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.     

Phase transformations in carbon fullerenes at high shock pressures

C(60) powders were shock-compressed quasi-isentropically and quenched from pressures in the range 10 to 110 GPa (0.1 to 1.1 Mbar). Recovered specimens were analyzed by Raman spectroscopy and optical microscopy. C(60) fullerenes are stable into the 13- to 17-GPa pressure range. The onset of a fast ( approximately 0.5 micros) reconstructive transformation to graphite occurs near 17 GPa. The graphite recovered from 27 GPa and about 600 degrees C is relatively well ordered with crystal planar domain size of about 100 A. Above 50 GPa a continuous transformation to an amorphous state is observed in recovered specimens. The fast transformation to graphite is proposed to occur by pi-electron rehybridization which initiates breakup of the ball structure and formation of the graphite structure at high density.     

Size and shape in biology

Arguments based on elastic stability and flexure, as opposed to the more conventional ones based on yield strength, require that living organisms adopt forms whereby lengths increase as the (2/3) power of diameter. The somatic dimensions of several species of animals and of a wide variety of trees fit this rule well. It is a simple matter to show that energy metabolism during maximal sustained work depends on body cross-sectional area, not total body surface area as proposed by Rubner (1) and many after him. This result and the result requiring animal proportions to change with size amount to a derivation of Kleiber's law, a statement only empirical until now, correlating the metabolically related variables with body weight raised to the (3/4) power. In the present model, biological frequencies are predicted to go inversely as body weight to the (1/4) power, and total body surface areas should correlate with body weight to the (5/8) power. All predictions of the proposed model are tested by comparison with existing data, and the fit is considered satisfactory. In The Fire of Life, Kleiber (5) wrote "When the concepts concerned with the relation of body size and metabolic rate are clarified, . . . then compartive physiology of metabolism will be of great help in solving one of the most intricate and interesting problems in biology, namely the regulation of the rate of cell metabolism." Although Hill (23) realized that "the essential point about a large animal is that its structure should be capable of bearing its own weight and this leaves less play for other factors," he was forced to use an oversimplified "geometric similarity" hypothesis in his important work on animal locomotion and muscular dynamics. It is my hope that the model proposed here promises useful answers in comparisons of living things on both the microscopic and the gross scale, as part of the growing science of form, which asks precisely how organisms are diverse and yet again how they are alike.     

Replicating form of a single-stranded DNA virus: isolation and properties

The replicating form of single-stranded DNA virus has been isolated in pure form by chromatography on columns of methylated albumin. Its buoyant density in CsCl and "melting temperature" are characteristic of a double stranded DNA structure containing 43 percent guanine-cytosine. The nearest neighbors to uridylate were compared in the RNA synthesized when replicating-form DNA and mature single-stranded DNA were employed as templates in an in vitro system. The mature DNA component of the replicating duplex does not serve as the sole source of complementary RNA. The results agree best with the assumption that both strands of the replicating form function as templates. It is important to note that this is contrary to the situation found in the intact cell where only one of the two strands appears to be transcribed into message.     

Influence of alginate oligosaccharides on growth, yield and alkaloid production of opium poppy (Papaver somniferum L.)

Opium poppy (Papaver somniferum L.), an important medicinal plant, produces several opiate alkaloids including morphine, thebaine, codeine, papaverine and noscapine. Polysaccharides, such as sodium alginate, have been used in depolymerized form as wonderful promoters of plant growth. The present study has revealed that application of alginate oligosaccharides (AO), obtained from sodium alginate irradiated by Co-60 gamma rays, significantly enhances certain physiological/biochemical parameters as well as the overall growth of opium poppy. The highest dose applied was the most effective in increasing the morphine and codeine contents as well as the overall yield of crude opium per plant.     

茶树丛枝菌根真菌的研究进展

丛枝菌根真菌是广泛存在于林地土壤中、与植物共生的重要的真菌类群,具有多种重要的有益功能。笔者综述了茶树丛枝菌根真菌的种类、形态结构、侵染率,及其对茶树在营养吸收、生长发育、矿质元素吸收、品质和抗逆性等方面的影响,并对其应用前景作了初步展望,以期为开展茶树AMF相关研究提供参考。     

Novel proteinaceous infectious particles cause scrapie

After infection and a prolonged incubation period, the scrapie agent causes a degenerative disease of the central nervous system in sheep and goats. Six lines of evidence including sensitivity to proteases demonstrate that this agent contains a protein that is required for infectivity. Although the scrapie agent is irreversibly inactivated by alkali, five procedures with more specificity for modifying nucleic acids failed to cause inactivation. The agent shows heterogeneity with respect to size, apparently a result of its hydrophobicity; the smallest form may have a molecular weight of 50,000 or less. Because the novel properties of the scrapie agent distinguish it from viruses, plasmids, and viroids, a new term "prion" is proposed to denote a small proteinaceous infectious particle which is resistant to inactivation by most procedures that modify nucleic acids. Knowledge of the scrapie agent structure may have significance for understanding the causes of several degenerative diseases.     

