Sub‐Micrometer Patterning of Amorphous‐ and β‐Phase in a Crosslinkable Poly(9,9‐dioctylfluorene): Dual‐Wavelength Lasing from a Mixed‐Morphology Device

The metastable β‐phase morphology, inherent to most polyfluorene homo‐polymers, is of interest due to its superior optical and electrical characteristics compared to its amorphous analogue. Here, a polyfluorene with vinyl‐ether‐functionalized aliphatic side‐chains that allow crosslinking is reported. It is demonstrated that the previously induced conformational morphology is preserved in the resulting polyfluorene network, which enables subsequent wet thin‐film processing. Electron‐beam lithography provides a means for sub‐(optical)‐wavelength patterning of the crosslinkable polyfluorene films. As a specific demonstration, optically‐pumped distributed‐feedback (DFB) lasers made from surface‐relief gratings in amorphous and β‐phase polyfluorene are presented. By backfilling gratings of one morphology by the other, devices are demonstrated that exhibit lasing at two wavelengths with a threshold (<1 μJ cm^?2) at least an order of magnitude lower compared with previous data.     

Self‐Assembled Conjugated Thiophene‐Based Rotaxane Architectures: Structural,Computational, and Spectroscopic Insights into Molecular Aggregation

A comparative study of the self‐assembly at a variety of surfaces of a dithiophene rotaxane 1 ?β‐CD and its corresponding dumbbell, 1, by means of atomic force microscopy (AFM) imaging and scanning tunneling microscopy (STM) imaging on the micrometer and nanometer scale, respectively. The dumbbell is found to have a greater propensity to form ordered supramolecular assemblies, as a result of π–π interactions between dithiophenes belonging to adjacent molecules, which are hindered in the rotaxane. The fine molecular structure determined by STM was compared to that obtained by molecular modelling. The optical properties of both rotaxane and dumbbell in the solid state were investigated by steady‐state and time‐resolved photoluminescence (PL) experiments on spin‐cast films and diluted solutions. The comparison between the optical features of the threaded and unthreaded systems reveals an effective role of encapsulation in reducing aggregation and exciton migration for the rotaxanes with respect to the dumbbells, thus leading to higher PL quantum efficiency and preserved single‐molecule photophysics for longer times after excitation in the threaded oligomers.     

Anisotropy of Charge Transport in a Uniaxially Aligned and Chain‐Extended,High‐Mobility,Conjugated Polymer Semiconductor

Charge transport in the ribbon phase of poly(2,5‐bis(3‐alkylthiophen‐2‐yl)thieno[3,2‐b]thiophene) (PBTTT)—one of the most highly ordered, chain‐extended crystalline microstructures available in a conjugated polymer semiconductor—is studied. Ribbon‐phase PBTTT has previously been found not to exhibit high carrier mobilities, but it is shown here that field‐effect mobilities depend strongly on the device architecture and active interface. When devices are constructed such that the ribbon‐phase films are in contact with either a polymer gate dielectric or an SiO₂ gate dielectric modified by a hydrophobic, self‐assembled monolayer, high mobilities of up to 0.4 cm² V^?1 s^?1 can be achieved, which is comparable to those observed previously in terrace‐phase PBTTT. In uniaxially aligned, zone‐cast films of ribbon‐phase PBTTT the mobility anisotropy is measured for transport both parallel and perpendicular to the polymer chain direction. The mobility anisotropy is relatively small, with the mobility along the polymer chain direction being higher by a factor of 3–5, consistent with the grain size encountered in the two transport directions.     

Design Guidelines For Conjugated Polymers With Light‐Activated Anticancer Activity

Multifunctional materials that simultaneously provide therapeutic action and image the results provide new strategies for the treatment of various diseases. Here, it is shown that water soluble conjugated polymers with a molecular design centered on the polythiophene?porphyrin dyad are effective for killing neighboring cells. Following photoexcitation, energy is efficiently transferred from the polythiophene backbone to the porphyrin units, which readily produce singlet oxygen (¹O₂) that is toxic for the cells. Due to the light‐harvesting ability of the electronically delocalized backbone and the efficient energy transfer amongst optical partners, the polythiophene?porphyrin dyad shows a higher ¹O₂ generation efficiency than a small molecule analog. The fluorescent properties of these polymers can also serve to distinguish amongst living and dead cells. Polymers can be designed with folic acid grafted onto the polymer side chain that can specifically kill folate receptor‐overexpressed cells, thereby providing an important demonstration of anticancer specificity through molecular design.     

