Design of a Fluoride-Selective Colorimetric Receptor and Its Fluoride Recognition Mechan

［中文文摘］将酰胺识别基团耦合至基态具有分子内电荷转移特征的对硝基苯基偶氮苯胺分子中 ,设计合成了受体分子N 苯甲酰基 4 ( 4′ 硝基苯基偶氮基 )苯胺 ( 3 ) ,对氟离子表现出极高的识别选择性 .乙腈中该受体 3的最大吸收峰位于 3 80nm ,加入氟离子后 ,该吸收峰强度逐渐减弱 ,同时在 5 3 0nm处出现新的吸收峰 ,后者为受体分子与氟离子形成的 1∶1配合物的吸收峰 .溶剂极性效应实验表明 ,该吸收峰具有电荷转移特征 .引入氟离子后受体 3溶液的颜色由浅黄色转变为紫红色 ,可实现氟离子的裸眼检测 .质子溶剂效应 ,1HNMR滴定为受体分子 3与阴离子间的氢键作用本质提供了直接证据.［英文文摘］　This paper will report the design and synthesis of a fluoride2selective colorimetric receptor , N2benzoyl242 (4′2 nitrophenylazo) aniline , 3 , in which amide as recognition group was coupled to 42(4′2 nitrophenylazo) aniline (2) of ground2state intramolecular charge transfer character. It was found that 3 had an absorption maximum at 380 nm in acetonitrile , which decreased gradually upon addition of F- . A new band peaked at 530 nm appeared , which turned the solution from light yellow to purplish red. The new band due to the hydrogen bonding complex of 3 with F- was shown to be of charge transfer character by the observation of a substantial red shift with increasing solvent polarity. 1H NMR titrations confirmed hydrogen bonding interaction between 3 and F- .国家自然科学基金 (No .2 0 1 750 2 0 );福建省自然科学基金 (No.D0 2 2 0 0 0 1 );教育部优秀青年教师奖励计划 (2 0 0 1 );德国大众基金 (No .I/ 770 72 )资助项目

INTRAMOLECULAR CHARGE TRANSFER AND PROTON TRANSFER IN BENZANILIDE DERIVATIVES

苯甲酰苯胺衍生物分子内电荷转移与质子转移 摘要 本文系统研究了苯甲酰苯胺类衍生物分子内电荷转移（IntramolecularChargeTransfer,ICT）与质子转移（ProtonTransfer,PT）反应的取代基效应，揭示了取代基对CT与PT过程的不同调控功能，并初步探索了该类衍生物在荧光传感与分子识别中潜在的应用。全文共分四部分。 第一部分，分子内电荷转移荧光传感与分子识别。评述了对二甲氨基苯甲腈（DMABN）与苯甲酰苯胺（BA）两类ICT化合物分子内电荷转移研究以及基于电荷转移的荧光传感与分子识别研究的最新进展，分两章。 第一章简单介绍了经典的ICT化合物DM...INTRAMOLECULAR CHARGE TRANSFER AND PROTON TRANSFER IN BENZANILIDE DERIVATIVES ABSTRACT The abnormal emission behavior of benzanilide (BA) was first reported by O’Conell et al. in the early 1970’s and has become a subject of intense interest in the past few decades. A proton transfer (PT) model was first proposed by Kasha and co-workers, in which the abnormally long wavelength emission of B...学位：理学博士院系专业：化学化工学院化学系_分析化学学号：B20002501

Intramolecular Charge Transfer and Proton Transfer Fluorescence of Salicylanilides

