Theoretical evidence for a c60 "window" mechanism

On the basis of semiempirical and high-level ab initio calculations, theoretical evidence is presented of a "window" mechanism operable on the surface of C(60) and other fullerenes. Through this mechanism, large holes may be formed in fullerenes excited to their triplet state, openings through which atoms and small molecules can pass. This work provides a theoretical foundation for experiments that have prepared endohedral noble gas compounds of C(60) under thermal excitation. A method is proposed that could increase the efficiency of the process of noble gas insertion into C(60) and provide a more general means to create endohedral fullerene compounds.     

Energetics of large fullerenes: balls, tubes, and capsules

First-principles calculations were performed to compare the energies of 29 different fullerene structures, with mass number from 60 to 240, and of eight nonhelical graphite tubes of different radii. A quantity called the planarity, which indicates the completeness of the pi-bonding, is the single most important parameter determining the energetics of these structures. Empirical equations were constructed for the energies of nonhelical tubes and for those fullerene structures that may be described as balls or capsules. For a given mass number, bail-shaped fullerenes are energetically favored over capsular (tube-like) fullerenes.     

Chemistry of the fullerenes: the manifestation of strain in a class of continuous aromatic molecules

Within the wr-orbital axis vector theory, the total rehybridization required for closure of the fullerenes is approximately conserved. This result allows the development of a structure-based index of strain in the fullerenes, and it is estimated that about 80 percent of the heat of formation of the carbon atoms in C60 may be attributed to a combination of v strain and steric inhibition of resonance. Application of this analysis to the geometries of structurally characterized organometallic derivatives of C60 and C70 shows that the reactivity exhibited by the fullerenes may be attributed to the relief of a combination of local and global strain energy. C60 is of ambiguous aromatic character with anomalous magnetic properties but with the reactivity of a continuous aromatic molecule, moderated only by the tremendous strain inherent in the spheroidal structure.     

Spherical bilayer vesicles of fullerene-based surfactants in water: a laser light scattering study

The low solubility of fullerenes in aqueous solution limits their applications in biology. By appropriate substitution, the fullerenes can be transformed into stabilized anions that are water soluble and can form large aggregated structures. A laser light scattering study of the association behavior of the potassium salt of pentaphenyl fullerene (Ph5C60K) in water revealed that the hydrocarbon anions Ph5C60- associate into bilayers, forming stable spherical vesicles with an average hydrodynamic radius and a radius of gyration of about 17 nanometers at a very low critical aggregation concentration of less than 10(-7) moles per liter. The average aggregation number of associated particles in these large spherical vesicles is about 1.2 x 10(4).     

Electronic correlation effects and superconductivity in doped fullerenes

A theory of the electronic properties of doped fullerenes is proposed in which electronic correlation effects within single fullerene molecules play a central role, and qualitative predictions are made which, if verified, would support this hypothesis. Depending on the effective intrafulllerene electron-electron repulsion and the interfullerene hopping amplitudes (which should depend on the dopant species, among other things), the calculations indicate the possibilities of singlet superconductivity and ferromagnetism.     

Uranium stabilization of c28: a tetravalent fullerene

Laser vaporization experiments with graphite in a supersonic cluster beam apparatus indicate that the smallest fullerene to form in substantial abundance is C(28). Although ab initio quantum chemical calculations predict that this cluster will favor a tetrahedral cage structure, it is electronically open shell. Further calculations reveal that C(28) in this structure should behave as a sort of hollow superatom with an effective valence of 4. This tetravalence should be exhibited toward chemical bonding both on the outside and on the inside of the cage. Thus, stable closed-shell derivatives of C(28) with large highest occupied molecular orbital-lowest unoccupied molecular orbital gaps should be attainable either by reacting at the four tetrahedral vertices on the outside of the C(28) cage to make, for example, C(28)H(4), or by trapping a tetravalent atom inside the cage to make endothedral fullerenes such as Ti@C(28). An example of this second, inside route to C(28) stabilization is reported here: the laser and carbon-arc production of U@C(28).     

Encapsulation of molecular hydrogen in fullerene C60 by organic synthesis

In spite of their importance in fundamental and applied studies, the preparation of endohedral fullerenes has relied on difficult-to-control physical methods. We report a four-step organic reaction that completely closes a 13-membered ring orifice of an open-cage fullerene. This process can be used to synthesize a fullerene C60 encapsulating molecular hydrogen, which can be isolated as a pure product. This molecular surgical method should make possible the preparation of a series of C60 fullerenes, encapsulating either small atoms or molecules, that are not accessible by conventional physical methods.     

A rational chemical synthesis of C60

Isolable quantities of C60, the smallest stable fullerene, have been synthesized in 12 steps from commercially available starting materials by rational chemical methods. A molecular polycyclic aromatic precursor bearing chlorine substituents at key positions forms C60 when subjected to flash vacuum pyrolysis at 1100 degrees C. No other fullerenes are formed as by-products. The methods we have developed for the target-specific synthesis of fullerenes, applied here to a synthesis of C60, should make possible the directed laboratory preparation of other fullerenes as well, including those not accessible by graphite vaporization.     

