新型红光电磷光芴-alt-咔唑共聚物的合成与发光性能

通过Suzuki聚合反应合成了一系列以芴-alt-咔唑为主链, 铱配合物为侧链的深红色电磷光共轭聚合物. 发光器件结构为ITO/PEDOT∶PSS/PVK/Copolymer/Ba/Al, 基于共聚物PFCzIrNiq-1的器件在电流密度为9.4 mA/cm2时, 最大外量子效率为0.23%, 最大发射波长为680 nm.     

侧链含金属铱配合物的电磷光白光聚合物

设计了一系列新型芴-咔唑电磷光共轭聚合物.通过共价键将双(2-(9,9-二乙基-9H-芴-2-基)吡啶-N,C2’)合铱(III)(Ir Fpy)接枝到3,6-二溴咔唑的N-烷基侧链,采用Suzuki缩聚反应合成了铱配合物(Ir Fpy)含量分别为0.25 mol%,0.5 mol%和1 mol%的聚合物PF-Ir Fpy.当引入的配合物Ir Fpy含量为1 mol%时,得到的共轭聚合物发射色坐标为(0.44,0.56)的黄光.随着接枝的铱配合物Ir Fpy在共轭聚合物中含量降低,作为主体的聚(9,9-二辛基芴)蓝光发射不能被完全淬灭,得到共聚物同时发射主体蓝光及客体铱配合物黄光的单分子白光共轭聚合物.共聚物发光器件结构为ITO/PEDOT:PSS(50 nm)/polymer+PBD(30 wt%)(80nm)/Ba(4 nm)/Al(150 nm)[氧化铟锡/苯磺酸掺杂聚乙烯基二氧噻吩/聚合物+(2,4-二苯-5-4-叔丁基苯-1,3,4-噁二唑)(w=30%)/钡/铝],基于共聚物PF-Ir Fpy025的器件流明效率为3.97 cd/A,色坐标为(0.34,0.34),非常接近于标准白光发射的色坐标(0.33,0.33).为了研究采用共聚物PF-Ir Fpy025和PF-Ir Fpy05制备的白光器件的光谱稳定性,测试了外加电压在8~13 V范围内的EL光谱,当外加电压从8 V升高到13 V时,两个EL器件都表现出了良好的EL光谱稳定性.研究结果表明,在共轭聚合物侧链上引入螯合金属铱配合物单元是实现高效、稳定的白光电致磷光器件的有效方法之一.     

基于不同辅助配体螯合电磷光聚合物的合成与性能研究

通过A-A, B-B型的Suzuki缩聚反应将三个具有不同辅助配体的2-(2'-苯并[b]噻吩)吡啶(btp)双环铱金属配合物引入芴和咔唑交替共聚物(PFCz)的主链上, 合成一系列最大发光波长在660 nm的红光螯合电磷光聚合物, 并研究了它们的电致发光性能. 实验证明了在这类电磷光聚合物中配合物单元辅助配体合理的分子设计, 可以提高配合物单体的溶解度, 提高聚合物的分子量和发光性能. 通过优化器件结构, 聚合物PFBtpIrf5单层器件(ITO/PEDOT:PSS/polymer＋PBD(30 wt%)/Ba/Al)的性能最好: 在电流密度为14.3 mA/cm²时, 最大外量子效率为1.93%.     

芴-呋喃苯并噻二唑共聚物的光电性能

对芴-呋喃苯并噻二唑共聚物的吸收光谱、光致发光光谱、电致发光性能和光伏性能进行了研究. 共聚物在382 nm和530 nm处有两处明显的吸收峰, 其中530 nm处的吸收强度随着共聚物中呋喃苯并噻二唑单元(FBT)含量的增加而增加. 随着FBT单元含量的增加, 电致发光峰值从611 nm红移至702 nm. 以PVK为空穴传输层, 共聚物PFO- FBT0.1为发光层的发光器件, 在33 mA/cm2电流密度下的外量子效率达2.32%, 亮度为441 cd/m2. 实验中观察到快速的链内能量陷阱过程(从芴到FBT单元). 以共聚物PFO-FBT50为电子给体、PCBM为电子受体(重量比1:2)共混制备的光电池能量转换效率为1.13%, 开路电压0.85 V, 短路电流3.39 mA/cm2, 光谱响应边延伸至近750 nm.     

