Ferric perchlorate-promoted reaction of [60]fullerene with β-keto esters

The ferric perchlorate-promoted reaction of [60]fullerene (C60) with ethyl 2-methylacetoacetate generates fullerenyl hemiketal as a mixture of trans and cis isomers,while the reaction with ethyl acetoacetate gives a C 60-fused dihydrofuran derivative.A possible reaction mechanism for the formation of these products is proposed.     

富勒烯C_(60)接枝马来酸聚合物铅盐的制备与表征

以富勒烯C60和马来酸为原料合成得到一种新型富勒烯C60接枝马来酸聚合物,C60接枝马来酸聚合物再与硝酸铅反应得到C60接枝马来酸聚合物铅盐。通过单因素方法探讨了pH、反应物物料比、反应温度以及反应时间对C60接枝马来酸聚合物铅盐中铅含量的影响,获得其最佳合成工艺条件为:pH=6.92,C60接枝马来酸聚合物和硝酸铅的摩尔比为1∶7,反应时间2 h,反应温度30℃,该条件所得C60接枝马来酸聚合物铅盐中铅质量分数为56.09%。同时采用FT-IR、UV、GPC、AAS、XRD及XPS等测试手段对产物结构进行了表征。采用差热和热重分析法对C60接枝马来酸聚合物铅盐的热稳定性进行了研究,结果表明,在空气气氛下,DTA分解峰值温度为275、370、462℃,失重率为43.6%,表明产物热稳定性良好。     

Inhibition of DNA restrictive endonucleases and Taq DNA polymerase by trimalonic acid C60

Activities of trimalonic acid fullerene (TMA C_60) on DNA restrictive enzymatic reaction were investigated by using two restrictive endonucleases Hind III and EcoR I and plasmid pEGFP-N1 with single restric-tive site for both enzymes. Meanwhile, TMA C60 was also tested to clarify its effects on polymerase chain reaction (PCR) with the catalyst of Taq DNA polymerase and the template of plasmid pEGFP-N1. The products from restrictive reactions or PCR were detected by agarose gel electrophoresis. It was found that the product amounts from restrictive reactions or PCR decreased significantly with addition of TMA C60. The inhibition by TMA C60 was dose-dependent and IC50 values for reactions of Hind III, EcoR I and PCR were 16.3, 6.0 and 6.0 μmol/L, respectively. Addition of two scavengers of reactive oxygen species (ROS), L-ascorbic acid-2-phosphate ester magnesium and sodium azide at the con-centrations of 2―10 mmol/L did not antagonize the activities of TMA C60 against PCR and two restrictive reactions. However, increase of Taq DNA polymerase amounts in PCR system antagonized the activities of TMA C60. These data implied that TMA C60 was able to inhibit the activities of the three above-mentioned enzymes involved in DNA metabolism, and that this inhibition probably did not correlate to ROS.     

Synthesis of N-acetamide C60 nitride and its performance of optical limiting

N-acetamide C₆₀ nitride (N-acetamide-1,2-dihydro-1,2-aza-fullerene [60]) has been synthesized by the reaction of C₆₀ and azidoacetamide and initially characterized. Its mechanism was that the objective product is formed through intermediate triazoline. The computational study shows that N-nitride structure is thermodynamically more stable by using the semi-empirical AM1 SCF-MO method. The properties of optical limiting were tested by using double frequency Nd: YAG pulse laser system and showed that the optical limiting mechanism is reverse saturation absorption. At wavelength of 532 nm, compared with optical limiting for ns pulse, this new material has good optical limiting character for ps pulse. At wavelength of 707 nm, the capacity of optical limiting of the derivative is prior to C₆₀.     

