Synthesis of Fullerene-end Functionalized Poly（methyl methacrylate） via Reverse Atom Transfer Radical Polymerization

The use of the reverse atom transfer radical polymerization （RATRP） to end-functionalize poly（methyl methacrylate） （PMMA） with fullerenes, e.g. C60 and C70 was described in this paper. The Cl-terrninated PMMA was prepared via RATRP with designed molecular weight and narrow molecular weight distributions, and then directly used to react with fullerenes to produce C60（C70） terminated PMMA polymers in the presence of CuBr/Cu/bipy or FeCl2/bipy catalysts. The resultant polymers exhibit good solubility in some common organic solvents, e.g. THF, CHCl3 and toluene, and were well structurally characterized by a variety of physical techniques.     

Ru-catalyzed highly enantioselective hydrogenation of α-keto Weinreb amides

Asymmetric hydrogenation of α-keto Weinreb amides has been realized with [Ru((S)-Sunphos)(benzene)Cl]Cl as the catalyst and CeCl 3·7H2O as the additive.A series of enantiopure α-hydroxy Weinreb amides(up to 97% ee) have been obtained.Catalytic amount of CeCl3·7H2O is essential for the high reactivity and enantioselectivity and the ratio of CeCl3·7H2O to [Ru((S)-Sunphos)(benzene)Cl]Cl plays an important role in the hydrogenation reaction.     

Organic ammonium ion-occluded flexible coordination polymers: Thermal activation, structure transformation and proton transfer

Solvothermal reactions of 1,3,5-benzenetricarboxylic acid (H₃btc) with cadmium acetate or zinc acetate yielded two compounds formulated as (Me₂NH₂)[Cd(btc)]·DMA (1) (btc = 1,3,5-benzenetricarboxylate, DMA = N,N-dimethylacetamide) and (Me₂NH₂)[Zn(btc)]·DMF (2) (DMF = N,N-dimethylformamide). Both are 3-D frameworks with the rutile topology, which are constructed from six-connected dimeric metal cores and three-connected btc linkers. The solvent molecules and counter cations are located in the 1-D channels of the frameworks. A slight difference between the two compounds is the different connectivity modes of the metal atoms with the carboxylate groups of the ligands. However, this slight difference results in distinct flexibilities of the two frameworks. Variable-temperature powder X-ray diffraction studies revealed that the framework of 1 collapses when heated at 180 °C with loss of the guest species, but compound 2 undergoes two structural transformations below 380 °C. Thermogravimetry-infrared spectroscopy analysis for 2 showed that the two structural transformations are induced by separate losses of solvent molecules and counter cations, and that the dimethylammonium cations are eliminated as neutral dimethylamine molecules. IR spectroscopy demonstrated that the protons are transferred from the counter cations onto the uncoordinated carboxylate oxygen atoms on the channel walls. Sorption and proton conduction studies have also been performed for the compounds.     

Recent development of studies on the mechanism of resistive memories in several metal oxides

Resistive switching random access memories(RRAM)have been considered to be promising for future information technology with applications for non-volatile memory,logic circuits and neuromorphic computing.Key performances of those resistive devices are approaching the realistic levels for production.In this paper,we review the progress of valence change type memories,including relevant work reported by our group.Both electrode engineering and in-situ transmission electron microscopy(TEM)high-resolution observation have been implemented to reveal the influence of migration of oxygen anions/vacancies on the resistive switching effect.The understanding of resistive memory mechanism is significantly important for device applications.     

Compositions of aliphatic des-A-triterpenes in the Hani peat deposit,Northeast China and its biological significance

Aliphatic des-A-triterpenes, the degradation products of pentacyclic triterpenes have been tentatively assigned in samples taken from a 963-cm-thick peat sequence from the Hani region of Northeast China using gas chromatography-mass spectrometry (GC-MS) in order to understand and identify these des-A-triterpenes response to climate and ecology. The study indicates that aliphatic des-A-triterpenes are abundant in the Hani peat bog. The high relative abundance of the total des-A-triterpenes mainly occurs at the Holocene periods and is corresponding to the low sedimentation rate. The mechanism of des-A-triterpenes accumulation is not consistent with the previous studies. It is proposed that the biological community is also one influence factor. The obvious stage variations of the total des-A-triterpenes in the whole sequence reveal the different biological (microbes and plants) processes and responses, possibly revealing the four large replacements of biological community and functional composition in the swamp environment over the 16000 cal a BP. The low total des-A-triterpenes values occur at about 10200, 8700, 7700, 6600, 4480–3940 and 3040 cal a BP, reflecting the multiple millennial micro-environment oscillations under the macro-environment of the swamp during the Holocene. The ratios of diene and monoene des-A-triterpenes (DT/MT), des-A-lupane and diene and monoene des-A-triterpenes (DL/(DT+MT)), ratios of individual compounds exhibit vertical opposite to the total des-A-triterpenes. Namely, these ratios are high during the last deglaciation and late Holocene whereas they are low at other periods, indicating different compounds have different responses to micro-environment and microbial activities. This study discusses the diversity of biological community and biological functional composition response to micro-environment, which not only provides the complement in Northeast China, but also bears important fundamental information for the implication to ecological environment in the future.     

