Theoretical investigation of 5D-metal monocarbide

Bond distances, vibrational frequencies, electron affinities, ionization potentials and dissociation energies of the title molecules in neutral, positively and negatively charged ions were studied by use of density functional method. The calculated results were compared with previous theoretical and experimental studies. Ground states for each molecule were assigned. It was found that for some molecules, low-lying state, in which the energy is much close to the ground state, was obtained. In this case, further studies both experimentally and theoretically are necessary in order to find the true global minimum.

High-efficiency blue light-emitting diodes based on a polyphenylphenyl compound with strong electron-accepting groups

The synthesis and characterization of two new polyphenylphenyl compounds is reported. One compound (CPP) acts as a blue light-emitting material, but contains strong electron-accepting groups that form exciplexes with electron-donating arylamines that are widely used as hole-transporting materials. Inserting a layer of the other compound into the organic light-emitting diodes (see figure) suppresses the formation of exciplexes, and gives high-efficiency blue-light emission from the CPP layer.

Electronic structures of 3d-metal mononitrides

Bond distances, vibrational frequencies, electron affinities, ionization potentials, and dissociation energies of the title molecules in neutral, positively, and negatively charged ions were studied by use of density functional methods B3LYP, BLYP, BHLYP, BPW91, and B3PW91. The calculated results are compared with experiments and previous theoretical studies. It was found that the calculated properties are highly dependent on the functionals employed, in particular for the dissociation energy and vibrational frequency. For neutral species, pure density functional methods BLYP and BPW91 have relatively good performance in reproducing the experimental bond distance and vibrational frequency. For cations, hybrid exchange functional methods B3LYP and B3PW91 are good in predicting the dissociation energy. For both neutral and charged species, BHLYP tends to give smaller dissociation energy.

Electronic structures and chemical bonding in transition metal monosilicides MSi (M=3d, 4d, 5d elements)

Bond distances, vibrational frequencies, electron affinities, ionization potentials, dissociation energies, and dipole moments of the title molecules in neutral, positively, and negatively charged ions were studied using the density functional method. Ground state was assigned for each species. The bonding patterns were analyzed and compared with both the available data and across the series. It was found that besides an ionic component, covalent bonds are formed between the metal s, d orbitals and the silicon 3p orbital. The covalent character increases from ScSi (YSi) to NiSi (PdSi) for 3d (4d) metal monosilicides, then decreases. For 5d metal monosilicides, the covalent character increases from LaSi to OsSi, then decreases. For the dissociation of cations, the dissociation channel depends on the magnitude of the ionization potential between metal and silicon. If the ionization potential of the metal is smaller than that of silicon, channel MSi+-> M++Si is favored. Otherwise, MSi+-> M+Si+ will be favored. A similar behavior was observed for anions, in which the dissociation channel depends on the magnitude of electron affinity.

Chemical bonding and electronic structure of 4d-metal monocarbides

Bond distances, vibrational frequencies, dissociation energies, electron affinities, ionization potentials and dipole moments of the title molecules in neutral and charged ions were studied by use of density functional method. Ground states for each molecule were assigned. For neutral and cationic molecules, the bond distance decreases from YC (YC+) to RhC (RhC+), then increases, while for anionic molecules, the bond distance decreases from YC- to RuC-, then increases. Opposite trend was observed for vibrational frequency. The bond ionic character decreases from ZrC to PdC for neutral molecules. The bonding patterns are discussed and compared with the available studies.

Geometries and electronic properties of Ta-n, TanO and TaOn (n=1-3) clusters

Geometries, vibrational frequencies, electron affinities, ionization potentials and dissociation energies of the title clusters in both neutral and positively and negatively charged states were studied by use of density functional theory. For both neutral and charged species, different initial isomers were studied in order to determine the structure with the lowest energy. Vibrational analysis was also performed in order to characterize these isomers. For Ta-2, Ta-Ta metallic bond is strengthened by adding or removing an electron, i.e. the charged species are much more stable than the neutral counterpart. For Ta-3, equilateral triangle with D-3h symmetry has the lowest energy for both neutral and charged species (near equilateral triangle for cation). TaO and its charged species have much larger dissociation energy compared with other tantalum oxides. For Ta2O and TaO2. structure with C-2v symmetry is much more stable than linear chains. For Ta3O, planar structure with doubly bridging oxygen atoms of C-2v, symmetry is the global minimum for both neutral and charged species. While for TaO3, three-dimensional structures are favored for both neutral (C-1 symmetry) and charged species (C-3v symmetry).