Self-assembly of N-3-γ-pyridyl Aza[60]fulleroid on Au(111)

Self-assembled monolayers of novel C₆₀ derivative, N-3-γ-pyridyl Aza[60]fulleroid (C₆₀Py), on Au(111) were studied by a scanning tunneling microscope under ultrahigh vacuum (UHV). C₆₀Py molecules were assembled on Au (111) via pyridyl nitrogen-Au interaction. The sole assembly of C₆₀Py molecules on Au (111) only exhibited randoml aggregation of C₆₀Py even the films were annealed at 50 and 105°C. By co-assembling with benzyl mercaptan (BM), the C₆₀PyBM films showed highly dense aggregation, but C₆₀Py assemblies still had disordered structure. After the co-assembled C₆₀Py-BM films were annealed at 50°C, BM molecules were partially desorbed, but the assembly of C₆₀Py remained without obvious change. After the co-assembled C₆₀Py-BM films were further annealed at 105°C, the C₆₀Py monolayers with ordered structure were obtained, while the BM molecules were nearly thoroughly desorbed from the surface. Here, the BM molecules play a key role as a surfactant in the formation of the ordered C₆₀Py monolayer.     

Decoration of C60 nanorods with nickel and their magnetic properties

We studied the coating of C60 nanorods with nickel by electroless plating method and investigated their magnetic properties. The morphology and structure of the nickel layer coated on C60 nanorods were characterized by transmission electron microscopy （TEM）, energy-dispersive X-ray spectroscopy （EDX）, X-ray diffraction （XRD） and Raman spectroscopy. The coated nickel is in the form of nano-sized crystals and becomes a continuous layer as reaction time increases. The hysteresis loop shows a super paramagnetic characteristic similar to that of nanometer-sized nickel particle. These results suggest that the average size of nickel particles on C60 rods is below 10 nm. Our study has shown that electroless plating is an efficient and simple method for coating C60 nanorods with nickel.     

Spontaneous transformation of C60Br24 to C60 in solvents

It was found that C₆₀Br₂₄ transforms to C₆₀ spontaneously in some solvents. The intermediate, C₆₀Br₈, can be separated in some cases. When the bromine trap, phenol, was added,p-bromophenol and other brominated product were obtained and identified. The influences of time, the kind of solvent, etc were investigated. Possible mechanism was suggested. Supported by the National Natural Science Foundation of China Liu Ying: born in 1969, Ph. D     

Theoretical study on photophysical property of C60M（CO）5 （M=Cr,Mo and W）

Configurations of three η2 models of transition-metal [60]fullerene derivatives C60M（CO）5（M=Cr, Mo and W） have been optimized at B3LYP/LanL2DZ level. On the basis of the optimized geometrical structures, their electronic spectra and the frequency dependence of third-order nonlinear optical polarizabilities γ in different optical processes of third-harmonic generation （THG）, electric-field-induced second-harmonic generation （EFISHG） and degenerate four-wave mixing （DFWM） are calculated by using TDB3LYP model based on LanL2DZ level coupled with the SOS （sum-over-state） method. The obtained results show that their electronic spectra have a red shift compared with that of [60]fullerene and different transition-metal functional groups added to C60 cage may result in different spectrum properties. For the three studied species, （η^2-C60）Mo（CO）5 has the largest third-order nonlinear optical polarizability.     

Structural stability of C<Subscript>60</Subscript> films under the bombardment of 1.95 GeV Kr ions

The structural stability of C₆₀ films under the bombardment of 1.95 GeV Kr ions is investigated. The irradiated C₆₀ films were analyzed by Fourier Transform Infrared (FTIR) spectroscopy and Raman scattering technique. The analytical results indicate that the irradiation induced a decrease of icosahedral symmetry of C₆₀ molecule and damage of C₆₀ films; different vibration modes of C₆₀ molecule have different irradiation sensitivities; the mean efficient damage radius obtained from experimental data is about 1.47 nm, which is in good agreement with thermal spike model prediction.     

Biodistribution of fullerene derivative C60(OH)x(O)y

The biological behavior of fullerene derivatives shows their considerable potential application in medicine field. To understand the biodistribution of C₆₀ derivatives as drugs or drug carriers, a simple water-soluble derivative C₆₀(OH)_x(O)_y was labeled with^99mTc. A γ-counter and a single photo emission computed tomography (SPECT) were used to assess the biodistribution and metabolism of the labeled compound in mice and rabbits, respectively. The results showed that the compound could be absorbed rapidly by tissues, especially by coronal bone, breastbone, backbone, extremity honeycomb, liver and spleen. The clearance was slow from all tissues except for brain. The compound might be excreted through urine and enteron. The biodistribution shows some difference from that of Yamago et al. In this note, we discuss the possible reason leading to the difference. Further study is needed to find out to what extent the C₆₀ itself determines the biodistribution of derivatives.     

