A Convenient Synthesis of Novel Meldrum＇s Acid C60 Fullerene Derivatives

A series of novel Meldrum＇s acid C60 derivatives were prepared in moderate yields from a convenient one-pot reaction of C60, the Meldrum＇s acid derivatives, 12 and 1,8-diazabicyclo-[5,4,0]-undec-7-ene （DBU） in toluene at room temperature under nitrogen atmosphere. All the new compounds were fully characterized by the spectral data and elemental analysis. A carbene intermediate mechanism was proposed for this reaction.

Synthesis and Characterization of W-doped TiO_2 Supported by Hybrid Carbon Nanomaterials of Multi-walled Carbon Nanotubes and C_(60) Fullerene by a Hydrothermal Method

W-doped TiO2 supported by hybrid carbon nanomaterials of multi-walled carbon nanotubes and C60 fullerene was synthesized by a simple hydrothermal method. The material displayed high visible light photocatalytic activity. X-ray diffraction, field emission transmission electron microscopy, ultra violet/visible light absorption and photoluminescence spectroscopy were used to characterize the material as photoeatalyst. Photocatalytic activity on the degradation of Rhodamine B dye in an aqueous solution under ultraviolet light and visible light irradiation was also studied. The experimental results indicated that the photocatalytic activity of the material was much higher than that of pure TiO2 or Degussa P25 TiO2.

Highly soluble dendritic fullerene derivatives as electron transport material for perovskite solar cells

A series of shape-persistent polyphenylene dendritic C_(60)derivatives as the electron transport materials were designed and synthesized via a catalyst-free Diels-Alder[4+2]cycloaddition reaction.These increasing hyperbranched scaffolds could effectively enhance the solubility;notably,both first and second generation dendrimers,C_(60)-G1 and C_(60)-G2,demonstrated more than 5 times higher solubilities than pristine C_(60).Furthermore,both simulated and experimental data proved their promising solution-processabilities as electron-transporting layers(ETLs)for perovskite solar cells.As a result,the planar p-i-n structural perovskite solar cell could achieve a maximum power conversion efficiency of 14.7%with C_(60)-G2.

Effects of C60 on the Glass Transition Temperature of Carbazole-based Photorefractive Polyphosphazenes

The bi-functional carbazole-based photorefractive polyphosphazenes with different content of C_（60）-doped were fabricated. The glass transition temperature（T_g） of these polymer composite materials was determined using a differential scanning calorimetric（DSC） method. According to the DSC measurement results with different heating rates, the variation of T_g and the active energy of glass transition（E_g） were analyzed in detail. The analysis results indicate that the transition region shifts to higher temperatures with increasing heating rate, and C_（60） content（below 1.0 wt%） can influence the T_g of photorefractive polyphosphazenes. The T_g first increases and then decreases with the C_（60） content（below 1.0 wt%）. The probable causes of the influence of C_（60） on T_g was proposed.

In situ electrical resistance and activation energy of solid C_(60) under high pressure

The in situ electrical resistance and transport activation energies of solid C60 fullerene have been measured under high pressure up to 25 GPa in the temperature range of 300-423 K by using a designed diamond anvil cell. In the experiment, four parts of boron-doped diamond films fabricated on one anvil were used as electrical measurement probes and a W-Ta thin film thermocouple which was integrated on the other diamond anvil was used to measure the temperature. The current results indicate that the measured high-pressure resistances are bigger than those reported before at the same pressure and there is no pressure-independent resistance increase before 8 GPa. From the temperature dependence of the resistivity, the C60 behaviors as a semiconductor and the activation energies of the cubic C60 fullerene are 0,49, 0.43, and 0.36 eV at 13, 15, and 19 GPa, respectively.

