含双吸电子基团的三苯胺染料在太阳电池中的应用

合成了两种具有不同共轭链长度的双吸电子基团的三苯胺类染料TPAR3和TPAR6, 研究了它们的光物理与光电化学性质, 并将它们用作TiO2纳米晶电极的光敏化剂引入太阳电池. 结果表明, 与含有乙烯基共轭桥的染料TPAR3相比, 含有丁二烯基共轭桥的染料TPAR6在甲醇溶液和TiO2膜上的最大吸收均发生一定程度的红移和宽化; 但TPAR6表现出比TPAR3差的光电性能, 主要是因为前者更易发生顺反异构化, 电子不能够顺利地从染料激发态注入到TiO2导带中, 光电流的产生得到抑制. 考察了基于TPAR3的太阳电池在电解液中加入不同浓度的硫氰酸胍(GT)对光电性能的影响, 发现在GT浓度为0.100 mol·L-1时效率达到最大(4.02%).     

三苯胺甲醛二苯腙的合成及其光电性能研究

合成了一种新型的三苯胺类载流子传输材料三苯胺甲苯二苯腙,通过一系列手段对该化合物性能进行了表征,并以此化合物为载流子空穴传输材料,Y-型酞菁氧钛为载流子产生材料制备了光导器件,测定了该光电器件的光电性能,显示出良好的光电性能(E_1/2=1.0lx.s),可以替代常用的载流子传输材料二乙基苯甲醛二苯腙.     

含三苯胺单元的共轭聚合物的合成、表征及应用

采用 Wittig 方法制得了未封端及封端的线性聚三苯胺-对苯乙烯撑型聚合物(分别简称为:TPA-DOPPV1,TPA-DOPPV2),并对共轭聚合物进行了表征和性能测试.封端后的聚合物溶液和固体膜在紫外光照射下均发出较强的绿光.对这类聚合物在硝基化合物检测方面的应用进行了初步研究,结果表明:封端后的共轭聚合物在邻硝基甲苯(o-NT)荧光检测上的性能明显提高,当o-NT 浓度为 21.5×10-3 mol/L 时,荧光猝灭效果达到了 96%;在2,4-二硝基甲苯(DNT)、对硝基甲苯(P-NT)和对苯醌(p-BQ)蒸汽中放置 10 s 时,其薄膜的荧光猝灭效率分别达到 30%、15.6%和 3.1%.TPA-DOPPV2 的合成操作较为简便,具有一定的检测灵敏性,是一种潜在的硝基类爆炸物荧光检测材料.     

磺酸盐取代三苯胺类共轭聚电解质的合成及应用研究

通过水相Suzuki偶合反应合成了两种磺酸盐基团取代的三苯胺类共轭聚电解质PTP11和PTP31,对其化学结构进行了表征.通过对其光学和电化学性能进行测试得知,此类聚合物具有和ITO功函数相近的HOMO能级及较高的LUMO能级.磺酸盐基团的存在使得此类聚电解质具有和电中性聚合物所不同的溶解性,当其作为空穴传输材料应用于多层结构的聚合物电致发光器件(PLED)中时,可有效避免空穴传输层-发光层之间的界面混溶问题.以这两种聚合物作为空穴传输材料应用于以PFO-DBT15为发光层的红光PLEDs中时,器件的性能得到了显著提高.此外,磺酸盐基团的不同取代方式会对器件的性能产生一定的影响.     

含三苯胺结构癈聚酰亚胺的合成及光电转换性能研究

通过缩聚方法合成了主链含三苯胺结构的苝聚酰亚胺，将其负载在纳米二氧化钛膜上，光电转换性能测定结果表明，含三苯胺结构苝聚酰亚胺具有良好的光电转换特性，其光电流比不含三苯胺结构的苝聚酰亚胺大11倍。     

三苯胺亚胺类化合物的合成

以三苯胺为起始原料,经硝化、还原和胺醛缩合反应合成了4个三苯胺亚胺类化合物,其结构经1H NMR和IR确证。     

3,5-二氯-2,4,6-三硝基苯胺及其衍生物的合成

分别以3,5-二氯苯胺为原料,经N保护、硝化、水解以及以1,3,5-三氯-2,4,6-三硝基苯(TCTNB)为原料,经叔丁胺化,再在三氟乙酸中脱叔丁基2种方法合成了3,5-二氯-2,4,6-三硝基苯胺。 与甲胺反应,合成了3,5-二甲氨基-2,4,6-三硝基苯胺,收率85%,再用混酸硝化合成了3,5-二甲硝胺基-2,4,6-三硝基苯胺的硝酸盐,收率70%。 采用核磁共振、质谱、红外和元素分析等进行了结构表征。 探讨了不同参数下TCTNB的氨化结果。 优化的条件为：n(TCTNB)∶n(叔丁胺)=1∶2,CuO为催化剂,KHCO3为碱。     

