Synthesis and characterization of HPMA copolymer-5-FU conjugates

N-（2-Hydroxypropyl） methacrylamide copolymer-5-fluorouracil （PHPMA-FU） conjugates were synthesized by a novel and simplified synthetic route, and characterized by UV, FTIR and HPLC analyses. The conjugated content of 5-fluorouracil （5-FU） was 3.41 ± 0.07 wt%. The stabilities of PHPMA-FU conjugates under different conditions were studied. The results showed that HPMA copolymer was a potential carrier for tumor-targeting delivery of 5-FU.

Control over the aggregated structure of donor–acceptor conjugated polymerfilms for high-mobility organicfield-effect transistors

Donor–acceptor(D-A)conjugated polymers have demonstrated great potential in organicfield-effect transistors application,and their aggregated structure is a crucial factor for high charge mobility.However,the aggregated structure of D-A conjugated polymerfilms is complex and the structure–property relationship is difficult to understand.This review provides an overview of recent progress in controlling the aggregated structure of D-A conjugated polymerfilms for higher mobility,including the mechanisms,methods,and properties.Wefirst discuss the multilevel microstructures of D-A conjugated polymerfilms,and then summarize the current understanding of the relationship betweenfilm microstructures and charge transport properties.Subsequently,we review the theory of D-A conjugated polymer crystallization.After that,we summarize the common methods to control the aggregated structure of semi-crystalline and near-amorphous D-A conjugated polymerfilms,such as crystallites and aggregates,tie chains,film alignment,and attempt to understand them from the basic theory of polymer crystallization.Finally,we provide the current challenges in controlling the aggregated structure of D-A conjugated polymerfilms and in understanding the structure–property relationship.

基于交联型窄带隙D-A共聚物的高效平面-本体异质结聚合物太阳电池

通过溶液法将平面异质结与本体异质结相结合,构筑了平面-本体异质结集成结构聚合物太阳能电池。在光活性层与阳极缓冲层(PEDOT:PSS)之间插入了一层光交联D-A共轭聚合物(PBDTTT-Br25)给体材料。经紫外光照处理后,PBDTTTBr25层可以实现交联,交联后的聚合物薄膜具有良好的抗溶剂性。PBDTTT-Br25给体层的引入使器件构筑了一个平面-本体异质结集成结构,该结构增加了给体/受体之间的接触界面,为空穴传输到阳极提供了一条空间无障碍通道,从而可以降低载流子的复合几率。采用该集成结构的聚合物太阳电池在一个太阳光光照条件下光电转换效率可达到5.24%,比采用单纯本体异质结结构的聚合物太阳电池效率(3.17%)提高了65%。

用核磁共振氢谱分析氢化苯乙烯-共轭二烯烃嵌段共聚物的苯环加氢度

采用核磁共振氢谱测定了苯乙烯-共轭二烯烃嵌段共聚物及其加氢反应产物氢化苯乙烯-共轭二烯烃嵌段共聚物(HSBC)的微观结构和组成,计算了HSBC的苯环加氢度,并与紫外光谱法的计算结果进行对比分析。结果表明,与紫外光谱法相比,核磁共振氢谱法具有步骤简单、快捷高效等优势,由其计算所得HSBC的苯环加氢度与紫外光谱法计算结果具有较好的一致性。

Heteroatom Structural Engineering Enables Ethenylene-Bridged Bisisoindigo-Based Copolymers to Exhibit Unique n-Type Transistor Performance

