Intermacromolecular complexes by in situ polymerization

Hydrogen-bonded complexes of poly(acrylic acid) and poly(ethyl oxazoline) (PEOx) were prepared by photopolymerization of acrylic acid in which PEOx was dissolved. The glass transition temperatures (T_g) of the complexes are not only higher than those of the blends but also higher than the T_g value of either component polymer. The complexes dissolve in strong proton-accepting solvents like dimethyl formamide or dimethyl sulphoxide (DMSO), are swollen to various degrees in water and methanol, but are resistant to swelling by dioxane. When the density of hydrogen bond donor groups in the chain is reduced by 50% with the use of a copolymer of acrylic acid and methyl methacrylate, intermolecular association still takes place, although the affinity of complexation is reduced to some extent. When interpenetrating networks (semi-IPNs) are prepared by this method, about half of the PEOx can be extracted by DMSO after 4 days. The incomplete removal is probably a result of topographical constraints against diffusion.     

Synthesis and Polymerization of Cationic bis(cyclopentadienyliron)arene Complexes Containing Arylazo Dyes

The synthesis of the title complexes was achieved via the reaction of -p-dichlorobenzene- -cyclopentadienyliron cations with 4,4′-bis(4-hydroxyphenyl)valeric acid to produce the diiron complexes which were then reacted with a number of arylazo dyes to give cationic bis(cyclopentadienyliron)arene complexes containing the arylazo dyes. These iron-containing monomers were subsequently polymerized via nucleophilic aromatic substitution using 1,8-octanedithiol, 4,4′-thiobisbenzenethiol, or bisphenol A to produce the desired coloured cationic organoiron polymers. The weight – average molecular weights were estimated to range from 11,800 to 31,600. UV–vis studies conducted in dimethylformamide (DMF) showed that the metallated polymers exhibited of 412–491 nm. Addition of HCl to the polymer solution caused a bathochromic shift into the range of 515–530 nm. Thermogravimetric analysis (TGA) revealed that the iron moieties were cleaved between 205 and 248 °C while the polyether/thioether backbone degraded between 380 and 613 °C. Differential scanning calorimetry (DSC) showed that the polymers exhibited glass transition temperatures (Tg) ranging from 106 to 184°C.This paper is dedicated to Professor Richard J. Puddephatt in recognition of his outstanding contribution to the field of metal-containing polymers.     

Organoiron Polyelectrolytes: Synthesis and Characterization of Cationic Cyclopentadienyliron Complexes of Polyarylether-Imines

The synthesis of an aromatic ether complex of cyclopentadienyliron containing two terminal aldehyde groups was achieved via metal-mediated nucleophilic aromatic substitution reactions. This dialdehyde monomer was subsequently reacted with a variety of aliphatic and aromatic diamines to produce the corresponding soluble cationic organoiron polyether-imines. These cationic organometallic polymers were characterized using IR, ¹H, and ¹³C NMR, viscosity and thermogravimetric analysis. Viscosity measurements showed that these polymers exhibited polyelectrolyte effects in DMSO solutions. Thermogravimetric analysis showed that decoordination of the iron moieties occurred at about 300°C for polymers with aliphatic spacers in their backbones, while the cyclopentadienyliron moieties were cleaved from the polymers with aromatic spacers in their backbones at about 200°C. Photolytic demetallation of the organoiron polymers resulted in the removal of the pendent cyclopentadienyliron moieties and allowed for the isolation of their organic analogs. While the organoiron polymers were soluble in polar organic solvents, the corresponding organic polymers exhibited very limited solubilities or were insoluble. The organic polymers had glass transition temperatures between 101 and 120°C     

梯级水电枢纽群巨灾风险分析与防控研究综述

伴随超标准巨震、极端暴雨洪水、巨型滑坡等灾害频繁发生,极端载荷作用下梯级水电枢纽群的灾害风险分析与防控等问题成为当前水利工程领域的研究热点。为分析梯级水电枢纽群巨灾风险研究现状,绘制了国内外水库大坝溃坝事件的时间序列图,分析了梯级水电枢纽群的风险特征,总结评述了梯级水电枢纽群巨灾风险分析和巨灾防控研究进展,主要结论如下：1)梯级水电枢纽群巨灾风险是我国水利水电工程风险防控面临的主要问题;2)梯级水电枢纽群风险分析方面主要聚焦于梯级水库连溃概率的分析和计算,对于溃决可能产生的巨灾损失的量化研究不足,缺乏对巨灾因子及其相关影响作用下巨灾风险的评估;3)缺乏对梯级枢纽群灾害链的阻断技术研究和应急避险方案设计研究。为此提出了梯级水电枢纽群可能最大灾难(Probable Maximum Disaster, PMD)的科学内涵,考虑可能遭遇的多种致灾因子和承灾体特征,分析相互因果关系和极端荷载组合情况,初步建立了PMD评估的理论模型,为绘制梯级水电枢纽群在巨灾情景下的灾难空间外包线和估算PMD损失上限值提供科学依据,为梯级水电枢纽群巨灾风险分析和防控提供理论基础和技术支持。     

