水中苯胺类化合物检测试验剂盒的研制与筛选

本文筛选并研制出三种检测水中苯胺类化合物的试剂盒:邻甲氧基苯酚试剂盒、8-羟基喹啉试剂盒和1-萘酚试剂盒。邻甲氧基苯酚、8-羟基喹啉和1-萘酚分别在pH 9.2、12.2、12.2的氢氧化钠介质中与苯胺形成黄色、橙色和橙色偶氮化合物,它们的最大吸收波长分别位于450、480和491nm处,显然反应的摩尔吸光系数分别为3.036、4.235和4.146×104L.m o-l 1.cm-1,线性范围分别为0-5.6、0-4.8和0-4.0m g/L,检出限分别为8.0、0.0和12μg/L。这三种试剂盒用于水中苯胺类化合物的测定更加方便、快速、灵敏,线性范围更宽。这三种试剂盒应用于环境水样的测定,均获得了满意的分析结果。     

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。     

非线性光学偶氮分子的合成和跃迁偶极矩的测定

以对硝基苯胺、苯胺、5 氨基嘧啶和N,N 二羟乙基苯胺为原料通过两步重氮化-偶合反应合成了两种给体-受体型非线性光学偶氮分子,用红外光谱、核磁共振、熔点、紫外光谱进行了表征,测定了分子的跃迁偶极矩,两个化合物的跃迁偶极矩分别为7 12D和8 76D,它们在不同极性溶剂中表现出明显的溶致变色效应,紫外吸收最大位移分别达到20nm和15nm。     

三苯胺-alt-4,7-二(3-己基噻吩)-[2,1,3]苯并噻二唑共聚物的合成及表征

通过Suzuki偶联聚合反应,合成了一类新型低带隙交替共聚物-三苯胺-alt-4,7-二(3-己基噻吩)-[2,1,3]苯并噻二唑 (PTPADHDBT).聚合物数均分子量Mn=9420,分散系数Mw/Mn=3.2.PTPADHDBT溶液的两个吸收峰分别位于355nm与514nm, 光学带隙为2.02eV.而聚合物薄膜的吸收峰分别位于356nm与523nm,与溶液中的吸收峰相比红移了9nm;聚合物溶液和薄膜的荧光发射峰分别为677nm和683nm,与溶液的发射峰相比,薄膜的荧光发射峰红移了6nm.     

甲氧基修饰平面化三苯胺电子给体的合成与性能研究

以2-氨基苯甲酸甲酯为原料，经过Ullmann反应、亲核加成等反应，合成了一种甲氧基修饰的平面化三苯胺电子给体CMo,通过¹H NMR确定结构的正确性。与常见电子给体三苯胺TPA、吲哚啉YD作对比，紫外吸收光谱显示，CMo的最大吸收波长为304 nm,相比YD(298 nm)和TPA(297 nm)发生了红移，且最大吸收峰随极性的增强变化率大，表明CMo可离域化程度很大，给电子能力更好；循环伏安测试表明，CMo的HOMO能级(-5.21 eV)和LUMO能级(-1.48 eV)都高于YD(-5.38 eV、-1.70 eV)和TPA(-5.53 eV、-1.79 eV),可以作为新的电子给体材料应用于有机光电器件中。     

树枝状咔唑基环金属铱配合物的合成及其性能

咔唑类似于三苯胺玻璃化温度高,具有很高的空穴迁移率,是目前最常用的空穴传输材料和主体材料。基于此,通过醚化反应、环金属化反应、去桥联反应合成得到了一种含树枝状咔唑的2-吡啶甲酸类辅助配体及其环金属铱配合物,通过1H NMR表征了中间体及目标化合物的分子结构,研究了环金属铱配合物的溶液及固体膜状态下的紫外吸收和光致发光性能,获得了一类最大发光波长为471 nm的树枝状蓝色电致磷光材料。     

