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 %     

苯并噻二唑类和苯并噻唑类化合物的合成及生物活性

合成了33个苯并噻唑和苯并噻二唑类化合物，所有新化合物经过元素分析、^1H NMR和IR确认，初步的离体生物活性结果表明：I-09、II-01、II-05、II-06、III-01、III-03和III-05的活性较好，对黄瓜灰霉病菌具有良好的抑制作用。活体抗菌诱导生物活性测定结果表明：I-04、I-07、II-09、II-13、III-02、III-071000mg／L在离体条件下对黄瓜灰霉病没有抑制作用，在活体条件下有一定的抑制作用，抑制率在55．0％-84．4％，表明具有良好的诱导抗性活性。     

Melatonin content in grape: myth or panacea?

Melatonin (N‐acetyl‐5‐methoxytryptamine) was detected by a modified HPLC method and ELISA tests in extracts of eight different Vitis vinifera cultivars, namely Nebbiolo, Croatina, Sangiovese, Merlot, Marzemino, Cabernet Franc, Cabernet Sauvignon and Barbera. Its concentration varied greatly among the cultivars, being the highest in Nebbiolo (0.965 ng g^?1) and Croatina (0. 870 ng g^?1). Field treatments of grapevine with the plant defence activator benzothiadiazole, greatly improved the melatonin content in berry skin extracts, indicating a possible strategy to raise the content of this important pharmaconutrient in plants, while inducing resistance to pathogens. The finding of this compound in grape suggests that the well‐established pharmaconutritional properties of this fruit are due not only to the presence of polyphenolic nutraceuticals, such as resveratrol, anthocyanins and proanthocyanidins, but also to the powerful antioxidant activity of melatonin. Copyright © 2006 Society of Chemical Industry     

聚(苯撑乙炔-苯并噻二唑)共聚物光伏器件性能

分别制备了ITO/PEDOT-PSS/C8-PPE-BT PCBM(1/4,w/w)/Ba/Al、ITO/PEDOT-PSS/C8-PPE-BT MEH-PPV(1/1,w/w)/Ba/Al两种本体异质结光伏器件,发现这两种器件均表现出光伏效应.其中PPE-BT PCBM器件表现出较高的能量转换效率达到0.084%,EQE为2.7%,比单层C8-PPE-BT器件的EQE提高了23倍.但当C8-PPE-BT与给体MEH-PPV构成器件时,其能量转换效率较差,分别为3.67×10-3%和2.54×10-3%.说明电子在C8-PPE-BT中的迁移率较小,尽管存在光诱导的电荷转移,但在未到达电极就被捕获.     

苯并噻二唑处理对柑橘果实采后病害控制效果及机制分析

以‘丰脐’柑橘果实为试材,研究了不同浓度苯并噻二唑（benzothiadiazole,BTH）和青霉菌 （Penicillium italicum）、绿霉菌（Penicillium digitatum）、炭疽菌（Colletotrichum gloeosporides）同孔、异孔接 种对柑橘果实青霉病、绿霉病、炭疽病的控制效果,筛选出针对这3 种病害控制效果最适宜的BTH浓度,在此浓 度下考察打孔和浸泡处理对果实果皮内源水杨酸含量和抗病性相关酶活力的影响。实验结果表明：0.25、0.50、 1.00 mmol/L 3 种浓度的BTH与P. italicum、P. digitatum、C. gloeosporioides同孔或异孔接种均可以降低果实青霉病、 绿霉病、炭疽病的病斑直径,其中,0.50 mmol/L的BTH效果最好;在病害发病率方面,3 种浓度的BTH处理均在果 实发病初期有效果,后期效果不显著,相比之下,0.50 mmol/L的BTH效果较好。最适浓度下,通过对果实果皮内源 水杨酸含量和抗病性相关酶活力的研究发现,BTH损伤接种能增加果皮内源水杨酸的含量,BTH浸泡处理对果皮内源 游离态水杨酸含量无显著影响,但能促进果皮内源结合态水杨酸含量的积累;BTH损伤接种和浸泡处理均能增加柑橘 果皮β-1,3葡聚糖酶、几丁质酶、苯丙氨酸解氨酶、过氧化物酶和多酚氧化酶的活力。由此推测,BTH处理诱导柑橘果 实提高了其采后抗病性。     

