Macrocyclization of polymers via ring‐closing metathesis and azide/alkyne‐“click”‐reactions: An approach to cyclic polyisobutylenes

The end‐to‐end cyclization of telechelic polyisobutylenes (PIB's) toward cyclic polyisobutylenes is reported, using either ring‐closing metathesis (RCM) or the azide/alkyne‐“click”‐reaction. The first approach uses bisallyl‐telchelic PIB's (M_n = 1650, 3680, 9770 g mol^?1) and Grubbs 1st‐, 2nd‐, and 3rd‐generation catalyst leading to cyclic PIB's in 60–80% yield, with narrow polydispersities (M_w/M_n = 1.25). Azide/alkyne‐“click”‐reactions of bisalkyne‐telechelic PIB's (M_n = 3840 and 9820 g mol^?1) with excess of 1,11‐diazido‐undecane leads to the formation of mixtures of linear/cyclic PIB's under formation of oligomeric cycles. Subsequent reaction of the residual azide‐moieties in the linear PIB's with excess of alkyne‐telechelic PEO enables the chromatographic removal of the resulting linear PEO‐PIB‐block copolymers by column chromatography. Thus pure cyclic PIB's can be obtained using this double‐“click”‐method, devoid of linear contaminants. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 671–680, 2010     

ZL201合金半固态二次加热时的组织演变

利用理论计算与实际观测等手段,研究了采用近液相线方法铸造的ZL201合金坯料在进行二次加热时,α晶粒形貌演变和长大的规律.结果表明,半固态二次加热时,α晶粒形态的整个演变过程可以分为三个阶段:第一阶段为共晶组织的熔化阶段;第二阶段为α晶粒的球化阶段;第三阶段为理论液固成分的平衡阶段.在第一、二阶段α晶粒以合并方式长大;第三阶段α晶粒按Ostwald模型长大.二次加热温度影响组织演化进程,而保温时间决定α晶粒球化效果.在较高的温度下进行二次加热,能够在较短的保温时间内得到适合于触变成形的均匀细小的近球形组织.     

Influence of the Structure of an Inhomogeneously Broadened NMR Line on the Shape of the Free Precession Signal

We have obtained theoretically an expression for the nuclear free precession signal in an inhomogeneously broadened spin system with a complex structure of the NMR spectrum. It is shown that in this case in the nuclear precession signal there appear maxima the moments of whose formation depend on the detuning of the pulse carrier frequency from the central frequencies of the NMR lines, their widths, and the Rabi frequency. The theoretical results are in good agreement with the experimental data on the observation of proton free precession in toluene. We have constructed a physical model explaining the appearance of maxima in the free precession signal of the spin system.     

Materials with a desired refraction coefficient can be made by embedding small particles

A method is proposed to create materials with a desired refraction coefficient, possibly negative one. The method consists of embedding into a given material small particles. Given n₀(x), the refraction coefficient of the original material in a bounded domain , and a desired refraction coefficient n(x), one calculates the number N(x) of small particles, to be embedded in D around a point xD per unit volume of D, in order that the resulting new material has refraction coefficient n(x).     

Living fluids

One of the major emerging fields of research of the beginning of this century concerns living fluids. By “living fluids”, we mean two major categories of complex fluids: (i) fluids which are essential to life, like blood, and (ii) active fluids made of particles that are able to propel themselves in the suspending fluid by converting a form of their energy into mechanical motion. Studies on active fluids have known a considerable interest since the last decade. Blood might be viewed as an old topic, but the progresses in experimental techniques, analytical concepts and numerics, have contributed nowadays to a dramatic renewal of the interest in this field, with a great potential towards understanding physical and mechanical factors in cardiovascular diseases. These fields have considerably strengthened interdisciplinary research. The series of reviews of this dossier focus on the tremendous recent progress achieved in research on living fluids both from the experimental and theoretical points of views. These reviews present also the major open issues, making of this dossier a unique guide for future research in these fields. This project grew up thanks to the international summer school that we organized on the topic “living fluids” at the IES (Institut dʼétudes scientifiques) of Cargèse (Corsica) in 2012.     

Synthesis and characterization of novel resorcinarene‐centered amphiphilic star‐block copolymers consisting of eight ABA triblock arms by combination of ROP,ATRP, and click chemistry

Novel amphiphilic eight‐arm star triblock copolymers, star poly(ε‐caprolactone)‐block‐poly(acrylic acid)‐block‐poly(ε‐caprolactone)s (SPCL‐PAA‐PCL) with resorcinarene as core moiety were prepared by combination of ROP, ATRP, and “click” reaction strategy. First, the hydroxyl end groups of the predefined eight‐arm SPCLs synthesized by ROP were converted to 2‐bromoesters which permitted ATRP of tert‐butyl acrylate (tBA) to form star diblock copolymers: SPCL‐PtBA. Next, the bromide end groups of SPCL‐PtBA were quantitatively converted to terminal azides by NaN₃, which were combined with presynthesized alkyne‐terminated poly(ε‐caprolactone) (A‐PCL) in the presence of Cu(I)/N,N,N′,N″,N″‐pentamethyldiethylenetriamine in DMF to give the star triblock copolymers: SPCL‐PtBA‐PCL. ¹H NMR, FTIR, and SEC analyses confirmed the expected star triblock architecture. The hydrolysis of tert‐butyl ester groups of the poly(tert‐butyl acrylate) blocks gave the amphiphilic star triblock copolymers: SPCL‐PAA‐PCL. These amphiphilic star triblock copolymers could self‐assemble into spherical micelles in aqueous solution with the particle size ranging from 20 to 60 nm. Their micellization behaviors were characterized by dynamic light scattering and transmission electron microscopy. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2905–2916, 2009     

Tadpole‐shaped amphiphilic copolymers prepared via RAFT polymerization and click reaction

The tadpole‐shaped amphiphilic copolymers with cyclic polystyrene as the head and a linear poly(N‐isopropylacrylamide) as the tail have been successfully synthesized by combination of reversible addition‐fragmentation chain transfer (RAFT) polymerization and “click” reaction. The synthesis involves two main steps: (1) preparation of a linear acetylene‐terminated PNIPAAM‐b‐PS with a side azido group anchored at the junction between two blocks; (2) intramolecular cyclization reaction to produce the cyclic PS block using “click” chemistry under high dilution. The structures, molecular weights, and molecular weight distributions of the resulted intermediates and the target polymers were characterized by their ¹H NMR, FTIR, and gel permeation chromatography. The difference of surface property between tadpole‐shaped polymer and its linear precursor was observed, and the water contact angles on the former surface are larger than that of the latter surface. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2390–2401, 2008     

Bursting and synchronization transition in the coupled modified ML neurons

Bursting is an important electrical behavior in neuron’s firing. In this paper, based on the fast/slow dynamical bifurcation analysis and the phase plane analysis, two types of bursting are presented in the modified Morris–Lecar neuronal model, and the associated bifurcation mechanisms of switching between the active phase and the silent phase are analyzed. For two coupled bursters, it is found that the same type of coupled bursters may have different synchronization transition path from that of two different types of coupled bursters. The analysis of bursting types and the transition to synchronization may provide us with better insight into neuronal encoding and information transmission.