Geometries and electronic properties of AunPdm (n=1-4, m =-1, 0, 1) clusters

Possible conformers for AunPdm (n = 1-4, m = -1, 0, 1) clusters have been presented and studied by use of density functional theory. The results indicate that for n = 2, linear conformer with C-infinityv symmetry is the most stable for anion species, while for cation and neutral species, conformer with C-2v symmetry is the most stable. For n = 3, 4, conformers with C-2v symmetry (kite-shape) are energetically favored. The calculated electron affinities (EAs) and vertical detachment energies (VDEs) are in good agreement with experiments for n = 1-4. It is also interesting to note that for even n (n = 2, 4), the most stable conformers do not give the best agreement between calculated and experimental EA and VDE values, while for odd n (n = 3), the lowest energy conformer also gives the best agreement. The ionization potentials (IPs) of AunPd clusters are calculated as well.

Characterization of cyclic arylether ketone (sulfone) containing hexafluoroisopropylidene unit by matrix-assisted laser desorption ionization time-of-flight mass spectrometry

The cyclic aryletherketone( sulfone) oligomers containing hexafluoroisopropylidene unit were characterized by matrix-assisted laser desorption ionization time-of-night mass spectrometry(MALDI-TOF-MS) using Na+ and Ag+ as cationization agents. The affinities of cyclic oligomers to the cation were studied. The analysis result showed that 1,8,9-dithranol, in the presence of silver trifluoroacetate, was very effective for the characterization of cyclic arylether ketone ( sulfone) containing hexafluoroisopropylidene unit.

Effects of La3+ and Gd3+ on Ca2+ influx in rat hepatoma H-35 cells

Effects of La3+ and Gd3+ on Ca2+ influx were investigated in rat hepatoma H-35 cells by measuring the initial rate of Ca-45(2+) uptake. It was found that the maximum initial rate of Ca2+ uptake was increased six- to ten-fold at low concentrations of La3+ and Gd3+. Kinetic analyses by measuring the initial rate of Ca2+ influx at different external Ca2+ concentrations indicated the existence of two intracellular exchangeable components in the basal Ca2+ system, with low and high affinities for Ca2+, and only one class of Ca2+ binding sites was observed in the La3+- or Gd3+-treated cells. For high affinity, La3+ and Gc(3+) increased both kinetic parameters K-m and V-max of basal Ca2+ influx. La3+ and Gd3+ compete directly with Ca2+ for Ca2+ binding site for low affinity. The kinetics is competitive.

Intensity exaggeration of endohedral metallofullerenes in laser-desorption-ionization time-of-flight mass spectrometry

The laser-desorption-ionization time-of-flight mass spectrometry and desorption-electron-ionization mass spectrometry were employed for the characterization of metallofullerenes extract. it was found that the relative intensities of metallofullerenes in this positive-ion, negative-ion LD-TOF MS and DEI MS were much different. This phenomenon should have relationship with the peculiar ionization energies and electron affinities of metallofullerenes.

