Reversible addition-fragmentation chain transfer mediated radical polymerization of asymmetrical divinyl monomers targeting hyperbranched vinyl polymers

Reversible addition-fragmentation chain transfer (RAFT) mediated radical polymerizations of allyl methacrylate and undecenyl methacrylate, compounds containing two types of vinyl groups with different reactivities, were investigated to provide hyperbranched polymers. The RAFT agent benzyl dithiobenzoate was demonstrated to be an appropriate chain-transfer agent to inhibit crosslinking and obtain polymers with moderate-to-high conversions. The polymerization of allyl methacrylate led to a polymer without branches but with five- or six-membered rings. However, poly(undecenyl methacrylate) showed an indication of branching rather than intramolecular cycles. The hyperbranched structure of poly(undecenyl methacrylate) was confirmed by a combination of H-1, C-13, H-1-H-1 correlation spectroscopy, and distortionless enhancement by polarization transfer 135 NMR spectra. The branching topology of the polymers was controlled by the variation of the reaction temperature, chain-transfer-agent concentration, and monomer conversion. The significantly lower inherent viscosities of the resulting polymers, compared with those of linear analogues, demonstrated their compact structure,

2-cyanoprop-2-yl dithiobenzoate mediated reversible addition-fragmentation chain transfer polymerization of acrylonitrile targeting a polymer with a higher molecular weight

The reversible addition-fragmentation chain transfer (RAFT) polymerization of acrylonitrile (AN) mediated by 2-cyanoprop-2-yl dithiobenzoate was first applied to synthesize polyacrylonitrile (PAN) with a high molecular weight up to 32,800 and a polydispersity index as low as 1.29. The key to success was ascribed to the optimization of the experimental conditions to increase the fragmentation reaction efficiency of the intermediate radical. In accordance with the atom transfer radical polymerization of AN, ethylene carbonate was also a better solvent candidate for providing higher controlled/living RAFT polymerization behaviors than dimethylformamide and dimethyl sulfoxide. The various experimental parameters, including the temperature, the molar ratio of dithiobenzoate to the initiator, the molar ratio of the monomer to dithiobenzoate, the monomer concentration, and the addition of the comonomer, were varied to improve the control of the molecular weight and polydispersity index. The molecular weights of PANS were validated by gel permeation chromatography along with a universal calibration procedure and intrinsic viscosity measurements. H-1 NMR analysis confirmed the high chain-end functionality of the resultant polymers.

A novel route to polyethylene-polystyrene blends through the fragmentation of porous polystyrene beads supported metallocene in ethylene polymerization

Polyethylene-polystyrene blends were synthesized by in situ ethylene polymerization with polystyrene porous beads supported metallocene; the influence of fragmenting support beads on the morphology and the mechanical performance of the blends was investigated.

Dibenzyl trithiocarbonate mediated reversible addition-fragmentation chain transfer polymerization of acrylonitrile

Reversible addition-fragmentation chain transfer polymerization has been successfully applied to polymerize acrylonitrile with dibenzyl trithiocarbonate as the chain-transfer agent. The key to success is ascribed to the improvement of the interchange frequency between dormant and active species through the reduction of the activation energy for the fragmentation of the intermediate. The influence of several experimental parameters, such as the molar ratio of the chain-transfer agent to the initiator [azobis(isobutyronitrile)], the molar ratio of the monomer to the chain-transfer agent, and the monomer concentration, on the polymerization kinetics and the molecular weight as well as the polydispersity has been investigated in detail. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and H-1 NMR analyses have confirmed the chain-end functionality of the resultant polymer.

Fragmentation reactions of adduct ions [M+CH3CO](+) of isomeric phenylenediamines

The dissociation routes of the adduct ions [M+CH3CO](+) formed by ion-molecule reaction of isomeric phenylenediamines with acetyl ion from acetone under chemical ionization condition were investigated by using collision-induced dissociation (CID) technique performed at ion kinetic energies of 40eV. The adduct ions are intermediate ion-neutral complexes.

Mass spectrometry study combined with theoretical calculation on the unimolecular fragmentation of tetrahydroimidazole-substituted methylene beta-diketones

Studies of low-energy collision-induced dissociation and isotopic labeling on ionized tetrahydroimidazole-substituted methylene P-diketones by tandem mass spectrometry showed that their unimolecular fragmentations may involve the reactions of intermediate ion/neutral complexes and multistep rearrangements. The corresponding mechanisms were proved by semiemipirical calculations of PM3 and AM1 methods.

Sites of protonation and unimolecular fragmentation of protonated N-hydroxyphthalimide in the gas phase

The low energy collision-induced dissociation, linked scan techniques and isotopic labeling experiment were used to investigate the unimolecular fragmentation of protonated N-hydroxyphthalimide under electron impact and chemical ionization conditions. It was found that this compound shows an unusual reactivity towards protonation. Two possible sites of protonation have been proposed to explain the corresponding fragmentation processes, one is that the protonation takes place on the oxygen atom of hydroxyl group, resulting in the loss of water and the other is the formation of an intermediary proton-bound complex in the fragmentation process, giving rise to the fragment ions of m/z 133 and m/z 135. The results show both cases are coexistence in the fragmentations of protonated N-hydroxyphthalimide, and the unimolecular fragmentation pathways are available.