Crystal structure of a silyl cation with no coordination to anion and distant coordination to solvent

The crystal structure of a stable silyl cation, triethylsilylium, in the form of its tetrakis (pentafluorophenyl)borate salt [Et(3)Si(+) (C(6)F(5))(4)B(-)] (Et, ethyl) shows no coordination between cation and anion. The closest silicon-fluorine distance is greater than 4 angstroms. A toluene solvent molecule is close enough to cause some deviations from planarity at the silicon, but the silicon-toluene distance is well beyond the sum of the silicon and carbon covalent radii. The toluene molecule is essentially planar and undistorted, as expected if little or no positive charge has been transferred from silicon to toluene.     

Ballistic electron microscopy of individual molecules

We analyzed the transport of ballistic electrons through organic molecules on uniformly flat surfaces of bismuth grown on silicon. For the fullerene C60 and for a planar organic molecule (3,4,9,10-perylene-tetracarboxylic acid dianhydride), the signals revealed characteristic submolecular patterns that indicated where ballistic transport was enhanced or attenuated. The transport was associated to specific electronic molecular states. At electron energies of a few electron volts, this "scanning near-field electron transmission microscopy" method could be applied to various adsorbates or thin layers.     

Synthesis and Single-Crystal X-ray Structure of a Highly Symmetrical C60 Derivative, C60Br24

C(60) and liquid bromine react to form C(60)Br(24), a crystalline compound isolated as a bromine solvate, C(60)Br(24)(Br(2))(x), The x-ray crystal structure defines a new pattern of addition to the carbon skeleton that imparts a rare high symmetry. The parent C(60) framework is recognizable in C(60)Br(24), but sp(3) carbons at sites of bromination distort the surface, affecting conformations of all of the hexagonal and pentagonal rings. Twenty-four bromine atoms envelop the carbon core, shielding the 18 remaining double bonds from addition. At 150 degrees to 200 degrees C there is effectively quantitative reversion of C(60)Br(24) to C(60) and Br(2).     

Crystallographic evidence for a free silylium ion

Evidence for a three-coordinate silyl cation is provided by the crystal structure of [(Mes)3Si][H-CB11Me5Br6].C6H6 (where Mes is 2,4,6-trimethylphenyl). Free (Mes)3Si+ cations are well separated from the carborane anions and benzene solvate molecules. Ortho-methyl groups of the mesityl substituents shield the silicon atom from the close approach of nucleophiles, while remaining innocent as significant ligands themselves. The silicon center is three-coordinate and planar. The downfield 29Si nuclear magnetic resonance chemical shift in the solid state (226.7 parts per million) is almost identical to that in benzene solution and in "gas phase" calculations, indicating that three-coordination can be preserved in all phases.     

"Microsome" fraction of brain: structural changes induced by ascorbic acid

The usual vesicular configuration of membrane fragments in the brain "microsome" fraction is radically altered by treatment with ascorbic acid and adenosine monophosphate. Lightscattering measurements and electron micrographs show that the treated membranes assume predominantly planar forms. This change in structure appears to be contingent upon a continued transport of electrons from ascorbic acid.     

Randomization and social affairs: the 1970 draft lottery

Randomization has played an important role in social affairs, going back at least to biblical days. The drawing of lots, one of the simplest forms of randomization, has been used publicly in many different contexts. Although the legal use of randomization techniques and lotteries in the United States dates back at least to the mid-19th century, only recently have the federal courts recognized the need for proper randomization to assure fairness, lack of bias, and lack of discrimination. A recent presidential commission has supported the call for all-volunteer armed forces (29), but it appears that the recommendations of this commission are at least several years away from becoming law. In fact, it has been suggested that the present lottery system is retarding any moves toward allvolunteer armed forces by reducing the number of draft-induced volunteers, and thereby necessitating an increase in the number of draftees. So, in the short run, it appears that the draft lottery will be the means by which the United States will man much of itsarmed forces. Since this is the case, it is important that future lotteries achieve equity in selection and that the lack of randomization present in previous lotteries be eliminated. [Indeed, it is interesting to note that several young men have filed suit in federal court, seeking to void the 1970 drawing and to force a new lottery. The basis of these suits is the lack of proper randomization (30).] The 1917 and 1940 Selective Service draft lotteries have served in the past as indications that the commonly held notion of "randomness" is often at variance with the strict statistical meaning. The 1970 draft lottery has not helped to mitigate the doubts of many regarding the equity and fairness of random drawings, although the recent 1971 draft lottery sets a very positive example, which, it is hoped, will counteract the effects of the earlier lotteries. Since randomization does have a role in the everyday workings of society, it is important that the public be educated to accept the proper use of randomization, while rejecting attempts to use chance as a disguise for inequity, bias, and unlawful discrimination. As one step toward this end, future draft lotteries should adhere to a reasonable definition of randomness, and the public should be well informed of the precautions taken to preclude arbitrary features that have marred previous draft lotteries. In addition, it is clearly desirable that the Selective Service provide the public with an official statement giving all relevant details on the design and execution of the lotteries. The most recent draft lottery serves as an admirable model in this regard. Note added in proof: Professor Hans Zeisel has brought to my attention the details of the draft procedure used in Austria-Hungary between 1889 and the start of World War I. This draft procedure was also based on a lottery, with every person liable for the draft (or a representative) drawing a slip of paper on which was recorded a number indicating a place in the draft list. It is conceivable that Selective Service officials, in charge of the World War I lottery in the United States, were familiar with the details of this draft lottery procedure.     

