Mass spectrometric studies of metallofullerene

The endrohel metallofullerene, Gd@C-82, Gd@C-80, Gd-2@C-80 were synthesized by using K-H method. The technique of two-step of high pressure and high temperature extraction with 1, 3, 5-trimethylbenzene (first step) and pyridine(second step) has been successfully utilized to extract metallofullerene of Gd@C-82 The gas-phase negative ions of fullerenes C-n(n= 60, 70, 78, 82, 84...) and metallofullerene (Gd@C-82) have been studied by the ESI-MS, REC-MS and MALDI-TOF-MS. The differences among the mass spectra of ESI-MS, REC-MS and MALDI-TOF-MS have been observed and explained. In contrast to the empty fullerene C-82 , the metallofullerene Gd@C-82 should have a larger HOMO-LUMO gap. Experimental results suggest that Gd@C-82 is polarized and Gd3+ located in the off-center position of C-82 cage after Gd3+ is trapped into C-82 cage.

Synthesis and spectroscopic studies of endohedral metallofullerenes Tb@C-2n

Endohedral metallofullerenes Tb@C-2n were synthesized and extracted with high-yield by K-H carbon-are evaporation and an effective pyridine extraction technique at high-temperature high-pressure. Laser-desorption-ionization time-of-flight (LD-TOF) mass spectrometry, X-ray photoelectron spectroscopy (XPS), solid-state fluorescent emission spectroscopy and gas phase derivation reaction with the self-chemical ionization mass spectrometric ion system of vinyl acetate were employed for studying the electronic structures, fluorescent properties and gas phase reactivities of metallofullerenes Tb@C-2n. The experimental results suggest that endohedral metallofullerenes Tb@C-2n would have the approximate structures of Tb3+@C-2n(3-) similar to other metallofullerenes, good fluorescent emission properties and active reactivities in gas phase ion-molecular reactions.

Synthesis, extraction and electronic structure of Ce@C-2n

In view of the growing interest in endohedral lanthanide fullerenes, Ce, as a typical +4 oxidation state lanthanide element, has been systematically studied. The synthesis, extraction and electronic structure of Ce@C-2n are investigated. Soot containing Ce@C-2n was synthesized in high yield by carbonizing CeO2-containing graphite rods and are back-burning the CeC2-enriched cathode deposit in a DC are plasma apparatus. Ce@C-2n, dominated by Ce@C-82, can be efficiently extracted from the insoluble part of the soot after toluene Soxhlet extraction by pyridine at high temperature and high pressure in a closed vessel. About 60% Ce@C-2n (2n = 82,80,78,76) and 35% Ce@C-82 can be enriched in the pyridine extract. This fact is identified by desorption electron impact mass spectrometry (DEI MS). The electronic structure of Ce@C-2n is analyzed by using X-ray photoemission spectroscopy (XPS) of pyridine-free film. It is suggested that the encapsulated Ce atom is in a charge state close to +3 and was effectively protected from reaction with water and oxygen by the enclosing fullerene cage. Unlike theoretical expectation, the electronic state of Ce@C-82 is formally described as Ce+3@C-82(3-). (C) 1997 Elsevier Science Ltd.

Lutetium: A special lanthanide prefers dimer in fullerene cages

Endohedral dilutetium fullerenes, Lu-2@C-2n(2n = 76 similar to 112), have been extracted from the soot prepared by are-burning method for the first time and different from other lanthanide encapsulated fullerenes, there is no signal corresponding to Lu@C-82 even in mass spectrum of the high-temperature, high-pressure extract.

Formation and special solubility of endohedral thulium metallofullerenes

Endohedral metallofullerenes Tm@C-2n were synthesized with the carbon-arc discharge method of activating the Tm2O3-containing graphite anode in situ and back-burning technique, Toluene soxhlet extraction, toluene and pyridine high-temperature and high-pressure extraction technique were employed for the effective extraction of Tm@C-2n. The formation of Tm@C-2n was confirmed by LD-TOF and DEIMS characterization. The mass spectrometric results indicate that Tm@C-2n have a better solubility in toluene and worse solubility in pyridine than other metallofullerenes.