Herein,we report three novel electron-deficient aromatics,ethenylene-bridged bisisoindigos 3,3′-((3E,3′E)-((E)-ethene-1,2-diyl)bis(1-(4-decyltetradecyl)-2-oxoind-oline-6-yl-3-ylidene))bis(1-(4-decyltetradecyl)-1,3-dihydro-2H-pyrrolo[2,3-b]pyridin-2-one)(NCCN),3,3′-((3E,3′E)-((E)-ethene-1,2-diyl)bis(1-(4-decyltetradecyl)-7-fluoro-2-oxoindoline-6-yl-3-ylidene))bis(1-(4-decyltetradecyl)-1,3-dihydro-2H-pyrrolo[2,3-b]pyridin-2-one)(NFFN),and(3E,3″E)-6,6″-((E)-ethene-1,2-diyl)bis(1,1′-bis(4-decyltetradecyl)-[3,3′-bipyrrolo[2,3-b]pyridinylidene]-2,2′(1H,1′H)-dione)(NNNN),and their derived donor–acceptor(D–A)copolymers,namely poly[3,3′-((3E,3′E)-((E)-ethene-1,2-diyl)bis(1-(4-decyltetradecyl)-2-oxoindoline-6-yl-3-ylidene))bis(1-(4-decyltetradecyl)-1,3-dihydro-2H-pyrrolo[2,3-b]pyridin-2-one-6-yl)]-alt-[5,6-difluoro-4,7-di[(thiophen-2-yl)-5-yl)]benzo[c][1,2,5]thiadiazole](PNCCN-FBT),poly[3,3′-((3E,3′E)-((E)-ethene-1,2-diyl)bis(1-(4-decyltetradecyl)-7-fluoro-2-oxoindoline-6-yl-3-ylidene))bis(1-(4-decyltetradecyl)-1,3-dihydro-2H-pyrrolo[2,3-b]pyridin-2-one-6-yl)]-alt-[5,6-difluoro-4,7-di[(thiophen-2-yl)-5-yl)]benzo[c][1,2,5]thiadiazole](PNFFNFBT),and poly[(3E,3″E)-6′,6‴-((E)-ethene-1,2-diyl)bis(1,1′-bis(4-decyltetradecyl)-[3,3′-bipyrrolo[2,3-b]pyridinylidene]-2,2′(1H,1′H)-dione-6-yl)]-alt-[5,6-difluoro-4,7-di[(thiophen-2-yl)-5-yl)]benzo[c][1,2,5]thiadiazole](PNNNN-FBT),in which 5,6-difluoro-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole(FBT)acts as the electron-donating units.The ethenylene-bridging unit reduces the steric hindrance of the three bisisoindigos.Incorporation of heteroatoms,such as fluorine and sp2-nitrogen atoms,endows them with multiple CH···F,CH···N,and N···S intramolecular hydrogen bonds/nonbinding interactions,resulting in increasing backbone planarity from NCCN,NFFN,to NNNN,and thus from PNCCN-FBT,PNFFN-FBT,to PNNNN-FBT.We found that all copolymers formed an improved molecular packing in the 1-chloronaphthalene(CN)-processed thin film compared with the 1,2-dichlorobenzene-processed one.The CN-processed PNCCN-FBT-based polymer field-effect transistors showed ambipolar transport characteristics with the electron mobility(μe)and hole mobility of 1.20 and 0.46 cm^(2)V^(−1)^s(−1),respectively,while the PNFFN-FBT-and PNNNN-FBT-based ones afforded unique n-type transport characteristics with impressively highμe up to 3.28 cm^(2)V^(−1)^s(−1).The lower frontier molecular orbital energy levels of PNFFN-FBT are the key reason for its higherμe.This study demonstrated that heteroatom structural engineering on ethenylene-bridged bisisoindigos is an effective way to construct high-performance n-type polymer semiconductors.

A Cyano-Substituted Organoboron Electron-deficient Building Block for D-A Type Conjugated Polymers

The development of donor-acceptor(D-A)type conjugated polymers depends largely on the design of novel A building blocks.Herein,we report a novel A building block based on the cyano-substituted organoboron unit(SBN-3).Compared with the most common fluorine-substituted B←N unit,SBN-3 displays a significantly downshifted LUMO energy level because of the strong electron-withdrawing ability of cyano groups.In addition,due to the greater impact of cyano substitution on LUMO than on HOMO,SBN-3 exhibits a reduced band gap,nearinfrared absorption and fluorescence properties.The D-A type conjugated polymers based on the cyano-substituted B←N unit with thiophene-based units show narrow optical band gaps of ca.1.3 e V as well as distinctive electronic structures,i.e.,delocalized LUMOs and localized HOMOs.This work thus provides not only an effective approach to design strong A units but also a new electron-deficient building block for D-A type conjugated polymers.

Copolymers of Styrene with Conjugated Dienes by Titanium Catalysts:Synthesis,Characterization and Evaluation of the Mechanical Properties

1 Results Polymerization of butadiene,isoprene and styrene and binary copolymerization of styrene with butadiene and isoprene were investigated using the catalyst Ti(η5-C5H5)(η2-MBMP)Cl (1) (MBMP=2,2′-methylenebis(6-tert-butyl-4-methylphenoxo) activated with methylaluminoxane (MAO).Syndiotactic polystyrene, cis-1,4- polybutadiene and cis-1,4-polyisoprene were obtained in good yields at 50 °C.Binary copolymerization of styrene with butadiene yielded block copolymers containing segments of cis-1,4-polybut...