2,5-双〔4-(N,N-二苯基)氨基苯基〕吡啶的合成及光谱性质

三芳胺是传统的空穴传输材料,该文将其引入磷光配体2-苯基吡啶中,得到一种具有双重性质的磷光配体2,5-双〔4-(N,N-二苯基)氨基苯基〕吡啶,并通过元素分析,核磁共振氢谱对其结构进行了确认。通过比较其与另外两种磷光配体在二氯甲烷中的紫外吸收光谱和光致发光光谱表明,由于二苯胺这样一个强供电子性基团的引入,增强了π电子的离域范围,降低了这种磷光配体的HOMO轨道和LUMO轨道之间的能壑,使其最大吸收峰波长红移99 nm,最大发射峰波长红移48 nm,且吸收和发射的强度增加,Stokes位移为72 nm。     

基于不对称螺二芴芳胺类蓝光发光材料的合成与性能研究

螺二芴衍生物作为蓝光发光材料被广泛应用于有机发光半导体（OLED）器件。以螺二芴为母体,在2,7位分别引入具有空穴迁移率高的二苯胺和三苯胺基团,设计合成了不对称的螺二芴芳胺类发光材料7-(4-(二苯胺)苯基)-N,N-二苯-9,9’-螺二芴-2-胺。研究表明,该化合物具有较高的热稳定性,其荧光发射波长为445nm,位于蓝光区域。同时具有高度扭曲的分子结构,有利于抑制分子间相互作用和自聚集,有效抑制非辐射,可应用于构建高效的有机蓝光发光材料。     

三波长吸收光谱法测定药物中的氨曲南

在酸性Tris-HCl介质中,氨曲南与甲基绿反应生成具有3个正吸收峰的绿色二元离子缔合物,最大正吸收峰位于661 nm,其他2个吸收峰分别位于565 nm和420 nm,在此三波长处,氨曲南的质量浓度在0～11. 0 mg/L范围内服从朗伯-比尔定律,表观摩尔吸光系数(κ)分别为1. 25×104(420 nm)、1. 91×104(565 nm)、2. 33×104L/(mol·cm)(661 nm),当用双波长叠加法或三波长叠加法测定时,其表观摩尔吸光系数(κ)可达4. 24×104L/(mol·cm)(565 nm+661 nm)和5. 49×104L/(mol·cm)(420 nm+565 nm+661 nm)。由此建立了测定氨曲南的单波长(SWO-VIS)、双波长(DWO-VIS)和三波长(TWO-VIS)吸收光谱法;还探讨了吸收光谱特征、显色反应条件及共存物质的影响。将TWO-VIS法用于氨曲南实际药品的测定,回收率为97. 7%～103%,相对标准偏差RSD(n=5)为2. 1%～2. 7%。     

碱性高锰酸钾三波长分光光度法测定维生素B6的含量

基于在氢氧化钠介质中高锰酸钾与维生素B₆可发生氧化还原反应产生绿色的锰酸钾,显色产物最大吸收波长分别位于420 nm和600 nm,同时使高锰酸钾褪色,褪色波长位于525 nm,提出了高锰酸钾三波长可见分光光度测定维生素B₆含量的新方法。在以上三波长下,维生素B₆浓度的线性范围分别为2～14 mg·L^-1、2～14 mg·L^-1和2～18 mg·L^-1。本研究所拟方法成功地测定了维生素B₆原料药、片剂和注射液的含量,结果与紫外光度法所测一致。     

The synthesis and photophysical properties of novel triphenylamine derivatives containing α, β-diarylacrylonitrile

α, β-Diarylacrylonitrile halides were prepared by condensation of appropriate arylaldehydes and arylacetonitrile halides using a catalytic amount of NaOCH₃ at room temperature. The diarylamines were reacted with various α, β-diarylacrylonitrile halides to afford several triphenylamine compounds, which displayed efficient hole transportation in the presence of Pd(OAc)₂/P(o-tolyl)₃ catalyst, thereby constituting organic light emitting device materials. The novel triphenylamine derivatives were characterized using FTIR, ¹H NMR, ¹³C NMR, MS and elemental analysis. The UV–vis absorption and photoluminescence spectra of the compounds were investigated. The lowest absorption band of α, β-diarylacrylonitrile-containing, triphenylamine derivatives, which occurred at ～400 nm, was assigned to charge-transfer transitions with an emission at 500–574 nm in different solutions and in the solid state.     

