Design and Assemblying of Fluorescent Receptors for Molecular Recognition and Chemosensing

本论文共分五章。 第一章为绪论，介绍了分子识别与荧光传感领域所取得的最新研究成果及发展趋势。包括：(1)金属离子识别的传感体系；(2)糖的识别机理及荧光受体分子设计；(3)激发态非辐射内转换的研究进展；(4)自组装膜的构建、类型及其应用。 评述了分子识别与荧光传感体系中受体分子的设计思路以及自组装膜的最新研究进展，在此基础上提出论文设想。 第二章，基于激发态非辐射内转换(IC)原理设计荧光分子并建立对溶剂极性等介质环境敏感的识别体系。近期的研究认为1-N,N-二甲基氨基萘(DMAN)的荧光量子产率和荧光寿命随溶剂极性减小而减小和缩短的现象是IC所致，IC的发生与相邻的激发态S1,S2间能...This thesis consists of five chapters. In Chapter One, the discovery and developments in the field of fluorescent sensing and molecular recognition were briefly reviewed. Examples include (1) important sensing mechanisms for metal ions, (2) design of recognition systems for saccharides, (3) recognition systems based on fast radiationless internal conversion (IC) and (4) fabrication and applicati...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：B19992500

Dual Fluorescence from Aqueous 1-Naphthylamine Solutions of High pH ——Excited-State Acidic Dissociation of Naphthylamine

Dual fluorescence at ca. 447 nm and 545 nm w as observed from the aqueous 12naph thylam ine (NA ) solutions at pH h igher than 1316. Sim ilar dual fluorescence was also found w ith sodium12naph thylam inoacetate (NAA ) , but not w ith N , N 2disubstituted 12am inonaph thalenes such as sodium 12 naph thylam inodiacetate (NADA ) and 12dimethylam inonaph thalene (DMAN ). No change in absorption spectra of NA and NAA w as observed in th is pH region. It w as p roposed that the dual fluorescence ob2 served w ith NA and NAA w as due to the excited state dissociation of the p rimary and secondary am ines at h igh pH. F rom the dual fluorescence intensity ratio pH titration curve, the pK 3 ’ a s of NA and NAA w ere estimated to be betw een 14 and 15 w h ich aremuch low er than the ground state pK a. The novel app roatch is such a simp le, convenient and frequent analysis technique that it can bew idely used in detecting the sub2stitutional derivatives of am inonaph thalene.教育部优秀年轻教师基金(批准号 :教人司 2 0 0 0 -11);国家自然科学基金(批准号 :29975023)

Dual fluorescence from aqueous 1-naphthylamine solutions of high pH - Excited-state acidic dissociation of naphthylamine

Dual fluorescence at ca. 447 nm and 545 nm was observed from the aqueous 1-naphthylamine (NA) solutions at pH higher than 13.6. Similar dual fluorescence was also found with sodium 1-naphthylaminoacetate(NAA), but not with N, N-disubstituted 1-aminonaphthalenes such as sodium 1-naphthylaminodiacetate (NADA) and 1-dimethylaminonaphthalene (DMAN). No change in absorption spectra of NA and NAA was observed in this pH region. It was proposed that the dual fluorescence observed with NA and NAA was due to the excited state dissociation of the primary and secondary amines at high pH. From the dual fluorescence intensity ratio pH titration curve, the pK(a)(.)'s of NA and NAA were estimated to be between 14 and 15 which are much lower than the ground state pK(a). The novel approach is such a simple, convenient and frequent analysis technique that it can be widely used in detecting the substitutional derivatives of aminonaphthalene

GaNxAs1-x(x＜0.01)中合金态的光学特性

应用多种光谱手段研究了分子束外延生长在半绝缘的(001,GaAs衬底上的低氮含量的GaNAs中三元合金态的光学特性.变温PL谱揭示了合金态的本征特性以及其与氮的杂质态的根本区别,而脉冲激发的光荧光谱则进一步显示了合金态的本征光学特性.最后还研究了GaNAs的吸收光谱特征

