Polymer-supported distannanes: a new and efficient synthesis of highly effective reagents for iodine atom transfer cyclisations

Polymeric distannanes were synthesised by the cross-linking of polystyrene bound tin hydride functionalities using a palladium mediated dehydrogenative coupling. The polymers were characterised by spectroscopic methods (IR and ¹³C, ¹¹⁹Sn NMR) and elemental analysis and were successfully applied to two iodine atom transfer cyclisations, performing as well as solution based hexaalkylditin reagents and significantly better than previously reported polymer-supported ditin reagents.     

Synthesis of branched polystyrene by ATRP exploiting divinylbenzene as branching comonomer

Branched polystyrenes have been synthesized using atom transfer radical polymerization (ATRP) of styrene in the presence of divinyllbenzene (DVB) as branching comonomer. The synthesis was completed via facile one pot approach. Mole ratio of styrene to DVB in range of 5:1-30:1 was employed to obtain soluble polymers. The kinetics of the polymerization and evolution of polymer compositions were revealed by determining the conversions of reactants by gas chromatography (GC). The growth of molecular weight was monitored by GPC and the results indicate that the branched polymers were formed by self-condensing vinyl polymerization (SCVP) of AB^∗ monomer or macromonomers. The branched structure of the resulting polymers was confirmed by the remarkable discrepancies of the weight average molecular weights determined by GPC and multi angle laser light scattering (MALLS). The specific viscosity of the resulting polymer is also much lower compared with that of linear analogues. The influence of dosage of initiator and catalyst on the yield and molecular weights of the resulting polymers was also investigated.     

一种含乙氧羰基偶氮苯液晶三嵌段共聚物的合成与表征

利用原子转移自由基聚合(ATRP),合成了一种含有乙氧羰基偶氮苯的液晶三嵌段共聚物,并合成了一种同样偶氮生色团的均聚物进行对比.均聚物(PC6ET)由偶氮单体甲基丙烯酸{6-[4-(4-乙氧羰基苯基偶氮)苯氧基]己酯}(C6ET)的ATRP反应制备.嵌段共聚物的合成,先通过聚环氧乙烷(PEO)和过量的2-溴异丁酰溴、三乙胺反应,得到双端大分子引发剂(Br-PEO-Br);再进一步通过C6ET的ATRP反应,得到了三嵌段共聚物(PC6ET-PEO-PC6ET).热分析、偏光显微镜观察和X射线衍射实验证实,合成的均聚物和嵌段共聚物均为近晶型液晶聚合物.三嵌段共聚物的液晶清亮点比均聚物的稍低.     

Characterization of a phosphorylated peptide and peptoid and peptoid-peptide hybrids by mass spectrometry

Nano-electrospray tandem mass spectrometry (nano-ES-MS/MS) was used to record collision-induced dissociation (CID) spectra of a set of peptoid-peptide hybrids and the complete peptoid derived from the phosphopeptide Ac-pTyr-Glu-Thr-Leu-NH(2) (1). The presence of B and Y'-type fragment ions in the tandem mass spectra of the protonated molecular ions [M + H](+) allowed confirmation of sequence similar to mass spectrometric sequence analysis in peptides. In the isomeric peptoid compounds studied, one or several amino acid residues were replaced by peptoid residues (N-substituted glycine residues), which resulted in characteristic tandem mass spectra with differently increased relative abundances of Y'-and B-type fragment ions. The increment of a particular Y'-ion was directly correlated to the position of a peptoid residue present. In addition to these increased peak intensities, other characteristic peaks were also observed compared with the spectrum of reference peptide 1. When a peptoid phosphotyrosine was incorporated, the presence of this residue was apparent from the occurrence of a relatively intense peak at m/z 187 representing the positively charged side-chain of phosphotyrosine, which was almost absent in the spectrum of the reference peptide 1. Since the threonine side-chain had to be translated into the homo peptoid analog this substitution was apparent from the presence of [M + H](+) and fragment ions 14 mass units higher than observed in the spectrum of the reference phosphopeptide 1. The presence of an NLeu peptoid residue could be confirmed by the specific fragmentation of the immonium ion showing an intense peak in its tandem mass spectrum at m/z 57, which results from the loss of an neutral imine molecule leading to a positively charged [C(4)H(9)](+) ion. By means of these mass spectrometric characteristics, all isomeric peptoid compounds could be distinguished from each other and characterized. The methods used appear to be very useful in future studies of peptoids and peptoid-peptide hybrids.     

