Bipolar copolymers comprised mesogen‐jacketed polymer containing oxadiazole units and PVK as host materials for electroluminescent devices

Nonconjugated bipolar transport polymers have been developed as host materials for electroluminescent devices by incorporating both electron‐transporting and hole‐transporting functionalities into copolymers. The random copolymer PCt‐nvk3‐7 containing mesogen‐jacketed segment of P‐Ct have been synthesized and characterized. The effect of mesogen‐jacketed segment content of these bipolar copolymers on device performance has been investigated. The results of polymer light‐emitting diodes (PLEDs) show that the jacketed content of copolymers has a significant effect on device performance: lowering charge transport and facilitating the hole‐electron recombination leads to much higher current efficiency. Applying these high triplet random copolymers as host, the maximum current efficiency of 0.70 cd/A and the maximum brightness of 1872.8 cd/m² was achieved for PCt‐nvk3‐7 with an orange‐emitting complex dopant. The results suggest that the bipolar copolymers PCt‐nvks can be good host polymers for electrophosphorescent devices. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7861–7867, 2008     

水／离子液体两相体系中出芽短梗霉催化4-氯-乙酰乙酸乙酯不对称还原合成（S）-4-氯-3-羟基-丁酸乙酯

考察了水/离子液体两相体系中出芽短梗霉(Aureobasidium pullulansCGMCC1244)催化4-氯乙酰乙酸乙酯(COBE)不对称还原生成光学活性(S)-4-氯-3-羟基丁酸乙酯((S)-CHBE)的性能,并对反应条件如摇床转速、相体积比、温度、初始底物浓度和pH值等进行了优化.结果表明,在水/1-丁基-3-甲基咪唑六氟磷酸盐体系中,出芽短梗霉催化COBE不对称还原生成(S)-CHBE,在30℃,pH6·6,摇床转速180r/min和不对称反应8h条件下,反应物的转化率、产物ee值和浓度分别达到95·6%,98·5%和47·1g/L.在控制pH值为6·6的情况下,通过分添加底物可有效提高产物(S)-CHBE浓度至75·1g/L.     

The Synthesis of a New Macrocyclic Dinucleating Ligand,3,6,9,17,20,23-Hexaaza-29,30-Dihydroxy-13,27-Dimethyl-Tricyclo[23,3,1,1~(11,15)]Triaconta-1(28),11,13, 15(30),25,26-Hexaene

Thecoordinationchemistryofbinuclearmetalcomplexeshasbeenasubjectofextensiveinvestigationrelatingtothesynthesisofmodelcompoundsforthemetal-bindingsitesofmetal1oproteinsthatrequirethepresenceoftWometalcentersl.Duringthe1astdecade,anumberofsyntheticstructuraImodeIsfortheseproteinswiththeuseofseveraltypesofligandshavebeenreportedinIiterature2-4.ForIigandswithanappropriatedispositionofdonoratoms,ithasbeenpossibletoshowthepresenceofhydroxo,imidazolato,azido,andthiocyanatobridgesbetweenmetalions5.T…     

2,7-二苯芴酮伴随巨大红移的聚集诱导发光：真实还是假象？

先前报道的2,7-二苯芴酮具有不寻常的,伴随150 nm荧光红移的聚集诱导发光现象. 通过重复实验,发现这种异常行为由合成的2,7-二苯芴酮中少量2,7-二苯芴(DPF)造成. 固态纯2,7-二苯芴酮分子在528 nm处确实有强烈的荧光,是在二氯甲烷稀溶液中的4∽5倍(542 nm),但在固体中是蓝移而不是红移. 合成的2,7-二苯芴酮固体的荧光增强和波长红移现象由少量2,7-二苯芴杂质造成. 在稀溶液中,2,7-二苯芴的荧光远强于2,7-二苯芴酮且波长较短,当2,7-二苯芴酮中含有痕量(约1%)2,7-二苯芴时,主要的荧光峰来自于2,7-二苯芴. 因为2,7-二苯芴的吸收峰与2,7-二苯芴酮重叠,所以2,7-二苯芴的电子能可以转移到2,7-二苯芴酮上. 随着浓度的增加,因为2,7-二苯芴与周围2,7-二苯芴酮分子的距离更近,能量转移会变快. 这造成了2,7-二苯芴的荧光猝灭(356和372 nm)和2,7-二苯芴酮的荧光增强(溶液中542 nm,固体中528 nm). 因此,在高浓度溶液或者固体中,仅有542或528 nm的荧光峰出现,356和372 nm 处荧光峰消失.     

