Facile synthesis of dendrimers combining aza‐Michael addition with Thiol‐yne click chemistry

We report a highly efficient approach to prepare dendrimers by taking advantage of the orthogonal characteristic of aza‐Michael addition and thiol‐yne reactions. A fifth generation dendrimer was synthesized within five steps without protection/activation procedures. The reactions proceed under benign conditions without byproducts, and the target products can be easily purified via extraction or precipitation without chromatography. The structure of each generation dendrimer was characterized using NMR spectroscopy, size exclusion chromatography, and mass spectrometry. The obtained dendrimers can have peripheral amine or alkyne groups. We demonstrated that these groups can be used for selective and specific conjugation with various functional groups. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

聚合物共混物的超高效液相色谱-空间排阻色谱在线联用分离与表征

黏合剂和涂料行业中, 聚合物共混物表征是分析的难题, 分离技术的研究一直备受关注. 本文设计并搭建了超高效液相色谱-空间排阻色谱在线联用系统(UHPLC-SEC), 采用羟基聚丁二烯(HTPB)考察了二维色谱系统的溶剂兼容性及正交性, 以苯乙烯-丁二烯嵌段共聚物(SBS)、 苯乙烯-异戊二烯嵌段共聚物(SIS)和聚甲基丙烯酸酯(PMMA)共混物研究了二维色谱系统的适用性. 结果表明, HTPB分子量及分布的UHPLC-SEC测定结果与SEC测定结果一致, 峰尖分子量(M_p)为3407 Da, 重均分子量(M_w)为6573 Da, 分散系数(PDI)为2.36, 相对标准偏差(RSD)均小于5.7%, 系统的溶剂兼容性和正交性良好. UHPLC-SEC法测得聚合物共混物中PMMA, SBS和SIS的M_p, M_w和PDI与单个聚合物的SEC测定结果的相对误差均小于7.1%. PMMA, SBS和SIS共混物在200 °C加热3 h后, PMMA 稳定不变, SBS和SIS组分明显降解. UHPLC-SEC在线联用方法对聚合物共混物的表征结果准确、 重复性好, 为聚合物配方产品的失效分析提供了一种重要且有效的手段.     

氧化石墨烯插层聚β-羟基丁酸酯复合材料的结晶形态与宏观性能

由微生物直接合成的聚β-羟基丁酸酯（PHB）可实现从原料合成到加工成型和回收降解的全周期生态循环, 在生物医用和包装材料等领域有着重要的应用前景. 受制于PHB自身成核能力差导致的球晶尺寸偏大等不利结晶形态特点, 其制品存在抗冲韧性差、 延展率低和易蠕变等缺陷. 本文提出了水相加工和受限成型相结合的制备方法, 将氧化石墨烯（GO）纳米片在水溶液中充分剥离后, 直接包覆于亚微米级PHB微颗粒表面形成PHB@GO复合物, 然后在压力场下受限成型获得GO插层PHB纳米复合材料. 研究结果表明, 即使在极低GO添加量（质量分数0.1%）下, PHB的等温和非等温结晶能力都有显著提高, 并获得晶核密度高且晶体尺寸均一的结晶形态. 插层GO纳米片还促使复合材料发生了脆-韧转变, 使其拉伸强度和延展性均成倍提高, 同时显著增强了动态热力学性能、 抗蠕变性能和热学性能.     

二氟甲基自由基反应及其在18F标记中的应用

随着正电子发射断层扫描(PET)技术的进步, 高效¹⁸F标记反应显现出重大的研究价值. 同时, 在有机氟化学的快速发展下, 研究人员已开发出一系列产生二氟甲基自由基(·CHF₂)的一碳合成子, 得以被引入到¹⁸F标记反应中. 本文从化学原理出发, 总结了近年来·CHF₂合成子、 碳氢键活化反应及¹⁸F标记的研究, 并展望了未来的研究趋势.     

A high‐order compact scheme for the nonlinear fractional Klein–Gordon equation

In this article, a high‐order finite difference scheme for a kind of nonlinear fractional Klein–Gordon equation is derived. The time fractional derivative is described in the Caputo sense. The solvability of the difference system is discussed by the Leray–Schauder fixed point theorem, while the stability and L_∞ convergence of the finite difference scheme are proved by the energy method. Numerical examples are provided to demonstrate the theoretical results. © 2014 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 31: 706–722, 2015     

A compact ADI scheme for the two dimensional time fractional diffusion‐wave equation in polar coordinates

In this article, we consider finite difference schemes for two dimensional time fractional diffusion‐wave equations on an annular domain. The problem is formulated in polar coordinates and, therefore, has variable coefficients. A compact alternating direction implicit scheme with accuracy order is derived, where τ, h₁, h₂ are the temporal and spatial step sizes, respectively. The stability and convergence of the proposed scheme are studied using its matrix form by the energy method. Numerical experiments are presented to support the theoretical results. © 2015 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 31: 1692–1712, 2015     