卟啉多孔化合物的合成及其在光电免疫传感器中的应用

构建了以卟啉多孔化合物-金纳米颗粒(Au NPs@PAF)为固定基质的无标记型C-反应蛋白(CRP)光电免疫传感器。在最优条件下,采用计时电流法实现了对CRP的定量检测。该传感器在CRP质量浓度0.05～60 ng/mL范围内与光电流有较好的线性关系,检出限为0.017 ng/mL,相关系数为0.994 6,平均回收率为102%,具有良好的选择性,为C-反应蛋白的检测提供了一种灵敏的方法。     

功能高分子材料载体在检测诊断中的应用

综述了作为生物活性分子载体用功能高分子材料（生物传感器、胶乳、磁性粒子、凝胶）的合成、特点及其在检测诊断中的应用。     

两个以杂环为共轭桥、含三苯胺基团化合物的合成及其发光性能

我们成功地合成了两种以杂环为共轭桥、含三苯胺基团的“D-π-D”型小分子, 初步研究结果表明：它们可以作为有机发光材料得到实际的应用。     

Synthesis and Properties of Novel Luminescent Compounds Containing Triphenylamine and Bipyridine Units

Blue luminescent compounds T1-T4 containing triphenylamine donors,bipyridine acceptors and olefinic linkers were synthesized and characterized by 1H NMR,13C NMR and high resolution mass spectrometry(HR...     

Synthesis and Characterization of Newly Designed and Highly Solvatochromic Double Squaraine Dye for Sensitive and Selective Recognition towards Cu2+

Synthesis and characterization of a novel and zwitterionic double squaraine dye (DSQ) with a unique D-A-A-D structure is being reported. Contrary to the conventional mono and bis-squaraine dyes with D-A-D and D-A-D-A molecular frameworks reported so far, DSQ dye demonstrated strong solvatochromism allowing for the multiple ion sensing using a single probe by judicious selection of the suitable solvent system. The DSQ dye exhibited a large solvatochromic shift of about 200 nm with color changes from the visible to NIR region with metal ion sensitivity. Utilization of a binary solvent consisted of dimethylformamide and acetonitrile (1:99, v/v), highly selective detection of Cu²⁺ ions with the linearity range from 50 μM to 1 nM and a detection limit of 6.5 × 10⁻¹⁰ M has been successfully demonstrated. Results of the Benesi–Hildebrand and Jobs plot analysis revealed that DSQ and Cu²⁺ ions interact in the 2:1 molecular stoichiometry with appreciably good association constant of 2.32 × 10⁴ M⁻¹. Considering the allowed limit of Cu²⁺ ions intake by human body as recommended by WHO to be 30 μM, the proposed dye can be conveniently used for the simple and naked eye colorimetric monitoring of the drinking water quality.     

基于催化发卡自组装和 Ru(NH3)63+ 的核酸光电化学灵敏分析

基于催化发卡自组装反应（CHA）和电活性材料[Ru(NH₃)₆]Cl₃,发展了一种“信号增强”型光电化学生物传感器,实现了核酸的灵敏检测. 首先,采用逐层离子吸附法（SILAR）将CdS 固定于TiO₂/ITO 电极表面. 光电材料CdS 不仅能够将TiO₂ 的吸收范围从紫外光区拓展到可见光区,而且还能提高光电转换效率. 之后,通过Cd-S 键将捕获DNA（C-DNA）固定于CdS/ TiO₂/ITO 电极表面. 与此同时,将Au 结合的发卡DNA 探针1（Au-HP1）,发卡DNA 探针2（HP2）和目标DNA（T-DNA）混合物于溶液中进行CHA 反应,得到大量的Au-HP1:HP2 复合物. 再通过Au-HP1:HP2 复合物与C-DNA 的杂交反应将大量的双链DNA 引入到电极表面. 最后,将电活性物质Ru(NH₃)₆³⁺嵌入DNA 的磷酸骨架中,从而使得光电流大幅度的增强. 该光电生物传感器检测核酸的线性范围为10 fmol·L^-1 到 1500 fmol·L^-1,检测线为6.19 fmol·L^-1,在生物分析、新药筛选以及疾病的早期诊断等方面具有潜在的应用前景.     

