Synthesis of high molecular weight and narrow molecular weight distribution poly(acrylonitrile) via RAFT polymerization

Well‐defined polyacrylonitrile (PAN) of high viscosity‐average molecular weight (M_η = 405,100 g/mol) was successfully synthesized using reversible addition‐fragmentation chain transfer polymerization. The polymerization exhibits controlled characters: molecular weights of the resultant PANs increasing approximately linearly with monomer conversion and keeping narrow molecular weight distributions. The addition of 0.01 equiv (relative to monomer acrylonitrile) of Lewis acid AlCl₃ in the polymerization system afforded the obtained PAN with an improved isotacticity (by 8%). In addition, the influence of molecular weights and molecular weight distributions of PANs on the morphology of the electrospun fibers was investigated. The results showed that, under the same conditions of electrospinning, average diameter (247–1094 nm) of fibers increased with molecular weights of PANs, and it was much easier to get “uniform” diameter fibers while using PANs with narrow molecular weight distributions as the precursor of electrospinning. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Formal and total synthesis of (±)-cycloclavine

A ring fragmentation and intramolecular azomethine ylide 1,3-dipolar cycloaddition sequence of reactions was successfully used in the preparation of a known (±)-cycloclavine precursor in good overall yield. Results of efforts to incorporate the tetrasubstituted cyclopropane ring present in cycloclavine are also discussed.     

The effect of cation size (H+, Li+, Na+, and K+) on McLafferty-type rearrangement of even-electron ions in mass spectrometry

Protonation and alkali-metal cation adduction are the most important ionization processes in soft-ionization mass spectrometry.Studies on the fragmentation mechanism of protonated and alkali-metal-cationized compounds in tandem mass spectrometry are essential and helpful for structural analysis.In some cases,it was often observed that a compound attached by different alkali-metal cations(or proton)exhibits similar fragmentation patterns but the relative abundances of product ions are different.This difference was considered to derive from the different electrostatic interactions of alkali-metal cations(or the bonded effect of proton)with the analyte.The alkali-metal cation with a smaller ionic radius shows stronger electrostatic interaction with the molecule because of its higher charge density.In addition,the bonded effect of the proton is stronger than the electrostatic interaction of the alkali-metal cation.In the present study,which used McLafferty-type rearrangements of even-electron ions([M+Cat]+,Cat=H,Li,Na,K)as model reactions,the effect of cation size in mass spectrometric fragmentation reactions is highlighted.These considerations were also successfully applied to interpret the similar but distinct fragmentation behavior of proton and alkali-metal cation adducts of a synthetic compound(2-(acetamido(phenyl)methyl)-3-oxobutanoate)and a drug(entecavir).     

Well‐Defined High Molecular Weight Polystyrene with High Rates and High Livingness Synthesized via Two‐Stage RAFT Emulsion Polymerization

A highly living polymer with over 100 kg mol⁻¹ molecular weight is very difficult to achieve by controlled radical polymerization since the unavoidable side reactions of irreversible radical termination and radical chain transfer to monomer reaction become significant. It is reported that over 500 kg mol⁻¹ polystyrene with high livingness and low dispersity could be synthesized by a facile two‐stage reversible addition–fragmentation transfer emulsion polymerization. The monomer conversion reaches 90% within 10 h. High livingness of the product is ascribed to the extremely low initiator concentration and the chain transfer constant for monomer unexpectedly much lower than the well‐accepted values in the conventional radical polymerization. The two‐stage monomer feeding policy much decreases the dispersity of the product.

     