Two-step-method extraction of endohedral metallofullerenes

A new and efficient extraction method of endohedral metallofullerenes, especially of rare-earth elements encapsulated metallofullerenes, has been reported in this paper. Soxhlet-extraction of raw soot with toluene was used in the first step to wash away most accompanying C-60, C-70. Then pyridine was chosen as solvent to obtain high-temperature and high pressure extract. Two kinds of extract were analysed by DEI-MS and LDI-MS, the results indicate that this two-step method can provide the extract which has the highest fraction of endohedral metallofullerenes. So it will greatly simplify the following separation and purification processes of metallofullerenes.

The phase transitions of hetero atoms substituted molecular sieves Me-VPI-5(Me=Mg, Ti, Sn, Si) and their influence on spectra structures of Eu(III) ion

The hetero atom substituted aluminophosphate molecular sieves Me-VPI-5(Me = Mgt Ti, Sn, Si) were synthesized hydrothermally. Rare earth ions are originally doped into these microporous materials by aqueous solution ion exchange procedures. The phase transitions of the microporous materials are investigated by high-temperature and high-pressure experimental techniques. The influence of the phase transitions on the rare earth ions' spectral structures is discussed, With the increase of temperature, Eu(II)Mg-VPI-5 is converted into Eu(II)Mg-AIPO(4)-8, then into tridymite phase. The pressure has a notable influence on Eu(II) ion's spectral structures. The spectral structures have changed regularly with the increase of pressure.

MOLECULAR CHARACTERISTICS AND CRYSTALLINE-STRUCTURE OF ETHYLENE-DIMETHYLAMINOETHYL-METHACRYLATE COPOLYMERS

The relationship between molecular and crystalline structural characteristics of the ethylene -dimethylaminoethylmethacrylate copolymers (EDAM) was investigated and related to melt flow index MI and average gross content of DAM comonomer, in comparison with low density polyethylene (LDPE) produced by the common high-pressure radical polymerization process. Although the average molecular weight and its distribution are influenced predominantly by the polymerization conditions, DAM-content seems not to depend significantly on molecular weight according to the GPC-FT/IR measurement. Comonomer sequence distributions were determined quantitatively with the C-13-NMR spectra entirely assigned by DEPT and H-1-C-13 COSY techniques. The result suggests the alternating copolymerization tendency and surprisingly coincides with the simulation out-puts based on the assumption of continuous complete mixing reactor model, using Mayo-Lewis equation and the same Q-e values as previously reported on different types of copolymers such as EVA and St.DAM (VA;vinylacetate, St;styrene). It was confirmed by WAXD and SAXS analyses that the crystallinity X(c) and the thickness of lamellar crystal l(c) decreased with increasing DAM-content, whereas the a-lattice and b-lattice dimensions enlarged. X(c) and l(c) can definitely be correlated to the heats of fusion and crystallization measured by DSC. The average size of spherulites measured with light scattering photometry tends to be enlarged with decreasing molecular weight (increasing MI) and DAM-content.

Tank cultivation of the red alga Palmaria palmata: Effects of intermittent light on growth rate, yield and growth kinetics

Tank cultivation of marine macroalgae involves air-agitation of the algal biomass and intermittent light conditions, i.e. periodic, short light exposure of the thalli in the range of 10 s at the water surface followed by plunging to low light or darkness at the tank bottom and recirculation back to the surface in the range of 1-2 min. Open questions relate to effects of surface irradiance on growth rate and yield in such tumble cultures and the possibility of chronic photoinhibition in full sunlight. A specially constructed shallow-depth tank combined with a dark tank allowed fast circulation times of approximately 5 s, at a density of 4.2 kg fresh weight (FW) m(-2) s(-1). Growth rate and yield of the red alga Palmaria palmata increased over a wide range of irradiances, with no signs of chronic photoinhibition, up to a growth-saturating irradiance of approximately 1600 mumol m(-2) s(-1) in yellowish light supplied by a sodium high pressure lamp at 16 h light per day. Maximum growth rate ranged at 12% FW d(-1), and maximum yield at 609 g FW m(-2) d(-1). This shows that high growth rates of individual thalli may be reached in a dense tumble culture, if high surface irradiances and short circulation times are supplied. Another aspect of intermittent light relates to possible changes of basic growth kinetics, as compared to continuous light. For this purpose on-line measurements of growth rate were performed with a daily light reduction by 50% in light-dark cycles of 1, 2 or 3 min duration during the daily light period. Growth rates at 10degreesC and 50 mumol photon m(-2) s- 1 dropped in all three intermittent light regimes during both the main light and dark periods and reached with all three periodicities approximately 50% of the control, with no apparent changes in basic growth kinetics, as compared to continuous light.

