Synthesis and characterization of a wide bandgap polymer based on a weak donor-weak acceptor structure for dual applications in organic solar cells and organic photodetectors

We synthesized a novel wide bandgap polymer, PDTFBT, forming a weak donor (WD)-weak acceptor (WA) structure for use in organic photodetectors (OPDs) and organic solar cells (OSCs). The fluorination in the D unit and the alkoxy substitution in the A unit induced WD and WA properties, respectively. The WD-WA structure of PDTFBT effectively broadened the bandgap compared to typical D-A structures, and the S-F and S-O dipole-dipole interactions induces a highly planar backbone structure with excellent π-π stacking in the vertical direction. In OPDs, conformationally less disordered PDTFBT polymer retained the constant responsivity and significantly improved the detectivity of PDTFBT:PC₇₁BM devices even with a thick active layer of 470 nm, contrary to the variation in the responsivity of P3HT:PC₆₁BM devices depending on the thickness. In OSCs, the deep HOMO energy level (−5.57 eV) of PDTFBT led to high Voc of 0.92 V in PDTFBT:PC₇₁BM devices, which was 0.3 eV higher than that of P3HT:PC₆₁BM devices (0.62 V), resulting in 1.8-fold enhanced power conversion efficiency. We demonstrated that the WD-WA structure with S-F and S-O interactions is highly promising strategy to make wide bandgap polymers for organic photodetectors and for the bottom cell of tandem architecture.     

Pyrrole‐based narrow‐band‐gap copolymers for red light‐emitting diodes and bulk heterojunction photovoltaic cells

A series of narrow‐band‐gap conjugated copolymers (PFO‐DPT) derived from pyrrole, benzothiadiazole, and 9,9‐dioctylfluorene (DOF) is prepared by the palladium‐catalyzed Suzuki coupling reaction with the molar feed ratio of 4,7‐bis(N‐methylpyrrol‐2‐yl)‐2,1,3‐benzothiadiazole (DPT) around 1, 5, 15, 30, and 50%. The obtained polymers are readily soluble in common organic solvents. The solutions and the thin solid films of the copolymers absorb light from 300 nm to 600 nm with two absorbance peaks at around 380 nm and 505 nm. The PL emission consists mainly of DPT unit emission at around 624–686 nm depending on the DPT content in solid film. The EL emission peaks are red‐shifted from 630 nm for PFO‐DPT1 to 660 nm for PFO‐DPT50. Bulk heterojunction photovoltaic cells fabricated from composite films of copolymer and [6,6]‐phenyl C₆₁ butyric acid methyl ester (PCBM) as electron donor and electron acceptor, respectively, in device configuration: ITO/PEDOT : PSS/PFO‐DPT : PCBM/Ba/Al shows power conversion efficiencies 0.15% with open‐circuit voltage (V_oc) of 0.60 V and short‐circuit current density (J_sc) of 0.73 mA/cm² under AM1.5 solar simulator (100 mW/cm²). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Poly(diketopyrrolopyrrole‐benzothiadiazole) with Ambipolarity Approaching 100% Equivalency

As a characteristic feature of conventional conjugated polymers, it has been generally agreed that conjugated polymers exhibit either high hole transport property (p‐type) or high electron transport property (n‐type). Although ambipolar properties have been demonstrated from specially designed conjugated polymers, only a few examples have exhibited ambipolar transport properties under limited conditions. Furthermore, there is, as yet, no example with ‘equivalent’ hole and electron transport properties. We describe the realization of an equivalent ambipolar organic field‐effect transistor (FET) by using a single‐component visible–near infrared absorbing diketopyrrolopyrrole (DPP)‐benzothiadiazole (BTZ) copolymer, namely poly[3,6‐dithiene‐2‐yl‐2,5‐di(2‐decyltetradecyl)‐pyrrolo[3,4‐c]pyrrole‐1,4‐dione‐5’,5’’‐diyl‐alt‐benzo‐2,1, 3‐thiadiazol‐4,7‐diyl] ( PDTDPP‐alt‐BTZ ). PDTDPP‐alt‐BTZ shows not only ideally balanced charge carrier mobilities for both electrons (?_e = 0.09 cm²V^?1s^?1) and holes (?_h = 0.1 cm²V^?1s^?1) but also its inverter constructed with the combination of two identical ambipolar FETs exhibits a gain of ～35 that is much higher than usually obtained values for unipolar logic.     