新型超支化聚(芴-co-吡啶并[3,2-b]吡嗪)共聚物的合成与发光性能

合成了新型三溴代的含有吡啶并[3,2-b]吡嗪的化合物, 通过Suzuki缩聚反应合成了以吡啶并[3,2-b]吡嗪为核, 以9,9-二辛基芴为枝的超支化共聚物. 该共聚物在甲苯和四氢呋喃等有机溶剂中具有较好的溶解性能. 采用共聚物制备了结构为ITO/PEDOT/polymer/Ca/Al的发光器件, 其中基于共聚物PFPQ-2的器件在电流密度为3.8 mA/cm²时得到蓝光发射, 最大外量子效率为1.29%, 最大亮度为1173 cd/m², 色坐标为(0.16, 0.11).     

利用Cs基衍生物作为n型掺杂剂改善蓝色有机发光二极管的效率

利用两种Cs基衍生物碳酸铯(Cs2CO3)和醋酸铯(CH3COOCs)作为n型掺杂剂掺入到一种新型的电子传输材料2,9-二(2-萘基)-4,7-二苯基-1,10-菲啰啉(NBPhen)中来提高有机发光二极管(OLEDs)的效率.实验结果表明:器件的驱动电压明显降低,并且优化后得到的Cs基n型掺杂器件(ITO/β-NPB/CBP:5%(w)N-BDAVBi/NBPhen/NBPhen:Cs2CO3(or CH3COOCs)/Al)呈现出较好的电致发光性能,在14 V时电流密度分别为551.80和527.88 mA·cm-2,对应的亮度分别达到39750和39820 cd·m-2,电流效率在亮度为10000 cd·m-2时分别为14.60 cd·A-1(Cs2CO3掺杂)和14.40 cd·A-1(CH3COOCs掺杂),这些参数明显优于传统器件的发光性能(ITO/β-NPB/CBP:5%(w)N-BDAVBi/NBPhen/Cs2CO3/Al,其在14 V时电流密度为312.39 mA·cm-2,对应的亮度为25190 cd·m-2;电流效率在亮度为10000 cd·m-2时为9.45 cd·A-1.此外,基于有机半导体掺杂原理和器件的能级结构对n型掺杂器件效率提高的原因进行了分析.     

胺烷基侧链取代三苯胺类红光聚合物的合成及性能研究

通过Suzuki偶合反应合成了一系列胺烷基侧链取代的基于三苯胺和芴的共轭聚合物聚[4-(N,N-二甲基胺丙氧基)苯-4,4′-二苯胺-9,9-二辛基芴-4,7-二噻吩-2-基-2,1,3-苯并噻二唑](PFTD), 并对其化学结构和光电性能进行了表征. 末端胺基的存在提高了此类聚合物作为发光层应用于聚合物电致发光器件的性能(采用高功函数的金属铝作为阴极时). 结构为ITO/PVK/PFTD-5(DBT摩尔分数为5%时的聚合物)/Al的器件最大电致发射峰位于647 nm, 最大外量子效率达到了1.24%.     

一类窄带隙芴基共聚物的合成及其在发光二极管和太阳电池中的应用

基于9,9-二辛基芴(DOF)与窄带隙单体2,3-二甲基-5,8-二噻吩-喹喔啉(DDQ),通过Suzuki偶合反应,合成了一系列无规和交替窄带隙的芴基共聚物(PFO-DDQ),并对它们的紫外-可见吸收光谱、光致发光光谱、电致发光性能和光伏性能进行了初步研究.共聚物在380 nm和490 nm处有两处明显的吸收峰,其中490nm处的吸收强度随着共聚物中窄带隙单元(DDQ)含量的增加而成比例加强.随着共聚物中窄带隙单元(DDQ)含量的增加,电致发光峰值从580 nm红移到了635 nm.基于该类材料的橙红或饱和红色发光二极管最大外量子效率为1.33%,流明效率为1.54 Cd/A.试验中观察到了窄带隙单元的能量陷阱机制.以窄带隙单元含量为30%的聚合物(PFO-DDQ30)为电子给体、PCBM为电子受体所制备的共混体相异质结太阳电池最大能量转换效率为1.18%,开路电压0.9 V,短路电流密度2.66 mA/cm2.光敏曲线覆盖300 nm~700 nm.     