All-conjugated amphiphilic diblock copolymers for improving morphology and thermal stability of polymer/nanocrystals hybrid solar cells

Herein, the ability to optimize the morphology and photovoltaic performance of poly（3-hexylthiophene） （P3HT）/ZnO hybrid bulk-heterojunction solar cells via introducing all-conjugated amphiphilic P3HT-based block copolymer （BCP）, poly（3- hexylthiophene）-block-poly（3-triethylene glycol-thiophene） （P3HT-b-P3TEGT）, as polymeric additives is demonstrated. The results show that the addition of P3HT-b-P3TEGT additives can effectively improve the compatibility between P3HT and ZnO nanocrystals, increase the crystalline and ordered packing of P3HT chains, and form optimized hybrid nanomorphology with stable and intimate hybrid interface. The improvement is ascribed to the P3HT-b-P3TEGT at the P3HT/ZnO interface that has strong coordination interactions between the TEG side chains and the polar surface of ZnO nanoparticles. All of these are favor of the efficient exciton dissociation, charge separation and transport, thereby, contributing to the improvement of the efficiency and thermal stability of solar cells. These observations indicate that introducing all-conjugated amphiphilic BCP additives can be a promising and effective protocol for high-performance hybrid solar cells.

High-Performance D-A Copolymer Donor Based on Difluoroquinoxaline A-Unit with Alkyl-Chlorothiophene Substituents for Polymer Solar Cells

Side chain engineering with fluorine substitution is widely used to enhance photovoltaic performance of polymer donors in the research field of polymer solar cells(PSCs).However,fluorine substitution has disadvantages of complicated synthesis and high cost.Herein,we synthesized a novel D-A copolymer donor PBQ9 based on difluoroquinoxaline A-unit with chlorine substitution on its alkyl-thiophene side chains instead of fluorine substitution in the polymer donor PBQ6,which greatly shortens the synthetic route and reduces the cost.Interestingly,the optimized binary PSC with PBQ9 as polymer donor and m-TEH as acceptor demonstrated a high power conversion efficiency(PCE)of 18.81%(certified PCE of 18.33%by National Institute of Metrology,China)with a high fill factor of 80.59%,and the photovoltaic performance of the PSCs is insensitive to the different batches of the polymer donor.The results indicate that PBQ9 is a high-performance polymer donor and that chlorine substitution is an effective strategy to improve photovoltaic performance and reduce the cost of polymer donors.

Effect of furan π-bridge on the photovoltaic performance of D-A copolymers based on bi(alkylthio-thienyl)benzodithiophene and fluorobenzotriazole

The medium band gap donor-acceptor （D-A） copolymer J61 based on bi（alkylthio-thienyl）benzodithiophene as donor unit and fluorobenzotriazole as acceptor unit and thiophene as n-bridge has demonstrated excellent photovoltaic performance as donor material in nonfullerene polymer solar cells （PSCs） with narrow bandgap n-type organic semiconductor ITIC as acceptor. For studying the effect of n-bridges on the photovoltaic performance of the D-A copolymers, here we synthesized a new D-A copolymer J61-F based on the same donor and acceptor units as J61 but with furan n-bridges instead of thiophene. J61-F possesses a deeper the highest occupied molecular orbital （HOMO） level at -5.45 eV in comparison with that （-5.32 eV） of J61. The non-fullerene PSCs based on J61-F：ITIC exhibited a maximum power conversion efficiency （PCE） of 8.24% with a higher open-circuit voltage （Voc） of 0.95 V, which is benefitted from the lower-lying HOMO energy level of J61-F donor material. The results indicate that main chain engineering by changing n-bridges is another effective way to tune the electronic energy levels of the conjugated D-A copolymers for the application as donor materials in non-fullerene PSCs.