Intramolecular Charge Transfer and Electron Transfer in N-(1-Naphthyl)aminoacetic Acid in Aqueous Solution

pH titration of the fluorescence of N-(1-naphthyl)aminoacetic acid(NAA) was performed in aqueous solution over pH range of 1 5â 12 5. Despite no shift in the fluorescence maximum wavelength, the titration curve showed an Ω-shaped profile with increasing pH with two inflection points at pH 4 1 and pH 11 5, respectively. These values correspond to the excited-state pK *_a î ±s of carboxylic group and ammonium cation, respectively, which are both higher than those of the corresponding ground-state pK_as of 2.64 and 11.83,of which the former changes more.The substantial weakening of the proton dissociation of carboxy lic group in the excited state should be indicative of the decrease in the inductive +I-effect of the ammonium cationat the B-position due to the excited-state intramolecular charge transfer from naphthalene moiety to ammonium.The latter was also confirmed by the slight increase inthe exited-statepK*a2. The fact that the increase inpK*a1is larger than that in pK*a2 suggests that the effect of the intramolecular charge transfer on the involved moiety be weaker than that on are motemoiety in the samespecies.This could be taken into consideration for designing means of tuning the structures and properties of peptide andp roteinvia photo-excitation.It was identified that the NAAzwitterion(â ¡)was the emissivespecies.The fluorescence quenching at high pH was assumed to be due to the photoinduced intramolecular electron transfer between carboxy late anion and the excited naphthalene moiety.The present caserep resents an example in which both in -tramolecular charge transfer and electron transfer occur to shape the pH titration profile.教育部优秀青年教师基金;留学回国人员基金;德国洪堡基金

A Bilayer Self-assembled Membrane Electrode for Fluorescence and Its Electrochemical Characterization

　以半胱胺酸为中介,利用荧光试剂1＿萘胺二乙酸钠(NADA)和DL＿半胱胺酸(Cys)的静电吸引作用,将荧光试剂NADA间接组装在金电极表面,形成自组装双层膜电极NADA/Cys/Au,该双层膜电极对金属离子具有荧光识别和电化学传感功能,本文着重研究了双层膜电极NADA/Cys/Au的电化学性能,并将其用于超痕量铜离子和镍离子的电化学分析连续测定.The bilayer membrane was assemblied on Au electrode by the electrostatic interaction between the fluorescence regent 1_naphthylamine diacetate acid(NADA) and DL_Cysteine. The SAMs electrode NADA/Cys/Au can be used as fluorescence and electrochemical sensor for metal ions. This paper states the electrochemical characterization of NADA/Cys/Au and SAMs' application in continous determination for Cu2+ and Ni2+.作者联系地址：华侨大学材料科学与工程学院,华侨大学材料科学与工程学院,厦门大学化学系 福建泉州362011,厦门大学化学系,福建厦门361005 ,福建泉州362011 ,福建厦门361005Author's Address: 1.College of Material Sciences and Engineering, Huaqiao University,Quanzhou 362011,China, University, Xiamen 361005,Chin

Enhanced methane production from SCFAs wastewater using single-chamber microbial electrolysis cell

传统厌氧消化基质转化慢,甲烷产率和能量回收效率较低.本研究模拟厌氧酸化产生的短链脂肪酸(SCFAs)废水,在批式条件下,利用单室无膜微生物电解池辅助厌氧消化(MEC-AD)产甲烷,考察不同外加电压(0.4 V、0.6V、0.8 V)对底物降解、甲烷产生和能量回收效率的影响.结果表明,进水化学需氧量(C OD)浓度约为7 000 mg/L时,COD的平均去除负荷由AD的(3.34±0.09)k g m-3 d~(-1)提高到MEC-AD的(6.86±0.04)kg m-3 d~(-1)(外加0.8 V),增加了1.06倍.外加电压与脂肪酸组分的降解呈正相关,即随着外加电压的升高,底物各SCFA降..