[中文文摘]将苯甲酰苯胺(BA)类电荷转移(CT)反应基团耦合到具有激发态分子内质子转移(ESIPT)反应通道的水杨酸(SA)分子中,设计合成了苯胺对/间位取代的水杨酰苯胺及其羟基甲基化衍生物邻甲氧基苯甲酰苯胺,考察了环己烷、乙醚、乙腈和甲醇中两类水杨酰苯胺衍生物吸收光谱和荧光光谱的溶剂效应和取代基效应.结果表明,水杨酰苯胺的荧光为SA-型质子转移(PT)荧光,对取代基的依赖性较小;当电子给体苯胺基的给电子能力提高时,如N-甲基水杨酰苯胺分子,其荧光为BA-型CT荧光.而羟基甲基化后的衍生物邻甲氧基苯甲酰苯胺则表现出与BA类似的荧光光谱特性,具有明显的取代基效应.认为水杨酰苯胺衍生物的激发态存在着相互竞争的BA-型CT和SA-型PT通道,二者可经苯胺基上取代基的电子效应调控.[英文文摘]The intramolecular charge transfer(CT)reaction known to occur in benzanilide(BA)derivatives was coupled to salicylic acid(SA)for understanding the substituent e ffect on the proton transfer fluorescence in comparison with that on the CT fluore scence.A series of salicylanilides1,in which the SA structural framewor k was incorporated in the electron acc eptor moiety of the BA-like CT fluoro phore,were designed and their absor ption and fluorescence spectra were investigated in aprotic solvents CHX,DEE,and ACN and protic solven MeOH.国家自然科学基金(20175020);福建省自然科学基金(D0220001);教育部优秀青年教师奖励计划(2001);德国大众基金(I/77072)资助项目

Recognition of Anion by Dual Fluorescent Sensor Based on the Intramolecular Charge Transfer in p-Dimethylaminobenzoylhydrazine

In t ramo lecu lar charge t ran sfer ( ICT ) dual f luo rescence of p 2dim ethylam ino2 benzoylhydrazine (DMABH ) in aceton it rile w as found to show a h igh ly select ive respon se to HSO -4 over several other an ions. The inten sity rat io of the CT to L E em ission and the to tal f luo rescence intensity of DMABH decreased with increasing bisulfate concent ration. While the dual f luo rescence respon se w as very sim ilar to that of DMABA at a low HSO4 concen t rat ion, the CT in ten sity decreased drast ically and the L E in ten sity rem ained almo st con stan t, how ever, the difference w as ob served at a h igh HSO -4 concen t rat ion, in w h ich bo th the CT and L E in ten sit ies of DMABH decreased. A different recogn it ion m echan ism f rom that of DMABA w as suggested fo r DMABH in w h ich hydrogen bonding and p ro ton izat ion w ere the recogn it ion in teract ion s at low and high HSO4 concen t rations,respectively.国家自然科学基金 (批准号 :2 0 175 0 2 0 );福建省自然科学基金重点课题 (批准号 :D0 2 2 0 0 0 1);教育部优秀青年教师奖 励计划 ( 2 0 0 1年 )和德国大众基金 (批准号 :I/770 72 )资助

BENZANILIDES: A KIND OF INTRAMOLECULAR CHARGE TRANSFER FLUORESCENCE PROBE

[中文文摘]评述了苯甲酰苯胺及其衍生物的发光行为和电荷转移 /质子转移光物理模型的研究进展 ,并展望了该类新型分子内电荷转移荧光体在化学及生物分子识别与传感中的潜在应用前景。[英文文摘]The research developments in the luminescence behavior and photophysics of benzanilide and its derivatives were reviewed in terms of the PT/ICT and TICT models that have been proposed to interpret the abnormal long-wavelength fluorescence emission. The potential applications of this class of novel intramolecular charge transfer fluorescence probes for chemo- and bio-molecular recognition and sensing were discussed. Forty-three important references were cited.国家自然科学基金资助项目 ( 2 0 1 75 0 2 0 );教育部优秀年轻教师基金;优秀青年教师奖励计划

应对方式、人格特征与应激水平的关系

目的：研究应对方式、人格特征与应激水平的相互关系。方法：对某企业集团中不同职业群体的4745名职工采用特质应对量表(TCSQ)、大五人格问卷(NEO-FFl)和自制的社会应激事件凋查表进行调查。结果：男性、20～30岁组、文化程度高的被试，其消极应对(NC)和积极应对(PC)高，应激水平高。NC与人格中的神经质(N)显著正相关，与外倾性(E)和严谨性(C)显著负相关；PC与N呈显著负相关，与E、C、宜人性(A)显著正相关逐步回归分析表明，影响应激水平的因素依次为NC、N、C、E、PC、A。结论：人格特征、应对方式与应激水平呈显著相关。性别、年龄、文化程度的差异对应对方式有一定影响