The synthesis and two-photon excited fluorescence properties of novel branched fluorene derivatives

Two novel, V-shaped fluorene derivatives branched from triphenylamine and their linear analogue were synthesized via Cu-mediated Ullmann condensation and subsequent Pd-catalyzed Heck coupling reaction. Their two-photon excited fluorescence properties as well as their linear absorption and single-photon excited fluorescence properties were examined. When excited at 730 nm by a Ti:sapphire femtosecond laser, the compounds exhibited strong two-photon excited blue fluorescence. The two-photon excited fluorescence cross-sections of V-shaped derivatives in toluene at 730 nm were ∼506 GM in the case of N, N-bis{7-[4′-(N, N-diphenylamino)styryl]-9,9-diethyl-9H-fluorene-2-yl}-aniline) and 397 GM for N, N-Bis{7-[4′-(N, N-diphenylamino)styryl]-9,9-diethyl-9H-fluorene-2-yl}-4-acetyl-aniline), respectively.     

The synthesis and two-photon excited fluorescence properties of novel branched fluorene derivatives

Two novel, V-shaped fluorene derivatives branched from triphenylamine and their linear analogue were synthesized via Cu-mediated Ullmann condensation and subsequent Pd-catalyzed Heck coupling reaction. Their two-photon excited fluorescence properties as well as their linear absorption and single-photon excited fluorescence properties were examined. When excited at 730 nm by a Ti:sapphire femtosecond laser, the compounds exhibited strong two-photon excited blue fluorescence. The two-photon excited fluorescence cross-sections of V-shaped derivatives in toluene at 730 nm were 506 GM in the case of N, N-bis{7-[4′-(N, N-diphenylamino)styryl]-9,9-diethyl-9H-fluorene-2-yl}-aniline) and 397 GM for N, N-Bis{7-[4′-(N, N-diphenylamino)styryl]-9,9-diethyl-9H-fluorene-2-yl}-4-acetyl-aniline), respectively.     

Two-photon absorption properties of hyperbranched conjugated polymers with triphenylamine as the core

Two new hyperbranched phenylene vinylenes (HPVs) with triphenylamine as the core, 2,5-dihexyloxyl substituted phenylene vinylene as the connecting unit, and electron-donating triphenylamine or electron-deficient nitrobenzene as the different terminal groups were synthesized by modified Wittig polymerization reaction. Their one- and two-photon absorption (TPA) properties have been investigated. The two-photon absorption cross sections of the two polymers were performed by open-aperture Z-scan experiment using 120 femtosecond (fs) pulse, and their TPA cross section were determined to be 1.43 and 0.64×10⁻²⁰ cm⁴/GW per repeating unit at 800 nm, respectively. In chloroform, HPVs exhibit intense frequency up-converted fluorescence under the excitation of 120 fs pulses at 800 nm with the peaks located at 544 and 554 nm, respectively.     