Molecular systematics and biogeography of Crawfurdia, Metagentiana and Tripterospermum (Gentianaceae) based on nuclear ribosomal and plastid DNA sequences

Background and Aims The systematic position of the genus Metagentiana and its phylogenetic relationships with Crawfurdia, Gentiana and Tripterospermum have not been explicitly addressed. These four genera belong to one of two subtribes (Gentianinae) of Gentianeae. The aim of this paper is to examine the systematic position of Crawfurdia, Metagentiana and Tripterospermum and to clarify their phylogenetic affinities more clearly using ITS and trnL intron sequences.Methods Nucleotide sequences from the internal transcribed spacers (ITS) of nuclear ribosomal DNA and the plastid DNA trnL (UAA) intron were analysed phylogenetically. Ten of fourteen Metagentiana species were sampled, together with 40 species of other genera in the subtribe Gentianinae.Key Results The data support several previously published conclusions relating to the separation of Metagentiana from Gentiana and its closer relationships to Crawfurdia and Tripterospermum based on studies of gross morphology, floral anatomy, chromosomes, palynology, embryology and previous molecular data. The molecular clock hypothesis for the tested sequences in subtribe Gentianinae was not supported by the data (P < 0.05), so the clock-independent non-parametric rate smoothing method was used to estimate divergence time. This indicates that the separation of Crawfurdia, Metagentiana and Tripterospermum from Gentiana occurred about 11.4-21.4 Mya (million years ago), and the current species of these three genera diverged at times ranging from 0.4 to 6.2 Mya.Conclusions The molecular analyses revealed that Crawfurdia, Metagentiana and Tripterospermum do not merit status as three separate genera, because sampled species of Crawfurdia and Tripterospermum are embedded within Metagentiana. The speciation and rapid radiation of these three genera is likely to have occurred in western China as a result of upthrust of the Himalayas during the late Miocene and the Pleistocene.