二-[2',6'-二氟-2,3'-联吡啶- N,C4'][2,4-戊二酮-O,O]铱(III)的合成及其光致和电致发光性能

以2',6'-二氟-2,3'-联吡啶(Hdfpypy)为主配体,乙酰丙酮为辅助配体,合成了二-[2',6'-二氟-2,3'-联吡啶-N,C4'][2,4-戊二酮-O,O]铱(Ⅲ)配合物((dfpypy)2Ir(acac))。在THF溶液中,该配合物溶液最大光致发光光谱为465 nm(半峰宽为53 nm),同时伴有490 nm的肩峰,与面式-Ir(dfpypy)3在438和463 nm两个强度相近的发光光谱相比,发生了红移。配合物在脱气四氢呋喃溶液中的PL量子效率为0.41。将(dfpypy)2Ir(acac)以不同的浓度掺杂在主体材料聚乙烯基咔唑(PVK)中,制备了器件结构为:ITO/PEDOT∶PSS(聚二氧乙基噻吩∶聚对苯乙烯磺酸)/PVK∶(dfpypy)2Ir(acac)(100∶x)(70 nm)/Ba/Al的蓝色聚合物发光器件(x代表掺杂量)。在驱动电压为15.4 V时,2%掺杂器件的最大发光亮度为1400 cd/m2。当电流密度为0.23×10-3A/cm2时,2%掺杂器件最大亮度效率(ηc)为1.6 cd/A。器件的色坐标(CIE)值为(0.15,0.27)。     

铱配合物为核、聚对苯为枝的超支化电磷光聚合物的合成与发光性能

用Suzuki缩聚反应合成了以三-(2-间溴苯基吡啶)合铱为核,以聚2,5-二辛氧基苯为枝的超支化电磷光绿光聚合物（PPPIrppy）。 聚合物中当铱配合物摩尔分数大于0.5%时,主体的发射被完全淬灭,电致发光（EL）光谱只有位于520 nm处的绿光发射,表明主客体之间发生了有效的能量转移。 基于铱配合物摩尔分数为1％的聚合物的发光器件(器件结构：ITO/PEDOT:PSS/emissive layer/Ba/Al)在电流密度为40×10-3 A/cm2时,最大电流效率达到2.89 cd/A,器件的最大亮度达到1 689 cd/m2,色坐标为（0.34,0.59）。     

Phenothiazine-phenylquinoline donor-acceptor molecules: effects of structural isomerism on charge transfer photophysics and electroluminescence

Large differences in the intramolecular charge-transfer fluorescence quantum yields and electroluminescence efficiencies were observed among the isomeric donor-acceptor molecules 2-(4-phenyl-2-quinolyl)-10-methylphenothiazine (2PQMPT) and 3-(4-phenyl-2-quinolyl)-10-methylphenothiazine (3PQMPT). In solution, the 2PQMPT isomer had a larger positive solvatochromism and thus a greater degree of charge transfer, whereas 3PQMPT had a larger fluorescence quantum yield (71%) compared to 2PQMPT (46%). High brightness (23750 cd/m(2)) and high efficiency (8.18 cd/A, 4.45 lm/W, 2.42% external quantum efficiency at 1015 cd/m(2)) green electroluminescence was achieved from 3PQMPT diodes. In contrast, green light-emitting diodes with lower brightness (8900 cd/m(2)) and efficiencies (4.79 cd/A, 2.36 lm/W, 1.41% external quantum efficiency at 690 cd/m(2)) were obtained from 2PQMPT. The two isomeric donor-acceptor molecules had identical HOMO (5.1 eV) and LUMO (2.4 eV) energy levels derived from electrochemistry. Density functional theory (DFT) calculations provided insights into the molecular geometry, electronic structures, and properties of the donor-acceptor isomers. These results demonstrate the pronounced influence of the donor/acceptor connection on the charge-transfer emission efficiency of donor-acceptor molecules and the performance of solid-state light-emitting devices based on them.     