Dual Flrorescence of Anilino Substituted Benzanilides in Non-polar Solvent Cyclohexane——Direct Spectroscopic Evidence for the Excited-state Charge Transfer

The f luo rescence spect ra in cyclohexane of a series of benzan ilides (BA s) with different p a ra2sub st ituen t s at the an ilino mo iety revealed that BA s em it ted dual f luo rescence, w ith one no rm al w eak em ission at ca. 330 nm and an abno rm ally long2w avelength em ission ranging f rom 460 to 550 nm. The long2w avelength em ission w as found st rongly dependen t of the elect ron donat ing capacity of the sub st ituen t at the an ilino mo iety and a st ronger elect ron donat ing sub st ituen t led to a red2sh if t in the em ission. The energies of the long2w avelength em ission of the BA s w ere co rrelated to the ox ida2t ion po ten t ials of the dono rs, EDöD + , and a n ice linear co rrelat ion w as found w ith a slope of + 0166, w h ich clearly po in ted to the charge t ran sfer character of the em issive state fo r the long2w avelength e2 m ission and the h igh decoup ling ex ten t of the charges in the CT state. Th is is the f irst repo rt that show s the direct evidence fo r the CT natu re. The resu lt sm igh t be of sign if icance in understanding the photophysics of pep t ide and p ro tein and in designing novel fluorescent chemosensors.国家自然科学基金 (批准号 :2 9975 0 2 32 0 175 0 2 0 );教育部优秀青年教师奖励计划 (2 0 0 1年 );德国大众基金 (批准号 :I/770 72 )资助

A novel fluorescent aminoacid designed for fluorometric detection of Cu (II)

A fluorescent aminoacid was designed for selective and sensitive detection of Cu(II) in aqueous solution. The designing of this Cu(II) fluorescent chemosensing molecule, N-(1-naphthyl)aminoacetic acid (NAA), was based on the binding of Cu(B) to aminoacetic acid and the novel charge transfer photophysics of 1-aminonaphthalenes. The fluorescence of NAA was found quenched by Cu (H) and several other metal ions of similar electronic structure such as Co(II), Ni(II) and Zn(II). The quenching was shown to occur via electron transfer within the metal-NAA complex, which required an optimal combination of high binding affinity and favorable redox properties of the components in the metal-NAA complex and hence afforded selective fluorometric detection of Cu(II). The calibration graph obeyed Stern-Volmer theory and was shown for Cu(II) over the range of 0-2.75 x 10(-4) mol/L. The quenching constant of Cu(II) was measured as 8.0 x 10(3) mol/L that was two orders of magnitude higher than those of Co(II), Ni(II) and Zn(II). The 3SD limit of detection for Cu(II) was 8.00 x 10(-6) mol/L with a coefficient of variation of 1.65%. Linear range for quantitative detection of Cu (II) was 2.67 x 10(-5)-2.75 x 10(-4) mol/L. The method was applied to synthetic sample measurements which gave recoveries of 105%-112%

Study on Determination of Iodine Ion at Chitosan Modified Glassy Carbon Electrode

　应用共价键合法将壳聚糖修饰在玻碳电极表面,研究了I-在该修饰电极上的微分脉冲阳极溶出伏安特性,并对相关机理进行探讨.实验表明,修饰电极在pH为4.0的0.1mol·L-1KH2PO4溶液中,对I 具有良好的吸附性和选择性,电极响应灵敏.其阳极溶出峰电流在2.0×10-6～2.0×10-3mol·L-1I-浓度范围内呈良好线性关系,检出下限达2.0×10-7mol·L-1.该法应用于食用碘盐中总碘量的测定,取得较好的结果.In this paper, a chitosan modified glassy carbon electrode was prepared by the method of covalent-bond reaction, and the anodic stripping voltammetric characteristics of iodine on the modified electrode was studied. The results showed that the modified electrode has higher adsorption and selectivity for I~-, and the sensitivity for I~- has been much improved in 0.1 mol·L~(-1) KH_2PO_4 solution (pH=4.0). The anodic stripping peak current of I~- on the modified electrode varied linearly with I~- concentration in the range of 2.0×10~(-6)～2.0×10~(-3) mol·L~(-1), and the detection limit reached 2.0×10~(-7) mol·L~(-1).作者联系地址：华侨大学材料科学与工程学院,华侨大学材料科学与工程学院,华侨大学材料科学与工程学院 福建泉州362011 ,福建泉州362011 ,福建泉州362011Author's Address: College of Materials Science and Engineering,Huaqiao University, Quanzhou 362011,Chin