Anion Recognition by N-Benzamido-N′-phenylthioureas inAqueous-Organic Binary Solvents

[中文文摘]设计合成了三种N 取代苯甲酰胺基 N′ 苯基硫脲 ,应用吸收光谱考察了CH3 CN以及 1%～ 10 %H2 O CH3 CN溶液中其与CH3 CO-2 ,H2 PO-4,HSO-4,ClO-4,Cl-和Br-等阴离子的相互作用 .结果表明 ,该类主体分子与阴离子形成氢键配合物 ,溶液由无色转变为黄色 .通过改变苯甲酰基上的取代基可有效调控识别结合作用的选择性 ,在含水介质中苯甲酰基上对乙氧基取代的主体分子可高选择性识别CH3 CO-2 .探讨了主客体之间的作用机理 ,并用于水相中无机醋酸盐的直接显色测定 .[英文文摘]　Three N2benzamido2N′2 phenylthiourea receptors were designed and synthesized and their interactions with anions such as CH3CO- 2 , H2PO-4 , HSO-4 , ClO-4 , Cl - and Br - in acetonitrile and acetonitrile2water binary solvents were investigated by using absorption spectroscopy. The results showed that hydrogen2bonding complexes were formed between receptors and anions , which turned the solution to yellow from colorless. It was found that the selectivity of receptors to anion could be efficiently tuned by increasing solvent polarity or by substitution at the N2benzoyl moiety. The recognition mechanism and binding mode were discussed and the anion recognition was successfully applied to inorganic CH3CO2NH4 in 10 % H2O2CH3CN. These findings are expected to be of significance for designing and developing novel color2based anion sensors operated in aqueous solution.国家自然科学基金 (Nos.2 99750 2 3;2 0 1 750 2 0 ) ;福建省自然科学基金 (No.D0 2 2 0 0 0 1 ) ;德国大众基金 (No .I/770 72 );教育部优秀青年教师奖励计划(2 0 0 1 )资助项目

A Study on Relationship Among Coping, Personality, and Stress

目的 :研究应对方式、人格特征与应激水平的相互关系。方法 :对某企业集团中不同职业群体的 4 74 5名职工采用特质应对量表 (TCSQ)、大五人格问卷 (NEO -FFI)和自制的社会应激事件调查表进行调查。结果 :男性、2 0～ 30岁组、文化程度高的被试 ,其消极应对 (NC)和积极应对 (PC)高 ,应激水平高。NC与人格中的神经质 (N)显著正相关 ,与外倾性 (E)和严谨性 (C)显著负相关 ; PC与N呈显著负相关 ,与E、C、宜人性 (A)显著正相关。逐步回归分析表明 ,影响应激水平的因素依次为NC、N、C、E、PC、A。结论 :人格特征、应对方式与应激水平呈显著相关。性别、年龄、文化程度的差异对应对方式有一定影响

基于速度场的人工势场法机械臂动态避障研究

为了提高机械臂在动态避障时的安全性和精确性，提出一种基于速度场的人工势场避碰算法。首先，建立吸引速度场，得到机械臂对运动目标追踪的轨迹；然后，结合危险场法构建排斥速度场，使机械臂可以在多障碍物的环境下实现动态避障和安全性评估；最后，针对人工势场法易陷局部最小值的问题，提出在和速度的法方向添加附加速度的方法逃逸局部最小值。利用Matlab Robotics Tool对算法进行了验证，结果表明，基于速度场的人工势场法可实现机械臂的动态目标的追踪、移动障碍物避碰和安全性评估

军人心理应激研究及其进展

综述应激的基本模式 ,军人心理应激反应的类型、应对及研究进展。分析影响军人心理健康的主要因素 ,提出军人心理应激管理应注意从个体水平和组织水平两方面进行