西天山造山带古生代构造演化与地壳增生—来自花岗岩和蛇绿岩的证据

The Central Asian Orogen Belt (CAOB), which is different from the subductional orogen and the collisional orogen, is known as the most important site of crustal growth in the Phanerozoic, and it has been a ‘hot spot’ for studying the orogenic belts. The Chinese West Tianshan Orogen is occupying the west-southern part of the CAOB and is of great importances to understand the orogenic processes and the continental growth in the Central Asia. The West Tianshan Orogen had undergone complex tectonic evolutional processes in Paleozoic times and large volumes granitic rocks have recorded important information about these processes. Litter is known about Phanerozoic continental growth in the Western Tianshan area so far, compared with the other areas of the CAOB, such as eastern Junggar, western Junggar, Altai and Alakol. The aim of this dissertation is to set up the chronology frame of granitoids in western Tianshan, provide new evidence for the tectonic evolution and discuss the Paleozoic continental growth in this area, on the basis of the studies on the isotopic chronology, major element, trace element and Nd-Sr isotopic geochemistry of granitoids and the isotopic chronology and geochemistry of the ophiolites in this area, especially the Kule Lake ophiolites. 25 precise SHRIMP U-Pb zircon and LA-ICPMS U-Pb zircon ages have been obtained in this dissertation. The granitic rocks in western Tianshan had been formed during two periods: the granitic gneiss with an age of 896Ma, possibly representing the forming age of the Precambrian basement; the granitic rocks with ages varying from 479Ma to 247Ma, recording the Paleozoic orogenic process of western Tianshan. The granitoids in western Tianshan are composed of intermediate-basic rocks, intermediate rocks, intermediate-acid rocks and acid rocks, mainly intermediate-acid rocks and acid rocks. They are mostly granite, granodiorite, quartz syenite and monzodiorite. Different types of granitic rocks are exposed in different tectonic units. The granitoids on the northern margin of the Yili Plate mainly formed in late Paleozoic (413Ma ~ 281Ma), those with ages varying from 413Ma to 297Ma show continental arc affinities and the magnesian calc-alkalic metaluminous diorite of 281Ma display the geochemical characteristics similar to those of granites formed during the post-orogenic period. The granitiods on the southern margin of the Yili Plate include the adakite diorite of 470Ma which was formd by partial melting of thickened lower crust, the post-collisional alkali-feldspar granite of 430Ma, the volcanic arc granite of 348Ma and the Triassic post-collisional granite. The granitoids in the Central Tianshan Plate formed in 479Ma ~ 247Ma, mainly in 433Ma ~ 321Ma. The granitic rocks with ages of 479Ma ~ 321Ma are magnesian calc-alkalic to alkalic rocks with continental arc affinities. A few post-collisional granitoids of 276Ma ~ 247Ma may have inherited the geochemical characteristics of pre-existing arc magma. The granitic rocks in Southern Tianshan (northern margin of the Tarim plate) formed two stages, 420Ma ~ 411Ma and ca. 285Ma. The magnesian calcic to alkalic granites of 420Ma ~ 411Ma may formed during the extension process of the continental margin. The granite of 285Ma includes mostly ferroan calc-alkalic to alkali-calcic rocks with high SiO2 and high alkaline contents, and obviously negative anomaly of Eu, Ba, Sr, P, Ti, similar to the geochemical characteristics of the A-type granite which is formed during post-collisional extension. The Kule Lake ophiolite in southern Tianshan shows the affinity of N-MORB. A SHRIMP zircon U-Pb age of 425±8Ma has obtained for gabbros. Some zircons have given another group of 206Pb/238U age 918Ma, which may indicate the information of the pre-exist old basement rock. The small oceanic basin represented by Kule Lake ophiolite probably developed on the split northern margin of Tarim block. A model for Paleozoic tectonic evolution of the West Tianshan Orogen has been proposed here on the basis of the new results obtained in this dissertation and the previous published data. In Early Cambrian, the Terskey Ocean occurred along the North Nalati fault (NNF), and it separated the Yili plate from the Central Tianshan plate which was probably connected with the Tarim plate. The Terskey Ocean probably subducted towards south under the Central Tianshan plate and towards north under the Yili plate simultaneously. In the early stage of Late Ordovician, the Terskey Ocean had been closed, and the Yili and Central Tianshan plates collided. Meanwhile, extension happened within the joint Central Tianshan and Tarim plates gradually and the Paleo-South Tianshan Ocean had been formed. In Early Silurian, the Paleo-South Tianshan Ocean began to subduct beneath the composite Yili-Central Tianshan plate, which was intruded by volcanic arc granitoids. In Middle Silurian, the Paleo-South Tianshan Ocean, which had reached a certain width, was subducting strongly. And this subduction may have produced voluminous granitoids in the Central Tianshan plate. In the latest stage of Carboniferous, the Paleo-South Tianshan ocean closed, and the Yili-Central Tianshan plate and Tarim plate collided. In Late Cambrian, Paleo-Junggar Ocean occurred to north of the Yili plate; and started to subduct towards south under the Yili plate in Ordovician. This subduction may have produced a magma arc on the northern margin of the Yili plate. In Late Carboniferous, the Paleo-Junggar Ocean had been closed. The Yili-Central and Junggar plates amalgamated together. The West Tianhan Orogen may undergo a post-collisional collapse since Permian. And the magmatic activities may continue to early Triassic. The initial 87Sr/86Sr ration of the granitic rocks in the western Tianshan Mountains varies from 0.703226 to 0.716343, and Nd（t）from -6.50 to 2.03. The characteristics of Sr-Nd isotope indicate that the source of granitic material is not a sole source, which may be produced by mantle-crust magma mixing. In Paleozoic time, lateral growth of the continental crust along active continental margins was dominant, whereas the vertical growth of continental crust resulted from post- collisional mantle derived magmas was not obvious.