A Novel Molecularly Imprinted Photoelectrochemical Sensor Based on g‐C3N4‐AuNPs for the Highly Sensitive and Selective Detection of Triclosan

A novel molecularly imprinted polymer (MIP) photoelectrochemical sensor was fabricated for the highly sensitive and selective detection of triclosan. The MIP photoelectrochemical sensor was fabricated using graphite‐like carbon nitride (g‐C₃N₄) and gold nanoparticles (AuNPs) as photoelectric materials. The MIP/g‐C₃N₄‐AuNPs sensor used photocurrent as the detection signal and was triggered by ultraviolet light (UV‐Light 365 nm). g‐C₃N₄‐AuNPs was immobilized on indium tin oxide electrodes to produce the photoelectrochemically responsive electrode of the MIP/g‐C₃N₄‐AuNPs sensor. A MIP layer of poly‐o‐phenylenediamine was electropolymerized on the g‐C₃N₄‐AuNPs‐modified electrode to act as the recognition element of the MIP/g‐C₃N₄‐AuNPs sensor and to enable the selective adsorption of triclosan to the sensor through specific binding. Under optimal experimental conditions, the designed MIP/g‐C₃N₄‐AuNPs sensor presented high sensitivity for triclosan with a linear range of 2×10⁻¹² to 8×10⁻¹⁰ M and a limit of detection of 6.01×10⁻¹³ M. Moreover, the MIP/g‐C₃N₄‐AuNPs sensor showed excellent selectivity. The sensor had been successfully applied in the analysis of toothpaste samples.     

Electrochemical and Photoelectrochemical Sensing of NADH and Ethanol Based on Immobilization of Electrogenerated Chlorpromazine Sulfoxide onto Graphene‐CdS Quantum Dot/Ionic Liquid Nanocomposite

Here, a simple one‐step solvothermal procedure was employed to synthesize a nanocomposite containing graphene‐nanosheets and CdS quantum dots (GNs‐CdS QDs). The electrochemical oxidation of chlorpromazine (CPZ) to chlorpromazine‐sulfoxide (CPZ‐SO) onto a GNs‐CdS QDs/ionic liquid (IL) nanocomposite modified glassy carbon (GC) electrode give rise to redox‐active products which showed excellent electrocatalytic and photoelectrocatalytic activity toward NADH oxidation at reduced overpotential. A linear response up to 200 µM was obtained for photoamperometric determination of NADH with detection limit 1 µM. Immobilizing alcohol dehydrogenase(ADH) onto the modified electrode via a simple cross linking procedure, the photoelectrochemical capability of the proposed system toward ethanol biosensing was clearly shown.     

Ru(Ⅱ) Bipyridyl Complex and TiO2 Nanocomposite Based Biomolecule-free Photoelectrochemical Sensor for Highly Selective Determination of Ultra-trace Hg^2+ in Aqueous Systems

A biomolecule-free photoelectrochemical(PEC) probe(denoted as Ru-1) was designed, synthesized and coupled with TiO2 nanoparticles(NPs) for the highly sensitive and selective PEC detection of Hg^2+, a model analyte with hypertoxicity to both human health and ecosystem. The probe Ru-1 was designed with Ru(Ⅱ) bipyridyl complex as the chromophore, thiocyanate ligand as the recognition unit, and carboxylate group as the linkage site to connect Ru-1 to TiO2 nanoparticles. Under irradiation, Ru-1 shows strong affinity to TiO2 and good photophysical properties of strong visible light absorption, slow electron-hole(e-h^+) recombination, and fast photoelectron injection to TiO2 nanoparticles via the bridge of 4-(2,2-bipyridin)-4-yl-thiophene moiety. However, the specific coordination of Hg^2+ with Ru-1 via the thiol moiety in the thiocyanate enlarges the band gap of tlie complex and reduces the photocurrent significantly. The synergistic interaction between TiO2 nanoparticles and the Ru-1 complex led to a selective PEC sensing strategy for Hg^2+ detection. Detectable linear ranges from 10^-12 g/mL to 10^-7 g/mL and from 10^-7g/mL to 10^-3 g/mL were obtained without the interference from possibly co-existed metal ions. The good analytical performances indicate the chemical probe based biomolecule-free PEC platform may offer a new route for the detection of biologically and environmentally important small molecules.     

高效自组装二氧化钛纳米管阵列光电催化降解葡萄糖的动力学和机理

 研究了自组装 TiO2 纳米管 (TNAs) 光电催化降解葡萄糖的动力学和机理. 利用薄层反应器进行耗竭反应, 研究了 TNAs 表面催化反应和溶液本体-扩散层传质有关的葡萄糖降解过程. 采用电流-时间曲线以及相应的微分曲线分析了光电化学催化降解的微观进程. 结果表明, 葡萄糖的初始浓度与降解的起始电流强度符合 Langmuir 吸附等温式 I0ph = 0.00008c0/(1 + 0.69274c0) + 0.00034, 葡萄糖在 TNAs 薄膜催化剂表面的吸附为单一分子层吸附, 其光电催化降解反应符合一级反应动力学, 葡萄糖降解反应经历了三个不同的反应过程.     