Fullerenes from the geological environment

By means of high-resoluton transmission electron microscopy, both C(60) and C(70) fullerenes have been found in a, carbon-rich Precambrian rock from Russia The fullerenes were confirmed by Fourier transform mass spectrometry with both laser desorption and thermal desorption/electron-capture methods to verify that the fullerenes were indeed present in the geological sample and were not generated by the laser ionization event. The mass spectra were measured under conditions sufficient to resolve the (13)C/(12)C isotopic ratios for C(60) and C(70) and indicate that these ratios correspond to the normal range of isotopic values.     

Fullerenes in the 1.85-billion-year-old Sudbury impact structure

Fullerenes (C60 and C70) have been identified by laser desorption, laser desorption post-ionization, and high-resolution electron-impact mass spectrometry in shock-produced breccias (Onaping Formation) of the Sudbury impact structure in Ontario, Canada. The C60 isotope is present at a level of a few parts per million. The fullerenes were likely synthesized within the impact plume from the carbon contained in the bolide. The oxidation of the fullerenes during the 1.85 billion years of exposure was apparently prevented by the presence of sulfur in the form of sulfide-silicate complexes associated with the fullerenes.     

Fullerene isomerism: isolation of c2v,-c78 and d3-c78

Early reports on the formation of the higher fullerenes C(76), C(78), C(84), C(90), and C(94) by resistive heating of graphite stimulated theoretical calculations of possible cage structures for these all-carbon molecules. Among the five fullerene structures with isolated pentagons found for C(78), a closed-shell D3h-isomer was predicted to form preferentially. Two distinct C(78)-isomers were formed in a ratio of approximately 5:1 and could be separated by high-performance liquid chromatography. The carbon-13 nuclear magnetic resonance (NMR) spectrum of the major isomer is uniquely consistent with a C2v-structure. The NMR data also support a chiral D(3)-structure for the minor isomer. The isolation of specifically these two isomers of C(78) provides insight into the stability of higher fullerene structures and into the mechanism for fullerene formation in general.     

Self-assembled aggregates of rod-coil block copolymers and their solubilization and encapsulation of fullerenes

Amphiphilic poly(phenylquinoline)-block-polystyrene rod-coil diblock copolymers were observed to self-organize into robust, micrometer-scale, spherical, vesicular, cylindrical, and lamellar aggregates from solution. These diverse aggregate morphologies were seen at each composition, but their size scale decreased with a decreasing fraction of the rigid-rod block. Compared to coil-coil block copolymer micelles, the present aggregates are larger by about two orders of magnitude and have aggregation numbers of over 10(8). The spherical and cylindrical aggregates have large hollow cavities. Only spherical aggregates with aggregation numbers in excess of 10(9) were formed in the presence of fullerenes (C60, C70) in solution, resulting in the solubilization and encapsulation of over 10(10) fullerene molecules per aggregate.     

Cyclocarbon coalescence: mechanisms for tailor-made fullerene formation

The availability of macroscopic quantities of fullerenes has resulted in a vast number of physical and chemical studies of these new materials. However, the mechanisms that lead to the formation of these spherical carbon allotropes are not well understood. Mass spectral evidence has been obtained for the size-selective growth of fullerenes through the coalescence of cyclo[n] carbons, molecular carbon allotropes consisting of monocyclic rings with n carbon atoms. Whereas coalescence of cyclo[30]carbon (cyclo-C(30)) produces predominantly buckminsterfullerene (C(60)), the smaller rings cyclo-C(l8) and cyclo-C(24) preferentially produce fullerene C(70) through distinct intermediates. The present studies not only provide new insights into fullerene formation mechanisms but also raise the possibility of tailoring the size distributions of fullerenes by variation of the appropriate properties of the precursors.     

Production of perfluoroalkylated nanospheres from buckminsterfullerene

Perfluoroalkylated nanospheres have been prepared by reaction of fullerenes with a variety of fluoroalkyl radicals. The latter are generated by thermal or photochemical decomposition of fluoroalkyl iodides or fluorodiacyl peroxides. Up to 16 radicals add to C(60) to afford easily isolable fluoroalkylated derivatives. The monosubstituted radical adducts were detected by electron spin resonance in the early stages of the fluoroalkylation reactions. These spheroidal molecules are thermally quite stable, soluble in fluoroorganic solvents, chemically resistant to corrosive aqueous solutions, and more volatile than the parent fullerenes. Films of the sublimed material display properties typical for a perfluoroalkylated material.     