A model of calcium signaling and degranulation dynamics induced by laser irradiation in mast cells

Recent experiments show that calcium signaling and degranulation dynamics induced by low power laser irradiation in mast cells must rely on extracellular Ca^2＋ influx. An analytical expression of Ca^2＋ flux through TRPV4 cation channel in response to interaction of laser photon energy and extracellular Ca^2＋ is deduced, and a model characterizing dynamics of calcium signaling and degranulation activated by laser irradiation in mast cells is established. The model indicates that the characteristics of calcium signaling and degranulation dynamics are determined by interaction between laser photon energy and Ca^2＋ influx. Extracellular Ca^2＋ concentration is so high that even small photon energy can activate mast cells, thus avoiding the possible injury caused by laser irradiation with shorter wavelengths. The model predicts that there exists a narrow parameter domain of photon energy and extracellular Ca^2＋ concentration of which results in cytosolic Ca^2＋ limit cycle oscillations, and shows that PKC activity is in direct proportion to the frequency of Ca^2＋ oscillations. With the model it is found that sustained and stable maximum plateau of cytosolic Ca^2＋ concentration can get optimal degranulation rate. Furthermore, the idea of introducing the realistic physical energy into model is applicable to modeling other physical signal transduction systems.     

Magnetostratigraphy of the Zanda basin in southwest Tibet Plateau and its tectonic implications

The Zanda basin is one of the very important basins at the north slope of the Himalaya Range. Thus the study of the basin strata will provide critical information about the tectonic evolution of the Himalayan Orogenic Belt. 268 oriented block samples were collected in the 750-m-thick sections of the Zanda basin. The characteristic remanent magnetization （ChRM） was isolated that decays linearly to the origin between 500℃ and 690℃for most studied samples. An age range of 9.5-2.6 Ma was estimated from the correlation between our observed polarity column and the Geomagnetic Polarity Time Scale （GPTS）. The age of the Zanda basin does not support the models that the South Tibetan Detach system （STDS） is one of the basin controlling faults. Given the sedimentological features in the basin and the tectonic features at the north edge of the basin, the Zanda basin was a half graben that was possibly controlled by the Karakorum fault on the northeast.     

Understanding the interactions between tris(pentafluoroethyl)-trifluorophosphate-based ionic liquid and small molecules from molecular dynamics simulation

Tris(pentafluoroethyl)trifluorophosphate ([FEP])-based ionic liquids have been widely applied in many fields. For better understanding the properties of [FEP]-based ionic liquids, the interactions between 1-hexyl-3-methylimidazolium ([hmim])[FEP] and small molecules were investigated by molecular dynamics simulations in this work. The small molecules are water, methanol and dimethyl ether. The united-atom (UA) force fields were proposed for methanol and dimethyl ether based on AMBER force field. The densities, enthalpies of vaporization, excess molar properties, and diffusion coefficients of the mixtures were calculated, as well as the microscopic structures characterized by radial distribution functions. Both of the results of the excess energies and microscopic properties show that the strongest interaction is between [hmim][FEP] and dimethyl ether, whereas the interaction between [hmim][FEP] and water is the weakest. Moreover, [hmim][FEP] is more hydrophobic than [hmim] hexafluorophosphate ([PF6]), and the three solutes are mainly distributed around [FEP] anion.     

离子液体的前沿、进展及应用

离子液体作为一类新型绿色介质,近年来获得了突飞猛进的发展.离子液体的多项应用研究正在进行中试或工业性试验,甚至已经进入产业化阶段.推动离子液体研究迅速发展的直接动力来源于国际社会对清洁生产、环境保护、循环经济的强烈愿望,以及离子液体本身的科学探索价值和巨大的应用潜力.离子液体不仅可替代传统有机溶剂或酸碱成功用作化工反应和分离的新介质,而且展示了作为新型磁性材料、纳微结构功能材料、润滑材料、航空航天推进剂等潜力,甚至有望成为食品和医药.