二咔唑四苯乙烯多功能发光化合物的合成与性能

合成了一种新型的具有压致荧光变色效应的聚集诱导增强发光(PAIE)化合物二咔唑四苯乙烯; 通过核磁共振、质谱和元素分析等手段对其进行了结构表征; 利用紫外吸收光谱、荧光发射光谱、热分析和X射线衍射等手段研究了化合物的基本性能. 实验结果表明, 随着水含量的增加, 该化合物溶液荧光强度增强了171倍, 荧光量子产率提高了100倍, 表现出明显的聚集诱导增强发光效应; 在外界因素作用下该化合物固体样品可实现结晶态与无定形态的相互转变. 结晶态的荧光发射波长为450 nm, 无定形态为480 nm, 相差30 nm, 说明该化合物具有明显的压致荧光变色效应; 将该化合物用于制备发光器件, 未经优化的器件亮度达2438 cd/m², 电流效率为2.87 cd/A, 流明效率为1.81 lm/W. 该化合物是一种多功能材料.     

新型三唑基咔唑衍生物的合成及其光学性质

合成了一种新型的三唑基咔唑衍生物--3,6-二(1,2,4-三唑)-N-己基咔唑(4),其结构经1H NMR, IR和MS表征.利用UV,单光子荧光光谱和固体荧光光谱研究了4的线性光学性质,结果表明4有望成为具有应用价值的发光材料.     

2-糠醛缩N-乙基-3,6-二氨基咔唑双席夫碱的合成及其性能

以咔唑为起始原料经N-取代、硝化和还原反应制备中间体N-乙基-3,6-二氨基咔唑,然后以其与2-糠醛发生缩合反应制得新型双席夫碱化合物N-乙基-3,6-二(2-亚糠基亚氨基)咔唑,产率为72.36%。通过元素分析、FTIR、UV-Vis、1H NMR、溶液及固体荧光光谱、循环伏安(CV)和TG-DTA分析研究了标题化合物的分子结构、光物理特性、电化学特性和热稳定性。结果表明,化合物的DMF稀溶液在200~400 nm波段有较宽较强的紫外吸收;在365nm波长激发下,溶液发射深蓝色荧光,λem为446nm,固体荧光为λem=467nm的蓝色荧光,与溶液荧光相比固体荧光红移了21nm。由循环伏安测试得到产物的Eg=2.19e V,IP=4.99e V以及EA=2.80e V,说明其具有良好的空穴和电子传输材料性能。TG-DTA测试显示目标产物具有良好的热稳定性。该化合物在有机荧光、空穴注入传输材料以及电子传输材料方面具有潜在应用前景。     

聚丙烯酸修饰咔唑的电化学聚合及表征

合成了侧链带有咔唑的N-丙烯酰氧己基咔唑(MACZ),通过自由基聚合得到聚N-丙烯酰氧己基咔唑(PMACZ),在四氢呋喃含10%三氟化硼乙醚与四氟化硼四丁基胺的混合电解质溶液中,直接阳极氧化PMACZ获得自支撑交联网状的聚(聚N-丙烯酰氧己基咔唑)(PPMACZ)薄膜.PPMACZ薄膜具有良好的氧化还原性和热稳定性,电导率为1.34×10-5S·cm-1.1HNMR和红外光谱表明PMACZ二次聚合反应发生在咔唑单元的3,6位上,荧光光谱表明PPMACZ薄膜是一种良好的蓝色发光材料.     

