基于共轭高分子材料的光学生物传感器

以聚芴、聚噻吩、聚乙炔为典型代表的共轭导电高分子材料,是作为传感元件进行光、电信号传导的优异材料,目前已成为生物传感器领域研究的热点。基于不同类型,不同性质的共轭高分子所设计的传感策略特色各异,功能也不尽相同,例如,利用共轭高分子可以与某些电子/能量受体之间发生电子/能量转移的特点,可以使传感器的检测信号得到数百万倍的放大,从而极大地提高检测的灵敏度;利用共轭高分子的光学性质随构象变化而变化的特点,则可以实现对靶介导的生物分子的构象或结构转变的检测。本文对各种基于不同传感策略的共轭高分子光学生物传感器研究进行了综述,并对该领域的发展前景进行了展望。     

过渡金属离子识别的1，8-萘二甲酰亚氨衍生物作为荧光传感器的研究

Two fluorosensor systems have been designed and synthesized with their photophysical properties and fluorescence responses toward the transition metal ions studied. The fluorosensor was composed of 1,8-naphthalimide and 4-chloro-1,8-naphthalimide as fluorophore respectively, an amino moiety as the receptor and a hydrocarbon chain as the spacer to link the fluorophore and receptor. Fluorescence intensity of these systems is very weak due to the process of the efficient intramolecular photoinduced electron transfer （PET） in the absence of metal ions. Titration of the transition metal ions can switch on the fluorescence immediately. The intensity of released fluorescence is even higher than the expected from the consideration of the PET in these systems. It may be rationalized that the receptor bound to transition metal ions and the solvation of the fluorophore by the water molecules from the hydrated transition metal salts, may significantly cause fluorescence enhancement.     

叔丁基取代二苯并-18-冠-6的合成

以二甘醇和邻苯二酚为原料制得二苯并-18-冠-6;以多聚磷酸为催化剂和溶剂,将二苯并-18-冠-6与叔丁醇反应实现叔丁基化;利用正庚烷重结晶对叔丁基化反应产物进行纯化,得到4,4′-二叔丁基二苯并-18-冠-6和4,5′-二叔丁基二苯并-18-冠-6两种对称的二叔丁基二取代苯并冠醚产品.利用红外光谱和核磁共振谱表征了二叔丁基二取代苯并冠醚产物的结构。     

2，3-二氨基萘荧光光度法测定楚雄地区糖尿病患者发硒含量

采用2,3-二氨基萘荧光光度法测定了楚雄地区糖尿病患者发硒含量,选取糖尿病患者50例,健康人群30例进行测定。结果表明,楚雄地区糖尿病患者发样中硒含量总体平均值为（0．3052±0．1263）μg/g,健康人群发样中硒含量总体平均值为（0．3345±0．1512）μg/g,糖尿病患者发样中硒含量明显低于健康人群,差异有统计学意义。     

氯化铜对6-甲氧基-2-酰基萘选择性氯化反应

甲氧基酰基萘;甲氧基萘;氯化铜对6-甲氧基-2-酰基萘选择性氯化反应     

吖啶基功能化二苯并-18-冠-6的合成

通过改变离去基团的活性、亲核试剂、溶剂的极性、离子性及反应温度等,对传统的U llm ann合成法进行了优化,将二苯并-18-冠-6进一步功能化,合成了未见文献报道的N,N′-二-(9-吖啶基)-4,4′-二氨基二苯并-18-冠-6,收率在87%以上。其结构经1H NMR,IR及元素分析表征。     

微波辅助二苯并-18-冠-6的合成

以邻苯二酚与二甘醇二取代物为原料,氢氧化钾为碱和模板剂,在微波辅助下,采用“一锅煮”法合成二苯并-18-冠-6。 经单因素及正交实验考察了原料、溶剂、时间、温度和功率对反应收率的影响,获得了最佳的工艺条件：以邻苯二酚与二氯乙醚为原料,二甲亚砜为溶剂,反应温度70 ℃,时间60 min,功率500 W,收率可达46.3%。     

4＇，4＂（5＂）-{二-[1，3]二氧[4，5-g]喹啉}-二苯并-18-冠-6的合成

6-氨基胡椒醛与4＇，4＂（5＂）-二乙酰基二苯并-18-冠-6进行Friedlander缩合得到新的冠醚衍生物——4＇，4＂（5＂）-{二-[1，3]二氧[4，5-g]喹啉}-二苯并-18-冠-6（3），产率62％。3的结构经UV，^1H NMR，^13C NMR，IR和MS表征。     