北山及邻区古生代-早中生代增生与碰撞大地构造格局

The Beishan orogenic collage locates at the triple-joint among Xinjiang, Gansu, and Inner Mongolia Provinces, at which the Siberian, Tarim and North China plates join together. It also occupies the central segment of the southern Central Asian Orogenic Belt (CAOB). The main study area in the present suty focused on the southwest part of the Beishan Mountain, which can be subdivided into four units southernward, the Mazhongshan continental block, Huaniushan Arc, Liuyuan suture zone and Shibanshan-Daqishan Arc. 1. The Huaniushan Arc was formed by northernward dipping subduction from the Orcovician to Permian, in which volcanic rocks ranging from basic to acidic with island arc affinity were widely developed. The granitiod intrusions become smaller and younger southward, whichs indicates a southward rollback of slab. The granitiod intrusions are mainly composed of I type granites, and their geochemical compositions suggest that they have affinities of island arc settings. In the early Paleozoic（440Ma-390Ma）. The Shibanshan-Daqishan Arc, however, were produced in the southernward dipping subduction system from Carboniferous to Permian. Volcanic rocks from basic to acidic rocks are typical calcic-alkaline rocks. The granitiod intrusions become smaller and younger northernward, indicating subdution with a northernward rollback. The granitiod intrusions mainly consist of I-type granites, of which geochemical data support they belong to island arc granite. 2. Two series of adakite intrusions and eruptive rocks have been discovered in the southern margin of the Huaniushan Island Arc. The older series formed during Silurian (441.7±2.5Ma) are gneiss granitoid. These adakite granites intruded the early Paleozoic Liuyuan accretionary complex, and have the same age as most of the granite intrusions in the Huanniushan Arc. Their geochemical compostions demonstrate that they were derived from partial melting of the subudcted oceanic slab. These characteristics indicate a young oceanic crust subduction in the early Paleozoic. The late stage adakites with compositons of dacites associate with Nb-enriched basalts, and island arc basalts and dacites. Their geochemistries demonstrate that the adakites are the products of subducted slab melts, whereas the Nb-enriched basalt is products of the mantle wedge which have metasomatized by adakite melts. Such a association indicates the existences of a young ocean slab subduction. 3. The Liuyuan suture zone is composed of late Paleozoic ophiolites and two series of accretionary complexes with age of early Paleozoic. The early Paleozoic accretionary complex extensively intruded by early Palozioc granites is composed of metamorphic clastics, marble, flysch, various metamorphic igneous rocks (ultramafic, mafic and dacite), and eclogite blocks, which are connected by faults. The original compositions of the rocks in this complex are highly varied, including MORB, E-MORB, arc rocks. Geochronological study indicates that they were formed during the Silurian (420.9±2.5Ma and 421.1±4.3Ma). Large-scale granitiods intruded in the accretionary complex suggest a fast growth effect at the south margin of the Huaniushan arc. During late Paleozoic, island arc were developed on this accretionary complex. The late Paleozoic ophiolite has an age of early Permian (285.7±2.2Ma), in which the rock assemblage includes ultra-mafic, gabbros, gabbros veins, massive basalts, pillow basalt, basaltic clastic breccias, and thin layer tuff, with chert on the top.These igneous rocks have both arc and MORB affinities, indicating their belonging to SSZ type ophiolite. Therefore, oceanic basins area were still existed in the Liuyuan area in the early Permian. 4. The mafic-ultramafic complexes are distributed along major faults, and composed of zoned cumulate rocks, in which peridotites are surrounded by pyroxenite, hornblendites, gabbros norite and diorite outward. They have island-arc affinities and are consistent with typical Alaska-type mafic-ultramafic complexes. The geochronological results indicate that they were formed in the early Permian. 5. The Liuyuan A-type granite were formed under post-collisional settings during the late Triassic (230.9±2.5Ma), indicating the persistence of orogenic process till the late Triassic in the study area. Geochronological results suggested that A-type granites become younger southward from the Wulungu A-type granite belt to Liuyuan A-type granite belt, which is in good agreement with the accretionary direction of the CAOB in this area, which indicate that the Liuyuan suture is the final sture of the Paleo-Asin Ocean. 6. Structural geological evidence demonstrate the W-E spreading of main tectonic terrenes. These terrenes had mainly underwent through S-N direction contraction and NE strike-faulting. The study area had experienced a S-N direction compression after the Permian, indicating a collisional event after the Permian. Based on the evidene from sedimentary geology, paleontology, and geomagnetism, our studies indicate that the orogenic process can be subdivided into five stages: (1) the pre-orogenic stage occurred before the Ordovicain; (2) the subduction orogenic stage occurred from the Orcovician to the Permian; (3) the collisional orogenic stage occurred from the late Permian to the late Triassic; (4) the post-collision stage occurred after the Triassic. The Liuyuan areas have a long and complex tectonic evolutional history, and the Liuyuan suture zone is one of the most important sutures. It is the finally suture zone of the paleo-Asian ocean in the Beishan area.