基于加权网络和局部适应度的蛋白质复合物识别算法

蛋白质复合物识别对分析蛋白质网络的结构特征和模块功能具有重要意义。通常在蛋白质网络中挖掘稠密子图或模块来识别其中的蛋白质复合物,限制了其应用范围和识别的准确性。针对该问题,提出了一种基于加权网络和局部适应度的蛋白质复合物识别算法,该算法综合稠密子图的密度指标和模块性定义了新的局部适应度函数,并基于边聚集系数构建加权的蛋白质网络,根据权值选择边,在加权蛋白质网络中将种子边不断聚类扩展,从而获取具有最大综合适应度的子图作为蛋白质复合物。在酵母蛋白质等多个实际网络中试验表明,该算法能够有效提升蛋白质复合物识别的准确性。     

双核稀土配合物Gd_xSm_(1-x)(TTA)_3phen的制备及发光性能

合成了系列钆钐双核稀土有机配合物GdxSm1-x(TTA)3phen(x=0~0.9).红外光谱(IR)、X射线衍射(XRD)、热重(TG)结果推测了配合物可能的分子结构;紫外可见光谱(UV/vis)结果表明,该系列稀土有机配合物能有效的吸收紫外光,吸收峰主要来自于有机配体TTA和phen(270nm和351nm处);荧光光谱(FS)结果表明,Gd3+对于Sm3+具有荧光增效,当Gd3+的摩尔分数为0.6时,Gd0.6Sm0.4(TTA)3phen类配合物的特征荧光(562nm,596nm和643nm处)强度均达到最大.     

Synthesis and Characterization of Heteropoly Complexes of Indium with Metal－centred Undecatungstate Ligan

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Preparation and structural characterization of perovskite-type LaxLn1−x″CoO3 by the thermal decomposition of heteronuclear complexes, LaxLn1−x″| Co(CN)6| · nH2O (Ln″ = Sm and Ho)

Perovskite-type La_xLn_1−x″CoO₃ oxides are prepared by the thermal decomposition of La_xLn_1−x″ [Co(CN)₆] · nH₂O hetero-nuclear complexes. Except for LaCoO₃ (hexagonal), the structures observed for La_xSm_1−xCoO₃ are othorhombic. While the perovskite-type oxide HoCoO₃ is not formed by decomposition at 1000°C of the corresponding hexacyano complex, the partial replacing of Ho with La is effective in forming the pervoskite-type oxide having an orthorhombic structure containing Ho even at 800°C. A monotonous correlation (quasi-linear relationship) was found between the b- and c-lattice constants of the orthorhombic structures of the perovskite-type oxides and the effective radii of Ln ions, defined as r_eff = xr_1.a + (1 − x)r_1.0″. The distortion parameter for the orthorhombie cell (3″a/b−1) increaseswith decrease in r_eff and is expected to be 0.270 for perovskite-type HoCoO₃. The crystal structure of the La_xLn_1−x″, CoO₃ oxides is mainly controlled by the effective radii of Ln ions.     

An entropy-based persistence barcode

In persistent homology, the persistence barcode encodes pairs of simplices meaning birth and death of homology classes. Persistence barcodes depend on the ordering of the simplices (called a filter) of the given simplicial complex. In this paper, we define the notion of “minimal” barcodes in terms of entropy. Starting from a given filtration of a simplicial complex K, an algorithm for computing a “proper” filter (a total ordering of the simplices preserving the partial ordering imposed by the filtration as well as achieving a persistence barcode with small entropy) is detailed, by way of computation, and subsequent modification, of maximum matchings on subgraphs of the Hasse diagram associated to K. Examples demonstrating the utility of computing such a proper ordering on the simplices are given.     

In-focus electron microscopy of frozen-hydrated biological samples with a Boersch phase plate

We report the implementation of an electrostatic Einzel lens (Boersch) phase plate in a prototype transmission electron microscope dedicated to aberration-corrected cryo-EM. The combination of phase plate, C_s corrector and Diffraction Magnification Unit (DMU) as a new electron-optical element ensures minimal information loss due to obstruction by the phase plate and enables in-focus phase contrast imaging of large macromolecular assemblies. As no defocussing is necessary and the spherical aberration is corrected, maximal, non-oscillating phase contrast transfer can be achieved up to the information limit of the instrument. A microchip produced by a scalable micro-fabrication process has 10 phase plates, which are positioned in a conjugate, magnified diffraction plane generated by the DMU. Phase plates remained fully functional for weeks or months. The large distance between phase plate and the cryo sample permits the use of an effective anti-contaminator, resulting in ice contamination rates of <0.6 nm/h at the specimen. Maximal in-focus phase contrast was obtained by applying voltages between 80 and 700 mV to the phase plate electrode. The phase plate allows for in-focus imaging of biological objects with a signal-to-noise of 5-10 at a resolution of 2-3 nm, as demonstrated for frozen-hydrated virus particles and purple membrane at liquid-nitrogen temperature.