脉冲激光法制备修饰纳米Eu_2O_3/聚苯胺导电杂化薄膜

采用聚焦脉冲激光法(PLA-IT/SFL)制备修饰纳米Eu2O3/聚苯胺有机溶胶及其杂化薄膜材料。考察了制备条件对修饰纳米Eu2O3/聚苯胺有机溶胶荧光性能的影响。TEM显示Eu2O3粒子粒径约为15 nm且其在聚苯胺中有较高的稳定性。荧光光谱表明该杂化薄膜材料在紫外光照射下发出强烈的红光,且荧光强度达2.53×105a.u。杂化薄膜材料的电导率为1.13×10-2S.cm-1。热分析表明该杂化薄膜比导电性聚苯胺(PAN-HCSA)薄膜具有更好的热稳定性。该杂化薄膜材料可望用于电致发光领域。     

离子自组装超分子荧光材料及其光致各向异性特性

采用离子自组装的方法,制备了侧链含有肉桂酸光敏基元和二苯乙烯荧光基元的新型超分子复合物PCAMSTIL.通过核磁共振(NMR)和红外光谱(FT-IR)表征了该超分子复合物的结构,并用热重分析(TGA)、紫外可见光谱(UV-Vis)和荧光光谱(FL)研究了其热稳定性和光学性能.将PCAMSTIL旋涂成膜,薄膜经过266 nm偏振脉冲激光辐照后,肉桂酸发生轴向选择的[2+2]加成,薄膜垂直于激光偏振方向的紫外可见吸收明显大于平行方向的吸收,证实薄膜具有取向性.取向薄膜的最大吸收二向色性取向值最大可达0.103,优于一般肉桂酸材料的取向性,肉桂酸分子的取向也引起二苯乙烯荧光分子的协同取向,荧光偏振发射比可达1.73.     

新型吡唑基咔唑衍生物的合成及其光学性质

以咔唑为原料,合成了一种新型的咔唑衍生物--9-丁基-3,6-二[3'-(5'-三氟甲基)吡唑基]咔唑(4),其结构经1H NMR,IR和MS表征.运用UV和单光子荧光光谱研究了中间体和4的光学性质,结果表明:4有望成为具有应用价值的发光材料.     

多色显示树枝状聚(3, 6-双噻吩咔唑)及其共聚物的电化学和电致变色性能

设计合成了一种新型的基于咔唑单元的树枝状3, 6-双噻吩咔唑衍生物(BTCPh),通过电化学聚合法制备出其均聚物及与3, 4-乙烯二氧噻吩(EDOT)的共聚物薄膜.利用电化学工作站-紫外可见光谱联用装置对两种聚合物的光谱电化学和电致变色(EC)性能进行表征.测试结果表明,均聚物(PBTCPh)薄膜在不同电压下可显示黄、绿、蓝、灰四种颜色;而EDOT单元的引入使共聚物P(BTCPh-EDOT)进一步增加了掺杂态,从而显示出更加丰富的五种颜色(橙、绿、棕绿、蓝、灰).此外,两种聚合物薄膜均具有良好的光学对比度和快速的响应速度,因而使其在智能窗及显示器方面展现了潜在的应用前景.     

咔唑及其衍生物在蓝光OLED中的应用

咔唑及其衍生物因其特有的电学性能、电化学性能和光物理性能而被广泛研究。由于这类材料不仅可以作为良好的空穴传输材料,而且在咔唑化合物的不同位置引入电子传输修饰基团,可以使得电子和空穴更加易于注入,并且可以很好地调节两者的平衡,因此,咔唑及其衍生物被认为是一类重要的蓝光荧光材料。咔唑及其衍生物不仅可以以小分子形式应用到蓝光荧光材料、蓝光磷光材料和热致延迟荧光材料,同样可以以高分子形式应用到蓝光荧光材料中。近年来,关于咔唑及其衍生物发光材料的合成及应用成为蓝光OLED研究的热点。本文综述了近年来国内外小分子咔唑及其衍生物作为蓝光有机电致发光主体材料的研究状况,对其分子结构设计光、电子轨道结构、物理性质、热学性质、电化学性质及器件性能等方面作了详细归纳比较,同时归纳了含咔唑结构的聚合物蓝光有机电致发光材料的研究进展,最后展望了咔唑基蓝光有机电致发光主体材料的发展前景和趋势。从光电转换效率及价格方面来说,热致延迟荧光材料和聚合物(含咔唑类基团)发光材料是最具有前景的蓝光OLED材料。     