D-A Copolymers Based on a Pentacyclic Acceptor Unit and a 3,3′-Difluoro-2,2′-bithiophene for Solar Cells

A D-A copolymer, P2FBTTPTI, was developed by copolymerizing a pentacyclic acceptor unit, thieno[2′,3′：5,6]pyrido[3,4-g]thieno[3,2-c]isoquinoline-5,11（4 H,10 H）-dione（TPTI）, with 3,3′-difluoro-2,2′-bithiophene（2 FBT）. P2 FBTTPTI possessed a low highest occupied molecular orbital（HOMO） energy level（-5.50 e V） and a good hole mobility（4.14 × 10^-4 cm^2·V^-1·s^-1）. P2FBTTPTI：PC_（71）BM solar cells gave a decent power conversion efficiency（PCE） of 7.64% and a high open-circuit voltage（Voc） of 0.95 V.

Synthesis and EL Properties of Conjugated Copolymer Materials Containing Various Comonomers

1 Results Polymeric light-emitting diodes (PLEDs) have attracted much scientific and technological research interest due to a number of advantages over inorganic or organic small molecules for use in LEDs: better processability,lower operating voltages,faster response times,lower production costs,and high flexibility.Polyfluorene has been selected for the polymer backbone,because of its large band gap,facile substitution at the C9 position of fluorene,good chemical and thermal stability,and high photolu...

A new building block with intramolecular D-A character for conjugated polymers: ladder structure based on B←N unit

The general strategy to construct D-A type conjugated polymers is alternating copolymerization of electron-donating(D)monomer and electron-accepting(A)monomer.In this article,we report a new strategy to develop D-A type conjugated polymers,i.e.first fuse the D and A units into a polycyclic structure to produce a building block and then polymerize the building block with another unit.We develop a new building block with ladder structure based on B←N unit,B←N bridged dipyridylbenzene(BNDPB).In the skeleton of BNDPB,one diamine-substituted phenylene ring(D unit)and two B←N-linked pyridyl rings(A unit)are fused together to produce the polycyclic structure.Owning to the presence of intramolecular D-A character,the building block itself exhibits narrow bandgap of 1.74 eV.The conjugated polymers based on BNDPB show unique electronic structures,i.e.localized HOMOs and delocalized LUMOs,which are rarely observed for conventional D-A conjugated polymers.The polymers exhibit smaller bandgap than that of the building block BNDPB and display near-infrared(NIR)light absorption(λabs=ca.700 nm).This study thus provides not only a new strategy to design D-A conjugated polymers but also a new kind of building block with narrow bandgap.

A novel water-soluble anionic conjugated copolymer containing poly(p-phenylene vinylene) segments:Copolymer synthesis and multilayer construction by assembling poly(diallyl dimethyl ammonium chloride)

This paper reports the synthesis of a water soluble conjugated polymer poly(p-phenylene vinyleneco-sodium methacrylate) (ws-P(PV-co-SMA)) and the multilayer of the derived copolymer assembling poly(diallyl dimethyl ammanium chloride) (PDDA). The self-assembling process of the multilayer was monitored by UV-vis absorption spectroscopy, and the data indicated a linear increase in film thick- ness with a number of ws-P(PV-co-SMA)/PDDA bilayers. The alternative deposition of ws-P (PV-co-SMA) and PDDA allowed the insertion of a non-conjugated layer between the conjugated layers, thus the migration of the photogenerated polarons was effectively confined in the isolated ws-P (PV-co-SMA) chains. Consequently, the photoluminescence quantum yield reached 0.68, 30 times higher than that of pure poly(p-phenylen vinylene). The distinct electronic interactions between conjugated segments were confirmed by comparative analyses of the excitation spectra and time-resolved photoluminescence spectra of ws-P(PV-co-SMA) solid film and the assembled multilayers. The confinement effect of the PDDA layer on the photogenerated carriers was verified by the surface photovoltage spectroscopic measurement on both ws-P(PV-co-SMA) solid film and self-assembled multilayers.

芴基红光共聚物的合成及发光性能

采用钯催化的Suzuki偶合方法合成了一系列9,9-二辛基芴(DOF)和4,7-二噻吩-2,1,3-苯并硒二唑的红光共聚物PFO-BTSe。当在聚芴主链中引入4,7-二噻吩-2,1,3-苯并硒二唑后,其发光波长发生红移,最大发光波长由PFO-BTSe0.1时的669 nm红移至PFO-BTSe35时的727 nm。当BTSe的摩尔分数为0.5%时,芴链段在420 nm左右的发光已完全被淬灭,其能量已完全转移到BTSe单元。由这些聚合物所制得的器件最大外量子效率为1.24%,亮度为83 cd/m2,对应的BTSe单元的摩尔分数为0.1%。

共轭/非共轭嵌段聚苯撑乙烯(PPV)类共聚物的合成与性能

用活性中间体直接引发共轭 /非共轭单体聚合的新方法合成了 3种 PPV嵌段共聚物 ;用核磁共振谱和 FTIR光谱确定了共聚物的结构 .引入非共轭片段 PS缩短了 PPV共轭链的长度 ,改善了聚合物的溶解性和可加工性 .荧光光谱结果表明 ,嵌段聚合物可使发射峰蓝移 ,发光的量子效率明显提高 ,进而调节了发光颜色 .

