield the corresponding new hydrophilic carbon materials, and the obtained products were subjected to infrared spectroscopy and elemental analysis. The DLS particle size analysis demonstrated the relatively high dispersion of hydrophilic fullerene soot with a diameter of ?70 nm in water, while the hydrophilic activated carbon obtained by the same treatment showed the larger aggregation with diameters of 200 and 970 nm. The surface analysis using FE-SEM showed the difference in morphology between fullerene soot and activated carbon as well as between before and after hydrophilic treatment of the soot with hydrogen peroxide. Moreover, this hydrophilic fullerene soot exhibited high antioxidant activity (%AOA) up to 87% compared with fullerenol C₆₀(OH)₃₆ (54%) and C₆₀ (50%) evaluated by β-carotene bleaching method.     

Equation of State for <Emphasis Type="Italic">C</Emphasis><Subscript>60</Subscript> Fullerene Aqueous Solutions

In the present work PVT data of the C₆₀ fullerene aqueous solution (C₆₀ FAS) were measured as a function of the concentration of C₆₀ molecules using the variable cell method with metal bellows in the temperature range from 295 to 360 K at pressures from 0.1 to 103.2 MPa. On the liquid–vapor equilibrium line the density (ρ) of the C₆₀ FAS was measured using the pycnometer method. As a result, numerical values for the isothermal modulus of elasticity (K_T), isobaric expansivity (α_P), isothermal deviation of entropy factor (TΔS), enthalpy (ΔH), and internal energy (ΔU) have been determined. Finally, an equation of state for the C₆₀FAS was obtained for the first time.     

Star‐like Fullerene Containing Poly(Vinylpyrrolydone) Derivatives: Chloroform Solution Properties

Abstract

Star‐like fullerene C₆₀ derivatives with different branch number, synthesized by the reaction of fullerene with poly(vinylpyrrolydone) (PVP) macromolecules bearing the terminal amino‐groups, were investigated in solution by the viscometry, dielectric, and electrooptical Kerr‐effect methods in comparison with the ordinary linear PVPs of the same molecular mass. It was shown that covalent linkage of branches to fullerene through amino‐groups leads to appearance of a polar and optically anisotropic nanoparticle (amine‐substituted C₆₀) in the center of the coil of star‐like polymers that radically changes dielectric and electrooptical properties of the initial polymer. Effect of fullerene on the dimension of polymer coil had been detected also.