Highly Sensitive Enzyme-free Sensor Based on a Carbon Paste Electrode Modified with Binary Zinc Oxide/Polyaniline Nanocomposites for Dopamine,Ascorbic Acid and Uric Acid Sensing

Hybrid composites ZnO/PANI were facily synthesized by a sonication process at room temperature. This procedure is non-expensive, time/energy saving and environmentally safe. The as-prepared ZnO/PANI were characterized by FTIR, UV-vis spectroscopies and SEM in order to investigate the structure and morphology of the studied composites. The samples were used to modify carbon paste electrode (CPE) in order to develop electrochemical biosensors (ZnO/PANI/CPE). The sensing properties of the nanoparticles were evaluated for dopamine, ascorbic acid and uric acid non-enzymatic detection. The effect of percentage of polyaniline in the composites and the effect of calcination on the biosensor's response were also examined in the present study. It was revealed that the existence of PANI in ZnO/PANI/CPE largely enhanced the electroactive surface area and therefore the sensitivity for electrochemical sensing. A good electrochemical behavior was noted for ZnO/40 wt% PANI-cal/CPE modified electrode toward DA, AA and UA oxidation. The electroactive surface area of the previously mentioned modified electrode (0.235 cm²) was two times higher than that of the bare electrode (0.117 cm²). The liner relationships between current intensities and concentrations were found to be 0.01–1.4 mM, 0.1–1.3 mM and 0.01–0.12 mM, with detection limit of 0.029 mM, 0.063 mM and 0.007 mM, for DA, AA and UA respectively. In the mixtures of ascorbic acid (AA), dopamine (DA) uric acid (UA) and glucose (Glu) the sensor showed high selectivity of DA with low interference of ascorbic acid by a current change of 14 %. The as-prepared ZnO/PANI/CPE biosensor displayed a good reproducibility and stability.     

Highly Emissive Metal-Organic Frameworks for Sensitive and Selective Detection of Nitrofuran and Quinolone Antibiotics

The overuse of antibiotics makes its detection very significant for human health. New facile methods and high-performance sensory materials will be urgently needed for detection of antibiotics. Unfortunately, there are few reports on fluorescence enhancement of antibiotics detection. Herein, based on the modulability of the coordination mode, we proposed two MOFs with different coordination modes based on different metal ions: Zn-MOF ( 1 ) and Cd-MOF ( 2 ). The fluorescence of 1 and 2 can be efficiently and selectively quenched by nitrofuran antibiotics (nitrofurazone, NFZ and furazolidone, FZD) and chloramphenicol (CAP), respectively. Particularly, the matched energy levels between 2 and enrofloxacin (ENR) enables 2 with turn-on sensing for ENR. Moreover, apart from the sensitivity and selectivity, 1 and 2 also have strong recyclable ability, fast response time and anti-interference ability, which make them great potential sensory materials to detect antibiotics.     

Ruthenium(II) and Osmium(II) Vinyl Complexes as Highly Sensitive and Selective Chromogenic and Fluorogenic Probes for the Sensing of Carbon Monoxide in Air

The detection of carbon monoxide in solution and air has been achieved using simple, inexpensive systems based on the vinyl complexes [M(CH?CHR)Cl(CO)(BTD)(PPh₃)₂] (R=aryl, BTD=2,1,3‐benzothiadiazole). Depending on the nature of the vinyl group, chromogenic and fluorogenic responses signalled the presence of this odourless, tasteless, invisible, and toxic gas. Solutions of the complexes in CHCl₃ underwent rapid change between easily differentiated colours when exposed to air samples containing CO. More significantly, the adsorption of the complexes on silica produced colorimetric probes for the naked‐eye detection of CO in the gas phase. Structural data for key species before and after the addition of CO were obtained by means of single X‐ray diffraction studies. In all cases, the ruthenium and osmium vinyl complexes studied showed a highly selective response to CO with exceptionally low detection limits. Naked‐eye detection of CO at concentrations as low as 5 ppb in air was achieved with the onset of toxic levels (i.e., 100 ppm), thus resulting in a remarkably clear colour change. Moreover, complexes bearing pyrenyl, naphthyl, and phenanthrenyl moieties were fluorescent, and greater sensitivities were achieved (through turn‐on emission fluorescence) in the presence of CO both in solution and air. This behaviour was explored computationally using time‐dependent density functional theory (TDDFT) experiments. In addition, the systems were shown to be selective for CO over all other gases tested, including water vapour and common organic solvents. Supporting the metal complexes on cellulose strips for use in an existing optoelectronic device allows numerical readings for the CO concentration to be obtained and provision of an alarm system.