SYNTHESIS AND PROPERITIES OF SHISH-KEBAB-TYPE LIQUID CRYSTALLINE POLY(p-PHENYLENE)S

Abstract The novel shish-kebab-type liquid crystalline poly（p-phenylene）s were synthesized through Suzuki coupling reaction from 2,5-bis[（4-n-alkoxyl）benzoyloxy]1,4-dibromobenzene （monomer 1） and 1,4-benzenediboronic acid bistrimethylene cyclic ester （monomer 2）. Their structure and properties were characterized by GPC, DSC, X-ray diffraction and polarizing optical microscope （POM）. It was found that the polymers turned to liquid crystalline phase above their melting point. The melting point （Tm） of the polymers decreases when the length of the alkoxy tails of the mesogenic units increases. The mesophase was identified by X-ray diffraction method. The polymers could dissolve in common organic solvents and show strong blue fluorescence. The maximum absorption bands of polymers prepared from annealed films have large red-shift due to the spontaneous orientation of the liquid crystalline side chains. The same phenomena were also observed in the fluorescence spectra.

SYNTHESIS OF MAIN CHAIN LIQUID CRYSTALLINE COPOLYESTERS WITH X-SHAPED TWO-DIMENSIONAL MESOGENIC UNIT AND CROWN ETHER CYCLE

A novel series of main chain liquid crystalline copolyesters with X-shaped two-dimensional mesogenic unit and crown ether cycle of cis-4,4＇-bis（4-hydroxyphenylazo） dibenzo-18-crown-6 was prepared via solution condensation polymerization from 4,4＇-（a;arhexanedioyloxy） dibenzoyl dichloride （MI）, 2,5-bis（p-octyloxybenzoyloxy） hydro-quinone （M2） and cis-4,4＇-bis（4-hydroxyphenylazo） dibenzo-18-crown-6 （M3）. Monomer MI was synthesized by esterification and substitution of adipoyl chloride with p-hydroxybenzoic acid, monomer M2 was synthesized by esterfication and reduction reaction of 2,5-dihydroxybenzoquinone and p-octanoxybenzoyl chloride and monomer M3 was synthesized by diazotization and coupling reaction of cis-diaminodibenzo-18-crown-6 with phenol. The molecular weights of copolyesters are not high, and the intrinsic viscosity [η] of copolyesters ranges from 0.25-0.35. The monomers＇ structures were identified by using elemental analysis, IR, UV, ^1H-NMR, MS, etc. All the copolyesters are yellowish powders and insoluble in THF and CHC13 at room temperature except cPg. The properties of copolyesters were investigated by using GPC, [η] , DSC, TG, WAXD and POM. It was found that all the copolyesters entered into liquid crystal phase when they were heated to above their melting temperature （Tin）. The typical smectic and nematic phase texture can be observed on POM. Their mesophase transition temperature and thermal stability change regularly with varying the content of cis-4,4＇-bis（4-hydroxyphenylazo） dibenzo-18-crown-6 unit in the copolyesters.

NITROXIDE-MEDIATED FREE RADICAL SYNTHESIS OF MESOGEN-JACKETED LIQUID CRYSTAL POLYMERS

The first TEMPO-mediated 'living' free radical polymerization of liquid crystalline monomer, 2, 5-bis[(4-methoxyphenyl)oxycarbonyl]styrene (MPCS), was carried out at 130 degrees C with BPO as an initiator. The molecular weight of the polymer can be varied from rather low values to high values while maintaining narrow polydispersity. It was observed that the polymerization of MPCS proceeded much faster than that of styrene. A tentative explanation for this fast polymerization was suggested.

Simple cholangitis induces extremely and recurrently elevated serum carbohydrate antigen 19-9 level

To the Editor: The carbohydrate antigen 19-9 (CA19-9) is a tumor maker which is usually used in biliary and pancreatic malignancies [1]. However, the specificity of CA19-9 can be reduced by biliary inflammation and other benign diseases [2].

Ordered Bicontinuous Network Structures Regulated by Orientational Interactions in a Rod-Coil Block Copolymer

The rich phase behavior of block copolymers(BCPs)has drawn great attention in recent years.However,the double diamond(DD)phase is rarely obtained because of the competition between the minimization of interfacial energy and packing frustration.Here,a rod-coil BCP containing mesogen-jacketed liquid crystalline polymer is designed to acquire ordered bicontinuous network nanostructures.The reduction of internal energy originating from the orientational interaction among the rod blocks can compensate for the free energy penalty of packing frustration to stabilize the DD structure.The resulting BCP can also experience lamellae-to-DD and double gyroid-to-lamellae transitions by changing the annealing temperature.These results make the rod-coil BCP an excellent candidate for the self-assembly of ordered network structures,demonstrating great potential in nanopatterning and metamaterials.