三苯胺类自供能电致变色材料合成及器件开发

设计并合成了一种新型三苯胺衍生物: (4-((4-(二甲基氨基)苯基)(苯基)氨基)苄基)膦酸, 并研究了它的光谱电化学性质和光伏性质. 光谱电化学谱图表明该化合物具有电致变色性能: 通过施加不同电压, 该化合物薄膜可以在透明态和着色态之间转换, 且在629 nm处透过率对比度达到最大, 为64.2%. 由该材料组装成的自供能电致变色器件具有光伏性能, 光电转化效率可以达到0.32%. 和传统的光电变色器件相比, 该新型器件具有结构简单、制备成本低廉、绿色环保等特点, 预计在建筑、汽车、显示器等领域将有广泛的应用.     

罗丹明类荧光探针的合成及对铜离子的检测

合成了罗丹明类Cu2+荧光增强型分子探针3',6'-双(二乙氨基)-2-(N-乙叉基氨基)螺[异吲哚-1,9'-占吨]-3-酮（RA）,并研究了它的光谱性能及对铜离子的识别作用.在乙腈/水（体积比1/1）的介质中,当加入Cu2+后探针RA显玫瑰红色,最大吸收波长为548 nm,最大发射波长为571 nm,且荧光强度显著增强,但是,其它常见离子如Na+, K+, Mg2+, Ca2+, Mn2+, Cd2+, Cr3+, Co2+, Ni2+, Ag+, Pb2+, Zn2+, Fe3+, Hg2+不引起或引起很小的紫外/可见或荧光光谱变化.RA的选择性荧光增强主要是由于Cu2+诱导分子中的酰胺闭环结构发生开环,导致分子结构的共轭程度增大.在6.5×10-8～2.9×10-6 mol?L-1范围内RA可以有效检测Cu2+,检测限为5.0×10-8 mol?L-1.RA对Cu2+的识别不可逆,而且探针RA对pH值不敏感,可以在比较宽的范围内（pH=4.1～10.5）高灵敏、高选择性检测Cu2+.     

2'-硼酸基苯甲醛-7-(8-羟基-5-磺酸基)喹啉腙衍生物的合成及对Pb2+的识别

合成了2', 3'和4'-硼酸基苯甲醛-7-(8-羟基-5-磺酸基)喹啉腙衍生物(化合物1~3), 研究了硼酸基团取代位置对主体分子识别金属离子客体性能的影响, 比较了不同主体分子与Pb2+结合能力的差异. 研究结果表明, 在pH=7.0的KH2PO4-NaOH缓冲溶液中, 3种腙衍生物对Pb2+均具有选择性识别作用, 主客体分子间形成1∶1型的发光配合物. 其中邻位取代的化合物1与Pb2+的结合能力比化合物2和3强, 配合物1-Pb2+的最大发射波长为477 nm, 稳定常数为1.1×103 L/mol. 其它金属离子如Cu2+, Mn2+, Mg2+, Fe2+, Ca2+, Co2+, Ni2+, Hg2+, Cd2+和Ag+ 等对主体分子荧光光谱的影响较小. 同时, 荧光强度的变化值与Pb2+浓度在0.36~10 μmol/L范围内呈现良好的线性关系, 相关系数R=0.9976(n=16), 检出限为0.23 μmol/L. 将此方法用于环境水样中Pb2+的测定, 回收率为92%~108%.     

基于双发射免标记核酸探针的比率型荧光传感器用于银的检测

构建了一种新型免标记的双发射荧光比率核酸探针(GelRed/[G40]/Tb^3+)并用于Ag+的检测。对于GelRed/[G40]/Tb^3+探针,GelRed作为一种核酸染料嵌入到单链DNA-[G40]中,形成的GelRed/[G40]作为稳定的内置参照标准,在激发波长290 nm处,发射荧光强度固定不变的红色荧光(发射波长为635 nm),而[G40]/Tb^3+作为敏感的响应信号,随着Ag^+浓度的增加,产生的绿色荧光逐渐增强(发射波长为545 nm),[G40]/Tb3+与GelRed/[G40]发射的荧光强度比值也发生相应的改变,从而实现对Ag^+的定量检测。在优化的实验条件下,[G40]/Tb^3+与GelRed/[G40]荧光强度比值和Ag^+浓度在0~7.5μmol/L的范围内具有较好的线性关系,Ag^+检出限为0.156μmol/L。本传感器在10 min内就可完成对Ag^+的分析。方法已用于自来水样中Ag^+的检测,与ICP-MS法检测结果一致。     