Polypyrrole/graphene composite-coated fiber for the solid-phase microextraction of phenols

A polypyrrole (Ppy)/graphene (G) composite was developed and applied as a novel coating for use in solid-phase microextraction (SPME) coupled with gas chromatography (GC). The Ppy/G-coated fiber was prepared by electrochemically polymerizing pyrrole and G on a stainless-steel wire. The extraction efficiency of Ppy/G-coated fiber for five phenols was the highest compared with the fibers coated with either Ppy or Ppy/graphene oxide (GO) using the same method preparation. Significantly, compared with various commercial fibers, the extraction efficiency of Ppy/G-coated fiber is better than or comparable to 85 μm CAR/PDMS fiber (best extraction efficiency of phenol, o-cresol, and m-cresol in commercial fibers) and 85 μm polyacrylate (PA) fiber (best extraction efficiency of 2,4-dichlorophenol and p-bromophenol in commercial fibers). The effects of extraction and desorption parameters such as extraction time, stirring rate, and desorption temperature and time on the extraction/desorption efficiency were investigated and optimized. The calibration curves were linear from 10 to 1000 μg/L for o-cresol, m-cresol, p-bromophenol, and 2,4-dichlorophenol, and from 50 to 1000 μg/L for phenol. The detection limits were within the range 0.34-3.4 μg/L. The single fiber and fiber-to-fiber reproducibilities were <8.3 (n=7) and 13.3% (n=4), respectively. The recovery of the phenols spiked in natural water samples at 200 μg/L ranged from 74.1 to 103.9% and the relative standard deviations were <3.7%.     

Synthesis and characterization of polyfluorenes containing bisphenazine units

Novel conjugated copolymers based on 9,9‐dioctylfluorene and bisphenazine (BP) were synthesized by Suzuki polymerization. Energy transfer from the conjugated main chain to the BP moieties was observed. Full energy transfer was achieved when the molar content of the bisphenazine was 20% (20BPPF) in toluene solution. The similar phenomena were observed even for 1% bisphenazine content copolymer (1BPPF) in film. The lowest occupied molecular orbital (LUMO) energy levels (?3.06 eV) of the copolymers were lower than that of the polyfluorene homopolymer (PFO; ?2.65 eV), indicating that the introduction of the BP unit was benefit to electron injection. Single‐layer electroluminescent devices (ITO/PEDOT:PSS/polymer/LiF/Al) were fabricated to investigate their electroluminescence (EL) performances. The maximum brightness and current efficiency of all BPPF copolymers surpassed the PFO homopolymer. The best single‐layer device was based on 5BPPF, with a maximum brightness of 1532 cd/m² and current efficiency of 1.09 cd/A. Much higher efficiency could be achieved for multilayer EL devices of 5BPPF (ITO/PEDOT:PSS/PVK/polymer/TPBI/LiF/Al), which showed a maximum current efficiency of 10.01 cd/A. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1990–1999, 2010     

Poly(lactic-co-glycolic acid) microspheres for the controlled release of huperzine A: in vitro and in vivo studies and the application in the treatment of the impaired memory of mice

Huperzine A loaded poly(D,L-lactic-co-glycolic acid) (PLGA) microspheres were prepared by an oil/water (o/w) solvent evaporation technique. With a decrease of the ratio of o/w from 1 : 100 to 1 : 50, the encapsulation efficiency was reduced about 4%. Increasing the PVA concentration from 0.5 to 2% reduced the percentage encapsulation efficiency of huperzine A from 60.7 to 47.4% and the particle size of microspheres from 84.2 to 26.2 microm. The addition of stearic acid improved the encapsulation efficiency, but also accelerated the in vitro release of hupezine A from microspheres. After i.m. administration of huperzine A loaded microspheres in mice, huperzine A was sustained released from the PLGA microspheres up to 12 d with a low initial burst. Passive avoidance test of mice showed that the microspheres formulation offered an improved therapeutic efficiency in the treatment of the impaired memory of the mice superior to injection gastric (i.g.) administration of huperzine A suspension at the same dose, whose therapeutic efficiency was similar as that of a 50% reduced dose of the microspheres formulation.     