可作为碳纳米管片段的共轭芳烃大环的设计合成

设计合成可作为碳纳米管片段的共轭芳烃大环近年来吸引了化学家们广泛的研究兴趣,人们希望从这些共轭芳烃大环出发,通过利用"自下而上"的策略合成单壁碳纳米管。需要指出的是,传统制备碳纳米管的方法,如电弧法、化学气相沉积法等,都很难形成均一的单壁碳纳米管。而这种"自下而上"的策略为高效合成尺寸均一的单壁碳纳米管提供了可行的方法,这种合成方法因此成为了当下合成单壁碳纳米管的热点,但也仍是一大挑战。本文从二维碳纳米环、碳纳米带和三维碳纳米笼三个方面概述关于这类共轭芳烃大环研究的新进展,着重介绍了共轭碳纳米环的设计原则和合成方法,并突出介绍了多环芳烃碳纳米环。多环芳烃通常具有优良的光电性质,以其为基元构筑的共轭碳纳米结构不仅可以作为碳纳米管的合成前体,而且其自身也会表现出新的光电性质。

铂···铂相互作用诱导逐级自组装促进圆偏振光信号放大

高效圆偏振发光材料在传感、光学器件、不对称合成等领域有着广泛的应用,设计和制备圆偏振发光材料引起了人们的广泛关注.然而,构筑具有高发光不对称因子的圆偏振发光材料仍然是一个挑战.这里,我们制备了一种手性超分子组装金属大环,该超分子组装金属大环可以通过分子间铂···铂相互作用诱导逐级自组装促进圆偏振光的放大.值得注意的是,超分子组装金属大环显示出高的发光不对称因子以及较强的圆偏振光信号,而其对应的组装配体没有显示出圆偏振光信号.通过紫外-可见吸收光谱和发射光谱、核磁共振氢谱、扫描电镜、透射电镜、原子力显微镜、粗粒化分子动力学模拟和含时密度泛函理论计算等手段对圆偏振光放大的机理进行了研究.该研究展示了第一例基于铂···铂相互作用驱动的逐级自组装策略制备的高效圆偏振发光材料.

Liquid Crystalline Polymers

History of Liquid Crystalline PolymersThe liquid crystalline(LC)state was first observed by Austrian botanist and chemist F.Reinitzer more than a century ago,and it was then confirmed in 1888 by German physicist O.Lehmann who named such a state of matter as"liquid crystal"in 1900.While low molecular mass(LMM)liquid crystals were successfully used in LC displays(LCDs),the development of LC polymers(LCPs)followed an independent path.Conceptually,LCPs are prepared with the incorporation of mesogenic groups that are responsible for the formation of LC mesophases,such as rod-like(calamitic)and discotic ones,into polymer chains.Depending on where the mesogens are attached,traditionally there are three major categories of LCPs.Main-chain LCPs(MCLCPs)have mesogens in the polymer backbone,while mesogens of side-chain LCPs(SCLCPs)are incorporated as side groups in a polymer with a relatively flexible main chain.In main-chain/side-chain combined LCPs(MCSCLCPs),mesogens are in both the backbone and side chains.Other classes of LCPs include mesogenjacketed LCPs(MJLCPs),dendronized LCPs,and LC networks(LCNs).

EDITORIAL

The year 2022 marks the 40th anniversary of the Chinese Journal of Polymer Science(CJPS)—a true milestone to be celebrated!In the early stage of the reform and opening,there was an increasing demand for international academic communications.To facilitate these communications.

Construction of Metallacycle-Linked Heteroarm Star Polymers via Orthogonal Post-Assembly Polymerization and Their Intriguing Self-Assembly into Large-Area and Regular Nanocubes

of main observation and conclusion In recent years,synthesis of hybrid heteroarm star polymer with precisely defined arms has evolved to be one of the most attractive topics within polymer chemistry.In this study,we present the successful synthesis of metallacycle-linked heteroarm star polymers(HASPs)composed of crystalline poly(e-caprolactone)(PCL)and polyacrylate(poly(N-isopropylacrylamide)(PNIPAM)segments via combination of ring-opening polymerization(ROP)and reversible addition-fragmentation chain transfer(RAFT)controlled radical polymerization.Firstly,a hexagonal metallacycle containing three hydroxy groups and three chain transfer agent moieties at the alternative vertexes was designed and synthesized based on the general principle of coordination-driven self-assembly.Subsequently,upon combination of two orthogonal post-assembly polymerizations,a new family of HASPs containing a well-defined hexagonal metallacycle with precisely controlled position of polymer arms was facilely prepared.Interestingly,the obtained HASPs could spontaneously self-assemble into large-area and regular cubic nanoparticles in tetrahydrofuran(THF)/methanol(MeOH)mixed solvents under specific conditions as confirmed by scanning electron microscopy(SEM)and atomic force microscopy(AFM).This study provides a simple route to the controllable preparation of HASPs,and opens up a new way for further study on self-assembly of different HASPs systems.