Theoretical study on the unimolecular fragmentation of ionized tetrahydroimidazole-substituted methylene beta-diketones

Semiempirical molecular orbital calculations on the unimolecular mass spectrometric fragmentation of tetrahydroimidazole-substituted methylene beta-diketones are carried out by Austin Model 1 method, and the calculated results give a strong support to our experimental results reported previously. The optimum of the investigated molecular configuration indicates that the two hydrogen atoms attached to nitrogen atom have different activities due to their chemical environment; the relative energies of the ions in fragmentation pathway of ionized tetrahydroimidazole-substituted methylene beta-diketones provide indirectly an evidence for both the existence of ion/neutral complex and the stabilities of these ions.

Comparative Study Of The Influence Of Natural Convection On Directional Solidification Of Al-3.5 Wt% Ni And Al-7 Wt% Si Alloys

We present numerical simulations of thermosolutal convection for directional solidification of Al-3.5 wt% Ni and Al-7 wt% Si. Numerical results predict that fragmentation of dendrite arms resulting from dissolution could be favored in Al-7 wt% Si, but not in Al-3.5 wt% Ni. Corresponding experiments are in qualitative agreement with the numerical predictions. Distinguishing the two fragmentation mechanisms, namely dissolution and remelting, is critical during experiments on earth, when fluid flow is dominant. (C) 2007 COSPAR. Published by Elsevier Ltd. All rights reserved.

Adiabatic shear localization: occurrence, theories, and applications

濒危物种保护、生境破碎化及其恢复

保护区是否真的能起保护作用？保护区究竟如何布局？这是自然保护区的建设一直争论不休的课题。就大熊猫保护而言，目前面临的最紧迫问题可能不是保护区数量多少的问题，而是这些多个保护区组成的保护区群的配置或格局是否合理。因此，本研究以岷山大熊猫保护区群为研究对象，分析现有大熊猫及栖息地及其保护现状，指出目前保护区存在的问题，并对岷山大熊猫自然保护区群合理布局提出建议性设计，以期为大熊猫保护及自然保护区建设的理论提供借鉴。 到目前，为了保护大熊猫，在岷山地区已经建立了1 7个自然保护区，这些保护区的建立对大熊猫的保护起到了非常重要的重要。但是，大熊猫栖息地仍然持续下降。就其原因有两方面，即岷山地区人为活动的干扰，如旅游业的盲目发展。但，同时大熊猫自然保护区本身的布局存在一定的不合理性。最后，从景观尺度上提出岷山大熊猫保护区群合理建设的布局，即在分析现有保护布局基础上，找到优先保护的敏感地带建立廊道，将所有保护区连成布局合理的保护区群。 大熊猫受威胁的关键因子并不是竹子，而是森林．竹子复合系统的破碎化或质量的退化，故保护大熊猫应从保护森林、恢复森林．竹子复合生态系统的质量入手。但是，具体实践中究竞采取什么模式来恢复退化的大熊猫栖息地？选取不同模式的科学依据是什么？如何评判不同恢复模式的成本和效益？这些方面的工作到目前缺少系统研究。本研究在分析了岷山地区自然、社会与经济条件的基础上，从荒山荒地造林、天然林保护与低效林地改造主要植被恢复措施着手，全面分析各类植被恢复措施所形成植被的生态效益（保持水土、涵养水源、保持肥力等）、经济收益（木材、果品和林副特产品）、社会效益（种植结构、劳动力再分配等），总结出植被恢复成本和效益的构成要素，计算主要植被恢复模式的成本和效益，为选择适宜的植被恢复措施、典型植被恢复模式和合理确定植被恢复技术提供科学依据，从而推动岷山植被快速健康地恢复，为大熊猫提供适宜的生存空间。 三峡大坝的建设使其固有水域的人为改造导致水位上升，使原本连续的山地生态系统被分割成大小不等的岛屿。水位变化导致的这种生境岛屿化为栖息地破碎化和岛屿生物地理学提供了十分难得的实证研究的机会。然而，同时，这种栖息地的片段化无疑对三峡库区生物多样性保护和生态系统的完整性造成威胁。到目前，为了监测库区建设对生态环境的影响，已经建立了22个定位观测站，但没有一个是生境破碎化方面的，为此建议尽快建立生境破碎化方面的定位研究站。三峡库区生物多样性丰富，但保护区面积仅仅占库区面积的6.9%，而同期我国已经建立了1 999个自然保护区，占国土面积的15%，因此，非常迫切建立更多的保护区（至少达到全国平均水平）。为了从宏观尺度上加强对库区的综合保护，建议从景观生态学的角度出发，将库区作为一个自然、社会和经济复合生态系绕对待。