不饱和环缩醛与苯乙烯的原子转移自由基共聚合反应

不饱和环状单体与烯类单体共聚所得的共聚物 ,已经或正在开发成一系列新的产品 .例如 ,水解后得到末端带有—OH,— SH,—COOH等官能团的聚苯乙烯、聚乙烯、聚甲基丙烯酸甲酯等的低聚物[1] ,用于制备新型聚酯和聚氨酯 ;与乙烯的共聚物可在细菌作用下彻底分解成脂肪酸或醇 ,可赋予聚合物生物降解活性 ;与双甲基丙烯酸酯等的共混物 ,可用于制作高强度补牙材料[2 ] 等 .以前报道的不饱和环状单体与烯类单体的共聚反应 ,均为无规共聚 ,而且是普通自由基引发聚合 ,不能控制分子量 ,分子量分布很宽 .原子转移自由基聚合是近几年发展起来的实现…     

CuX2络合物催化甲基丙烯酸甲酯的氧化聚合

研究了高氧化态过渡金属卤化物络合物催化甲基丙烯酸甲酯(MMA)的氧化聚合.首先在叔胺类聚合物存在条件下以CuBr2/2,2′-联吡啶(bPy)络合物催化MMA在不同溶剂中的氧化聚合,结果在环己酮中得到PMMA均聚物,CuBr2/bPy同叔胺的氧化还原引发可以忽略.随后在环己酮中分别以不同络合物催化MMA的氧化聚合.结果...     

Electric-field-modified Feshbach resonances in ultracold atom–molecule collision

We present a detailed analysis of near zero-energy Feshbach resonances in ultracold collisions of atom and molecule,taking the He–PH system as an example, subject to superimposed electric and magnetic static fields. We find that the electric field can induce Feshbach resonance which cannot occur when only a magnetic field is applied, through couplings of the adjacent rotational states of different parities. We show that the electric field can shift the position of the magnetic Feshbach resonance, and change the amplitude of resonance significantly. Finally, we demonstrate that, for narrow magnetic Feshbach resonance as in most cases of ultracold atom–molecule collision, the electric field may be used to modulate the resonance, because the width of resonance in electric field scale is relatively larger than that in magnetic field scale.     

不对称强阻尼反应中超重碎块的产生

用改进的量子分子动力学模型研究了原子核强阻尼反应232Th +250 Cf。在入射能量范围从800-2000 MeV时,研究了反应产生的原子序数大于等于114的超重碎块的几率随入射能量的依赖情况。计算发现在不对称的强阻尼反应体系232Th +250 Cf 中超重碎块的产生几率高于在对称反应244Pu +244Pu 和 238U +238U 中超重碎块的产生几率。计算表明初级碎块的质量（电荷）分布和超重碎块的激发能分布也强烈依赖于入射能量。研究了强阻尼反应产物的衰变过程：两种不同的衰变斜率表示不同的衰变机制。它们分别相应于巨复合体系的衰变和巨复合体系的衰变碎块包括超重碎块的衰变（包含发射中子、质子和其他轻带电粒子及裂变过程）。超重碎块的衰变斜率明显低于巨复合体系的衰变斜率,可能有助于超重碎块的存活。     

离散效应对高强度激光三次谐波转换的影响

使用分步傅里叶变换和四阶龙格库塔法(R-K) ，对高强度激光以Ⅰ/Ⅱ类角度失谐方式，在KDP晶体中的谐波转换进行了研究，详细讨论了离散效应对三次谐波转换的影响。结果表明，离散效应不但降低了三次谐波转换效率，而且使谐波光束质量显著降低；初始入射基频光束腰半径较小时，离散效应是二次谐波转换和三次谐波转换效率降低的主要因素，失谐角对三次谐波转换的影响较小；随着束腰半径的增加，离散效应的影响逐渐减小，失谐角对三次谐波转换的影响逐渐增加。     

在同位旋SU(2)不变耦合模型中研究 p pbar -> n nbar 核子反应的重整化无穷阶链图效应

本文采用描述中性及荷电 pion 介子（pion0,pion+,pion-）与核子-反核子强相互作用的同位旋SU(2)不变耦合模型,计算出在pion0 及 pion+, pion- 重整化链图传播下 p pbar -> n nbar 核子反应微分截面的“精确”解析结果;并且将此结果与在 pion0 及 pion+, pion- 树图传播下的微分截面作了对比分析,得到相应的辐射修正重要信息。本文完成的工作对进一步深入研究三种荷电状态 pion 介子与核子-反核子强相互作用的同位旋SU(2)不变耦合模型以及深入理论探讨质子-反质子对撞实验,都将提供某些理论研究的参考价值。