Extraction of Lithium from Salt Lake Brine with Triisobutyl Phosphate in Ionic Liquid and Kerosene

Three ionic liquids(ILs), namely, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-me- thylimidazolium bis[(trifluoromethyl)sulfonyl]imide and 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sul- fonyl]imide with the triisobutyl phosphate(TIBP) and kerosene system were respectively used to extract lithium ion from salt lake brine with a high concentration ratio of magnesium and lithium experimentally. Results indicate that the highest extraction selectivity for lithium was obtained with IL 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)- sulfonyl]imide. The effects of solution pH and phase ratio R(O/A) on the extractive step and the influence of acid concentration of the stripping solution and R(O/A) on the back extraction step were also investigated systematically. The single-step extraction efficiency of lithium ion was 83.71% under the optimal extraction conditions, and the single-step back extraction efficiency was 85.61% with a 1.0 mol/L HCl in 1.0 mol/L NaCl medium as stripping agent at R(O/A)=2. The liquid-liquid extraction mechanism and the complex of the ligand with lithium were proposed.     

TiO_2/CdS/Ru(bpy)_2(NCS)_2作为太阳电池光阳极的探讨

将 Cd S纳米粒子复合在 Ti O2 纳米多孔膜上 ,用染料 Ru( bpy) 2 ( NCS) 2 对此复合半导体纳米膜电极进行敏化 ,测量了不同 Cd S复合量的 ITO/Ti O2 /Cd S/Ru( bpy) 2 ( NCS) 2 光阳极组成光电池的能量转换效率 .实验证明 ,ITO/Ti O2 /Cd S/Ru( bpy) 2 ( NCS) 2 作为太阳电池光阳极的能量转换效率与 Ti O2 /Cd S复合半导体中 Cd S的含量有关 .当 Cd S复合时间为 5 min的电池的短路电流为 5 .2 3A/m2 ,开路电压为 0 .71 6 V,能量转换效率为 0 .77% .     

Hermetic Seal of Organic Light Emitting Diode with Glass Frit

The components of OLED encapsulation with hermetic sealing and a 1026-day lifetime were measured by PXI-1033. The optimal characteristics were obtained when the thickness of the TPBi layer was 20 nm. This OLED obtained a maximum luminance (Lmax) of 25,849 cd/m² at a current density of 1242 mA/cm², an external quantum efficiency (EQE) of 2.28%, a current efficiency (CE) of 7.20 cd/A, and a power efficiency (PE) of 5.28 lm/W. The efficiency was enhanced by Lmax 17.2%/EQE 0.89%/CE 42.1%/PE 41.9%. The CIE coordinates of 0.32, 0.54 were all green OLED elements with wavelengths of 532 nm. The shear strain and leakage test gave results of 16 kgf and 8.92 × 10⁻⁹ mbar/s, respectively. The reliability test showed that the standard of MIL-STD-883 was obtained.     

