Topochemical polymerization of C70 controlled by monomer crystal packing

Polymeric forms of C60 are now well known, but numerous attempts to obtain C70 in a polymeric state have yielded only dimers. Polymeric C70 has now been synthesized by treatment of hexagonally packed C70 single crystals under moderate hydrostatic pressure (2 gigapascals) at elevated temperature (300 degrees C), which confirms predictions from our modeling of polymeric structures of C70. Single-crystal x-ray diffraction shows that the molecules are bridged into polymeric zigzag chains that extend along the c axis of the parent structure. Solid-state nuclear magnetic resonance and Raman data provide evidence for covalent chemical bonding between the C70 cages.     

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.     

Synthesis, Isolation, and Equilibration of 1,9- and 7,8-C70H2

Equilibration of 1,9- and 7,8-C(70)H(2) has allowed the relative free energy of these isomers to be measured. These "simplest hydrocarbon derivatives of C(70)" are formed by hydroboration of C(70) at room temperature. Analysis of the platinum-catalyzed equilibration of these isomers yielded a relative free energy at 295 kelvin of 1.4 +/- 0.2 kilocalories per mole, with the 1,9 isomer being more stable. This value is in excellent agreement with the ab initio HF/6-31 G(*) calculated energy difference of 1.3 kilocalories per mole, whereas semiempirical calculations gave poor agreement.     

饲料中C3植物含量对牛组织中稳定同位素碳、氮组成的影向

研究了饲料中C3植物含量不同时对牛不同组织中稳定性同位素碳、氮组成的影响。18头12~14月龄的青年牛随机分为6组,分别饲喂C3植物含量为50.0%、60.0%、70.0%、80.0%、90.0%、100.0%的饲料,132 d后屠宰。利用同位素比值质谱仪测定了牛尾毛、脱脂牛肉、粗脂肪、各种饲料的δ13C和δ15N值。结果表明,牛组织中碳同位素主要受饲料的影响,牛尾毛、脱脂肌肉、粗脂肪中的δ13C值随着C3植物含量在牛饲料中的比例增大而降低,并且均与C3植物含量呈极显著的负相关关系,用牛组织中的δ13C值可以预测饲料中C3植物所占的比例。牛组织中的氮同位素一定程度上受饲料因素的影响,但未随C3植物含量呈现规律性变化。牛不同组织中δ13C和δ15N与饲料之间的富集或贫化比例与其他报道并不一致。     

Large odd-numbered carbon clusters from fullerene-ozone reactions

The odd-numbered carbon clusters C(119), C(129), and C(139) have been observed in the mass spectra of toluene extracts of fullerene soots and of the products of ozone-fullerene reactions. Specifically, ozone-C(60) reactions yield C(119), ozone-C(70) reactions yield C(139), and ozone-(C(60)/C(70)) reactions produce C(119), C(129), and C(139). These unexpected species correspond to dimers of C(60), C(60)/C(70), and C(70), respectively, less one carbon atom, and are stable gas-phase ions with behavior similar to that of fullerenes. The results suggest a new route to functionalization and derivatization of fullerenes through controlled ozone-catalyzed cage-opening reactions.     

外方山草本植物叶片生长期C、N、P生态化学计量学特征的变化

为揭示同一生活型草本植物生长期内C、N、P生态化学计量学特征,在豫西南外方山设置羊胡子草(Carex rigescens)、芒草(Miscanthus sinensis)、野菊花(Dendranthema indicum)样地,测定生长期内叶片C、N、P含量及其生态化学计量比。结果表明:同一生活型种间植物叶片化学计量学特征具有多变性,胡子草、芒草、野菊花等3种植物生长期内叶片C含量平均为447.6 g/kg、448.1 g/kg和459.9 g/kg,N含量为26.8 g/kg、23.5 g/kg和25.6 g/kg,P含量为1.9 g/kg、1.5 g/kg和2.0 g/kg;3种植物综合变异系数排序为P含量(45.0%)C/P值(33.2%)N/P值(30.1%)C/N值(26.0%)N含量(25.3%)C含量(2.0%),C含量最稳定,N含量次之,P含量较不稳定;C含量与N、P含量负相关性均不显著(P0.05),P含量与N含量正相关性极显著(r=0.736,P0.01),N含量与C/N值负相关性极显著(r=-0.700,P0.01),P含量与C/P值负相关性极显著(r=-0.891,P0.01),C/N值与C/P值正相关性显著(r=0.283,P0.05);植物种类对叶片C含量影响显著(P0.05),N含量、P含量、C/N值与C/P值主要受生长期采样时间的影响(P0.05),物种种类与采样时间对N/P值影响不显著(P0.05)。研究区域植物叶片生态化学计量特征时,应考虑植物种类与生长期的影响。     