Synthesis, optical and electrochemical properties of new hyperbranched poly(triphenylamine amide)s

A new triphenylamine-containing AB₂ type monomer with one carboxylic acid and two amino groups, 4-(bis(4-aminophenyl)amino)benzoic acid (3), was synthesized and used for the preparation of hyperbranched poly(triphenylamine amide)s. The self-polycondensation of the AB₂ monomer (3) afforded hyperbranched poly(triphenylamine amide) with amino end groups. The molecular weight of the hyperbranched poly(triphenylamine amide) was 21,000 Da determined by light scattering. End-capped hyperbranched polyamides were isolated by the chemical modification of unreacted amino groups with various acid chlorides. All the hyperbranched poly(triphenylamine amide)s exhibit excellent solubility in organic solvents such as NMP, DMF, DMSO, and DMAc at room temperature. The viscosities of hyperbranched poly(triphenylamine amide)s are as low as about 0.15 dL/g due to their dendritic structures. Poly(triphenylamine amide)s end-capped with rigid benzene ring have higher thermal stability than those with amino or aliphatic end groups. The photoluminescence of the hyperbranched polyamides is blue-yellow emissions around 430-510 nm. The energy gaps of the hyperbranched poly(triphenylamine amide)s with different end groups are about 2.93 eV and are independent on the end groups, but the HOMO and LUMO energy levels are dependent on the end groups.     

Radical cation of octaisopropylcyclotetragermane generated by pulse radiolysis

The radical cation of octaisopropylcyclotetragermane, (ⁱPr₂Ge)₄, generated by the pulse radiolysis technique showed two transient absorption bands at 305 and 435 nm. These transient peaks were quenched with diphenylamine and triphenylamine as radical cation scavengers.     

Hole transport triphenylamine-spirosilabifluorene alternating copolymer: synthesis and optical, electrochemical and electroluminescent properties

A new copolymer, constituted by the regular alternation of a spirosilabifluorene with a triphenylamine moiety, P(TPA-SSBF), has been synthesized via Suzuki coupling reaction. The molecular, thermal, optical, electrochemical and electroluminescent properties have been characterized. The introduction of a spiro-structure in P(TPA-SSBF) leads to its high thermal stability and good solubility in common organic solvents. The alternating copolymer shows only an absorption peak of 342 nm, demonstrating that triphenylamine is significantly conjugated with fluorene rings in the polymer. P(TPA-SSBF) in chloroform solution and in solid state film exhibits blue emission peak at 423, 435 nm respectively. The electrochemical behaviors of the polymer were investigated by cyclic voltammetry. The reversible electrochemical oxidation and low ionization potential (5.47 eV) suggest that P(TPA-SSBF) might have potential application as hole transport material in polymer LEDs. The hole transport ability of P(TPA-SSBF) was verified by comparing the performance of the two types LED devices fabricated in this study.     

基于1,8-萘酰亚胺延迟荧光材料的合成及性能研究

通过Suzuki交叉偶联反应得到三苯胺和N-苯基咔唑分别取代的1,8-萘酰亚胺衍生物,化合物结构经1HNMR、质谱和元素分析表征。两种材料都是双极分子,存在分子内电荷转移,单线态-三线态能级差分别为0.40和0.32 eV。荧光量子效率和荧光寿命的测试结果表明,两种材料均能发射延迟荧光。     

The synthesis and characterization of novel dipolar fluorescent materials based on a quinoxaline core

A series of dipolar quinoxaline derivatives with quinoxaline as core which carry pendant carbazole or triphenylamine moieties were synthesized and fully characterized. As expected, the compounds display bipolar character and can be explored as potential emissive and electron-transport materials as organic light-emitting diodes. Fluorescence spectra showed that the compounds exhibit excellent blue-green fluorescence.     

一种Hg~(2+)离子荧光探针的合成及荧光性质

以喹啉为原料,通过氧化、脱水、合环和还原作用合成了中间体5,10-二羟基苯并喹啉-6,9-二酮,后者再与氨基硫脲缩合合成终产物6-氧代-5,10-二羟基苯并喹啉-9-酮缩氨基硫脲。经1 H-NMR对产物进行结构表征,研究了终产物紫外吸收光谱、荧光光谱及其与各种离子配合后的光谱变化,结果表明其能与Hg2+选择性配位,确定其最大发射波长为534nm,Stokes位移为138nm。