A novel wire-type lead-selective electrode based on bis (1'-hydroxy-2'-acetonaphthone)-2,2'-diiminodiethylamine

The preparation of a lead-selective electrode based on bis(1'-hydroxy-2'-acetonaphthone)-2,2'-diiminodiethylamine (L) as sensing material is reported. The plasticized PVC membrane containing 30% PVC, 67% ortho-nitrophenyloctylether (NPOE) and 3% ionophore L was directly coated on a graphite rod. This electrode exhibits a nearly Nernstian slope of 27.8+/-0.2 mV decade(-1) over a concentration range 10(-6)-10(-2) M with a detection limit of 4.0 x 10(-7) M. The response time of the electrode was found to be <20 s. The potential of the sensor was independent on pH variations in the range 5-7. The selectivity of the electrode towards lead ions over Na+, K+, Ag+, Ca2+, Sr2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, La3+, Sm3+ and Er3+ ions was investigated. The prepared electrode was successfully used as an indicator for titration of a lead solution with a standard solution of EDTA. The applicability of the sensor for Pb2+ measurement in various synthetic and real samples has been also demonstrated.     

A copper(II) ion-selective on-off-type fluoroionophore based on zinc porphyrin-dipyridylamino

A new copper(II) fluorescent sensor 5,10,15,20-tetra((p-N,N-bis(2-pyridyl)amino)phenyl)porphyrin zinc (1) has been designed and synthesized by the Ullmann-type condensation of bromoporphyrin zinc with 2,2'-dipyridylamine (dpa) under copper powder as a catalyst as well as with K2CO3 as the base in a DMF solution. It consists of two separately functional moieties: the zinc porphyrin performs as a fluorophore, and the dpa-linked-to-zinc porphyrin acts as a selected binding site for metal ions. It displays a high selectivity and antidisturbance for the Cu2+ ion among the metal ions examined (Na+, Mg2+, Cr3+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Ag+, Zn2+, Cd2+, Hg2+, and Fe3+) and exhibits fluorescence quenching upon the binding of the Cu2+ ion with an "on-off"-type fluoroionophoric switching property. The detection limit is found to be 3.3 x 10(-7) M (3s blank) for Cu2+ ion in methanol solution, and its fluorescence can be revived by the addition of EDTA disodium solution. The design strategy and remarkable photophysical properties of sensor 1 help to extend the development of fluorescent sensors for metal ions.     

水杨醛-4-甲氧基苯甲酰腙识别锌离子的研究

设计合成了荧光传感分子水杨醛-4-甲氧基苯甲酰腙(SAMB),通过IR、1HNMR和元素分析确证了其结构,利用紫外-可见吸收光谱和荧光光谱考察了其对不同阳离子的识别作用。结果表明,SAMB的荧光发射对锌离子表现出高选择性响应,且形成1∶1型配合物。乙醇中锌离子的加入导致SAMB的荧光增强328倍,而其他过渡金属离子只引起SAMB的荧光的略微增强。初步探讨了受体分子与锌离子的结合模式与荧光增强机理。     

Neutral bidentate organophosphorus compounds as novel ionophores for potentiometric membrane sensors for barium(II)

Bis(diarylphosphine oxide) naphthalene compounds are used as novel ionophores in plasticized poly(vinyl chloride) matrix membrane sensors for barium ions. The most favorable sensor was 1,2-bis(diethylphenylphosphine oxide)naphthalene containing potassium tetrakis(4-chlorophenyl)borate as lipophilic salt and o-nitrophenyloctyl ether as plasticizer for ion-selective electrode membrane construction. The electrode showed excellent properties. It gave a linear response with a Nernstian slope of 30 mV per decade within the concentration range 10(-1)-10(-5) mol L(-1) BaCl2. The electrode exhibits a high selectivity towards Ba2+ with respect to Li+, Na+, K+, Rb+, Cs+, NH4+, Ag+, Mg2+, Ca2+, Sr2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Pb2+, Al3+, La3+, and Ce3+ ions. The electrode response was stable over a wide pH range (3-11). The lifetime of the electrode was about 2 months. It was successfully applied to the determination of Ba2+ contents in some rocks.     