Stable Isotope Studies of Crop Carbon and Water Relations： A Review

Crop carbon and water relations research is important in the studies of water saving agriculture, breeding program, and energy and material cycles in soil plant atmosphere continuum （SPAC）. The purpose of this paper is to review the current state of knowledge on stable isotopes of carbon, oxygen, and hydrogen in the research of crop carbon and water relations, such as carbon isotope discrimination （△^13C） during carbon fixation process by photosynthesis, application of △^13C in crop water use efficiency （WUE） and breeding programs, oxygen isotope enrichment during leaf water transpiration, CO2 fixation by photosynthesis and release by respiration, application of hydrogen isotope composition （619） and oxygen isotope composition （6180） for determination of water source used by a crop, stable isotope coupling Keeling plot for investigating the carbon and water flux in ecosystem, energy and material cycle in SPAC and correlative integrative models on stable isotope. These aspects contain most of the stable isotope researches on crop carbon and water relations which have been widely explored internationally while less referred in China. Based on the reviewed literatures, some needs for future research are suggested.     

Organogenic elements and compounds in surface samples from the sea of tranquillity

Organogenic elements, mainly carbon, nitrogen, phosphorus, and sulfur are present in the particulate material and in a breccia rock from Tranquillity Base in amounts ranging from 5 to 4200 parts per million. The major compounds of carbon released by heating are carbon monoxide and carbon dioxide; the former predominates. Small amounts of other compounds of carbon have also been observed. Sulfur can be released as hydrogen sulfide by treatment with acid. The carbon isotopic delta(13L)C values are definitely nonterrestrial (+ 13 to + 18.5 per mil).     

Systematic inflation of buckminsterfillerene c60: synthesis of diphenyl fulleroids c61 to c66

The synthesis of a new family of spheroidal carbon molecules derived from the fullerenes is described. The fulleroids are produced by incremental addition of a divalent carbon equivalent that has two phenyl (Ph) rings to fullerene C(60). The fulleroids Ph(2)C(61), Ph(4)C(62), Ph(6)C(63), Ph(8)C(64), Ph(10)C(65), and Ph(12)C(66) have been prepared and characterized.     

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).     

Orientational disorder in solvent-free solid c70

The high-temperature structure of solvent-free C(70) has been determined with high-resolution x-ray powder difraction and electron microscopy. Samples crystallized from solution form hexagonal close-packed crystals that retain an appreciable amount of residual toluene, even after prolonged heating. Samples prepared by sublimation, which contain no detectable solvent, are primarily face-centered cubic with some admixture of a hexagonal phase. The relative volume of the hexagonal phase can be further reduced by annealing. The structures of both phases are described by a model of complete orientational disorder. The cubic phase contains an appreciable density of stacking faults along the [111] direction.     

Carbynes in meteorites: detection, low-temperature origin, and implications for interstellar molecules

Carbon from the Allende meteorite is not graphite but carbyne (triply bonded elemental carbon), inasmuch as on heating to 250 degrees to 330 degrees C it releases mainly triply bonded fragments: -(C identical withC)(n),- with n = 1 to 5, and -(C identical withC)(n)-CN, with n = 1 to 3. Although carbynes have been known to form only by condensation of carbon vapor above 2600 K or by explosive shock of > 600 kilobars, it is found that they also form metastably by the reaction 2CO --> CO(2) + C (solid) at 300 degrees to 400 degrees C in the presence of a chromite catalyst. Such low-temperature formation by surface catalysis may be the dominant source of carbynes on the earth and in meteorites, and a major source of interstellar carbynes and cyanopolyacetylenes.     

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.     

Detection of C5 in the Circumstellar Shell of IRC+10216

The C(5) molecule has been identified in the infrared spectrum of the prototypical obscured carbon star, IRC+10216. In addition to their astrophysical importance, pure carbon chain molecules such as C(5) are of interest in the chemistry of flames and propellants.     

18O/16O, 30Si/28Si, D/H, and 13C/12C Studies of Lunar Rocks and Minerals

The delta (18)O of minerals from lunar gabbros and basalts are: plgioclases +6.06 to +6.33), pyroxenes (+5.70 to +5.95), and ilmenites (+3.85 to +4.12). The uniformity of these results indicates isotopic equilibrium in the mineral assemblages. Estimated plagioclase-ilmenite temperautres range from 1150 degrees C to 1340 degrees C. The bulk (18)/ (16)O and (30)Si/ (28)Si ratios of these lunar rocks are identical with ratios of terrestrial basalts, but the lunar glass, breccia, and dust are slightly enriched in the heavier isotopes. The lunar hydrogen (formed from solar wind) has a delta D/H of less than-873 per mil and the value may be even lower, as it is probably contaminated with terrestrial hydrogen. The delta (13)C of lunar dust and breccia is unusually high relative to reduced carbon in meteorites or on earth.     