TiO_2/Mn-ZSM-5复合催化剂的光催化-臭氧耦合降解乙醛

采用离子交换法制备了Mn-ZSM-5系列催化剂,并利用浸渍法制备了TiO2/Mn-ZSM-5系列复合催化剂.通过Uv-Vis、BET、X射线衍射等手段对催化剂进行了表征,考察了臭氧存在下乙醛的降解性能.结果表明:臭氧能显著促进乙醛的光催化降解,在所制备的催化剂中TiO2/Mn-ZSM-5(1:2)对乙醛降解具有最好的活性,这归功于这种复合催化剂对臭氧和乙醛的吸附和催化协同效应.     

Catalytic mechanism of Golgi-resident human tyrosylprotein sulfotransferase-2: A mass spectrometry approach

Human tyrosylprotein sulfotransferases catalyze the transfer of a sulfuryl moiety from the universal sulfate donor PAPS to the hydroxyl substituent of tyrosine residues in proteins and peptides to yield tyrosine sulfated products and PAP. Tyrosine sulfation occurs in the trans-Golgi network, affecting an estimated 1% of the tyrosine residues in all secreted and membrane-bound proteins in higher order eukaryotes. In this study, an effective LC-MS-based TPST kinetics assay was developed and utilized to measure the kinetic properties of human TPST-2 and investigate its catalytic mechanism when G protein-coupled CC-chemokine receptor 8 (CCR8) peptides were used as acceptor substrates. Through initial rate kinetics, product inhibition studies, and radioactive-labeling experiments, our data strongly suggest a two-site ping-pong model for TPST-2 action. In this mechanistic model, the enzyme allows independent binding of substrates to two distinct sites, and involves the formation of a sulfated enzyme covalent intermediate. Some insights on the important amino acid residues at the catalytic site of TPST-2 and its covalent intermediate are also presented. To our knowledge, this is the first detailed study of the reaction kinetics and mechanism reported for human TPST-2 or any other Golgi-resident sulfotransferase.     

Influence of fluorinated substituent and terminal length on phase behavior of mesogen‐jacketed liquid crystalline polymers with a biphenyl mesogen

A series of mesogen‐jacketed liquid crystalline polymers, poly{2,2,3,3,4,4,4‐heptafluorobutyl 4′‐hydroxy‐2‐vinylbiphenyl‐4‐carboxylate} (PF3Cm, where m is the number of carbon atoms in the alkoxy groups, and m = 1, 4, 6, and 8), the side chain of which contains a biphenyl core with a fluorocarbon substituent at one end and an alkoxy unit of varying length on the other end, were designed and successfully synthesized via atom transfer radical polymerization. For comparison, poly{butyl 4′‐hydroxy‐2‐vinylbiphenyl‐4‐carboxylate} (PC4Cm), similar to PF3Cm but with a butyl group instead of the fluorocarbon substituent, was also prepared. Differential scanning calorimetric results reveal that the glass transition temperatures (T_gs) of the two series of polymers decrease as m increases and T_gs of the fluorocarbon‐substituted polymers are higher than those of the corresponding butyl‐substituted polymers. Wide‐angle X‐ray diffraction measurements show that the mesophase structures of these polymers are dependent on the number of the carbon atoms in the fluorocarbon substituent and the property of the other terminal substituent. Polymers with fluorocarbon substituents enter into columnar nematic phases when m ≥ 4, whereas the polymer PF3C1 exhibits no liquid crystallinity. For polymers with butyl substituents, columnar nematic phases form when the number of carbon atoms at both ends of the side chain is not equal at high temperatures and disappear after the polymers are cooled to ambient temperature. However, when the polymer has the same number of carbon atoms at both ends of the side chain, a hexagonal columnar phase develops, and this phase remains after the polymer is cooled. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

A novel mesogen‐jacketed liquid crystalline electroluminescent polymer with both thiophene and oxadiazole in conjugated side chain