The characteristics of fluid potential in mud diapirs associated with gas hydrates in the Okinawa Trough

Many mud diapirs have been identified in the southern Okinawa Trough from a seismic survey using R/V KEXUE I in 2001. The movement and accumulation of free gas related to mud diapirs are discussed in detail by an analysis of fluid potential which is based upon velocity data. It can be found that free gas moves from the higher fluid potential strata to the lower ones and the gas hydrate comes into being during free gas movement meeting the proper criteria of temperature and pressure. In fact, gas hydrates have been found in the upper layers above the mud diapirs and in host rocks exhibiting other geophysical characteristics. As the result of the formation of the gas hydrate, the free gas bearing strata are enclosed by the gas hydrate bearing strata. Due to the high pressure anomalies of the free gas bearing strata the fluid potential increases noticeably. It can then be concluded that the high fluid potential anomaly on the low fluid potential background may be caused by the presence of the free gas below the gas hydrate bearing strata.

Two modes of dipole events in tropical Indian Ocean

By analyzing the distributions of subsurface temperature and the surface wind stress anomalies in the tropical Pacific and Indian Oceans during the Indian Ocean Dipole (IOD) events, two major modes of the IOD and their formation mechanisms are revealed. (1) The subsurface temperature anomaly (STA) in the tropical Indian Ocean during the IOD events can be described as a "<" -shaped and west-east-oriented dipole pattern; in the east side of the "<" pattern, a notable tongue-like STA extends westward along the equator in the tropical eastern Indian Ocean; while in the west side of the "<" pattern, the STA has opposite sign with two centers (the southern one is stronger than the northern one in intensity) being of rough symmetry about the equator in the tropical mid-western Indian Ocean. (2) The IOD events are composed of two modes, which have similar spatial pattern but different temporal variabilities due to the large scale air-sea interactions within two independent systems. The first mode of the IOD event originates from the air-sea interaction on a scale of the tropical Pacific-Indian Ocean and coexists with ENSO. The second mode originates from the air-sea interaction on a scale of the tropical Indian Ocean and is closely associated with changes in the position and intensity of the Mascarene high pressure. The strong IOD event occurs when the two modes are in phase, and the IOD event weakens or disappears when the two modes are out of phase. Besides, the IOD events are normally strong when either of the two modes is strong. (3) The IOD event is caused by the abnormal wind stress forcing over the tropical Indian Ocean, which results in vertical transports, leading to the upwelling and pileup of seawater. This is the main dynamic processes resulting in the STA. When the anomalous easterly exists over the equatorial Indian Ocean, the cold waters upwell in the tropical eastern Indian Ocean while the warm waters pileup in the tropical western Indian Ocean, hence the thermocline in the tropical Indian Ocean is shallowed in the east and deepened in the west. The off-equator component due to the Coriolis force in the equatorial area causes the upwelling of cold waters and the shallowing of the equatorial India Ocean thermocline. On the other hand, the anomalous anticyclonic circulations and their curl fields located on both sides of the equator, cause the pileup of warm waters in the central area of their curl fields and the deepening of the equatorial Indian Ocean thermocline off the equator. The above three factors lead to the occurrence of positive phase IOD events. When anomalous westerly dominates over the tropical Indian Ocean, the dynamic processes are reversed, and the negative-phase IOD event occurs.