非共轭聚合物PPV衍生物中烷氧基团对发光性质的影响

研究了 3种非共轭PPV聚合物以及 3种共轭PPV衍生物的吸收谱和发光光谱的特性。非共轭PPV聚合物上的侧链烷氧基团有着很强的供电子能力 ,对调节非共轭聚合物能带带隙有重要的影响 ,且离主链较近的碳原子对能带结构也有一定的影响。但当侧链上的碳原子数量很大 ,从 7个小时一直变化到 1 0小时 ,共轭PPV衍生物的吸收光谱和发光光谱变化较少 。

键合紫杉醇的纳米胶束与C6胶质瘤细胞的相互作用

制备了键合紫杉醇(PTX)的聚乙二醇-聚乳酸嵌段共聚物(PEG-PLA/PTX)的纳米胶束,采用四氮唑(MTT)比色法、流式细胞术、透射电镜及激光共聚焦显微镜等技术,考察了PEG-PLA/PTX胶束对C6胶质瘤细胞的影响,包括C6细胞超微结构的变化和细胞周期的改变,以及纳米颗粒在细胞内的分布,探讨了PEG-PLA/PTX胶束对肿瘤细胞的作用机理.结果表明,PEG-PLA/PTX胶束进入到C6细胞内,聚集于细胞浆中,通过与细胞核中DNA的作用改变细胞生长的周期,造成在G2-M期的阻滞,引起细胞的凋亡.因此,PEG-PLA/PTX胶束有望用于脑胶质瘤的化疗.

SBS橡胶填充油的加氢应用技术

针对苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)合成橡胶填充油质量要求与国内原油特点,开发了中压加氢处理、两段法高压加氢、全氢型流程与加氢精制等技术,并进行了工业应用。利用这些技术分别以环烷基、中间基原油生产的SBS橡胶填充油的色度、相溶性、黄变性能等指标均达到国外同类产品质量水平,满足了市场需求。

键合表阿霉素纳米胶束对肝癌细胞和异体肝癌种植瘤凋亡的影响

目的 探讨键合表阿霉素纳米胶束（EPI-NPs）在肝癌Walker-256细胞以及肝癌异体种植肝癌瘤体大鼠组织中凋亡相关蛋白的变化,明确其对肝癌细胞凋亡的作用机制.方法 体外培养肝癌Walker-256细胞后,分为四组：正常组（更换培养液）、 空白键束组（5μg/ml空白键束培养液）、EPI组（5μg/ml EPI培养液）以及EPI-NPs组（5μg/ml EPI-NPs）.培养72 h后,Western Blot观察Bcl-2、Bax和Cleaved-caspase3蛋白的变化.腹水移植法制作肝癌大鼠异体种植模型,CT检查确认荷瘤成功.荷瘤8 d将大鼠随机分为四组,荷瘤组、 空白键束组、EPI组和EPI-NPs组分别给予同体积的生理盐水、 空白键束（2 mg/kg）、EPI（2 mg/kg）及EPI-NPs（2 mg/kg）.治疗14 d后处死大鼠,留取荷瘤组织,观察瘤体大小和Western Blot观察Bcl-2、Bax和Cleaved-caspase3的表达.结果 通过体外细胞实验发现：与空白键束组和EPI组相比,EPI-NPs组的Bax/Bcl-2值明显增高（P〈0.01）,同时发现Cleaved-caspase3也明显增高（P〈0.01）;体外实验发现：EPI-NPs组瘤体明显减小（P〈0.01）.与空白键束组和EPI组相比,EPI-NPs组Bax/Bcl-2值和Cleaved-caspase3明显增高（P〈0.01）.结论 键合表阿霉素纳米胶束能增高肝癌细胞和肝癌大鼠异体种植瘤的凋亡水平,可能通过线粒体凋亡途径发挥作用.