片段化森林中檵木幼苗种内叶经济性状变异及其驱动因子

在异质性生境中,种内功能性状变异有助于植物对环境的适应,进而影响种群更新、群落构建和生态系统过程。探讨了种内叶经济性状的变异及受生境异质性的塑造情况。以千岛湖片段化生境中的常见种檵木（Loropetalum chinense）的幼苗为研究对象,测定了200株檵木幼苗个体水平的7个叶经济性状（比叶面积SLA、叶全碳量C、叶全氮量N等）及其对应的生境因子（郁闭度、土壤全碳量、土壤全氮量等）,采用相关性检验、主成分分析和线性混合效应模型等方法探讨片段化森林中檵木幼苗的种内叶经济性状变异及生境异质性对该变异的驱动作用。结果显示：（1） 在7个叶经济性状所构成的21对相关性分析中,有12对显著相关。经主成分分析降维后,主成分1（PC1）占性状总变异的43.02%,主要与比叶面积、叶绿素浓度、叶全氮量呈正相关,与叶干物质质量分数和叶碳氮比呈负相关,体现了檵木的种内叶经济谱,可反映叶片的最大光合效率。（2）片段化对生境条件和叶经济性状均有影响。岛屿森林群落的郁闭度显著低于大陆。相对于大陆,岛屿中的檵木幼苗趋向于更小的PC1值（缓慢投资-收益策略）;大岛边缘较大岛内部偏向于更小的PC1值。（3）生境因子中,郁闭度对PC1具有显著正效应。研究表明,片段化生境中的檵木在幼苗阶段存在叶经济谱,生境片段化可通过影响生境条件进而改变檵木幼苗的叶经济性状。随着生境片段化程度的加剧,檵木幼苗的叶经济性状逐渐向缓慢投资-收益策略靠拢。     

Stochastic Theory of Discrete Binary Fragmentation—Kinetics and Thermodynamics

We formulate binary fragmentation as a discrete stochastic process in which an integer mass k splits into two integer fragments j, k−j, with rate proportional to the fragmentation kernel Fj,k−j. We construct the ensemble of all distributions that can form in fixed number of steps from initial mass M and obtain their probabilities in terms of the fragmentation kernel. We obtain its partition function, the mean distribution and its evolution in time, and determine its stability using standard thermodynamic tools. We show that shattering is a phase transition that takes place when the stability conditions of the partition function are violated. We further discuss the close analogy between shattering and gelation, and between fragmentation and aggregation in general.     

Photoinduced dissociation reactions of silver fluoride cluster ions

Photoinduced dissociation in the ultraviolet region has been investigated for Ag _nF _n-1 ⁺ cluster ions. Photodissociation spectrum of Ag₂F⁺ in the energy of 3.8–5.6 eV exhibits several sharp bands corresponding to the transition to electronically excited states. In this dissociation, only the Ag₂ ⁺ ion was observed as a fragment ion. Theoretical calculation indicates that the parent Ag₂F⁺ ion has a linear Ag-F-Ag equilibrium geometries in the ground and excited states. Since conformational changes by excitation of bending vibration are necessary for the fragmentation of an F atom, this indicates that production of Ag₂ ⁺ from Ag₂F⁺ is a result of internal conversion and following conformational changes.     

Collective bounce-off phenomenon in139La+Ag(Br) reaction at 1.1 A GeV energy

Out of a total statistics of 896¹³⁹La+Ag(Br) interactions, 128 interactions having multiplicity of target fragments (Z⩾1)⩾8 and projectile fragments (Z⩾2)⩾4 have been selected. They correspond to quasi-peripheral interactions. Azimuthal angle correlation between sources of target fragments (TFs) and projectile fragments (PFs) shows the existence of bounce-off effect. Using data of La+Ag(Br) and⁸⁴Kr+Ag(Br) reactions it is shown that individual helium [Z=2, PFs] and heavier fragment [Z⩾3, PFs] show different emission characteristics. Further, a two prong correlation functionT(Φ _ij ) plotted for heavier fragments and helium fragments separately, indicates the possibility of existence of different physical conditions. This observation is supported by the different momentum widths of helium fragments and heavier fragments. From the momentum width data of Kr+Ag(Br) reactions normalized density comes out to be ≈4.7. Using quasi-elastic kinematics for the bounce-off nuclei, the excitation energy has been computed from the experimental data of flow angles. The strength of bounce-off seems to decrease with the increase of excitation energy or temperature.     

Formation of small water cluster anions by attachment of very slow electrons at high resolution

Using a high resolution laser photoelectron attachment method, we have studied the formation of (H ₂ O) _q ^- (q = 2, 6, 7, 11, 15) cluster ions in collisions of slow free electrons (E = 1-80 meV) and Rydberg electrons (n = 12-300) with water clusters. Resonances at zero energy have been observed, the shapes of which are strongly dependent on cluster size. The results are discussed in terms of the formation of metastable negative ions. Received 8 March 1999     

BNL/AGS10.7A GeV金核诱发作用中核碎裂与粒子产生

研究了在美国BNL/AGS上能量10.7AGeV的¹⁹⁷Au离子诱发核作用,报告了EMU–01国际合作实验关于射弹核碎裂和产生粒子密度等最新实验结果.