穿甲弹发射故障的动态诊断

对某研制阶段的高膛压火炮发射穿甲弹研究发现,当静强度安全系数较大时多次发生断弹事故,这说明此时动强度已成为主要矛盾,应用模态实验技术研究了脱壳穿甲弹动态特性,获得了该脱壳穿甲弹结构模态参数,模态分析方法所获得的动态薄弱截面位置与试验弹断弹情况相吻合,为其发射故障诊断提供了实验依据。

三塘湖盆地牛圈湖区储层特征研究—以齐古组、头屯河组为例

In view of few researches into pore textures and anisotropy characteristics of Qiguzu-toutunhezu reservoir in Niuquanhu block in Santanghu Basin, in order to enhance the hydrocarbon recovery of the region of interest and improve the reservoir development effect, with the employment of the experiments like cast thin slice, scanning electron microscope, conventional high pressure mercury penetration, constant speed mercury penetration and nuclear magnetic resonance, the thesis makes a thorough research into pore texture characteristics and anisotropy characteristics of the sandstone reservoir. The research shows that the microscopic pore textures are complicated, the anisotropy is high and waterflood development water/oil displacement efficiency is low, which are mainly caused by the high microscopic anisotropy of the reservoir. Specially, the research shows that Qiguzu-toutunhezu reservoir belongs to braided delta front intrafacies, the intergranular pore is the main type of pores, which take up 65.50 percent of total pores, intergranular dissolved pores, feldspar dissolved pores and lithic dissolved pores are on the second place, and there are few carbonate dissolved pores. The reservoir belongs to mesopore-fine throat and mesopore-medium throat. The pore distribution of the sandstone reservoir is comparatively centralized. The reservoir inhomogeneity is mainly caused by the throat inhomogeneity. Diagenesis mainly includes compaction, cementation, metasomatism and dissolution. Compared with compaction， cementation exerts more direct impact on the decline of the porosity of the sandstone reservoir ( pore loss factor is 63.75 percent in the cementing process). Based on the classification of diagenetic stages, the reservoir diagenesis is on the stage of the late period of early diagenetic stage to early period of late diagenetic stage. The study area of the small sandstone reservoir layer of the anisotropy of the relatively strong; plane, the anisotropy of the relatively weak. microscopic anisotropy of its relatively strong.

芝麻坊石榴子石二辉橄榄岩多期变质演化及其地幔过程

Many garnet peridotite bodies are enclosed in ultrahigh-pressure (UHP) gneisses and/or migmatites in worldwide UHP terranes formed by subduction of continental crust. On the basis of petrochemical data, a group of garnet peridotites have been derived from depleted mantle and were subsequently metasomatized by melts and/or fluids derived from the subducted continental crust. However, their depletion and enrichment processes and tectonic evolutions are still in conflicts. New evidences for metamorphism of garnet lherzolite from Zhimafang, Donghai County, Sulu UHP terrane are reported. The garnet lherzolite have experienced a prolonged multistage metamorphic history. At least seven stages of recrystallization have been identified based on detailed analysis of reaction textures and mineral compositions. Stage I was a high-pressure and high-temperature enriched garnet lherzolite stage, which is inferred from the presence of high Ca-Cr core of garnet porphyroclast and inclusions of high-Mg clinopyroxene, high-Al-Cr orthopyroxene and high-Mg olivine. Stage II is a high-temperature and low-pressure depleted spinel-hurzbergite or spinel-dunite stage, as indicated by the presence of relict Al-rich spinel, very high-Mg and low-Ni olivine and high-Mg orthopyroxene included in the low-Cr mantle of the porphyroclastic garnet and core of fine-grained neoblastic garnet, clinopyroxene is absent in this stage. Stage III is an hydrous amphibole spinel-lherzolite stage, which recorded events of cooling and metasomatic re-enrichment, this stage is manifested by metasomatic origin of amphibole and phlogopite-bearing porphyroblastic clinopyroxene, and porphyroblastic orthopyroxene. Stage IV is a high-pressure amphibole garnet-lherzolite stage, which is indicated by the formation of low-Cr mantle of the porphyroclastic garnet and amphibole-bearing low-Cr core of neoblastic garnet. Stage V is an UHP metamorphic garnet-lherzolite stage, which is characterized by the formation of high-Cr rim of both porphyroclastic and neoblastic garnet and recrystallization of olivine, clinopyroxene and orthopyroxene in the matrix. During UHP metamorphism, the garnet lherzolite is dehydrated, hornblende decomposed to clinopyroxene and olivine. Stage VI is a high-pressure decompression amphibole garnet-lherzolite stage, indicated by formation of later coarse-grained pargasitic hornblende and phlogopite in the garnet stability field. Stage VII is a low-pressure decompression amphibole-chlorite spinel-lherzolite stage, indicated by replacement of garnet by kelyphite of high-Al orthopyroxene + aluminous spinel + tremolitic amphibole + chlorite + talc. The metamorphic evolutions of Zhimafang garnet lherzolite suggest that it displays progressive mantle wedge convection during the subduction of previous oceanic and subsequent continental slab. We propose that the Zhimafang garnet lherzolite were originated from enriched deep mantle wedge above the previously subducted oceanic slab, subduction of oceanic slab resulted in their convection to shallower back arc and sub-arc setting, decompressional melting transformed the enriched garnet-lherzolite to depleted spinel-hurzbergite or spinel-dunite, the spinel-hurzbergite or spinel dunite was then convected to the hydrous mantle wedge corner driven by corner flow and was cooled and metasomatized by slab-derived melts/fluids, and was transformed to enriched lherzolite. The lherzolites formed a downward mantle wedge layer above successively subducted continental crust. The peridotite subducted together with the underlying continental crust and suffered UHP metamorphism. Finally, the garnet-lherzolite exhumed to the earth surface together with the UHP terrane. Detailed analyses of reaction textures and mineral compositions revealed several stages of metasomatism related to continental subduction and exhumation.