Electroluminescence performances of 1,1-bis(4-(N,N-dimethylamino)phenyl)-2,3,4,5-tetraphenylsilole based polymers in three cathode architectures

A new silole monomer with two 4-(N,N-dimethylamino)phenyl substitutions on silicon atom as designed and synthesized.Three copolymers PF-N-HPS1,PF-N-HPS10 and PF-N-HPS20 were then obtained by copolymerizations of 2,7-fluorene derivatives with the silole monomer at feed ratios of 1%,10%,and 20%.Their UV-vis absorption,electrochemical,photoluminescent,and electroluminescent (EL) properties were investigated.PF-N-HPS possessed HOMO levels of 5.25-5.58 eV,and showed green emissions.Using PF-N-HPS as the emissive layer,three different polymer light-emitting diodes were fabricated as device A with ITO/PEDOT/PF-N-HPS/Al,device B with ITO/PEDOT/PF-N-HPS/Ba/Al,and device C with ITO/PEDOT/PF-N-HPS/TPBI/Ba/Al.For the device A,PF-N-HPS only showed very low EL efficiency of 0.06-0.33 cd/A,indicating that the Al cathode could not inject electron efficiently to the emissive polymers containing the 4-(N,N-dimethylamino)phenyl groups.For the device B,low work function Ba supplied better electron injections,and the EL efficiency could be improved to 0.85-1.44 cd/A.TPBI with a deep HOMO level of 6.2 eV could enhance electron transport and hole blocking.Thus modified recombinations and largely elevated EL efficiency of 4.56-7.96 cd/A were achieved for the device C.The separation of the emissive layer and metal cathode with the TPBI layer may also suppress exciton quenching at the cathode interface.     

Immobilisation and evaluation of a vancomycin chiral stationary phase for capillary electrochromatography

The macrocyclic antibiotic, vancomycin, is covalently bonded to LiChrospher diol silica packed columns and evaluated in capillary electrochromatography (CEC) both in the reversed-phase and polar organic mode. Initially, capillaries were packed with 5 microm LiChrospher 100 A diol silica and evaluated in CEC with a reversed-phase biphenyl-pyrene achiral test resulting in resolution and efficiency values of ca. 2.5 and 100000 plates meter(-1), respectively. Repeatability for this test (resolution and efficiency) was also examined and found to be acceptable for both run-to-run (n=5, 0.74% and 1.5%) and column-to-column (n=5, 3.4% and 9.0%), respectively. Similar results were obtained when the 10 microm LiChrospher 1000 A diol silica was examined with the exception of efficiency, where a reduced plate height value of four times lower was obtained compared to the 100 A material. A simple three step in-situ vancomycin immobilisation procedure was subsequently carried out on these packed diol columns. Selectivity was obtained for thalidomide enantiomers on this vancomycin chiral stationary phase in reversed-phase CEC with resolution and efficiency values of ca. 2.5 and 80000 plates meter(-1), with acceptable repeatability (n=8) 0.9% and 3.0%, respectively. Selectivity was also obtained for thalidomide enantiomers on this phase in the polar organic mode with resolution and efficiency values of ca. 2.5 and 120000 plates meter(-1), with acceptable repeatability (n=7) 0.9% and 2.0%, respectively. It was possible to deduce from a chemometric design carried out for evaluating the mobile phase component effects that organic modifier ratio, MeOH/MeCN, played a significant role in controlling both resolution and efficiency. It was also possible to separate a number of basic analytes including four beta-adrenergic blocking agents in the polar organic mode albeit with lower resolution and efficiency values, ca. 1.5 and 45000 plates meter(-1), respectively.     

还原变性核糖核酸酶在疏水性液-固界面上的复性

采用疏水相互作用色谱(HIC)对还原变性核糖核酸酶A (RNase A)在疏水性液-固界面上的复性进行了研究。详细讨论了流动相中脲的浓度、还原型谷胱甘肽/氧化型谷胱甘肽(GSH/GSSG)的比例、流动相pH和变性蛋白质浓度对还原变性RNase A复性效率和质量回收率的影响。结果表明,在最优化的复性条件(流动相中含有2.0 mol/L脲,GSH/GSSG的浓度比为8:1,流动相pH为8.0)下,还原变性RNase A能完全复性。当变性蛋白质质量浓度为5.0 mg/mL时,还原脲变性RNase A的活性回收率和质量回收率分别为98.0%和61.9%,还原胍变性RNase A分别为100.1%和66.8%。研究表明HIC是还原变性蛋白质复性的有力工具之一,可为蛋白质复性研究提供新方法和新思路。