2-甲基-6-乙酰基萘结构的表征

2-甲基-6-乙酰基萘是一种有发展前景的化工产品。本实验在合成和精制的基础上,采用气相色谱、质谱、^1H、^13C及二维核磁共振技术表征了2-甲基-6-乙酰基萘的结构,首次给出了该化合物的化学位移数据。     

二环己基并18冠6的制备方法

二苯并-18－冠-6;二环己基并18冠6的制备方法     

基于荧光共轭聚合物的金属离子检测

以聚乙炔、聚芴、聚噻吩、聚苯撑为代表的荧光共轭聚合物,由于具有独特的光学性能、自组装性能和结构与性能的可调控性,可作为优异的光学传感材料。利用其具有较高摩尔消光系数和荧光量子产率的特点,可设计具有较高灵敏度和选择性的传感器,这已成为生物传感领域的研究热点。以荧光共轭聚合物为基础的金属离子检测,最初是以非水溶性的共轭聚合物为主,通过金属离子与聚合物链上特定基团(如吡啶、冠醚)的结合引起的聚合物荧光性质的变化可实现对某些离子的检测。在共轭聚合物主链上引入亲水性侧链,可大大增强共轭聚合物的水溶性,为金属离子的生物传感检测提供了新的思路,例如可引入能与金属离子结合的生物分子(如DNA、糖基等)来设计传感策略,进一步提高检测的特异性和灵敏度。本文综述了近年来以非水溶性和水溶性荧光共轭聚合物为传感材料,对具有重要生物学意义的重金属离子(Hg²⁺、Pb²⁺)、过渡金属离子(Cu²⁺、Eu³⁺、Ni²⁺、Fe³⁺、Fe²⁺、Ru³⁺、Ag⁺)和碱金属离子(K⁺、Na⁺、Li⁺)进行高灵敏度检测方面的研究进展,并对该领域的发展前景进行了展望。     

Lead-Selective Membrane Electrode Based on Dibenzopyrydino-18-Crown-6

Abstract

A lead ion-selective electrode based on dibenzopyridino-18-crown-6 as membrane carrier was successfully prepared. The electrode exhibits a Nernstian response for Pb²⁺ ions over a wide concentration range. Influences of the nature of plasticizer, the concentrations of internal solutions in the electrodes and the composition of the membrane were investigated. The lead ion-selective electrode exhibited comparatively good selectivities with respect to alkali, alkaline earth and some transition and heavy metal ions.     

醇系溶剂中冠醚与碱金属离子的配位反应

The enthalpy changes, entropy changes and equilibrium constants of coordination reactions of 18-crown-6 with the alkali ions Na+ and K+ at 298.15K were measured by using RD-496 microcalorimeter with methanol, ethanol, n-propanol and n-butanol as solvents respectively. The results indicated that the enthalpy changes △rHm, entropy changes △rSm, and the stability of the complexes are closely related with the polarity of the solvents, and the order of the stability is ethanol>methanol>n-propanol>n-butanol>H2O for the same complex in the solvents investigated. The stability order was reasonably explained by relating the stability constants of the complexes with the dielectric constants of these solvents, and by using the model of solvated-desolvated ions and ion pair in the coordination reactions.     

1,8-萘酰亚胺为发色团的Zn2+荧光探针的合成及性能研究

合成了以1,8-萘酰亚胺为发色团,以联吡啶为离子受体的Zn²⁺荧光探针,并进行了表征及离子识别性能的研究。研究表明该化合物对Zn²⁺具有良好的识别性能,同时相对于Ca²⁺, Cd²⁺, Co²⁺, Cu²⁺, Hg²⁺, Fe³⁺, Mn²⁺, Ni²⁺, Pb²⁺等金属离子具有良好的选择性。     

Application of Ionic Complex of N 2 O 4 with 18-Crown-6 as an Oxidizing Agent for the Oxidation of Organosulfur Compounds

Complexation of gaseous N 2 O 4 with 18-Crown-6 affords an ionic complex of NO + ·;18-crown-6·;H(NO 3 ) m 2 . This reagent is a nitrosating agent for conversion of thiols to thionitrites. Disulfides can be obtained from coupling of thiols via thionitrites. Moreover this reagent is an oxidizing agent for conversion of thioethers into their corresponding sulfoxides and dithianes into their carbonyl compounds in an oxidative deprotection reaction.     