Packing C60 in boron nitride nanotubes

We have created insulated C60 nanowire by packing C60 molecules into the interior of insulating boron nitride nanotubes (BNNTs). For small-diameter BNNTs, the wire consists of a linear chain of C60 molecules.With increasing BNNT inner diameter, unusual C60 stacking configurations are obtained (including helical, hollow core, and incommensurate) that are unknown for bulk or thin-film forms of C60.C60 in BNNTs thus presents a model system for studying the properties of dimensionally constrained "silo" crystal structures. For the linear-chain case, we have fused the C60 molecules to form a single-walled carbon nanotube inside the insulating BNNT.     

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.     

Gas-phase ion chromatography: transition metal state selection and carbon cluster formation

Gas-phase ion chromatography can separate ions that have the same mass but differ in isomeric structure or electronic configuration. The main features of this technique are briefly outlined, and applications to a series of problems in transition metal chemistry and carbon cluster chemistry are described. Examples in transition metal chemistry include state-selective reactivity, excited state deactivation, and state-selective ligand binding energies. For clusters, ion chromatography was used to determine the structure of pure carbon cluster ions as a function of size from C(4) to C(84). The results indicate that carbon grows first in linear chains, transforms to monocyclic planar rings at about C(10), and forms new families of planar bi-, tri-, and tetracyclic rings at C(20), C(30), and C(40), respectively. Fullerenes, which mysteriously appear at C(30) and dominate by C(50), are generated by heating the planar ring systems above an isomerization barrier rather than by growth of graphite precursors.     

Sea Surface Temperature, Surface Wind Divergence, and Convection over Tropical Oceans

Large-scale convection over the warm tropical oceans provides an important portion of the driving energy for the general circulation of the atmosphere. Analysis of regional associations between ocean temperature, surface wind divergence, and convection produced two important results. First, over broad regions of the Indian and Pacific oceans, sea surface temperatures (SSTs) in excess of 27.5 degrees C are required for large-scale deep convection to occur. However, SSTs above that temperature are not a sufficient condition for convection and further increases in SST appear to have little effect on the intensity of convection. Second, when SSTs are above 27.5 degrees C, surface wind divergence is closely associated with the presence or absence of deep convection. Although this result could have been expected, it was also found that areas of persistent divergent surface flow coincide with regions where convection appears to be consistently suppressed even when SSTs are above 27.5 degrees C. Thus changes in atmospheric stability caused by remotely forced changes in subsidence aloft may play a major role in regulating convection over warm tropical oceans.     

A crystal structure of the complex between human complement receptor 2 and its ligand C3d

The interaction of complement receptor 2 (CR2)--which is present on B cells and follicular dendritic cells--with its antigen-bound ligand C3d results in an enhanced antibody response, thus providing an important link between the innate and adaptive immune systems. Although a cocrystal structure of a complex between C3d and the ligand-binding domains of CR2 has been published, several aspects of this structure, including the position in C3d of the binding interface, remained controversial because of disagreement with biochemical data. We now report a cocrystal structure of a CR2(SCR1-2):C3d complex at 3.2 angstrom resolution in which the interaction interfaces differ markedly from the previously published structure and are consistent with the biochemical data. It is likely that, in the previous structure, the interaction was influenced by the presence of zinc acetate additive in the crystallization buffer, leading to a nonphysiological complex. Detailed knowledge of the binding interface now at hand gives the potential to exploit the interaction in vaccine design or in therapeutics directed against autoreactive B cells.     

Atomlike, hollow-core-bound molecular orbitals of C60

The atomic electron orbitals that underlie molecular bonding originate from the central Coulomb potential of the atomic core. We used scanning tunneling microscopy and density functional theory to explore the relation between the nearly spherical shape and unoccupied electronic structure of buckminsterfullerene (C60) molecules adsorbed on copper surfaces. Besides the known pi* antibonding molecular orbitals of the carbon-atom framework, above 3.5 electron volts we found atomlike orbitals bound to the core of the hollow C60 cage. These "superatom" states hybridize like the s and p orbitals of hydrogen and alkali atoms into diatomic molecule-like dimers and free-electron bands of one-dimensional wires and two-dimensional quantum wells in C60 aggregates. We attribute the superatom states to the central potential binding an electron to its screening charge, a property expected for hollow-shell molecules derived from layered materials.