PHOTOCATALYTIC HYDROGEN EVOLUTION FROM WATER SPLITTING UNDER VISIBLE LIGHT IRRADIATION ON NOVEL PHOTOCATALYST FULLENES-PVP-ZN0.999NI0.001S

Fullerenes （C60/C70） linked up to Ni-doped ZnS through the medium of an amphalic polymer polyvinyl pyrrolidone （PVP） to form a new kind of photocatalyst for hydrogen evolution from aqueous Na2S/Na2SO3 solution under visible light irradiation, the photocatalytic activities of this novel photocatalyst C60/C70-PVP- Zn0.999Ni0.001S are 3-5 fold higher compared with that of precurse catalyst Zn0.999Ni0.001S. This result could be attributed to Schottky barrier layer built between C60/C70 and Zn0.999Ni0.001S due to the electro-negativity of C60 and characteristic of being used as a multiple electron acceptor. C60 or C60/C70 its moiety, with its low energy first excited singlet state, is a good energy acceptor and in addition readily accepts multiple electrons, making it a potential electron accumulate as we know, which could protect the separation between electrons and holes against combination. This is an important reason for the marked increase of amount of H2 evolution during the photocatalytic process for the composite system C60/C70-PVP- Zn0.999Ni0.001S.

Regulation of Glucose Oxidase Activity through Interaction with Fullerene Derivatives

The 2-（hydroxymethyl）pyridine modified C60 （PY-C60） and methoxydiglycol modified C60 （MDG-C60） are synthesized using Bingel-Hirsch reaction and characterized by nuclear magnetic resonance （NMR） and mass spectra. PY-C60 and MDG-C60 can bind to glucose oxidase （GOx） and quench the fluorescence of tryptophan （Trp） residue in GOx through static mechanism. The conformation of GOx is disturbed after formation of complex with these fullerene derivatives. Kinetic analysis indicates that PY-C60 and MDG-C60 may affect the catalytic activity of GOx with a partial mixed-type inhibition mechanism. In the plasma glucose concentration range （3.6--5.2 mmol·L-1）, PY-C60 may significantly accelerate the catalytic velocity of GOx, however, MDG-C60 exerts almost no obvious change to the initial velocity of GOx, suggesting that elaborate design of molecular structure of fullerene derivative is very important for regulating the biological activity of fullerene-enzyme complex.

Transient Absorption Spectral Characterization of Electron Transfer between Fullerenes (C_(60)/C_(70)) and N,N,N′,N′-Tetra(p-methylphenyl)-4,4′-diamino-1,1′-diphenyl Sulphide (TPDAS)

In search of new systems with a photoexcited redox pair which exhibits a strong and stable photoinduced absorption band to understand the photophyscial and photochemical properties of electron transfer between fullerenes (C 60/C 70) and organic donor [N,N,N′,N′-tetra(p-methylphenyl)-4,4′-diamino-1,1′-diphenyl sulphide (TPDAS)], we studied characteristic absorption spectra in the near-IR region obtained from 532 nm nanosecond laser flash photolysis of a mixture of the fullerenes (C 60/C 70) and TPDAS in polar solvents. When fullerenes (C 60/C 70) were photoexcited, the rise of the radical anion of fullerenes (C 60/C 70) with the rapid decay of their excited triplet states were observed in benzonitrile. It can be deduced that the electron transfer reaction does take place from TPDAS to excited triplet state of fullerenes (C 60/C 70). The rate constants (k et) and quantum yields (Φ et) of this process have been also evaluated.

Photoinduced Electron Transfer between N,N,N′,N′-Tetra-(p-methylphenyl)-4,4-diamino-1,1′-diphenyl Ether (TPDAE) and Fullerenes (C_(60)/C_(70)) by Laser Flash Photolysis

The photoinduced electron-transfer reaction of N,N,N′,N′-tetra-(p-methylphenyl)-4,4′-diamino-1,1′-diphenyl ether (TPDAE) and fullerenes (C 60/C 70) by nanosecond laser flash photolysis occurred in benzonitrile. Transient absorption spectral measurements were carried out during 532 nm laser flash photolysis of a mixture of the fullerenes (C 60/C 70) and TPDAE. The electron transfer from the TPDAE to excited triplet state of the fullerenes (C 60/C 70) quantum yields and rate constants of electron transfer from TPDAE to excited triplet state of fullerenes (C 60/C 70) in benzonitrile have been evaluated by observing the transient absorption bands in the near-IR region where the excited triplet state, radical anion of fullerenes (C 60/C 70) and radical cations of TPDAE are expected to appear.