Very Low Degree of Energetic Disorder as the Origin of High Mobility in an n‐channel Polymer Semiconductor

Charge transport is investigated in high‐mobility n‐channel organic field‐effect transistors (OFETs) based on poly{[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)} (P(NDI2OD‐T2), Polyera ActivInk? N2200) with variable‐temperature electrical measurements and charge‐modulation spectroscopy. Results indicate an unusually uniform energetic landscape of sites for charge‐carrier transport along the channel of the transistor as the main reason for the observed high‐electron mobility. Consistent with a lateral field‐independent transport at temperatures down to 10 K, the reorganization energy is proposed to play an important role in determining the activation energy for the mobility. Quantum chemical calculations, which show an efficient electronic coupling between adjacent units and a reorganization energy of a few hundred meV, are consistent with these findings.     

以Na2TeO3为碲源制备CdTe纳米晶及其表征

本文以巯基乙酸作为稳定剂,在水相中制备了CdTe纳米晶。以亚碲酸钠作为碲源,从而避免了以H2Te或NaHTe（用碲粉和硼氢化钠合成）作为碲源时,需要氮气或其它气体作为保护气体的过程,简化了制备工艺,并且提高了CdTe纳米晶的产量。用X射线衍射仪（XRD）、透射电镜（SEM）和荧光分光光度计对其进行了表征。分析表明CdTe纳米晶为立方相,并且有较窄的荧光发射峰。详细探讨了反应时间、pH值及前驱物浓度对CdTe纳米晶荧光性能的影响。     

用于水泥沥青砂浆的聚羧酸减水剂的制备

采用聚乙二醇单甲醚(1000、2000)、甲基丙烯酸、阻聚剂、催化剂、引发剂、苯乙烯、丙烯酰胺和对苯乙烯磺酸钠合成了用于水泥沥青砂浆的聚羧酸减水剂.研究了酸醇摩尔比和苯乙烯、丙烯酰胺、对苯乙烯磺酸钠的用量对合成减水剂性能的影响.对聚羧酸减水剂配比进行了优化,进行了中试,制备了CA砂浆样板,并进行性能测试.用GPC对中试聚羧酸减水剂进行了表征.结果表明:大单体的制备及减水剂聚合工艺是可行的.最佳酸醇摩尔比为4.0:1.0,苯乙烯和丙烯酰胺的最佳用量均为3％,对苯乙烯磺酸钠用量以不超过3％为宜.掺该合成聚羧酸减水剂的CA砂浆性能良好,制备的CA砂浆样板基本无缺陷.     

硫酸钠对不同强度混凝土性能的影响差异

为了探讨硫酸钠对不同强度混凝土性能的影响差异,研究了硫酸钠在不同掺量条件下对C 30和C 50混凝土工作性和抗压强度的影响。研究结果表明,硫酸钠对不同强度等级混凝土工作性能与抗压强度的影响规律并不一致。硫酸钠对低强度等级混凝土的出机坍落度和扩展度的影响较小,但会明显降低高强度等级新拌混凝土的工作性能;硫酸钠对混凝土具有一定的早强效果,对低强度等级混凝土的中后期抗压强度具有一定的增强效果,但会降低高强度等级混凝土的中后期强度。     

肝素钠和小剂量高渗盐水对复苏后兔小肠微循环灌注障碍的影响

目的研究CPR期间给予肝素钠和小剂量高渗盐水治疗对复苏后兔小肠微循环灌注障碍的影响。方法 60只家兔开胸致室性颤动（室颤）,室颤5 min后行胸内CPR,CPR过程中随机分为生理盐水（NS组）2 mL.kg-1.10 min-1或生理盐水2 mL.kg-1.10 min-1和普通肝素钠60 U.kg-1组（H组）或7.5%NaCl 2 mL.kg-1.10 min-1＋普通肝素钠60 U.kg-1组（HSH组）,每组20只。观察各组小肠灌注区域;室颤前及自主循环恢复（ROSC）后测血浆可溶性P选择素（sP）及内毒素（ET）浓度的变化情况。结果实验过程中各组之间的平均动脉压（MAP）差异无统计学意义（P〉0.05）,兔经历5 min心脏骤停（CA）和CPR后,ROSC后30 min仍有严重的微循环灌注障碍,H组和NS组相比二者之间差异有统计学意义（P〈0.01）;HSH组和其他2组相比差异均有统计学意义（P〈0.01）。ROSC后20、30 min HSH组血浆sP水平均明显低于其他2组（均P〈0.01）。各组之间ET基础值差异无统计学意义（P〉0.05）,CA后随着自主循环的恢复,兔血浆ET浓度明显升高,并随着自主循环恢复时间延长有逐渐升高的趋势。ROSC后30、60、120 min,ROSC 3、4 h时HSH组、H组ET浓度与NS组比较差异均有统计学意义（均P〈0.01）;而HSH组和H组之间差异无统计学意义（P〉0.05）。结论 CPR期间给予肝素钠和小剂量高渗盐水治疗可以改善复苏后兔小肠微循环灌注障碍,降低复苏后兔血浆内毒素浓度,并不增加出血的发生率。