Carbazole‐based colorimetric and fluorescent probe for Cu2+ and its utility in bio‐imaging and real water samples

A new carbazole functionalized Schiff base CBM was synthesized and characterized. CBM can selectively recognize Cu²⁺ via UV–vis and fluorescence signal among common biologically relevant metal ions. When Cu²⁺ was added to CBM, there was a significant enhancement at the maximum absorption wavelength of 393 nm and with a distinct blue shift. The maximum emission peak was significantly attenuated by a factor of about 15 times at 535 nm and the blue shift of emission wavelength was observed. When other metal ions were added, there was no remarkable change at the maximum absorption and emission peak. Under the illumination of 365 nm ultraviolet lamp, the color of the CBM solution changed from light blue to dark blue after the addition of Cu²⁺. The combination mechanism of CBM with Cu²⁺ was nicely explored by density functional theory studies. The probe CBM has good cell permeability, fluorescence electron microscopy experiments show that CBM can be used as a fluorescent probe to detect the presence or absence of Cu²⁺ in Hela cells. Furthermore, the probe CBM can also be used for the detection of copper ions in actual water samples.     

Mercury(II) ion-selective electrodes based on p-tert-butyl calix[4]crowns with imine units.

A PVC membrane incorporating p-tert-butyl calix[4]crown with imine units as an ionophore was prepared and used in an ion-selective electrode for the determination of mercury(II) ions. An electrode based on this ionophore showed a good potentiometric response for mercury(II) ions over a wide concentration range of 5.0 x 10(-5) - 1.0 x 10(-1) M with a near-Nernstian slope of 27.3 mV per decade. The detection limit of the electrode was 2.24 x 10(-5) M and the electrode worked well in the pH range of 1.3 - 4.0. The electrode showed a short response time of less than 20 s. The electrode also showed better selectivity for mercury(II) ions over many of the alkali (Na+, -1.69; K+, -1.54), alkaline-earth (Ca2+, -3.30; Ba2+, -3.32), and heavy metal ions (Co2+, -3.67; Ni2+, -3.43; Pb2+, -3.31; Fe3+, -1.82). Ag+ ion was found to be the strongest interfering ion. Also, sharp end points were obtained when the sensor was used as an indicator electrode for the potentiometric titration of mercury(II) ions with iodide and dichromate ions.     

4-[2-(二甲氨基)乙氧基]-N-十八烷基-1,8-萘酰亚胺荧光染料的合成及其性能研究

以4-溴-1,8-萘酐为原料,合成脂溶性4-[2-(二甲氨基)乙氧基]-N-十八烷基-1,8-萘酰亚胺。对其进行了1H NMR和IR表征。考察了荧光染料在DMF、乙腈、丙酮、乙酸乙酯和乙醚5种溶剂中的荧光光谱和吸收光谱,发现由于溶剂效应,随溶剂极性由小到大,荧光光谱和吸收光谱的最大峰值波长逐渐红移。考察了不同金属离子和pH对荧光染料荧光光谱的影响,结果表明荧光强度随Fe3+、Zn2+、Co2+浓度增大而逐渐增强,Fe3+的影响最为显著;当pH<7时,荧光强度随着pH的降低逐渐增强;进一步考察了Fe3+、Zn2+、Co2+对吸收光谱的影响,结果发现吸收光谱均蓝移。分析认为荧光染料的光致电子转移被阻碍,实验结果表明,合成的新型荧光染料可用于溶液中金属离子和pH的检测。