Investigation of tribological properties of composite C60-LB films

C60, as the third allotrope of carbon element, has al- ways received much attention from material scientists since it was found by Kroto in 1985. It is endowed with many special characteristics[1-4] due to its symmetrical structure such as photo-induced e…     

Fe3O4@NiSiO3纳米催化剂制备及催化臭氧化降解对苯二甲酸性能研究

采用水热法和溶胶凝胶法制备Fe₃O₄@SiO₂纳米颗粒,经表面镍刻蚀得到Fe₃O₄@NiSiO₃磁性纳米催化剂。利用XRD、TEM和VSM等手段表征催化剂的晶体和表面结构。构建类均相催化臭氧化体系,考察其催化降解对苯二甲酸性能。结果表明：在臭氧通入量10.52 mg.min_-1、催化剂投加量40 mg.L_-1和初始溶液pH=9的条件下,催化臭氧化反应20 min时对苯二甲酸降解率为78.13%,TOC去除率27.25%;5次循环实验后,PTA降解率仅下降2.75%。     

In situ observation of C60（C（COOH）2）2 interacting with living cells using fluorescence microscopy

1 Introduction In recent years, studies on biological effects of thenanoscale materials have become the cornerstone of rapidly developed nanomedical and nanobiological technologies. Moreover, studies on the bio-effects when the different kinds of nanoscal…     

Inhibition of M-MuLV reverse transcriptase activity by fullerene derivatives

The biological properties and biomedical application of fullerene (C60) and its derivatives are currently very active subjects concerning fullerene research. The bio logical effects of fullerene and its derivatives include enzyme inhibition, sites-selective DNA cleavage, antibacterial and antiviral activities, photocytotoxicity and antiapoptosis[1―4]. Especially, enzymes inhibited by fullerene derivatives mainly consist of oxidation-reduc- tion related enzymes such as glutathione transferase…     

Synthesis and magnetic property of a nitroxide based on C60

The compounds containing stable nitroxide radicals possess magnetic properties for the free radical have net magnetic moment. Oxidization of the [60]fulleropyrolidine obtained from the reaction of C₆₀ with diketone and 2-aminoisobutyric acid bym- chloroperoxybenzoic acid gives a new nitroxide integrated with C₆₀. The stable nitroxide based on C₆₀ is confirmed to be antiferro-magnetism with quantum design superconducting quantum interference device (SQUID).     

Vegetation evolution on the central Chinese Loess Plateau since late Quaternary evidenced by elemental carbon isotopic composition

There are many controversial issues in loess studies such as natural vegetation types on the Chinese Loess Plateau during the historical periods and the spatial and temporal evolution of C3/C4 plants. Elemental carbon isotopic composition （δ^13Cec） in the loess section may offer new evidence for these problems. Elemental carbon （EC） is produced by incomplete combustion of vegetation, and its carbon isotopic composition has a very small difference from that of the formal vegetation, then δ^13Cec can be used as a record to recover the changes of vegetation. Elemental carbon was extracted by applying the oxidation method from the Ioess-paleosol sequence in the central Chinese Loess Plateau, and its car- bon isotope composition was analyzed by the isotope mass spectrometer. The results showed that the vegetation in this region was a mixed type of C3 and C4 plants, dominated with C3 plants in most of the time. Since late Quaternary, C3/C4 plants may not follow a simple glacial-interglacial cycle mode on the Chinese Loess Plateau, but showing fluctuations. C3 plants increased gradually in L4 period, and more C3 plants occurred during $3 period, and C4 plants increased again during L3-- L2 periods, after that, Cs plants dominated again during S1 --S0 periods. During periods of paleosol development, C3 plants were abundant in S3 and S1, and there were more Ca plants in S2 and SO. During periods of loess sedimen- tation, there were more C3 plants in L4 and L1, and there were more C4 plants in L3 and L2. On the orbital timescale, the vegetation variations revealed by δ^13Cec record are consistent with the results of pollen data and also similar to the results obtained by organic carbon isotopic composition since the last glacial period.     