Fragmentation of <Emphasis Type="Italic">α</Emphasis>-radical cations of arginine-containing peptides

Fragmentation pathways of peptide radical cations, M^+·, with well-defined initial location of the radical site were explored using collision-induced dissociation (CID) experiments. Peptide radical cations were produced by gas-phase fragmentation of Co^III(salen)-peptide complexes [salen=N,N′-ethylenebis (salicylideneiminato)]. Subsequent hydrogen abstraction from the β-carbon of the side-chain followed by C_α-C_β bond cleavage results in the loss of a neutral side chain and formation of an α-radical cation with the radical site localized on the α-carbon of the backbone. Similar CID spectra dominated by radical-driven dissociation products were obtained for a number of arginine-containing α-radicals, suggesting that for these systems radical migration precedes fragmentation. In contrast, proton-driven fragmentation dominates CID spectra of α-radicals produced via the loss of the arginine side chain. Radical-driven fragmentation of large M^+· peptide radical cations is dominated by side-chain losses, formation of even-electron a-ions and odd-electron x-ions resulting from C_α-C bond cleavages, formation of odd-electron z-ions, and loss of the N-terminal residue. In contrast, charge-driven fragmentation produces even-electron y-ions and odd-electron b-ions.     

Biosilicification Templated by Amphiphilic Block Copolypeptide Assemblies

An amphiphilic poly(L ‐lysine·HBr)‐block‐poly(L ‐leucine) (KL) diblock copolypeptide and its supramolecular assembly are used as a template to direct silica formation, which proceeds by a cooperative process involving biomimetic mineralization and copolypetide reassembly under ambient conditions. Various silica structures can be obtained by using different counterions, changing the chain length of the KL diblocks, and applying a sol–gel mineralization method. We find that the chain length of the KL diblock is an important factor in terms of controlling biosilica morphologies. We also find that the nature of the counterions strongly affects the resulting silica structures. For the same KL diblock, variation of anions from phosphate to sulfate and to carbonate can produce hexagonal silica platelets, silica rods, and fused silica platelets, respectively. In contrast, application of a sol–gel method can replicate the copolypeptide fibril network morphology in water, while employment of ultrasonication to the sol–gel medium transforms the silica fibrils to rigid silica rods. The resulting silica morphology has been systematically characterized using SEM and TEM, and the polypeptide conformation is explored using FT‐IR and CD spectroscopy.

     

Clique-inserted-graphs and spectral dynamics of clique-inserting

Motivated by studying the spectra of truncated polyhedra, we consider the clique-inserted-graphs. For a regular graph G of degree r>0, the graph obtained by replacing every vertex of G with a complete graph of order r is called the clique-inserted-graph of G, denoted as C(G). We obtain a formula for the characteristic polynomial of C(G) in terms of the characteristic polynomial of G. Furthermore, we analyze the spectral dynamics of iterations of clique-inserting on a regular graph G. For any r-regular graph G with r>2, let S(G) denote the union of the eigenvalue sets of all iterated clique-inserted-graphs of G. We discover that the set of limit points of S(G) is a fractal with the maximum r and the minimum −2, and that the fractal is independent of the structure of the concerned regular graph G as long as the degree r of G is fixed. It follows that for any integer r>2 there exist infinitely many connected r-regular graphs (or, non-regular graphs with r as the maximum degree) with arbitrarily many distinct eigenvalues in an arbitrarily small interval around any given point in the fractal. We also present a formula on the number of spanning trees of any kth iterated clique-inserted-graph and other related results.     

Morphologies of multicompartment micelles formed by ABC miktoarm star terpolymers

Several new multicompartment micellar structures have been identified by cryogenic transmission electron microscopy (cryoTEM) from the aqueous self-assembly of mu-[poly(ethylethylene)][poly(ethylene oxide)][poly(perfluoropropylene oxide)] (mu-EOF) miktoarm star terpolymers. This work extends our previous studies, in which it was found that, upon decreasing the length of the hydrophilic block (O), the resulting micelles evolved from "hamburger" micelles to segmented worms and ultimately to nanostructured bilayers and vesicles. In the terpolymers examined here segmented ribbons and bilayers were found at an intermediate composition between segmented worms and nanostructured bilayers, provided that the fluoropolymer (F) was the minority component in the micelle core. On the other hand, when the F block exceeded the chain length of the hydrocarbon block (E), the superhydrophobic F block imposed a "double frustration" on the self-assembly of the mu-EOF(2-9-5) terpolymer; while F prefers to minimize its interfacial contact with the O corona, it must occupy the majority of the micellar core. Therefore, a richer variety of multicompartment micelles, including well-defined segmented worms, raspberry-like micelles, and multicompartmentalized worms, were formed from one terpolymer, as revealed by cryoTEM. Despite the complexity and variety of the observed aggregate morphologies, a small number of common structural elements can be invoked to interpret the observed micelles and to relate a given structure to the terpolymer composition.