淹水对三峡库区几种植物的生理生态影响

自然界木本植物在某些情况下可能面对淹水带来的胁迫伤害，木本植物对淹水的生理生态响应及适应机制的研究，不仅可以从机理上解释河岸带和消落区树种分布的规律，对于大型水库消落区的治理也能起到理论依据的作用，因此，木本植物对淹水的生理生态响应及适应机制历来是植物生理生态研究领域的热点问题之一。 三峡水库蓄水造成库区部分陆地岛屿化，这将对岛屿优势植物带来深远影响。短柄枹栎(Quercus glandulifera)、栓皮栎(Quercus variabilis)、马尾松(Pinus massoniana)是这些岛屿上的三种优势树种。在岛屿形成初期，应用生理生态学手段，在7月和9月分别对其水势和叶绿素荧光进行了野外测定，从而为岛屿化对植物生理生态影响的研究和监测提供重要的本底数据。研究结果表明马尾松较其它两种植物更耐旱。水势和Fv/Fm在清晨高中午低，经过一个晚上可以基本恢复，因此就目前状况看岛上的三种优势植物均生长健康。但是库区蓄水后，在淹水胁迫下植物的生理生态过程将如何变化，还需要后期的连续观测。 枫杨（Pterocarya stenoptera）、池杉（Taxodium ascendens）和栓皮栎（Quercus variabilis）是三峡库区河岸带和库塘消落区常见的植物，对于河岸带和库塘消落区的水土保持和水源涵养具有十分重要的作用。通过设计模拟淹水实验，研究了这三种植物对淹水的生理生态响应及适应机制。淹水对枫杨和栓皮栎生理生态过程的早期影响是快速降低了二者的最大净光合速率、气孔导度、最大光化学量子效率（Fv/Fm）。但经过最初的下降后，枫杨的最大净光合速率、气孔导度和最大光化学量子效率逐渐恢复，而栓皮栎的则持续下降。在试验过程中，枫杨和池杉均产生了有利于吸收氧气的不定根和肥大的皮孔，而栓皮栎没有产生不定根。随淹水时间的增加枫杨的叶绿素含量与对照没有显著差异;而栓皮栎的叶绿素含量在第33天后大幅降低，Chla/Chlb的比值下降。淹水后第10天和70天测定的清晨水势，受淹栓皮栎比对照高，而受淹枫杨比对照低。淹水导致池杉和栓皮栎的根/茎/叶膜质过氧化状态均呈现动态变化。淹水处理的栓皮栎根的MDA含量低于对照而池杉的高于对照，比如：淹水24天后，栓皮栎根的丙二醛含量是对照的73％;而池杉是对照的111.5％。淹水处理第10天和第24天两个种的叶和茎MDA含量均高于对照但第50天则略低于对照。淹水导致池杉和栓皮栎两个种的根/茎/叶可溶性糖含量呈现动态变化。持续淹水导致栓皮栎叶片可溶性糖含量相比于对照先略下降后上升，茎可溶性糖含量显著上升而根可溶性含量先下降后上升。而池杉根/茎/叶可溶性糖含量对照和处理之间差异不显著。淹水导致栓皮栎的比叶重（Leaf dry mass per area）持续升高，池杉的与对照没有显著差异。淹水导致栓皮栎的根系活力持续下降，池杉则开始时下降后又升高，这可能与池杉在淹水过程中产生了有利于吸收氧气的不定根，而栓皮栎没有产生不定根有关。 以上生理生态的实验结果说明相对枫杨和池杉，栓皮栎应属于对淹水较敏感的树种。并得到以下一些结论：1）间接支持了“长期淹水导致不耐淹种（如栓皮栎）库量减小，进而导致光合速率下降的负反馈效应”假说;2）淹水对不耐淹种光合速率下降的影响至少包括气孔开度降低、光化学量子效率降低和库尺寸下降导致的光合速率下调的负反馈效应（长期）三个生理生态原因;3）淹水对水势的影响与树种相关;4）淹水并未导致不耐淹种（如栓皮栎）根膜质过氧化状态上升，而是导致其下降。导致其下降的主要原因是根系缺氧造成的;5）淹水胁迫初期耐淹种（如枫杨和池杉）和不耐淹种（栓皮栎）均出现部分生理生态过程的下调，持续时间大概在1－10天内。随后耐淹种生理过程逐渐恢复而不耐淹种在略为恢复1－2天后逐渐下降到较低水平。耐淹种恢复的关键原因可能是不定根和肥大的皮孔的出现。 令人意外的是70天的淹水过程并没有导致栓皮栎的死亡，这说明该树种对淹水具有一定的忍耐能力。因此，栓皮栎分布于河岸带和消落区较高海拔处并很少受到季节性淹水影响的生理生态原因可能还包括其他方面。淹水后可能要面对土壤透气性恢复带来的生理干旱胁迫可能对栓皮栎的生理过程造成影响。因此进一步研究淹水后恢复过程中三个种的生理生态过程对于深刻理解河岸带和消落区树种分布的生理生态原因无疑具有十分重要的理论意义。