安多地区早中侏罗世岩浆岩岩石地球化学和同位素年代学研究及其对构造演化的制约

Anduo area is located in the Central Tibet, the middle segment of the Bangonghu-Nujiang suture. Anduo Block is the northern part of Lhasa terrane. The relationships among the different geological bodies were determined during the 1: 250000 regional geological surveying. Petrography, petrologic geochemistry, isotopic geochemistry and geochronology of igneous rocks from the suture and granitoids from Anduo Block were analyzed systematically as a whole for the first time. Then, their tectonic setting and history are discussed.Anduo ophiolitic melange consists of metamorphic peridotites, cumulates, plagiogranites, sheeted dykes swarm, pillow lava and radiolarian cherts. The concentration of Cr and Ni in the metamorphic peridotites is very high, with Mg# about 0.94 ~ 0.97, higher 87Sr/86Sr and Pb isotopic ratios, and lower 143Nd/i44Nd ratio. LREE is enriched relative to HREE and positive Eu anomaly is very clear. The REE distribution curve is U shape. Nb and Ta anomalies from cumulate gabbro and sheeted dyke swarm are not clear, while that are slightly negative from pillow lava. Plagiogranite belongs to strong calc-alkaline series with high Si, middle Al, low Fe, Mg and low K contents. Eu anomaly (~ 1.23) from plagiogranites is slightly positive. The character of all components of ophiolite is similar to that of the MORB, while to some extent the ophiolite was influenced by crustal material. Anduo ophiolite formed in a mature back-arc basin. Additionally, intermediate acidity volcanic rocks within Anduo phiolite melange are island arc calc-alkline rocks related to ocean subduction.The early-middle Jurassic plutonic rocks are tonalite, granodiorite bearing-phenocryst, magaporphyritic hornblende monzogranite, magaporphyritic monzogranite, monzogranite bearing-phenocryst and syenogranite in turn. They belong to calc-alkaline series which developed from middle K to high K series temporally. REE distribution curves of all plutonic rocks are similar and parallel to each other. SREE and negative Eu anomaly values decrease. In the multi-element spider diagram, the curves of different plutons are similar to each other, but troughs of Nb, Sr, P and Ti from young plutons become more evident. This suggests that thereare some closely petrogenetic affinities among plutonic rocks which make up amagma plutonism cycle of the early-middle Jurassic. Magma source is mainly crustal,but abundant mafic microgranular enclaves within granitoids indicate that crastalmagma should be mixed with mantle-derived magma and the mantle-derived magmadecreased subsequently. Tonalite has features of I-type granite, magaporphyriticmonzogranite is transition type, and monzogranite bearing-phenocryst is S-typegranite. The characteristic of granitoids from Anduo Block suggest that the formingtectonic setting is active continental margin.Reliable zircon U-Pb SHRIMP ages are obtained in the study area firstly. Plagiogranite from the Anduo ophiolite of the Bangonghu-Nujiang suture is 175.1 Ma, and granitoids from Anduo Block is 172.6-185.4 Ma. Additionally, plagioclase from the plagiogranite dates a 40Ar/39Ar age of 144 Ma, while biotite and hornblend from granitoids of Anduo Block give a 163-165 Ma.Similar cooling ages of plagiogranite from the Anduo ophiolitic melange and granitoids from Anduo Block and the spatial distribution of the ophiolitic rocks between Anduo, Naqu, and Shainzha area suggest that bilateral subduction of the Bangonghu-Nujiang oceanic basin took place in the early-middle Jurassic. During this subduction, Anduo ophiolitic rocks were related to north subduction of the Bangonghu-Nujiang oceanic basin and Anduo back-arc basin spreading, while granitoids from Anduo Block were related to south subduction.