Peroxyoxalate Chemiluminescence Based on Fluorescent Conjugated Polymer for the Determination of Triton X-100

A novel peroxyoxalate chemiluminescence system has been designed for the determination of Triton X‐100 (TX‐100), in which a hydrophobic fluorescent conjugated polymer, poly[2,5‐bisnonyloxy‐1,4‐phenylene‐ethynylene‐9,10‐anthrylene] (PPEA) was employed as a fluorophor. A strong enhanced intensity of chemiluminescence (CL) was observed in the presence of TX‐100, due to the improved emission efficiency of PPEA in the presence of TX‐100. Under optimum conditions, the detection range of Triton X‐100 is between 1.0×10^?7 and 1.0× 10^?4 mol·L^?1, with a detection limit at 6.0×10^?8 mol·L^?1. The relative standard deviation is 2.4% (n=6) for 1.0×10^?6 mol·L^?1 Triton X‐100. This method provides satisfying results in the detection of TX‐100 in nature water and biological samples with high sensitivity and wide linear range.     

Indium-based liquid clathrates. I. The preparation of the first indium liquid inclusion compound and crystal structure of its parent complex, [K · 18-Crown-6]2[InClI2(CH3)][InClI(CH3)2]

The synthesis of the first liquid clathrate derived from an indium precursor is described. The aromatic/anion ratio of the inclusion complex prepared using benzene is 12.4. The use of toluene results in the inclusion of 10.3 guest toluene molecules/anion. The crystal structure of the parent complex, [K·18-Crown-6]₂[InClI₂(CH₃)][InClI(CH₃)₂] was carried out. The compound belongs to the monoclinic space groupP2₁/c, witha=19.508(9),b=8.503(5), andc=29.437(9) Å, =96.55(3)°, andD _calc=1.83 g cm^–3 forZ=4. Least-squares refinement based on 3449 observed reflections led to a finalR=0.099. The structure displays two different environments for the two K⁺ cations in the asymmetric unit. One adopts the near-planar [K·18-crown-6]⁺ configuration while the other K⁺ resides 0.81 Å above the second 18-crown-6 plane. The latter K⁺ is apparently pulled out of the crown by a strong interaction with a Cl^– ion. Supplementary Data related to this article are deposited with the British Library as Supplementary Publication No. SUP 82046 (25 pages).     

A New Fluorescent Chemosensor for Cu2+ Based on 1,2,3,4,5,6,7,8,9,10‐Decahydroacridine‐1,8‐dione Fluorophore

A new chemosensor for Cu²⁺ was synthesized based on 1,2,3,4,5,6,7,8,9,10‐decahydroacridine‐1,8‐dione dyes, which exhibited an obvious fluorescent selectivity to the sensing of Cu²⁺ ions over other cations, such as Na⁺, K⁺, Ca²⁺, Cd²⁺, Co²⁺, Hg²⁺, Mg²⁺, Mn²⁺, Ni²⁺, Zn²⁺, Ag⁺ and Pb²⁺. Moreover, it presented a fluorescent switch function when EDTA was added to the compound‐Cu²⁺ complex in examined systems.     

Competitive Potentiometric Study of the Thermodynamics of Complexation of Some Transition and Heavy Metal Ions with Dibenzopyridino-18-crown-6 in Methanol using Ag+ Ion as a Probe

The complexation of dibenzopyridino-18-crown-6 with some transition and heavy metal ions in methanol solution at various temperatures was studied by a competitive potentiometric method using a Ag⁺/Agelectrode system. The stoichiometry and stability of the resulting complexes were computed by the MINIQUAD program. The stability of the resulting complexes varied in the order Ag⁺ > Pb²⁺ > Tl⁺ > Cu²⁺ > Cd²⁺ > Zn²⁺. The enthalpy and entropy of the resulting 1:1 complexeswere evaluated from the temperature dependence of the stability constants.The complexes of all cations were enthalpy-stabilized but entropy-destabilized,except for Ag⁺ and Pb²⁺ ions,which were also entropy-stabilized.     

基于多肽与金属离子作用的一种高选择性Cd2+荧光比率传感器

利用固相多肽合成法合成了一种新的多肽,将该多肽与荧光基团Dansyl偶联制备了一种新的荧光化学比率传感器:Dansyl-Cys-Pro-Pro-Cys-Trp-NH₂。利用荧光光谱研究了它与金属离子的相互作用。结果表明,与其它13种金属离子相比该多肽对金属Cd²⁺有很好的选择性。它能特异性识别Cd²⁺,具有水溶性好,响应时间快等优点。该肽对Cd²⁺具有很强的键合作用,其结合常数为3.0×10¹¹ L²·mol^-2,检出限为11.5 nmol·L^-1。