Fused Benzothiadiazole: A Building Block for n‐Type Organic Acceptor to Achieve High‐Performance Organic Solar Cells

Narrow bandgap n‐type organic semiconductors (n‐OS) have attracted great attention in recent years as acceptors in organic solar cells (OSCs), due to their easily tuned absorption and electronic energy levels in comparison with fullerene acceptors. Herein, a new n‐OS acceptor, Y5, with an electron‐deficient‐core‐based fused structure is designed and synthesized, which exhibits a strong absorption in the 600–900 nm region with an extinction coefficient of 1.24 × 10⁵ cm^?1, and an electron mobility of 2.11 × 10^?4 cm² V^?1 s^?1. By blending Y5 with three types of common medium‐bandgap polymers (J61, PBDB‐T, and TTFQx‐T1) as donors, all devices exhibit high short‐circuit current densities over 20 mA cm^?2. As a result, the power conversion efficiency of the Y5‐based OSCs with J61, TTFQx‐T1, and PBDB‐T reaches 11.0%, 13.1%, and 14.1%, respectively. This indicates that Y5 is a universal and highly efficient n‐OS acceptor for applications in organic solar cells.     

Incorporation of benzothiadiazole moiety at junction of polyfluorene–polytriarylamime block copolymer for effective color tuning in organic light emitting diode

Block copolymer consisting of polyfluorene and polytriarylamine with benzothiadiazole moiety at the junction is prepared in order to obtain an orange emitting polymer via Suzuki‐Miyaura followed by Buchwald‐Hartwig coupling reactions. Electroluminescent device fabricated with resulting block copolymer exhibit only orange emission, although slight blue emission is observed in the fluorescent spectrum for the thin film, indicating that benzothiadiazole part plays a role of an effective trap site. Devices based on polyfluorene homopolymer doped with block copolymer (10 wt %) or an orange emitting model compound at the corresponding content of benzotiadiazole unit are also fabricated. The device with the model compound exhibits orange emission with Commission Internationale de l'Éclairage (CIE) coordinate of (0.58, 0.42), whereas that with block copolymer pale orange with the coordinate of (0.44, 0.38). This fact is probably due to the preferential distribution of block copolymer at the vicinity of anode via hydrophilic interaction of trioxyethylene side chains with poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate). © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45393.     

采后苯并噻重氮处理对‘玉金香’甜瓜氨基酸代谢酯类香气物质及其代谢机理的影响

以‘玉金香’甜瓜为材料,采后常温贮藏期间分析其氨基酸含量、谷丙转氨酶（glutamate pyruvic transaminase,GPT）、谷草转氨酶（glutamic oxaloacetic transaminase,GOT）、丙酮酸脱羧酶（pyruvate decarboxylase,PDC）、丙酮酸脱氢酶（pyruvate dehydrogenase,PDH）活力及其代谢产物酯类香气物质含量的 变化,探讨采后苯并噻重氮（benzothiadiazole,BTH）诱抗处理对酯类香气物质氨基酸代谢途径影响的机理。结 果表明：BTH诱抗处理可延迟样品酯类香气物质释放高峰出现,抑制其释放,总含量比CK组（未经任何处理） 低19.10%。15 种游离氨基酸被分离确定,CK组氨基酸总含量峰值（14 597 μg/g）出现在第6天,BTH组峰值出现 在第8天,低于CK组9.47%（P＜0.05）。BTH处理抑制了贮藏期间GOT、PDC和PDH活力,与CK组相比,BTH处 理组果皮GOT、PDC和PDH活力峰值分别降低31.80%、16.86%和24.30%,果肉峰值分别降低19.10%、14.70%和 25.56%,果皮GOT活力被显著抑制（P＜0.05）;不同处理组间GPT活力差异不显著（P＞0.05）。氨基酸总含量、 GOT活力与酯类香气物质含量呈极显著正相关（P＜0.01）。水处理对氨基酸含量、代谢酶活力及其产物酯类香气 物质释放均有影响,但无明显作用规律。由此可见,BTH处理会减少氨基酸含量,抑制相关代谢酶活力,进而改变 其产物酯类香气物质的释放。     