Induced temperature-dependent DNA degradation by C60 without photoactivation

This study shows that C₆₀ can degrade pBR322 plasmid DNA at room temperature without photoactivation. The degradation was enhanced by increasing incubation temperature, reaction time or C₆₀ concentration. We also found that superoxide radical anions (O ₂ ^?· ) were formed in the C₆₀ solution. Superoxide dismutase significantly inhibited DNA cleavage and O ₂ ^?· generation induced by C₆₀. These results suggest that DNA cleavage was caused by the formation of reactive oxygen species induced by C₆₀ at room temperature. Furthermore, we demonstrate that the DNA degradation was significantly inhibited by acid amide chemicals such as formamide, and by increased ionic strength of the reaction solution. These results indicate that the DNA conformation stability and the surface properties of C₆₀ are important factors regulating DNA degradation. We propose that C₆₀ can bind DNA, decrease DNA conformation stability, and induce the formation of reactive oxygen species and DNA cleavage at room temperature. Our results provide a possible explanation for the genotoxicity of C₆₀, which should be considered in future use of this particular nano-material.     

二维Ti3C2Tx MXene材料的制备与工艺优化

二维（2D）过渡金属碳/氮化物（MXene）材料是当前最受关注的二维材料之一,其中二维碳化钛（Ti₃C₂T_x MXene）材料的研究最为广泛。该材料目前主要通过刻蚀三元碳化物或氮化物（MAX相）后进一步插层得到,因此MAX相材料的纯度和制备工艺条件直接决定了Ti₃C₂T_x MXene材料的物化性质。主要完成了不同Ti₃AlC₂ MAX相材料的筛选,选择氢氟酸（HF）刻蚀,并优化了不同的插层方法,制备了一系列Ti₃C₂T_x MXene材料。通过X射线衍射（XRD）、场发射扫描电镜（FESEM）、透射电子显微镜（TEM）、原子力显微镜（AFM）和X射线光电子能谱（XPS）等表征,确定使用原位锂离子（Li⁺）插层法可有效获得单层Ti₃C₂T_x MXene材料。制备的单层Ti₃C₂T_x MXene材料的表面平整,片径约为150 nm,厚度约为2 nm。同时,创新性地采用涡旋震荡辅助材料分层,极大地缩短了超声时间,提高了单层Ti₃C₂T_x MXene材料的产率（可达70%）,并且可以避免材料氧化,为Ti₃C₂T_x MXene材料未来应用提供了新方法。     

Electronic structures and infrared spectra of C120O2, C120OS and C120S2

Electronic structures and infrared spectra of C₁₂₀XY molecules (X, Y=O, S) and some of the corresponding ions are investigated using PM3 semi-empirical molecular orbital calculations with full optimization of geometrical structures. It is found that the energy penalty is about 30–42 kJ/mol due to introducing a double bond in the fivemembered ring except for C₁₂₀O₂ ⁻ and triplet C₁₂₀O₂ ²⁻. It is also found that the structures of neutral molecules and the corresponding ions are almost the same; for instance, the change of bond length is less than 0.001 nm. The change of frontier orbits from oxide to sulfide is little as well. The triplet states of C₁₂₀O₂ ²⁻ and C₁₂₀OS²⁻ are more stable than their singlet states, which means that C₁₂₀O₂ ²⁻ and C₁₂₀OS²⁻ follow the Hund’s rule. The vibration analysis showed that the infrared spectra of neutral C₁₂₀O₂ and C₁₂₀OS molecules are in good agreement with the experimental results. Compared with the neutral molecule, vibration frequencies of triplet C₁₂₀O₂ ²⁻ change little, but the vibration intensities are enhanced obviously.     

Orientational phase transition in C60 single crystal under high pressure

By using a piston-cylinder type hydrostatic high-pressure unit, the electrical dc conductance of bulk C₆₀ single crystal was measured in the pressure range of 0 to 0.6 GPa at 290 K. Wlth increasing pressure, a discontinuous increase of the conductance was observed at the pressure of 0.176 GPa, which can be ascribed to. the orientational ordering phase transition. In the simple cubic phase, the increase of conductance with increasing pressure is faster than that in the face-centered-cubic phase.