基于三苯胺的D-A-π-A-D型化合物的合成及光物理性能

以甲氧基三苯胺为电子供体,苯并噻二唑为电子受体,咔唑为共轭π桥,通过三步Suzuki偶联反应合成了D-A-π-A-D型荧光化合物4,4′-[(7,7′-9 H-咔唑-2,7-)-二(苯并噻二唑-7,4-)]-二(N,N-二(4-甲氧基苯基))苯胺(DTB-CZ),并用1HNMR、¹³CNMR、MALDI-TOF等手段对其结构进行表征。研究了它的光谱性能、电化学性能、轨道能级和热性能,并与D-π-D型化合物2TPA-CZ1的性能进行了比较。初步探索了DTB-CZ作为空穴传输材料在PSC中的应用。研究结果表明,DTB-CZ在甲苯溶液中的最大吸收波长为479 nm,最大发射波长为608 nm,在薄膜状态下最大吸收波长为495 nm,HOMO/LUMO能级为-4.91/-2.82 eV,带隙值为2.09 eV,热分解温度(T_5d)为449.6℃,玻璃化转变温度(T_g)为143.1℃。相比2TPA-CZ1,在甲苯溶液中吸收和发射波长分别红移了104、182 nm,在薄膜状态下吸收波长红移109 nm;带隙值降低0.84 eV;T 5d和T g分别提高了9.6、24.7℃。结果表明,苯并噻二唑的引入,使化合物的共轭程度增大,带隙值降低,使得吸收和发射波长红移,使其具有更好的热稳定性和形态稳定性。     

高效液相色谱法测定4,7-双（5-溴-4-已基噻吩-2-基）-2,1,3-苯并噻二唑

采用反相C18柱,流动相四氢呋喃-甲醇-水（体积比70∶12∶18）,320 nm作为检测波长。建立了4,7-双（5-溴-4-已基噻吩-2-基）-2,1,3-苯并噻二唑的反相高效液相色谱法检测方法。结果表明,方法精密度RSD为1.13%（n=9）,检出限0.003 mg/L,线性范围0.9～45 mg/L,线性相关系数为0.997 1。该方法简便、准确、重现性好,为此类苯并噻二唑中间体材料建立了一种有效的检测方法。     

苯并[1,2,3]噻二唑-7-醛的合成

以2-氯-3,5-二硝基苯甲酸为起始原料,经过取代、酯化、还原重氮化等反应,合成了苯并[1,2,3]噻二唑-7-羧酸乙酯。并采用二异丁基氢化铝将其一步还原制备了苯并[1,2,3]噻二唑-7-醛。     

Pure and Saturated Red Electroluminescent Polyfluorenes with Dopant/Host System and PLED Efficiency/Color Purity Trade‐Offs

Three kinds of red electroluminescent (EL) polymers based on polyfluorene as blue host and 2,1,3‐benzothiadiazole derivatives with different emission wavelengths as red dopant units on the side chain are designed and synthesized. The influence of the photoluminescence (PL) efficiencies and emission wavelengths of red dopants on the EL efficiencies and color purities of the resulting polyfluorene copolymers of dopant/host system is investigated by adjusting the electron donating ability of the donor units in D‐π‐A‐D typed 2,1,3‐benzothiadiazole derivatives. The devices of these red‐emitting polymers realize remarkable EL efficiency/color purity trade‐offs. The single‐layer devices with the configuration of ITO/PEDOT:PSS/Polymer/Ca/Al show pure red emission at 624 nm with a luminous efficiency of 3.83 cd A^?1 and CIE of (0.63, 0.35) for PFR1, saturated red emission at 636 nm with a luminous efficiency of 2.29 cd A^?1 and CIE of (0.64, 0.33) for PFR2, respectively. By introduction of an additional electron injection layer PF‐EP(Ethanol soluble phosphonate‐functionalized polyfluorene), high performance pure and saturated red emission two‐layer devices (ITO/PEDOT:PSS/Polymer/PF‐EP/LiF/Al) were achieved with maximum luminous efficiencies of 5.50 cd A^?1 and CIE of (0.62, 0.35) for PFR1, 3.10 cd A^?1 and CIE of (0.63, 0.33) for PFR2, respectively, which are the best results for pure and saturated fluorescent red EL polymers reported so far.     

Donor–acceptor–acceptor–donor small molecules for solution processed bulk heterojunction solar cells

We report on the optical and electrochemical characterization (experimental and theoretical) of two donor substituted benzothiadiazole with different cyano based acceptor π-linkers, tetracyanobutadiene (TCBD) SM1 and dicyanoquinomethane (DCNQ) SM2, and explore them as the donor component for solution processed bulk heterojunction organic solar cells, along with PC₇₁BM as the electron acceptor. The solution bulk heterojunction (BHJ) solar cells based on dichloromethane (DCM) processed active layer with SM1 and SM2 as donor and PC₇₁BM as acceptor achieve power conversion efficiency (PCE) of 2.76% and 3.61%, respectively. The solar cells based on these two small molecules exhibit good Voc, which is attributed to their deep HOMO energy level. The higher PCE of the device based on SM2 compared to SM1 is attributed to the its small bandgap, broader absorption profile and enhanced hole mobility. Additionally, the PCE of the SM2:PC₇₁BM based solar cells processed with 1-chloronaphthalene CN (3 v%)/DCM is further improved reaching upto 4.86%. This increase in PCE has been attributed to the improved nanoscale morphology and more balanced charge transport in the device, due to the solvent additive.