采后苯并噻重氮处理对厚皮甜瓜细胞膜磷脂代谢的影响

磷脂是细胞膜的重要组分,磷脂代谢直接影响细胞膜的稳定性,进而影响植物的生长、衰老和次生产物代 谢。诱抗剂苯并噻重氮（benzothiadiazole,BTH）可提高甜瓜（Cucumis melo L.）采后抗病性、延缓果实衰老、影 响果实次生代谢产物香气物质的释放。本研究以‘玉金香’甜瓜为实验材料,于采后贮藏期间分析样品果实中磷脂 酰胆碱（phosphatidyl cholines,PC）、磷脂酰肌醇（phosphatidylinositol,PI）和磷脂酸（phosphatidic acid,PA） 含量以及磷脂酶A2（phospholipase A2,PLA2）、磷脂酶C（phospholipase C,PLC）和磷脂酶D（phospholipase D, PLD）活力和相关基因表达水平,探讨采后BTH处理调控厚皮甜瓜磷脂代谢的机理。结果表明：BTH处理可抑制 厚皮甜瓜采后贮藏期间磷脂酶基因的表达和活力,果皮样磷脂酶活力峰值分别较CK组低7.11%（PLA2）、10.24% （PLC）和7.20%（PLD）;BTH处理组膜磷脂组分PC、PI的积累量较CK组增加,贮藏结束时果皮样峰值比CK组 高5.24%（PC）和2.08%（PI）,BTH处理组磷脂代谢产物PA的含量较CK组、CC组降低,贮藏结束时,BTH处理 组比CK组低20.72%（果皮）和8.51%（果肉）;BTH对不饱和脂肪酸的抑制率低于饱和脂肪酸。可见,采后BTH处 理可通过抑制PLC、PLD基因相对表达降低其活力,进而减少产物脂肪酸生成,改变脂肪酸不饱和度,然后影响细 胞膜代谢过程中的信号传导和次生代谢产物生成,降低甜瓜果实的采后病害。     

采前苯丙噻重氮喷洒抑制采后双孢菇的软化

目的：研究采前苯丙噻重氮（benzothiadiazole,BTH）喷洒对采后低温贮藏期间双孢菇软化的影响并探讨相关机理。方法：用200 mg/L BTH在原基期（双孢菇菌盖为针头大小时）对‘A15’双孢菇进行喷洒（以自来水喷洒作对照）,测定低温（4 ℃）贮藏期间双孢菇的质地、质量损失率,并分析几丁质、纤维素、总蛋白含量及相关酶活力。结果：与对照相比,采前BTH喷洒能显著降低冷藏期间双孢菇的质量损失率（第8天时比对照组低34.22%）（P＜0.05）;显著提高采收时以及冷藏期间双孢菇的硬度、弹性、咀嚼性和胶着性（P＜0.05）;显著降低采收时和冷藏期间双孢菇的几丁质酶和纤维素酶活力（P＜0.05）,显著提高几丁质和纤维素含量（P＜0.05）;显著降低采收时和冷藏期间双孢菇的中性、碱性和酸性蛋白酶活力（P＜0.05）,延缓蛋白质的降解。相关性分析表明,双孢菇硬度、弹性、咀嚼性、胶着性与几丁质、纤维素、总蛋白含量呈极显著正相关（P＜0.01）,与质量损失率呈极显著负相关（P＜0.01）。结论：采前BTH喷洒可显著延缓双孢菇冷藏期间的软化,其作用机制与抑制双孢菇细胞壁降解酶的活性、减少采后质量损失率密切相关。     

6-羧基-1,2,3-苯并噻二唑的合成研究

合成了用于诱导植物系统获得抗性的化合物 6 羧基 1,2 ,3 苯并噻二唑 ,其合成步骤如下 :以对氨基苯甲酸 (I)为原料 ,用乙酰酐作为乙酰化试剂 ,在加热回流下反应 4h ,将化合物I的氨基进行保护 ,得对 乙酰氨基苯甲酸 (Ⅱ )。将化合物Ⅱ在 12～ 15℃下缓慢加入到氯磺酸中去进行氯磺化反应 .氯磺酸对化合物Ⅱ的量比为n(氯磺酸 )∶n(对 乙酰氨基苯甲酸 ) =4∶1,反应温度维持在 6 0℃ ,得化合物 2 乙酰氨基 5 羧基苯磺酰氯 (Ⅲ )。以锌粉加醋酸作为还原剂 ,在 70℃下搅拌回流 6h ,将化合物Ⅲ还原为 3 巯基 4 氨基 -苯甲酸 (Ⅳ )。将化合物Ⅳ在 0～ 5℃下用亚硝酸钠加冰醋酸去进行重氮化反应 ,然后用乙醚萃取 ,蒸去溶剂后得红棕色固体产物 6 羧基 1,2 ,3 苯并噻二唑 (V) ,产率 43 %