俯冲带深部流体特征——以西南天山变质俯冲杂岩为例

The subduction zone is an important site of the fluid activity and recycling of chemical elements. The fluid characteristic of deep subduction zones is a top scientific problem attracting the petrologists, geochemists and tectonists. In this dissertation, the characteristics of fluid activity within a deep subduction zone have been explored on the basis of the studies on the petrography, mineral chemistry, fluid inclusions, geochemistry and metamorphic P–T conditions of the omphacite-bearing high-pressure veins and related hosts from the low-temperature/high-pressure metamorphic belt in southwestern Tianshan, China. Multiple high-pressure veins are exposed in host eclogites and blueschists. The veins are composed predominantly of omphacite, garnet, quartz, and other minerals. Some veins contain cm-sized rutiles. In general, the vein can be divided into three types, the ‘in situ dehydration’ vein, the ‘external transport’ vein and the ‘composite’ vein. The omphacites within the veins and related host rocks contain lots of two-phase or three-phase primary fluid inclusions. The final melting temperature (Tfm) of fluid inclusions varies mainly from -0.6 to -4.3 °C, the homogeneous temperature (Th) varies from 185 to 251 °C, the salinity varies from 1.1 to 6.9 wt.% NaCl equivalent and the density varies from 0.81 to 0.9 g/cm3. The fluids were released under the conditions of T = 520–580°C and P = 15–19 kbar at blueschist facies to eclogite facies transition. The fluids include not only Li, Be, LILE, La, Pb-enriched and HFSE- and HREE-depleted aqueous fluids but also HFSE (Ti-Nb-Ta)-rich aqueous fluids. The complex composed of aluminosilicate polymers and F was the catalyst which had caused the Ti-Nb-Ta to be dissolved into the fluids. During the transport of the LILE-rich and HFSE- and HREE-poor fluids, they can exchange some chemical elements with country rocks and leach some trace elements in some extent. The rutile could be precipitated from the HFSE (Ti-Nb-Ta)-rich aqueous fluids when CO2 was added into the fluids. The host rocks could obtain some elements, such as Ca, Cs, Rb, Ba and Th, from the external fluids. The fluids with complex composition had been released within the deep subduction zone (>50 km) in Early Carboniferous during the subduction of the South Tianshan Ocean under the Yili–Central Tianshan Plate. The results obtained in this dissertation have made new progress compared with the published data (e.g. Tatsumi, 1989; Becker et al., 1999; Scambelluri and Philippot, 2001; Manning, 2004; Hermann et al., 2006; Spandler and Hermann, 2006).