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.     

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。     

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.     

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.     

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.     

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.     

Manganese(III) acetate-mediated radical reaction of [60]fullerene with bromoacetic acid, 3-chloropropionic acid or 1-naphthylacetic acid

The manganese(III) acetate-mediated radical reaction of [60]fullerene (C₆₀) with three carboxylic acids, that is, bromoacetic acid, 3-chloropropionic acid, and 1-naphthylacetic acid, was investigated. The reaction of C₆₀ with bromoacetic acid in the presence of 4-(dimethylamino)pyridine afforded the anticipated C₆₀-fused lactone, while the reaction with 3-chloropropionic acid unexpectedly led to the formation of a novel C₆₀-fused lactone with the loss of one molecule of HCl. Interestingly, the reaction with 1-naphthylacetic acid under similar conditions gave both C₆₀-fused lactone and 1,4-adduct, yet each of them could be selectively obtained by controlling reaction conditions. It was also observed that the C₆₀-fused lactone bearing a bulky naphthyl group existed as two isomers.     

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.     

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.     

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.     

Distribution and characterization of C31 sterane from cretaceous sediments and oils, Songliao Basin, China

Relatively high abundance of C₃₁ steranes has been identified from cretaceous source rocks and crude oils in the Songliao Basin, China. C₃₁ steranes which occur as ten isomers were tentatively identified as 4, 22, 23, 24-tetrametyhlcholestane based on their retention time and mass spectrum. They bear a lower thermal stability and occur as important components in the immature oils of Chaochang region because they have three-methyl groups in their side chain. The relatively high abundance of C₃₁ steranes in the samples can indicate the source input of some special algae in the brackish and saline environment. Therefore they can be used as very useful bimarkers for organic facies analysis and oil correlation. Their biological source perhaps related to the dinoflagellate such asG. foliaceum andP. foliaceum. The gorgostanol are considered as possible precursors for the putative C₃₁4-methyl sterane which formed in the stage of diagenesis.     

Relationship between climatic conditions and the relative abundance of modern C3 and C4 plants in three regions around the North Pacific

Using −24‰ and −14‰ as the endpoints of stable carbon isotopic composition of total organic carbon (δ¹³C_TOC) of surface soil under pure C₃ and C₄ vegetation, and surface soil δ¹³C_TOC data from eastern China, Australia and the Great Plains of North Amer- ica, we estimate the relative abundance of C₃/C₄ plants (i.e., the ratio of C₃ or C₄ biomass to local primary production) in modern vegetation for each region. The relative abundance of modern C₃/C₄ vegetation from each region is compared to the corresponding climatic parameters (mean annual temperature and precipitation) to explore the relationship between relative C₄ abundance and climate. The results indicate that temperature controls the growth of C₄ plants. However, even where temperature is high enough for the growth of C₄ plants, they will only dominate the landscape when precipitation declines as temperatures increase. Our results are consistent with those of other investigations of the geographic distribution of modern C₄ plant species. Therefore, our results provide an important reference for interpretation of past C₃/C₄ relative abundance records in these three regions.     

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.     

Distribution of C4 plants along the Northeast China transect and its correlation to the environmental factors

The distribution of C₄ plants and the C₄/C₃ ratio along Northeast China transect (NECT) have been studied. A model to quantify their relation with environmental factors has been set up. The ratio of the number of C₄ plants to that of C₃ plants along NECT shows two low and two high trends from east to west, and their distribution is mainly decided by annual average temperature and precipitation.     

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…     

VUV threshold photoelectron spectroscopy of the C2H3Cl molecule

The threshold photoelectron spectrum of the C₂H₃Cl molecule is studied by using synchrotron radiation light source and supersonic molecular beam. The vertical ionization potentials of different orbital electrons and some vibrational structures are obtained. The observed Rydberg autoionization peaks are assigned by A²A¹ state of C₂H₃Cl₊.     

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 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.     

The formation and stability of Si1-x C x alloys in Si implanted with carbon ions

Si_1-xC_x alloys of carbon (C) concentration between 0.6%—1.0% were grown in Si by ion implantation and high temperature annealing. The formation of Si_1-xC_x alloys under different ion doses and their stability during annealing were studied. If the implanted dose was less than that for amorphizing Si crystals, the implanted C atoms would like to combine with defects produced during implantation and it was difficult to form Si_1-xC_x alloys after being annealed at 850℃. With the increment of implanted C ion doses, the lattice damage increased and it was easier to form Si_1-xC_x alloys. But the lattice strain would become saturate and only part of implanted carbon atoms would occupy the substitutional positions to form Si_1-xC_x alloys as the implanted carbon dose increased to a certain degree. Once Si_1-xC_x alloys were formed, they were stable at 950℃, but part of their strain would release as the annealing temperature increased to 1 000℃. Stability of the alloys became worse with the increment of carbon concentration in the alloys.     

Comparison of the carbon isotope composition of total organic carbon and long-chain <Emphasis Type="Italic">n</Emphasis>-alkanes from surface soils in eastern China and their significance

Surface soil samples collected over a high spatial resolution in eastern China were analyzed for carbon isotope composition （δ^13C） of total organic carbon （TOC） and higher plant-derived long-chain n-alkanes, with the latter reported as weighted mean values. The two sets of δ^13C values are significantly correlated and show similar trends in spatial variation. The spatial distribution of δ^13C shows less negative values in the mid-latitudes between 31°N and 40°N and more negative ones at higher and lower latitudes. This is consistent with previously reported carbon isotope data from surface soil phytoliths in the same region and suggests that the mid-latitude area provides relatively favorable growing condi- tions for C4 plants. Furthermore, δ^13C values of both TOC and long-chain n-alkanes from 12 surface soil samples collected from a small grassland in north China displayed similar carbon isotope values and the difference between paired δ^13C of a soil samples remains relatively constant. Our data demonstrate that in eastern China, soil δ^13C composition of both TOC and long-chain n-alkanes is effective indicators of C3/C4 ratios of the prevailing vegetation. This work suggests that -22‰ and -32‰ are good es- timated end members for the weighted mean δ^13C values of long-chain n-alkanes （C27, C29 and C31 n-alkanes） from soils under dominant C4 or C3 vegetation, allowing us to reconstruct paleovegetation trends.