Stable compounds of helium and neon: he@c60 and ne@c60

It is demonstrated that fullerenes, prepared via the standard method (an arc between graphite electrodes in a partial pressure of helium), on heating to high temperatures release (4)He and (3)He. The amount corresponds to one (4)He for every 880,000 fullerene molecules. The (3)He/(4)He isotopic ratio is that of tank helium rather than that of atmospheric helium. These results convincingly show that the helium is inside and that there is no exchange with the atmosphere. The amount found corresponds with a prediction from a simple model based on the expected volume of the cavity. In addition, the temperature dependence for the release of helium implies a barrier about 80 kilocalories per mole. This is much lower than the barrier expected from theory for helium passing through one of the rings in the intact structure. Amechanism involving reversibly breaking one or more bonds to temporarily open a "window" in the cage is proposed. A predicted consequence of this mechanism is the incorporation of other gases while the "window" is open. This was demonstrated through the incorporation of (3)He and neon by heating fullerene in their presence.     

石家庄市公园绿地中乡土树种的应用研究

通过对石家庄市公园绿地中乡土树种的实地调查,分析了乡土树种的种类、数量、配置形式和应用频率。调查显示,石家庄市公园绿地中乡土树种有75种,占所调查公园绿化树种总数的44.1%,可见石家庄市乡土树种应用种类偏少,常用树种过于集中。建议大力开发利用乡土树种,增强乡土树种的应用频率,丰富配置方式,注重乡土树种的生态效益,营造具有区域特色的乡土景观。     

Fullerenes from a fulgurite

Peaks at 720 and 840 atomic mass units were identified by mass spectrometry in a sample extracted from a fulgurite, which is a glassy rock that forms where lightning strikes the ground. The peaks are interpreted as arising from C(60) and C(70) and the associated peaks as produced from other fullerenes. The intense conditions generated by the lightning not only melted the rock it struck and fused the associated soil but also allowed fullerenes to form, presumably from the organic debris in the soil.     

Extraction and STM Imaging of Spherical Giant Fullerenes

High-temperature, high-pressure extracts of soot produced by the Kr?tschmer-Huffman technique (KH carbon) were characterized by mass spectrometry and imaging with scanning tunneling microscopes (STMs). The mass spectra of these samples are similar to those of ambient-pressure, high-boiling-point solvent extractions, supporting the idea that solvent temperature and possibly pressure are key parameters in extraction of the giant fuilerenes. The STM images show that the giant fullerenes in these samples are roughly spherical in shape and range in diameter from approximately 1 to 2 nanometers, corresponding to fullerenes containing 60 to 330 atoms. No evidence of bucky tubes was found.     

Annealing c60+: synthesis of fullerenes and large carbon rings

Laser vaporization of graphite generates C(60)(+) cluster ions that are fullerenes and a mixture of roughly planar polycyclic polyyne ring isomers. Experimental studies of the annealing of the non-fullerene C(60)(+) ions indicate that they can be converted (in the gas phase) into the fullerene and an isomer that appears to be a large monocyclic ring. Some fragmentation is associated with conversion to the fullerene geometry, but the majority of the non-fullerene C(60)(+) isomers are cleanly converted into an intact fullerene. The emergence of the monocyclic ring (as the clusters are annealed) suggests that this is a relatively stable non-spheroidal form of these all carbon molecules. The estimated activation energies for the observed structural interconversions are relatively low, suggesting that these processes may play an important role in the synthesis of spheroidal fullerenes.     

颗粒特性对矩形养殖舱中颗粒物去除效果的影响

养殖工船是拓展深远海养殖空间的新途径之一,在船载舱养过程中,如果未消化的饲料残渣和排泄物等颗粒物不能及时排出,则会对鱼类健康及其生长环境产生严重的负面影响。该文章采用FLOW-3D软件进行数值仿真计算,研究了静止状态下30万t级养殖工船养殖舱出水口数目对舱内流场特征的影响,并在此基础上探究不同粒径与密度的颗粒物在舱内的去除效果。结果表明：当总进出水流量与出水口总面积恒定时,出水口数目从1增加到4,V99%从0.244 m/s降低至0.232 m/s,V95%从0.215 m/s降低至0.203 m/s,随着出水口数目的增加,养殖舱内流速减小;以占总量95%的颗粒物排出养殖舱所需时间为评价标准,当颗粒物密度为1050 kg/m3时,粒径为1 mm的颗粒物排出需要约24 min,粒径为0.5 mm的颗粒物排出需要约45 min,粒径为0.1 mm的颗粒物排出需要约78 min,当颗粒物密度相同时,随着粒径增大,其在养殖舱内的停留时间减少;颗粒物粒径为1 mm时,密度为1100 kg/m3的颗粒物排出需要约15 min,密度为1150 kg/m3的颗粒物排出需要约11.6 min,当颗粒物粒径相同时,颗粒物密度越大,其在养殖舱流场内的停留时间越短。该研究形成了CFD数值仿真计算与数理统计有机结合的综合分析方法,为之后具有不同横摇周期和较大横摇幅值的复杂工况提供研究手段及理论依据。