Mesogen‐jacketed liquid crystalline polymers (MJLCPs) with both electron‐transport oxadiazole and hole‐transport thiophene in the side chain were reported for their promising electroluminescent property. Monomers of 2,5‐bis{5‐[(4‐alkoxyphenyl)‐1,3,4‐oxadiazole]thiophen‐2‐yl}styrene (M‐Cm, m is the number of the carbons in the alkoxy groups, m = 8,10) were synthesized and confirmed by ¹H‐NMR, mass spectrometry, and elemental analysis. The corresponding polymers were successfully obtained and characterized by thermal analysis, optical spectroscopy, cyclic voltammetry, electroluminescent analysis, polarized light microscopy (PLM), and wide‐angle X‐ray diffraction (WAXD). The polymers exhibited high decomposition temperatures reaching 382 °C and high T_g's reaching 184 °C. The absorption spectra indicated that both the monomers and polymers had little aggregation in film than that in solution, and the absorption spectra of the polymers showed an obvious blue‐shift compared with those of the monomers. Both the monomers and the polymers had blue‐green emission, and the photoluminescence spectra of the polymers in film suggested the formation of excimer or exciplex. The polymers showed lower HOMO energy levels and LUMO energy levels than those of the MJLCPs containing oxadiazole unit reported before. Electroluminescence study with the device configuration of ITO/PEDOT/PVK/polymer/TPBI/Ca/Ag showed maximum brightness and current efficiency of 541 cd/m² and 0.10 cd/A, which proved that the introduction of directly connected electron‐ and hole‐transport units could greatly improve the EL property of side‐chain conjugated polymers. The phase structures of the polymers were confirmed to be smectic A phase through the results of PLM and WAXD. The annealed samples emitted polarized photoluminescence at room temperature, which indicated potential utility for practical applications in display. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1502–1515, 2010     

Electroluminescent block copolymers containing oxadiazole and thiophene via ATRP

Block copolymers containing thiophene units in one block and oxadiazole (OXD) units in the other were prepared. Atom transfer radical polymerization method was used to obtain the thiophene‐containing mesogen‐jacketed polymers, and the kinetic study indicated that the polymerization was controllable and the polymers could be used to initiate the polymerization of the OXD‐containing monomers. Photoluminescent spectra indicated that the fluorescence quantum yields of the polymers increased with increasing content of OXD. And, more OXD domains, that is, more interfaces between the hole‐transport parts and electron‐transport parts, resulting in the higher probability of exciplex formation. The electroluminescent devices containing the block copolymer with 64 mol % OXD as the emissive layer had a maximum brightness of 127 cd/m² and an extremely low onset voltage of 7.7 V, which indicated that the injection and transport of charge carriers were facilitated and the number of charge carriers was sufficiently high in early time after the voltage was turned on. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

AB2‐type amphiphilic block copolymers composed of poly(ethylene glycol) and poly(N‐isopropylacrylamide) via single‐electron transfer living radical polymerization: Synthesis and characterization

Novel AB₂‐type amphiphilic block copolymers of poly(ethylene glycol) and poly(N‐isopropylacrylamide), PEG‐b‐(PNIPAM)₂, were successfully synthesized through single‐electron transfer living radical polymerization (SET‐LRP). A difunctional macroinitiator was prepared by esterification of 2,2‐dichloroacetyl chloride with poly(ethylene glycol) monomethyl ether (PEG). The copolymers were obtained via the SET‐LRP of N‐isopropylacrylamide (NIPAM) with CuCl/tris(2‐(dimethylamino)ethyl)amine (Me₆TREN) as catalytic system and DMF/H₂O (v/v = 3:1) mixture as solvent. The resulting copolymers were characterized by gel permeation chromatography and ¹H NMR. These block copolymers show controllable molecular weights and narrow molecular weight distributions (PDI < 1.15). Their phase transition temperatures and the corresponding enthalpy changes in aqueous solution were measured by differential scanning calorimetry. As a result, the phase transition temperature of PEG₄₄‐b‐(PNIPAM₅₅)₂ is similar to that in the case of PEG₄₄‐b‐PNIPAM₁₁₀; however, the corresponding enthalpy change is much lower, indicating the significant influence of the macromolecular architecture on the phase transition. This is the first study into the effect of macromolecular architecture on the phase transition using AB₂‐type amphiphilic block copolymer composed of PEG and PNIPAM. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4420–4427, 2009