退耕植茶地土壤碳氮磷生态化学计量学特征

研究不同退耕植茶年限土壤有机碳、全氮和全磷的质量分数分布及其生态化学计量学特征,以期为退耕植茶地土壤持续利用和茶园持续发展提供理论依据。选取退耕植茶2~3 a(RT2-3), 9~10 a(RT9-10)和16~17 a(RT16-17)的各5个样地为研究对象,以邻近耕地作为对照,采用野外调查与室内分析相结合的方法,按0~10,10~20和20~40 cm土层取样,测定土壤有机碳、全氮、全磷的质量分数,并计算了碳、氮、磷之间的计量比。结果表明:随着退耕植茶年限的延长,土壤有机碳、全氮质量分数表现为先显著降低后增加的趋势(P<0.05),全磷质量分数变化较为稳定。0~10 cm土层,退耕植茶地土壤碳氮比(C/N)显著高于对照地,退耕植茶地土壤碳磷比(C/P)和氮磷比(N/P)显著低于对照地;10~20 cm土层,退耕植茶地土壤碳氮比显著高于对照地,碳磷比在各样地间均无显著差异,氮磷比则表现为对照地土壤显著高于退耕植茶地;20~40 cm土层,碳氮比表现为RT2-3显著高于其他样地,碳磷比和氮磷比在各样地间均无显著差异。退耕植茶后,土壤碳氮比显著增加,有机质分解速率降低。退耕植茶有利于土壤有机碳、全氮的积累;虽有利于提高土壤中磷的有效性,但随着植茶年限的延长,磷素对退耕植茶地限制性逐渐增强。     

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.     

Synthesis of Linear Acetylenic Carbon: The "sp" Carbon Allotrope

A carbon allotrope based on "sp" hybridization containing alternating triple and single bonds (an acetylenic or linear carbon allotrope) has been prepared. Studies of small (8 to 28 carbon atoms) acetylenic carbon model compounds show that such species are quite stable (130 degrees to 140 degrees C) provided that nonreactive terminal groups or end caps (such as tert-butyl or trifluoromethyl) are present to stabilize these molecules against further reactions. In the presence of end capping groups, laser-based synthetic techniques similar to those normally used to generate fullerenes, produce thermally stable acetylenic carbon species capped with trifluoromethyl or nitrile groups with chain lengths in excess of 300 carbon atoms. Under these conditions, only a negligible quantity of fullerenes is produced. Acetylenic carbon compounds are not particularly moisture or oxygen sensitive but are moderately light sensitive.     

Ti8C12+-Metallo-Carbohedrenes: A New Class of Molecular Clusters?

During the course of studying the dehydrogenation reactions of hydrocarbons by titanium atoms, ions, and clusters, an exceptionally stable and abundant cluster which contains 8 titaniums and 12 carbons was discovered. "Titration" reactions with ND(3) reveal the uptake of eight molecules, pointing to the fact that the titanium atoms are at exposed positions of similar coordination. A dodecahedral structure of T(h) point group symmetry is proposed to account for the unusual stability of this molecular cluster. The Ti(8)C(12)(+) dodecahedron has 12 pentagonal rings and each of the rings is formed by two titanium and three carbon atoms, where each titanium is bound to three carbons. Based on the model, it is expected that neutral Ti(8)C(12) would be a stable metallo-carbododecahedral molecule and may comprise one member of a new class of molecules, namely metallo-carbohedrenes.     

活性元素对C/NiAl复合材料界面润湿及浸渗组织的影响

采用座滴法研究了真空、1800 ℃下NiAl在碳、TiC、SiC和ZrC上的润湿性,并通过铺展实验和熔渗实验优化了NiAl改性C/C复合材料的活性添加元素及添加量。采用真空熔渗法制备NiAl改性C/C复合材料,采用X射线衍射仪和扫描电镜分析了复合材料的微观结构和渗透机制。结果表明,NiAl与C或SiC的润湿性较差,与TiC或ZrC的润湿性很好;添加Ti能改善NiAl和C的润湿性,Ti粉含量为15% (质量分数) 时,C/C 复合材料熔渗NiAl的效果最佳,NiAl渗透层的厚度为0.8~0.9 mm;添加Ti利于C/C复合材料渗NiAl的主要原因是Ti与C反应形成TiC,改善了NiAl在C/C复合材料中的化学吸附和物理吸附特性,NiAl通过毛细管力作用渗入到C/C复合材料坯体中。